(Engineering Materials) Annelise Kopp Alves, Carlos P. Bergmann, Felipe Amorim Berutti (auth.)-Novel Synthesis and Characterization of Nanostructured Materials-Springer-Verlag Berlin Heidelberg (2013).pdf

Engineering Materials
Annelise Kopp Alves
Carlos P. Bergmann
Felipe Amorim Berutti
Novel
Synthesis and
Characterization
of Nanostructured
Materials
Engineering Materials
For further volumes:

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Annelise Kopp Alves · Carlos P. Bergmann
Novel Synthesis
and Characterization
of Nanostructured Materials
13
Annelise Kopp Alves
Carlos P. Bergmann
Escola de Engenharia
Departamento de Materiais - LACER
Universidade Federal do Rio
Grande do Sul
Porto Alegre
Brazil
ISSN 1612-1317 ISSN 1868-1212 (electronic)

ISBN 978-3-642-41274-5 ISBN 978-3-642-41275-2 (eBook)
DOI 10.1007/978-3-642-41275-2
Springer Heidelberg New York Dordrecht London
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Preface
This book contains an overview of Novel Synthesis and Characterization of

Nanostructured Materials. This kind of materials has been largely studied in the
past few years. They have great potential for applications in different fields such as
Engineering, Physics, Chemistry, Biology, and Medicine. Synthesis and character-
ization of nanostructured materials is a subject of great interest involving Science,
Technology, Market, Politicians, Government, and Society. Based on results
obtained by our research group during the past years, this book comes to present
novel techniques to synthesize nanostructured materials and characterize their
properties such as crystallinity and crystallite size, specific surface area, particle
size, morphology, and catalytic activity. This book is aimed for students, research-
ers, and engineers who search for general knowledge about the main methodolo-
gies to obtain and characterize nanostructures materials.
The following chapters present the general aspects of different synthesis of
nanostructured materials, such as Combustion Synthesis (Chap. 2), Spray Pyrolysis
(Chap. 3), Electrospinning (Chap. 4), Catalytical Chemical Vapor Deposition
applied in the Synthesis of Carbon Nanotubes and Carbon Nanotubes Forests
(Chap. 5), Hydrothermal Synthesis (Chap. 6) and High-Energy Milling (Chap. 7).
We hope that the clear language and the application-oriented perspective will
be suitable for professionals and students who want to access foremost knowledge
about Science and Technology concerning the synthesis and characterization of
nanostructured materials.
We would thank the staff of Springer Verlag for their professional guidance in
regard to this book.
Porto Alegre, Brazil, August 2013 A. K. Alves

C. P. Bergmann
F. A. Berutti
v
Contents
1 Introduction. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
2 Combustion Synthesis. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
2.1 Nanopowder Synthesis. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
2.2 Combustion Parameters. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
2.2.1 Flame Types. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
2.2.2 Characteristic Temperatures. . . . . . . . . . . . . . . . . . . . . . . . . . 15
2.2.3 Gas Generation. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
2.2.4 Atmosphere . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
2.2.5 Fuel-Oxidant Ratio. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
2.2.6 Chemical Composition of Precursor Chemicals . . . . . . . . . . 18
2.3 Fuels. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19
2.4 Oxidants. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19
References. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
3 Spray Pyrolysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23
3.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23
3.2 Spray-Pyrolysis Technique. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24
3.2.1 Atomization of Precursor Solution. . . . . . . . . . . . . . . . . . . . . 26
3.2.2 Aerosol Transportation. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 26
3.2.3 Decomposition of the Precursor. . . . . . . . . . . . . . . . . . . . . . . 27
3.2.4 Influence of Spray Parameters on the
Morphology of the Film. . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29
References. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29
4 Electrospinning. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 31
4.1 The Electrospinning Technique. . . . . . . . . . . . . . . . . . . . . . . . . . . . . 31
4.1.1 Jet Formation. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 34
4.1.2 Factors Influencing Fiber Characteristics. . . . . . . . . . . . . . . . 38
4.2 Electrospinning of Ceramic Fibers. . . . . . . . . . . . . . . . . . . . . . . . . . . 40
References. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 41
vii
viii Contents
5 CCVD Synthesis of Carbon Nanotubes. . . . . . . . . . . . . . . . . . . . . . . . . . 43

5.1 Carbon and Its Allotropes. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 44
5.2 Carbon Nanotubes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 46
5.2.1 Carbon Nanotubes Properties. . . . . . . . . . . . . . . . . . . . . . . . . 47
5.3 Carbon Nanotubes Synthesis. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 49
5.3.1 High Temperatures Methods . . . . . . . . . . . . . . . . . . . . . . . . . 49
5.3.2 CCVD. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 50
References. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 56
6 Hydrothermal Synthesis. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 61
6.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 61
6.2 Application. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 62
6.2.1 Hydrothermal Synthesis of Al2O3. . . . . . . . . . . . . . . . . . . . . . 65
6.2.2 Hydrothermal Synthesis of Zinc Oxide. . . . . . . . . . . . . . . . . 67
6.2.3 Titanium Oxide. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 69
References. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 74
7 High-Energy Milling. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 77
7.1 The High-Energy Milling Process. . . . . . . . . . . . . . . . . . . . . . . . . . . 78
7.2 Application of HEBM for Nanoparticle Production . . . . . . . . . . . . . 81
7.2.1 Nanotubes and Nanowires. . . . . . . . . . . . . . . . . . . . . . . . . . . 81
7.2.2 Ceramic Powders. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 82
7.2.3 Intermettalics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 83
References. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 84
Abstract
Nanotechnology is changing the way materials and devices are produced. The
ability to synthesize materials at the nanometer scale with precisely controlled
size and composition and to assemble them into large structures with unusual
properties and functions are revolutionizing all segments of material manufac-
turing for industrial applications. The properties of the nanopowders (crystalline
structure, amorphous structure, crystallite size, purity, specific surface area, and
particle agglomeration) depend heavily on the adopted technique and processing
parameters. Among the main techniques for generating nanoparticles Combustion
Synthesis, Spray Pyrolysis, Electrospinning, CCVD Synthesis of Carbon
Nanotubes, Hydrothermal Synthesis, and High-energy Milling are among the most
used. In this book, the reader will find an overview of how each of these main
techniques works with application examples.
Keywords Combustion synthesis • Spray pyrolysis • Electrospinning • CCVD

Synthesis of carbon nanotubes • Hydrothermal synthesis • High-energy milling
ix
Chapter 1
Introduction
The Science of Nanomaterials is proving to be one of the most attractive and

promising fields for technological development in this century. In the scientific lit-
erature several terms related to Nanoscience can be found, of which it is worth
highlighting nanoparticles, nanocrystals, nanofibers, nanotubes and nano-com-
posites. In fact, all these are related to nanostructured materials, which have well-
defined structural features. The physical and chemical properties of materials at
the nanometer scale (usually set in the range of 1–100 nm) are of immense interest
and increasing importance for future technological applications. Nanostructured
materials often exhibit different properties when compared to other materials.
The relationship between particle size and properties has been known since the
nineteenth century, when Faraday showed that the color of colloidal solution of Au
particles can be modified depending on their size. However, despite the long his-
tory of his discovery, the interest in nanoparticles has only increased significantly
in the last 15 years. The research activities related to this area were driven by the
ability to control material properties by controlling the size of the particles.
The Nanotechnology wave will likely change the way materials and devices are
produced in the future. The ability to synthesize crystallites at the nanometer scale
with precisely controlled size and composition and to assemble them into large
structures with unusual properties and functions will revolutionize all segments of
material manufacturing for industrial applications.
In the recent past years, a crescent number of research groups are involved
with the synthesis and characterization of nanostructured materials. The objec-
tive of most of such activities was to obtain materials with an unusual set of
properties, when comparing with the current existent materials. Hence, many
techniques to generate nanoparticles are focused on their eventual potential for
industrial application. The goal of all these processes is the production of high
purity powders with fine particle sizes, usually with small aggregation and or
agglomeration and with low production costs. The process of choice, however,
depends on the material in question, the application and the required amount of
reagents and products.
A. Kopp Alves et al., Novel Synthesis and Characterization of Nanostructured Materials, 1

Engineering Materials, DOI: 10.1007/978-3-642-41275-2_1,
2 1 Introduction
Fig. 1.1 Articles publishing survey regarding synthesis processes to obtain nanoparticles or

nanomaterials since 2003 (www.sciencedirect.com, accessed on 27th July 2013)
A way to see the importance that is given to nanostructured materials synthesis

processes is to consult the historical of article publishing concerning this subject.
Indeed, based on Fig. 1.1, which presents a survey about nanoparticles or nanoma-
terials synthesis processes, it is possible to observe a yearly increment of number
of papers published on this subject. For example, in 2012 only, over 19,000 papers
were available in the international literature regarding the synthesis of nanomaterials.
It is circa 18 % more than the year before and over nine times more than 2003.
Up to July 2013, the impressive number of 20,925 papers were already published
about this same subject.
Great part of these articles concerned about relative novel methods to produce
nanostructured materials, involving numerous ways in which nanoparticles can be
synthesized by solution processes, solid–solid or solid–gas reactions.
The solution processes have been increasingly investigated due to their peculiar
characteristics. Among these processes Solution Combustion Synthesis occupies a
special place, as a wet chemical route and a method for the preparation of highly
pure and homogeneous powders, with especial interest for obtaining nanocrys-
talline ceramic oxides. Figure 1.2 shows a historical survey of article publishing
regarding to the Solution Combustion Synthesis from 2003 up to mid-2013.
Spray-Pyrolysis process involves also a precursor solution that is sprayed through
an air atomizer on a heated substrate, producing thin films. It is well established that
1 Introduction 3
Fig. 1.2 Articles publishing survey regarding solution combustion synthesis techniques since

2003 (www.sciencedirect.com, accessed on 27th of July 2013)
the morphology and quality of the deposited films are strongly linked to the substrate
temperature. The films, dense or porous, have thicknesses ranging from 0.1 to
10 μm. Compared to the other techniques for the preparation of films, such as:
physical vapor deposition (PVD) and chemical vapor depositions (CVD), Spray-
Pyrolysis requires simple and inexpensive equipment and has as main advantages
the easy addition of doping materials, good reproducibility, high films growth rate,
chemical homogeneity in the final product and the potential for deposition over large
areas. An incremental number of articles in the last decade have been published con-
cerning Spray-Pyrolysis processes (Fig. 1.3).
Hydrothermal synthesis is another process that uses a precursor in solution.
It is known mainly by chemists as solvothermal synthesis, a term used to defined
chemical reactions in the presence of a solvent in supercritical or near supercriti-
cal conditions. Likewise, there are other terms such as glycothermal, allothermal,
ammonothermal, depending upon the type of solvent used in such reactions to dis-
solve and then recrystallize materials in a closed system. The purpose behind the
use of these different solvents in the chemical reaction is essentially to lower the
pressure and temperature for the reactions occurs. Figure 1.4 presents a historical
perspective of the number of article published regarding Hydrothermal Synthesis,
showing a rapid increasing of the number of investigations about this technique in
the international scenario.
4 1 Introduction
Fig. 1.3 Articles publishing survey regarding the Spray-Pyrolysis technique since 2003

(www.sciencedirect.com, accessed on 27th of July 2013)
Fig. 1.4 Growth of the number of articles published concerning the hydrothermal synthesis

from 2003 to mid-2013 (www.sciencedirect.com, accessed on 27th of July 2013)
1 Introduction 5
Fig. 1.5 Evolution of the number of papers published from 2003 to mid-2013 about electrospin-
ning synthesis (www.sciencedirect.com, accessed on 27th of July 2013)
A very interesting technique to produce nanostructured materials is electro-

spinning. This technique uses external electrical forces to produce polymeric
fibers of diameters in the range of 3–1,000 nm, depending upon the strength of
the applied voltage between a drop of the precursor solution and the collecting
surface. The possibility of extending this concept to ceramic oxide systems has
opened a new era in nanostructure research during the last 10 years, as suggested
by the increasing number of published articles on this topic (Fig. 1.5).
The outstanding electrical, thermal, mechanical and chemical properties of
carbon nanotubes (CNTs), especially single-walled carbon nanotubes (SWNT),
have interested researchers all over the world. One of the major problems concern-
ing the large scale use of CNT was the high cost and low efficiency of synthesis
and purification processes. Several different synthesis methods have been already
developed in the last decade (Fig. 1.6).
Synthesis of CNT over oxides supports by Catalytic Chemical Vapor Deposition
(CCVD) is one of the most important techniques for mass production of non-
aligned CNT. It could be useful for the production of composite materials, field
emission sources, fuel cells, supercapacitors among others technological applica-
tions. The CCVD method consists on the decomposition of a gas or a liquid pre-
cursor, which supplies carbon to the surface of the catalytic particles (e.g. Fe) in
a tube furnace at temperatures around 900 °C. This technique is scalable for mass
production at lower temperatures and could be adapted for continuous production.
6 1 Introduction
Fig. 1.6 Number of papers published concerning the production of carbon nano-tubes and carbon
nanotubes forests from 2003 to mid-2013 (www.sciencedirect.com, accessed on 27th of July 2013)
Fig. 1.7 Articles publishing survey concerning the high energy milling synthesis since 2003
(www.sciencedirect.com, accessed on 27th of July 2013)
Table 1.1 Comparison among nanomaterials synthesis methodologies
Method Advantages Disadvantages
Combustion synthesis • The reaction time is short and the process is simple • Agglomeration/aggregation can occur
• Low cost technique • Low crystallinity
1 Introduction
• Low heating temperature

• Used to prepare different types of materials (ceramic, intermetallic,
composite)
• Varied morphology of the produced powder
• Lower contamination
Spray pyrolysis • The time of the process is short • Non uniformity of the film thickness
• The equipment is simple • Wastage of solution
• Low cost • Low deposition rate
• Uniform and controllable distribution of particle diameters
• The purity of the products is high
• The process is continuous
• Multicomponent particles are easy to form
Electrospinning • Control over morphology, porosity and composition • Low productivity
• Simple equipment
• Low cost
• Different fibers materials can be product (ceramic, polymeric,
composite)
• Long continuous fibers can be produced
CCVD • Flexibility of using a wide range of chemical precursors • Hazards caused by the use of gaseous precursors
• Control of crystal structure, surface morphology and orientation • Difficult to deposit multicomponent materials
of the products
• Reasonable processing cost • The use of more sophisticated reactors can increase the
• Producing highly dense and pure materials productions costs
• Produces uniform films
• Relatively low deposition temperatures
7
(continued)
8
Table 1.1 (continued)
Method Advantages Disadvantages
Hydrothermal • Ability to synthesize crystals of substances which are unstable • High cost of the equipment
near the melting point
• Ability to synthesize large crystals of high quality • Inability to monitor crystals during the process
HEBM • Easy handling • Presence of impurities
• Relatively inexpensive • Low productivity
• Applicable to any class of materials
• Can be easily scaled up to large quantities
• Reproducible results
• Suitable for dry and wet operations
1 Introduction
1 Introduction 9
One of the latest advances in this field was the use of water vapor during the
synthesis. The addition of small fractions of water helps to keep the catalyst active
for much longer to selectively oxidize the amorphous carbon. Water assisted
CCVD greatly enhances the quality of the produced carbon nanotubes forests, not
only increasing their height (from micrometers to millimeters), but also reducing
the amount of impurities.
Nanoparticles can also be produced by mechanical attrition. Such nanoparticles
are formed in a mill in which energy is used to transform course-grained materials
into nanopowders. In the last decade, an increasing number of articles have been
published regarding High Energy Milling Synthesis (Fig. 1.7).
In this process, the particles themselves can have a size distribution of less than
100 nm, and then be called nanoparticles. Sometimes, as is common in materi-
als milled using mechanical attrition, the product is highly crystalline, and the
crystallite size is between 1 and 10 nm in diameter, and the system is then called
nanocrystalline materials.
These different techniques have particularities regarding the type of material
use, the production costs, the size distribution of the particle produced, the time
to obtain the products and the purity of the final product. The application and
the existence of adequate equipment help to select the best technique to obtain a
certain nanomaterial. Table 1.1 compares de advantages e disadvantages of these
different nanomaterials synthesis methods.

Chapter 2
Combustion Synthesis
The Science of Nanomaterials is proving to be one of the most attractive and

promising fields for technological development in this century. In the scientific lit-
erature several terms related to Nanoscience can be found, of which it is worth
highlighting nanoparticles, nanocrystals, nanofibers, nanotubes and nanocompos-
ites. In fact, all these are related to nanostructured materials, which have well-
defined structural features. The physical and chemical properties of materials at
the nanometer scale (usually set in the range of 1–100 nm) are of immense interest
and increasing importance for future technological applications. Nanostructured
materials often exhibit different properties when compared to other materials.
The relationship between particle size and properties has been known since the
nineteenth century, when Faraday showed that the color of colloidal Au particles
can be modified depending on their size. However, despite the long history of their
discovery, the interest in nanoparticles has only increased significantly in the last
15 years. The research activities related to this area were driven by the ability to
control material properties by controlling the size of the particles.
The nanotechnology wave will likely change the way materials and devices are
produced in the future. The ability to synthesize crystallites at the nanometer scale
with precisely controlled size and composition and to assemble them into large
structures with unusual properties and functions, will revolutionize all segments of
material manufacturing for industrial applications. Among the main techniques for
generating nanoparticles via the wet chemical route, combustion synthesis is the
one that stands out.
Solution combustion synthesis (SCS) is an effective method for the synthesis of
nanoscale materials and has been used in the production of various ceramic pow-
ders for a variety of advanced applications.
Ceramic oxide powders at the nanoscale using SCS can be prepared by the
combination of metal nitrates in an aqueous solution with a fuel. Glycine and
urea, in particular, are suitable fuels because they are amino acids that can act as
a complexing agent of the metal ion in the solution and also serve as fuel for the
synthesis of nanocrystalline metal oxides. This method can directly produce the

12 2 Combustion Synthesis
desired final product, although in some cases, a subsequent heat treatment of the
synthesized powder is needed to promote the formation of the required phase.
The properties of the resulting powders (crystalline structure, amorphous
structure, crystallite size, purity, specific surface area and particle agglomeration)
depend heavily on the adopted processing parameters. It is surprising, however,
how little information is available on the parameters of combustion and reaction
mechanisms, despite all SCS studies emphasizing the characterization of the syn-
thesized materials.
In the case of the synthesis of alumina, chrome, nickel, iron and nanocrystal-
line cobalt oxides using the solution combustion technique, for example, we lack,
so far, a deep understanding of the influence of the fuel-oxidant ratios well as a
model of the thermodynamic variables associated with enthalpy, adiabatic flame
temperature and the total number of moles of gas generated related to the powder
characteristics, such as crystallite size and surface area.
2.1 Nanopowder Synthesis
There are numerous ways in which ceramic powders can be synthesized: solution,
solid-solid or solid-gas processes. The solution processes have been increasingly
used due to their peculiar characteristics. The goal of all these processes is the pro-
duction of high purity powders with fine particle sizes, usually a small aggregation
and/or agglomeration and produced at low costs. The process of choice, however,
depends on the material in question, the application and the required amount of
reagents and products.
A method for the preparation of highly pure and homogeneous powders, espe-
cially interesting for obtaining nanocrystalline powders such as ceramic oxides, is
solution combustion synthesis (SCS).
Solution combustion synthesis makes use of salts, such as nitrates, metal sul-
fates and carbonates, as oxidants and, reducing reagents, fuels such as glycine,
sucrose, urea, or other water soluble carbohydrates. Nitrate acts as an oxidizer for
the fuel during the combustion reaction. The powder can be a pyrolysed product of
a single phase, but usually it is a combination of metal oxides and in some cases it
needs subsequent heat treatment to form single-phase products, which are usually
the results required in this process.
Solution combustion synthesis is a method based on the principle that once a
reaction is initiated under heating, an exothermic reaction occurs that becomes
self-sustaining within a certain time interval, resulting in a powder as final product.
The exothermic reaction begins at the ignition temperature and generates a certain
amount of heat that is manifested in the maximum temperature or temperature of
combustion. Solution combustion synthesis has the advantage of rapidly producing
fine and homogeneous powders. Since it is an exothermic, auto-propagated process,
and with a high heat release rate, it can be explosive and should be undertaken with
extra precautions.
2.1 Nanopowder Synthesis 13
Table 2.1 Some oxides prepared by combustion in solution

Material Fuela Particle size Application References
Al2O3 U 4 μm Abrasive [3]
MAl2O4 AM + U/CH/ODH/GLI 15–28 nm Catalyst support [4]
(M = Mn e Zn)
M/MgAl2O4, U 10 nm Catalyst [5]
M = Fe-Co/Ni
Co+2/Al2O3 U 0.2–0.3 μm Pigment [6]
Eu+3/Y3Al5O12 U 60–90 nm Red phosphorus [7]
Ce1−xTbxMgAl11O19 CH 10–20 μm Green phosphorus [8]
M/Al2O3, M = Pt, U 7–10 nm Catalyst [9, 10]
Pd, Ag
Pd/Al2O3 U 10–18 nm Catalyst [11]
CeO2-ZrO2 ODH 18 nm Oxigen storage [12]
GLI 100 μm Capasitor
M/CeO2, M = Pt, ODH 1–2 nm Catalyst [13, 14]
Pd, Ag
Ce1−xPtxO2 CH 4–6 nm H2-O2 combina- [15]
tion catalyst
Ni-YSZ, (Ni,Co/ U ~40 nm Combustion cell [16]
Fe/Cu) -YSZ anode (SOFC)
LaSrFeO3 CH/ODH 20–30 nm SOFC cathode [17]
LaCrO3 U 20 nm Interconnection [18]
for SOFC
LiCo0.5M0.5O2 U 5–10 μm Lithium battery [19]
MFe2O4/BaFe12O19 ODH 60–100 nm Magnetic oxide [20]
BaTiO3 GLI/AC 18–25 nm Dielectric material [21]
Pb(Zr,Ti)O3 AC 60 nm Piezoelectric [22]
material
ZnO U <100 nm Varistor [23]
aU urea, CH carbohydrazides, ODH oxalildihidrazida, GLI glycine, AC citric acid, AM metal
acetate
Solution combustion synthesis is a quick and easy process, with as main a dvantages
the saving of time and energy. This process is used directly in the production of high
purity, homogeneous ceramic oxide powders. This method is versatile for the synthesis
of a wide size range of particles, including nanometer size alumina powders, as reported
by Patil and Mimani [1]. Interestingly, the combustion of a mixture of redox metal
nitrate-glycine-nitrate ammonium acetate or mixtures of metal-aluminum nitrate-urea
combustion systems, showed no presence of a flame for obtaining oxide nanoparticles.
The foundation for the combustion synthesis technique lies in the thermody-
namic concepts used in the field of propellants and explosives, and its extrapo-
lation to the combustion synthesis of ceramic oxides and its thermodynamic
interpretation are discussed extensively by several researchers. The success of this
process is closely linked to the mix of constituents of a suitable fuel or complex-
ing agent (e.g., citric acid, urea, and glycine) in water and an exothermic redox
reaction between the fuel and the oxidant (e.g., nitrates).
In fact, the reaction mechanism of the combustion is very complex. There are
several parameters influencing the reaction such as the type of fuel, fuel-oxidizer
ratio, use of excess oxidizer, ignition temperature, and amount of water contained
in the precursor mixture. In general, a good combustion synthesis does not react
violently, produces non-toxic gases and acts as a complexant for metal cations.
The characteristics of the powders, such as crystallite size, surface area, nature
of agglomeration (strong and weak), is governed mainly by the enthalpy and
flame temperature generated during combustion, which in turn is dependent on the
nature of the fuel and the kind of fuel-oxidizer used in the reaction.
The rapid generation of a large volume of gases during combustion dissipates
the heat from the process and limits the temperature rise, reducing the possibility
of premature sintering between the primary particles. The generation of gases also
helps limit interparticle contact, resulting in a more powdery product.
The combustion technique appears to be controlled by the mass of the mix-
ture and the volume of the container. Studies conducted by Kingsley and Patil [2]
demonstrated that the mass/volume ratio is critical for the occurrence of combus-
tion synthesis, as compositions with less than 5 g in containers of 300 mL did not
undergo the ignition process.
The solution combustion synthesis method has proven to be a great technique
to obtain various types of oxides at the nanometer scale and is used for a variety of
technological applications, as can be seen in Table 2.1. This wide range of oxides
is prepared with an eye on their magnetic, mechanical, dielectric, catalytic, optical
and luminescent properties.
2.2 Combustion Parameters
The main parameters of combustion that have been widely investigated in the lit-
erature are: type of flame, temperature, generated gases, air-fuel-oxidant ratio and
chemical composition of the precursor reagents.
2.2.1 Flame Types
The formation of the combustion flame arises through the release of heat from the
chemical burning of the transformed substances. Combustion generates character-
istic types of flames as shown below in Table 2.2.
SCS synthesis, in general, under controlled conditions, generates a pecu-
liar kind of burning or smoldering type flame, depending on the employed fuel
and oxidizer-fuel ratio. The burning flame can endure for seconds or even min-
utes, while the smoldering flame does not rise or is extinguished in a few seconds.
The type of flame in the combustion plays an important role in controlling the par-
ticle size of as-synthesized powders.
2.2 Combustion Parameters 15
Table 2.2 Flame types [3]

Type Temperature Burning rate
Flaming (gas phase) Over 1,000 °C –
Smouldering (Solid-gas phase) Below 1,000 °C ~cm/s
Explosive type High temperature and pressure 4000–8000 m/s
Fig. 2.1 Smoldering flame type: the evolution of combustion reaction containing Ca(NO3)2,

Al(NO3)3 and β-alanine [24]
For example, Fig. 2.1 represents a SCS process using Ca(NO3)2, Al(NO3)3 and
β-alanine and a smoldering flame is observed. In Fig. 2.2, the same materials were
used but urea was used as an additional fuel, and flaming occur.
It should be noted that in any combustion process the mixture of the reactants (fuel
and oxidizer) may be hypergolic (ignition by contact) or the ignition may be con-
trolled by an external source. These conditions are crucial for generating the flame.
There is a dependence on the type of flames, linked to the fuel used, as can be
seen in the use of urea, which acts more reactive leading to the formation of flame
glow, than a solution in the presence of glycine, characterized by smoldering. The
reactivity of the combustion reaction is dependent on the ligand groups of the mol-
ecules of the fuel and the compositional ratio of fuel and oxidant.
2.2.2 Characteristic Temperatures
During the combustion synthesis reaction, there are four important temperatures
that can affect the reaction process and final product properties:
Initial temperature (To) is the average temperature of the reagent solution
before the reaction is ignited;
Ignition temperature (Tig) represents the point at which the combustion reaction
is dynamically activated without an additional supply of external heat;
Fig. 2.2 Flamming type reaction: the evolution of combustion reaction containing Ca(NO3)2,

Al(NO3)3, β-alanine and urea [24]
Adiabatic flame temperature (Tad) is the maximum combustion temperature

achieved under adiabatic conditions;
Maximum flame temperature (Tm) is the maximum temperature reached in the
actual configuration, i.e., under conditions that are not adiabatic.
The calculation of the ignition temperature is not as simple as the adiaba-
tic flame temperature. The ignition temperature is a complex quantity, not only
strictly related to the thermodynamics and thermal physics of the system, but also
the details of the reaction mechanism. As a general rule, the ignition process is
obtained with a small, but significant amount of reagent solution. When this solu-
tion is rapidly heated above the temperature where the chemical reaction rate is
high enough, you get a heat release rate greater than the dissipation of heat.
The flame temperatures are influenced by a large number of factors. The flame
temperature can be increased with the addition of excess oxidant, such as nitrate
ammonium, or the increase of the fuel-oxidant. The adiabatic flame temperature
can be calculated using the heat capacity of the products, the ignition temperature
and the heat of combustion, assuming that no heat is lost in the system. The flame
temperature measurements are almost always much smaller than the calculated
adiabatic values. Irradiated losses, incomplete combustion and air heating contrib-
ute to a decrease in the actual flame temperature.
2.2.3 Gas Generation
It is a well-established fact that in combustion synthesis, the powder morphol-

ogy, particle size and surface area are directly related to the amount of gases
that escape during combustion. The gases break large clusters and create pores
between particles. In fact, the clusters are disintegrated in conditions of high pro-
duction of combustion gases and in these conditions more heat is released from the
system, hindering particle growth.
The difference in particle size, using different fuels, depends on the number of
moles of gaseous products released during combustion. Thermodynamic modeling
shows an increase in gas generation with an increase of the fuel-oxidant.
2.2.4 Atmosphere
The effect of atmosphere composition and properties of combustion products

synthesized in solution is still poorly understood and studied in the literature.
The interference of the environment (O2 and CO2 in the air) and insufficient
reaction temperatures result in an incomplete combustion, forming products
with various metastable solid phases instead of the pure oxide and NOx or
CO gas.
Experiments carried out in argon atmosphere allowed the synthesis of single
phase magnetite (Fe3O4). Magnetite reacts with atmospheric O2, resulting in the
formation of the Fe2O3 phase.
2.2.5 Fuel-Oxidant Ratio
A fuel is a substance capable of burning the CH bonds (electrons acceptor). An

oxidant is a substance that helps in burning, providing oxygen (electrons donor).
Only when the oxidizer and fuel are intimately mixed in an appropriate proportion
can an exothermic chemical reaction be initiated that generates substantial heat.
The temperature reached when the reaction starts in the oxidizer and fuel solution,
is called the ignition temperature.
The ratio of fuel and oxidizer is considered one of the most important parame-
ters in determining the properties of synthesized powders obtained by combustion.
Product properties such as crystallite size, surface area, morphology, phase, degree
and nature of agglomeration, are generally controlled by adjusting the fuel-oxidant
ratio.
The fuel-oxidant ratio determines the influence of gases on the morphology of
the particles. The pore size depends on the fuel-oxidant ratio, because the greater
the amount of fuel, the larger the pore size of the particles.
Recent research on SCS has investigated the role of fuel in the control of par-
ticle size and microstructure of the products under different fuel-oxidant ratios
(Table 2.3). The fuel-oxidant ratio, however, is not always calculated using a ther-
modynamic modeling and/or theory of the propellants.
Table 2.3 Study of the influence of fuel-oxidant ratio in obtaining ceramic oxides by SCS

Material Fuela Particle size References
Al2O3 U 72–141 nm [25]
33–56 nm [26]
Al2O3 GLI 84–123 nm [27]
Al2TiO5 U ~927 nm [28]
Ce1−xZrxO2 CH/ODH 5–18 nm [12]
CeO2 GLI 3–28 nm [29]
CoAl2O4 AC 10–110 nm [30]
CoO/Co3O4/Co GLI 23–90 nm [31]
Cr2O3/CrO3 U/GLI 18–50 nm [32]
CuO-CeO2 U 5–24 nm [33]
Fe2O3-γ GOL 169–228 nm [34]
Fe3O4/Fe2O3-α U 20–105 nm [35]
La0.84Sr0.16CrO3 La0.5Sr0.5MnO3 GLI 5–40 nm [36]
Li2TiO3/LiNO3/TiO2 U/GLI/AC ~30 nm [37]
LnCrO3 GLI 11–59 nm [38]
MgAl2O4 U/S 3–32 μm [39]
NiO/NiFe2O4/Cu GLI <10 nm [40]
NiO/Ni GLI 4–18 nm [41]
Ni-YSZ (Cermet) CH 250–800 nm [16]
Ni-YSZ U 36–545 nm [42]
Pb(Zr0.6Ti0.4)O3 PVA 100–400 nm [43]
SrBi2Nb2O9 U 22–145 nm [44]
ThO2 GLI 15–23 nm [45]
Y2O3 GOL 3–17 nm [46]
Y2SiO5,/Y3Al5O12/Y2O3/BaMgAl10O27 U/GLI/CH >200 nm [47]
YFeO3 GLI 6–50 nm [48]
ZnO U <100 nm [23]
ZrO2 PVA 10–160 nm [49]
aU urea, GLI glycine, CH carbohydrazides; ODH oxalildihidrazida, AC citric acid, GOL glycol,
S sucrose, PVA polyvinyl acid
2.2.6 Chemical Composition of Precursor Chemicals
The type and amount of chemicals used in the reactions exert effect on the charac-
teristics of the resulting powders. The solubility of the fuel, the presence of water
and type of fuel used, are critical. In solution, mixtures of metal nitrates (oxidiz-
ers) and urea or glycine (fuel) are broken down quickly via deflagration burning or
combustion.
Excellent product homogeneity is achieved by the use of chemical precursors
intimately mixed. That happens, in general, when oxidants and fuels are dissolved
in water. The fuel also serves as complexing agent limiting the precipitation of
individual precursor components prior to ignition.
The addition of an inert salt in a mixture of redox solution for combus-
tion synthesis may result in the formation of well dispersed nanoparticles with
a more prominent increase in surface area. The addition of salt should break the
three-dimensional porous structure, typical of the resulting powders through com-
bustion and act as an inhibitor of the agglomeration. The inorganic salt is generally
low cost when compared with organic salts, readily soluble in water, thermally
stable at high temperatures, easily removed from the product-mix as-prepared and
recyclable.
2.3 Fuels
Glycine (NH2CH2COOH) is one of the cheapest amino acids and is known to act
as a complexing agent for a large amount of metallic ions. The glycine molecule
has a carboxylic acid group located at one end of the chain and an amino group at
the other. Both groups can participate in the complexation of metal ions. Alkaline
and earth alkaline cations are most effectively complexed by the carboxylic acid
groups, while many transition metals are complexed more effectively through the
amino group. The high solubility of metal ions in question, as well as the high
relative viscosity of the precursor solution, tends to inhibit the precipitation of het-
erogeneous compounds.
The amino acids become bipolar (zwitterionic or amphoteric) when in aqueous
solution by presenting positive and negative charges. This bipolar character of the
glycine molecule in solution can effectively act as a complexing agent for metal
ions of various sizes, which helps to prevent selective precipitation and maintain
compositional homogeneity among the constituents. In combustion synthesis gly-
cine serves as fuel during the reaction, being oxidized by nitrate ions.
Urea (NH2CONH2) is an attractive fuel for originating the formation of pow-
ders with crystallite sizes in the submicron/nanosized range and act as a com-
plexing agent for metal ions because it contains two amino groups located at the
extremes of its chemical structure. Deshpande et al. found that the chemical activ-
ity of the ligand-NH2 promotes more vigorous combustion reactions among vari-
ous fuels studied with iron nitrate.
2.4 Oxidants
Nitrates are chosen as metal precursors, not only because they are fundamental to
the combustion method, for providing the metal ion, but also because of their great
water solubility, allowing a greater homogenization.
Most oxides synthesized by combustion can be obtained by combining a metal
nitrate and fuel. Groups (NO3)—act as oxidizing agents.
Ammonium nitrate (NH4NO3) is used in combustion reactions to act as extra-
oxidant and without changing the proportion of other participants of the chemical
reaction. Another interesting feature is its low cost.
The excess addition of ammonium nitrate produces an increase in combustion

gas, and the effect of expanding the microstructure and eventually increasing the
surface area of the produced powder. As can be seen, the decomposition of ammo-
nium nitrate generates, in part, the same gases obtained for the pair of aluminum
nitrate and glycine, according to Eq. 2.1.
2NH4 NO3 (s) → 2N2 (g) + 4H2 O (g) + O2 (g) (2.1)
The ammonium dichromate—(NH4)2Cr2O7—is known to decompose and gener-
ate exothermic autocatalytic Cr2O3, N2, and H2O. This salt has advantages over
the nitrate because it decomposes into chromium at a lower temperature (170 °C)
and is more exothermic (ΔH: ±0.4–476.4 kJ/mol).
References
1. Patil, K.C., Mimani, T.: Solution combustion synthesis of nanoscale oxides and their com-
posites. Mater. Phys. Mech. 4, 134–137 (2001)
2. Kingsley, J.J., Patil, K.C.: A novel combustion process for the synthesis of fine particle
α-alumina and related oxide materials. Mater. Lett. 6, 427–432 (1988)
3. Mimani, T.: Fire synthesis: preparation of alumina related products. Resonance 5, 50–57
(2000)
4. Mimani, T.: Instant synthesis of nanoscale spinel aluminates. J. Alloys Comp. 315, 123–128
(2001)
5. Quenard, O., Grave, E., Laurent, C., Rousset, A.: Synthesis, characterization and thermal
behaviour of Fe0.65Co0.35MgAl2O4 and Fe0.65Ni 0.35MgAl2O4 nanocomposite powders. J.
Mater. Chem. 7, 2457–2467 (1997)
6. Mimani, T., Ghosh, S.: Combustion synthesis of cobalt pigments: blue and pink. Curr. Sci.
78, 892–896 (2000)
7. Shikao, S., Wang, J.: Combustion synthesis of Eu activated Y3Al5O12 phosphor nanoparti-
cles. J. Alloys Comp. 327, 82–86 (2001)
8. Ravichandran, D., Roy, R., Ravindranathan, P., White, W.B.: Combustion synthesis of hexa-
luminate phosphors. J. Am. Ceram. Soc. 82, 1082–1166 (1999)
9. Bera, P., Patil, K.C., Jayaram, V., Hegde, M.S., Subbana, G.N.: Combustion synthesis of
nano metal particles supported on α-Al2O3: CO oxidation and NO reduction catalysts. J.
Mater. Chem. 9, 1801–1805 (1999)
10. Bera, P., Patil, K.C., Hegde, M.S.: Oxidation of CH4 and C3H8 over combustion synthesized
nanosize metal particles supported on α-Al2O3. Chem. Phys. 2, 373–378 (2000)
11. Greca, M.C., Moraes, C., Segadães, A.M.: Palladium/alumina catalysts: effect of the process-
ing route on catalytic performance. Appl. Catal. A 26, 267–276 (2001)
12. Aruna, S.T., Patil, K.C.: Combustion synthesis and properties of nanostructured ceria–zirco-
nia solid solutions. Nanostruct. Mater. 10, 955–964 (1998)
13. Lamas, D.G., Juarez, R.E., Lascalea, G.E., Walsoe, N.E.: Synthesis of compositionally
homogeneous, nanocrystalline ZrO2-35 mol% CeO2 powders by gel combustion. J. Mater.
Sci. Lett. 20, 1447–1449 (2001)
14. Bera, P., Patil, K.C., Jayarama, V., Subbanna, G.N., Hegde, M.S.: Ionic dispersion of Pt and
Pd on CeO2 by combustion method: effect of metal–ceria interaction on catalytic activities
for NO reduction, CO and hydrocarbon oxidation. J. Catal. 196, 293–301 (2000)
15. Hariprakash, B., Bera, P., Martha, S.K., Gaffoor, S.A., Hegde, M.S., Shukla, A.K.: Ceria sup-
ported platinum as hydrogen-oxygen recombination catalyst for sealed lead-acid batteries.
Electrochem. Solid-State Lett. 4, A23–A26 (2001)
References 21
16. Aruna, S.T., Muthuraman, M., Patil, K.C.: Synthesis and properties of Ni-YSZ cermet anode
material for solid oxide fuel cells. Solid State Ionics 111, 45–51 (1998)
17. Suresh, K., Panchapagesan, T.S., Patil, K.C.: Synthesis and properties of La1−xSrx FeO3.
Solid State Ionics 126, 299–305 (1999)
18. Park, H.K., Han, Y.S., Kim, D.K., Kim, C.H.: Synthesis of LaCrO3 powders by microwave
induced combustion of metal nitrate-urea mixture solution. J. Mater. Sci. Lett. 17, 785–787
(1998)
19. Julien, C., Camacho-Lopez, M.A., Mohan, T., Chitra, S., Kalayani, P.: Combustion synthe-
sis and characterization of substituted lithium cobalt oxides in lithium batteries. Solid State
Ionics 141–142, 549–557 (2001)
20. Patil, K.C., Mimani, T.: Preparation and properties of nanocrystalline magnetic oxides. Mag.
Soc. India Bull. 22, 21–26 (2000)
21. Anuradha, T.V., Ranganathan, S., Mimani, T., Patil, K.C.: Combustion synthesis of nano-
structured barium titanate. Scripta Mater. 44, 2237–2241 (2001)
22. Schafer, J., Sigmund, W., Roy, S., Aldinger, F.: Low temperature method to obtain alternative
cermet materials for SOFC anodes. Synthesis of ultrafine Pb(Zr, Ti)O3 powder by sol-gel
combustion. J. Mater. Res. 12, 2518–2521 (1997)
23. Sousa, V.C., Segadães, A.M., Moreli, M.R., Kiminami, R.H.G.A.: Combustion synthesized
powders for varistor ceramics. Int. J. Inorg. Mater. 1, 235–241 (1999)
24. Ianoş, R., Lazău, I., Păcurariu, C., Barvinschi, P.: Fuel mixture approach for solution combus-
tion synthesis of Ca3Al2O6 powders. Cem. Concr. Res. 39, 566–572 (2009)
25. Bhaduri, S., Zhou, E., Bhaduri, S.B.: Auto ignition processing of nanocrystalline α-Al2O3.
Nanostruct. Mater. 7, 487–496 (1999)
26. Neiva, L.S., Gama, L., Lira, H.L., Fagury-Neto, E., Kiminami, R.H.G.A., Costa, A.C.F.M.:
Influência do Teor de Ureia na Obtenção de Pós de Al2O3 por Reação de Combustão. Anais
do 47° Congresso Brasileiro de Cerâmica, pp. 816–817 (2003)
27. Toniolo, J.C., Lima, M.D., Takimi, A.S., Bergmann, C.P.: Synthesis of alumina powders by
the glycine-nitrate combustion process. Mater. Res. Bull. 40, 561–571 (2005)
28. Segadães, A.M., Morelli, M.R., Kiminami, R.G.A.: Combustion synthesis of aluminium
titanate. J. Eur. Ceram. Soc. 18, 771–781 (1998)
29. Purohit, R.D., Sharma, B.P., Pillai, K.T., Tyagi, A.K.: Ultra-fine ceria powders via glycine-
nitrate combustion. Mater. Res. Bull. 36, 2711–2721 (2001)
30. Li, W., Li, J., Gou, J.: Synthesis and characterization of nanocrystalline CoAl2O4 spinel pow-
der by low temperature combustion. J. Eur. Ceram. Soc. 23, 2289–2295 (2003)
31. Toniolo, J.C., Takimi, A.S., Bergmann, C.P.: Nanostructured cobalt oxides (Co3O4 and CoO)
and metallic Co powders synthesized by the solution combustion method. Mater. Res. Bull.
45, 672–676 (2010)
32. Lima, M.D., Bonadiman, R., Andrade, M.J., Toniolo, J.C., Bergmann, C.P.: Nanocrystalline
Cr2O3 and amorphous CrO3 produced by solution combustion synthesis. J. Eur. Ceram. Soc.
26, 1213–1220 (2006)
33. Avgouropoulos, G., Ioannides, T.: Selective CO oxidation over CuO-CeO2 catalysts prepared
via the urea-nitrate combustion method. Appl. Catal. A 244, 155–167 (2003)
34. Venkataraman, A., Hiremath, V.A., Date, S.K., Kulkarni, S.D.: New combustion route to
γ-Fe2O3 synthesis. Bull. Mater. Sci. 24, 617–621 (2001)
35. Toniolo, J.C., Takimi, A.S., Bonadiman, R., Andrade, M.J., Bergmann, C.P.: Synthesis by the
solution combustion process and magnetic properties of iron oxide (Fe3O4 and α-Fe2O3) par-
ticles. J. Mater. Sci. 42, 4785–4791 (2007)
36. Chick, L.A., Pederson, L.R., Maupin, G.D., Bates, J.L., Thomas, L.E., Exarhos, G.J.:
Glycine-nitrate combustion synthesis of oxide ceramic powders. Mater. Lett. 10, 6–12 (1990)
37. Jung, C.H., Park, J.Y., Oh, S.J., Park, H.K., Kim, Y.S., Kim, D.K., Kim, J.H.: Synthesis of Li2TiO3
ceramic breeder powders by the combustion process. J. Nucl. Mater. 253, 203–212 (1998)
38. Kingsley, J.J., Pederson, L.R.: Combustion synthesis of perovskite LnCrO3 Powders using
Ammonium Dichromate. Mater. Lett. 18(1993), 89–96 (1993)
39. Ganesh, I., Srinivas, B., Johnson, R., Saha, B.P., Mahajan, Y.R.: Effect of fuel type on mor-
phology and reactivity of combustion synthesised MgAl2O4 powders. Br. Ceram. Trans. 101,
247–254 (2002)
40. Chick, L.A., Maupin, G.D., Pederson, L.R.: Glycine-nitrate synthesis of ceramic-metal com-
posite. Nanostruct. Mater. 5, 603–615 (1994)
41. Toniolo, J.C., Bonadiman, R., Oliveira, L.L., Hohemberger, J.M., Bergmann, C.P.: Synthesis
of nanocrystalline nickel oxide powders via glycine-nitrate combustion. South Braz. J. Chem.
13, 53–61 (2005)
42. Ringuedé, A., Labrincha, J.A., Frade, J.R.: A combustion synthesis method to obtain alterna-
tive cermet materials for SOFC anodes. Solid State Ionics 141, 549–557 (2001)
43. Das, R.N., Pathak, A., Saha, S.K., Sannigrahi, S., Pramanik, P.: Preparation, characterization
and property of fine PZT powders from the poly vinyl alcohol evaporation route. Mater. Res.
Bull. 36, 1539–1549 (2001)
44. Zanetti, S.M., Santiago, E.I., Bulhões, L.O.S., Varela, J.A., Leite, E.R., Longo, E.:
Preparation and characterization of nanosized SrBi2Nb2O9 powder by the combustion syn-
thesis. Mater. Lett. 57, 2812–2816 (2003)
45. Purohit, R.D., Saha, S., Tyagi, A.K.: Nanocrystalline thoria powders via glycine-nitrate com-
bustion. J. Nucl. Mater. 288, 7–10 (2001)
46. Dasgupta, N., Krishnamoorthy, R., Jacob, T.: Glycol-nitrate combustion synthesis of fine sin-
ter-active yttria. Int. J. Inorg. Mater. 3, 143–149 (2001)
47. McKittrick, J., Shea, L.E., Bacalski, C.F., Bosze, E.J.: The influence of processing param-
eters on luminescent oxides produced by combustion synthesis. Displays 19, 169–172 (1999)
48. Wu, L., Yu, J.C., Zhang, L., Wang, X., Li, S.: Selective self-propagating combustion synthe-
sis of hexagonal and orthorhombic nanocrystalline yttrium iron oxide. J. Solid State Chem.
177, 3666–3674 (2004)
49. Ray, J.C., Saha, C.R., Pramanik, P.: Stabilized nanoparticles of metastable ZrO2 with
Cr3+/Cr4+ cations: preparation from a polymer precursor and the study of the thermal and
structural properties. J. Eur. Ceram. Soc. 22, 851–862 (2002)
Chapter 3
Spray Pyrolysis
3.1 Introduction
The technologies of thin film making differ widely in terms of chemical and physical
principles of operation, as well as in the types of commercial equipment that are
available for its production. Due to these characteristics, each process is used and
developed according to what one wants to obtain, and this leads to advantages and dis-
advantages. Research on optimization of existing techniques and development of
new technologies are of great importance today.
Different processes for the preparation of films have been employed, such as:
physical vapor deposition (PVD), chemical vapor depositions (CVD), screen-
printing, sol-gel and spray pyrolysis. However, compared to the other techniques
mentioned, spray-pyrolysis requires simple and inexpensive equipment and has as
main advantages the easy addition of doping materials, good reproducibility, high
films growth rate, chemical homogeneity in the final product and the potential for
deposition over large areas. The films, dense or porous, have thicknesses ranging
from 0.1 to 10 μm.
The technique itself consists of a precursor solution that is sprayed through an
air atomizer on a heated substrate, producing thin films. It is well established that
the morphology and quality of the deposited films are strongly linked to the sub-
strate temperature. Defects, such as non-uniformity of the film, cracks and pores,
are among the most frequent problems presented in the films deposited by spray
pyrolysis [1].
For the technological use of the films obtained by spray pyrolysis it is neces-
sary that some of its interesting features are understood and controlled. The rela-
tionship between the procedural parameters, the characteristics of the deposit
microstructures and the final properties obtained, is the foundation for understand-
ing and mastering this technique.

24 3 Spray Pyrolysis
3.2 Spray-Pyrolysis Technique
The tendency to seek technological miniaturization of devices is associated with

a reduction in manufacturing costs (smaller amounts of reagents, lower operating
times, lower power consumption). The use of materials in the form of thin films,
therefore, has emerged as an alternative to fulfill these requirements. Thin films
can be produced by a variety of processes, but in any of them there are two basic
steps of nucleation and growth.
Studies on techniques for thin film deposition divide these into two groups,
depending on the nature of the deposition process. Physical methods include phys-
ical vapor deposition (PVD), laser ablation, molecular beam epitaxy and sputter-
ing. Chemical methods comprise of gas phase and solution deposition. The gas
phase techniques include chemical vapor deposition (CVD) and atomic layer epi-
taxy (ALE). Spray-pyrolysis deposition, sol-gel, spin-coating and dip-coating are
techniques based on solution deposition.
Spray pyrolysis is a technique through which dense or porous films and pow-
ders can be obtained by controlling the deposition parameters. This technique
involves the atomization of a precursor solution that is thrown directly over the
heated substrate where the film will be formed.
Compared with other techniques for obtaining films, this technique presents a
simple experimental arrangement and is a cost effective method, mainly due to its
simple equipment. It does not require the use of high quality reagents and sub-
strates. The composition of the films can be easily controlled with the reagents
used in the precursor solution. Several types of films have been deposited by spray
pyrolysis, and this technique has been used for decades in various industries, such
as in the production of glass, solar cells and electrical conductive electrodes [1].
The equipment used in the spray-pyrolysis technique consists basically of an
atomizer and a temperature controller. There are several types of atomizers. The
most common ones are compressed air atomizers [2] (when the spray of the pre-
cursor solution is produced by a jet of air), electric field atomizers [3] (when the
spray of the precursor solution is produced by an electric field) and ultrasound
atomizers [4] (when the spray of the precursor solution is produced through high
frequencies).
When the spray collides on a surface, the atoms lose energy to it. After the
impact, the atoms spread on the surface interacting with other adsorbed atoms. A
fraction of the atoms can initiate the formation of an island that can grow in size
and coalesce, forming a continuous film [5].
Yuan et al. used the technique of flame spray pyrolysis to prepare YSZ pow-
der with a narrow particle distribution [6]. Zhang and Messing [7] demonstrated
an important criterion for the synthesis of fine solid particles from the observa-
tion that the precipitated salt particles do not suffer plastic deformation or melt
during heating, because of the formation of droplets from reservoirs with low
permeability. Consequently, the residual solvent is trapped in the dried droplet,
resulting in an increase in pressure, because then the solvent cannot evaporate
3.2 Spray-Pyrolysis Technique 25
Fig. 3.1 Steps of powder production during the spray-pyrolysis
Fig. 3.2 Schematic diagram of the spray-pyrolysis film formation mechanisms
easily. Consequently, the shell breaks, producing secondary drops, breaking the
shell of the droplets formed above a powder, which produces an irregular shape
(Fig. 3.1). Liu et al. [8] also concluded that the high solubility of the salts is not
necessary for the formation of solid and uniform particles, as previously stated by
other authors.
There is a strong influence of deposition parameters in determining whether the
film deposited by being deposited is dense or porous (Fig. 3.2). If the intermediate
reactions occur at some distance from the substrate, the film will be porous, with
some cracks. If these same reactions occur near the substrate, but not touching it,
the film should be dense. In a third case, if these intermediate reactions occur well
before touching the substrate, a powdery film is formed [9]. Also by increasing
deposition temperature, the morphology of the film can be shifted from porous to
extremely dense.
The spray-pyrolysis technique has been used for the deposition of YSZ films on
top of cerium oxide substrates doped with gadolinium [10]. The authors obtained
porous or fractured thick films. The cracks in the film can be used as a composite
with the electrolyte, since the cells that contain a composite of ceria coated YSZ
exhibit higher open circuit voltage that the ceria alone [11] .
Charpentier et al. [12] deposited cathodes in the form of porous La0.7SrO0.3MnO3
films using spray pyrolysis over YSZ substrate. Porous structures with large pores
of an average size of 0.1 μm diameter were observed. An electrical conductivity of
10 S cm−1 was measured at room temperature for these films.
Several studies have been conducted to better understand what occurs dur-
ing the deposition by spray pyrolysis. Many authors have attempted to develop a
model to explain what happens during this process. There are several steps that
occur sequentially or simultaneously during film formation by spray pyrolysis and
they can be modeled simply. Understanding these steps can help improve the qual-
ity of the film. Spray-pyrolysis can be divided into three main steps: atomization
of the precursor solution, the transport of aerosols and the resulting decomposition
of the precursor solution on the substrate [1].
3.2.1 Atomization of Precursor Solution
Atomizing the precursor through a jet of compressed air, an ultrasonic system

and an electrostatic atomizer are the most commonly used methods in spray
pyrolysis.
Many articles have been published on the mechanism of atomization of precur-
sor solutions. Kufferath et al. [13] evaluated the influence of fluid properties on
the characteristics of the compressed air spray. Taniguchi et al. [14]. studied high
frequency atomization (ultrasound). Depending on the parameters of the spray jet
modes, a different particle size distribution was obtained.
Atomization by compressed air involves the use of air at high speeds to produce
an aerosol. The liquid is introduced into an air stream and drops are pulverized
through the energy of the gas stream [15]. Typically, the fraction of the deposited
material is small due to excess spray spread. Many drops are deflected or reflected
from the surface of the substrate, decreasing the deposition efficiency. In general,
the droplet size grows proportional to the increase of viscosity, surface tension and
density [1].
3.2.2 Aerosol Transportation
In the formed aerosol, droplets are transported and eventually evaporated. When
thick films are desired, it is important that during transport as many drops as pos-
sible fly into the substrate without the formation of particles before reaching the
substrate surface. In this process, the trajectory of the droplets and evaporation is
influenced by gravitational, electric or thermophoretic forces.
Particles that attach to the substrate form a powdery deposit. Some authors sug-
gest that forcing the drops closer to the heated substrate, without touching it, is the
most efficient way to improve this kind of film growth [1].
The solvent present in the droplets will evaporate during the transportation
from the atomizing nozzle to the substrate. This evaporation of the solvent leads to
a decrease in droplet size and therefore a concentration gradient of the salt precur-
sor. This precursor precipitates on the surface of the drop when the concentration
exceeds the solubility limit. The precipitation occurs due to rapid evaporation of
the solvent while the diffusion of the solvent is much slower. This situation will
result in a crust and subsequently in porous hollow particles. This effect is not
desired in film formation due to increased roughness of the film [1].
Yu and Liao [16] developed a model describing the evaporation of the solu-
tion drops before the formation of a porous crust. The transfer of mass, momen-
tum, temperature around the drop and the effect of precipitation of the precursor
were taken into account. The interaction between the droplets was ignored. Rapid
increases were observed in the temperature drop and evaporation starts at the same
time that the precipitation of the precursor begins. At the beginning of this process,
the evaporation rate increases rapidly to a maximum and then decreases until the
beginning of precipitation. By increasing the gas temperature, there is a marked
concentration gradient within this drop. According to the authors, the effects of
ambient humidity were insignificant.
3.2.3 Decomposition of the Precursor
Many processes can occur when the drop hits the surface of the substrate, such
as evaporation of the residual solvent, scattering of the drops and decomposi-
tion of salt. Many models exist for the decomposition of the precursor salt. But
most authors suggest that the process of CVD gives high-quality films by spray
pyrolysis.
Perednis [1] propose that the following processes may occur when the tempera-
ture is increased: at lower temperatures the drop spreads through the substrate and
then decomposes. At higher temperatures the solvent evaporates completely dur-
ing flight and the dried precipitate drop hits the substrate, where decomposition
occurs. At even higher temperatures the solvent also evaporates before the drop
reaches the substrate. Then the precipitated solid melts, vaporizes without decom-
position and the vapor diffuses into the substrate to undergo a CVD process. If
we increase the temperature furthermore the precursor evaporates before reaching
the substrate and consequently solid particles are formed after the chemical reac-
tion in the vapor phase. The author speculates that in the processes A and D rough
and non-adherent films are formed. Adherent films were obtained in the process of
chemical vapor deposition (CVD) at intermediate temperatures.
Chen et al. [17] studied the correlation between the morphology of the films
and the deposition parameters. They concluded that the most important parameter
is the deposition substrate temperature. The concentration of precursor solution

has a minor influence on the quality of the deposition.
The onset of salt decomposition is very important in the spray-pyrolysis tech-
nique. Stryckmans et al. [18] investigated the decomposition of magnesium acety-
lacetonate (Mg (C5H7O2)2) and suggested the following model: above the melting
point of 265 °C, Mg (C5H7O2)2 is not as stable. The molecules break up into
gaseous organic fragments (C5H7O2) and a liquid component containing magne-
sium (MgC5H7O2). The fragment is degraded into small gaseous molecules. The
component containing magnesium is slowly degraded to form MgO, along with
organic waste. The greatest loss of mass that is theoretically proposed for the for-
mation of MgO from MgC5H7O2 was observed in the temperature range between
Fig. 3.3 SEM images of YSZ films with pure ethanol in the precursor solution. Deposition tem-
peratures and times are: a 250 °C and 100 min, b 300 °C and 150 min, c 340 °C and 120 min,
and d 395 °C and 120 min [10]
290 and 600 °C. This indicates that the liquid phase of MgC5H7O2 is partially
evaporated. Plain films were deposited at temperatures between 350 and 420 °C.
Still, some cracks in the film were observed.
3.2.4 Influence of Spray Parameters on the Morphology

of the Film
The morphology of the film is highly dependent on the substrate temperature at

the time of deposit in spray-pyrolysis. Chen et al. [10] observed four types of
morphology: dense films, dense films with embedded particles, dense film with a
porous layer on top and porous morphology.
Ruiz et al. [19] investigated the influence of gas loading, substrate composi-
tion, temperature and time on the deposited film. The most important parameters
according to these authors were the drop size and substrate temperature. The
behavior of the spray droplet is determined by surface tension and roughness of
the substrate to be coated. The roughness of the substrate and porosity of the sub-
strate also significantly influence the film morphology.
Films with low porosity were produced when the precursor solution used sol-
vent high boiling temperatures solvents (Fig. 3.3) [10]. This was attributed to a
lower rate of evaporation of the solvent during the transport of droplets to the sub-
strate and hence a lower rate of precipitation of the precursor.
Organic precursors are more favorable to the spray-pyrolysis technique than
inorganic reagents. This is due to the fact that they have higher volatility (organic
solvents) and lower deposition temperatures. In organic precursors it is easier to
control grain size by changing the deposition parameters [20].
References
1. Perednis, D.: Thin film deposition by spray pyrolysis and the application in solide oxide fuel
cells. Ph.D. Thesis, Swiss Federal Institute of Technology Zurich (2003)
2. Balkenende, A.R., Bogaerts, A., Scholtz, J.J., Tijburg, R.R.M., Willems, H.X.: Thin MgO
layers for effective hopping transport of electrons. Philips J. Res. 50, 365–373 (1996)
3. Yoon, W., Chung, K.Y., Nam, K., Kim, K.: Characterization of LiMn2O4-coated LiCoO2 film
electrode prepared by electrostatic spray deposition. J. Power Sources 163, 207–210 (2006)
4. Konarova, M., Taniguchi, I.: Preparation of LiFePO4/C composite powders by ultrasonic
spray pyrolysis followed by heat treatment and their electrochemical properties. Mater. Res.
Bull. 43, 3305–3317 (2008)
5. Trommer, R.M.: Obtenção e caracterização de revestimentos de hidroxiapatita sobre substra-
tos de aço inoxidável 316L utilizando a técnica de deposição química de vapor assistida por
chama. Master Thesis, Universidade Federal do Rio Grande do Sul, Brazil (2006)
6. Yuan, F.L., Chen, C.H., Kelder, E.M., Schoonman, J.: Preparation of zirconia and yttria-sta-
bilized zirconia (YSZ) fine powders by flame-assisted ultrasonic spray pyrolysis (FAUSP).
Solid State Ionics 109, 119–123 (1998)
7. Zhang, S.C., Messing, G.L.: Synthesis of solid, spherical zirconia by spray pyrolysis. J. Am.
Ceram. Soc. 73, 61–67 (1990)
8. Liu, T.Q., Sakurai, O., Mizutani, N., Kato, M.: Preparation of spherical zirconia fine ZnO
particles by spray pyrolysis method using ultrasonic atomization techniques. J. Mater. Sci.
21, 3698–3702 (1986)
9. Choy, K.L., Su, B.: Growth behavior and microstructure of CdS thin films deposited by an
electrostatic spray assisted vapor deposition (ESAVD) process. Thin Solid Films 388, 9–14
(2001)
10. Chen, C.H., Varhaug, K.N., Schonman, J.: Coatings yttria-stabilized-zirconia (YSZ) thin
films on gadolinia-doped ceria (GCO) by the electrostatic spray deposition (ESD) technique.
J. Mater. Synth. Process. 4, 189–194 (1996)
11. Gaudon, M., Laberty-Robert, C.H., Ansart, F., Stevens, P.: Thick YSZ films prepared via
modified sol-gel route: thickness control (8–80 μm). J. Eur. Ceram. Soc. 26, 3153–3160
(2006)
12. Charpentier, P., Fraugnaud, P., Schleich, D.M., Lunot, C., Gehain, E.: Preparation of cathode
for thin film SOFCs. Ionics 3, 155–160 (1997)
13. Kufferath, A., Wende, B., Leuckel, W.: Influence of liquid flow conditions on spray charac-
teristics of internal-mixing twin-fluid atomizers. Int. J. Heat Fluid Flow 20, 513–519 (1999)
14. Taniguchi, I., Song, D., Wakihara, M.: Electrochemical properties of LiM1/6Mn11/6O4
(M = Mn, Co., Al and Ni) as cathode materials for Li-ion batteries prepared by ultrasonic
spray pyrolysis method. J. Power Sources 109, 333–339 (2002)
15. Kihm, K.D., Chigier, N.: Effect of shock waves on liquid atomization of a two-dimensional
airblast atomizer. Atomization Sprays 1, 113–136 (1991)
16. Yu, H.F., Liao, W.H.: Evaporation of solution droplets in spray pyrolysis. Int. J. Heat Mass
Transf. 41, 993–1001 (1998)
17. Chen, C.H., Kelder, E.M., Van Der Put, P.J.J.M., Schoonman, J.: Morphology control of thin
LiCoO2 films fabricated using the electrostatic spray deposition (ESD) technique. J. Mater.
Chem. 6, 765–771 (1996)
18. Stryckmans, O., Segato, T., Duvigneaud, P.H.: Formation of MgO films by ultrasonic spray
pyrolysis from β-diketonate. Thin Solid Films 283, 17–25 (1996)
19. Ruiz, H., Vesteghem, H., Giampaolo, A.R., Lira, J.: Zircônia coatings by spray pyrolysis.
Surf. Coat. Technol. 89, 77–81 (1997)
20. Hamedani, H.A., Dahmen, K., Li, D., Peydaye-Saheli, H., Garmestani, H., Khaleel, M.:
Fabrication of gradient porous LSM cathode by optimizing deposition parameters in ultra-
sonic spray pyrolysis. Mater. Sci. Eng. B 153, 1–9 (2008)
Chapter 4
Electrospinning
The idea of using an electric field for the production of textile fibers from a polymer
melt or solution was conceived in the early 30s [1]. In 1969, Taylor conducted a
study of a drop of polymer on the tip of a capillary in an electrospinning equip-
ment. This study led to a greater understanding of the behavior of polymer solu-
tions ejected from a capillary [2].
In a typical electrospinning process, high voltage between 5 and 50 kV is used
to create an electric field between a drop of polymer solution at the tip of a capil-
lary tube and a collector plate, as exemplified in Fig. 4.1.
An electrode is connected to a capillary tube and another to a collector, gener-
ally the ground system, thus creating a potential difference between the capillary
tip and collector. With increasing voltage, the electric field intensifies, causing the
formation of a drop hanging from the tip of the capillary. This force acts in the
opposite direction of the surface tension of the droplet, leading to its elongation.
By achieving a balance between surface tension and electrostatic force, a tapered
cone is formed, known as a Taylor cone.
4.1 The Electrospinning Technique
Cloupeau and Prunet-Foch [4] described the different modes of jets that can arise
when a potential difference is applied to the tip of a capillary containing a liquid.
The different modes depend on geometric factors (such as the distance between
the needle and the screen), the flow of the material properties of the liquid (such as
surface tension and electrical conductivity) and the applied potential.
In the drop form there is no electric field effect and the liquid flows drop by
drop. Increasing the potential from zero starts the so-called micro dripping. There
is an increase in speed and a reduction drip drop size. This behavior has two main
causes: the liquid is attracted to the grounded collector due to the action of the
external electric field and the surface tension is reduced due to the accumulation of
charges on the surface of the pendent drop [4, 5].

32 4 Electrospinning
Fig. 4.1 Schematic assembly of an electrospinning system [3]
At larger potentials the Taylor cone starts to form. The drop is deformed
by the electric field and takes the form of a cone [4, 5]. If the potential is
slightly lower than the potential to form a continuous stream, a flashing cone is
observed.
With even greater potentials, the cone becomes unstable and more jets emerge
from the surface of the liquid: it is the start of the so-called multi-jet. The number
of jets increases with the increase of the potential. Ramifications may occur due to
the high amount of electrical charges in the unstable fluid [4, 5]. The jet does not
have a uniform thickness and one or more jets emerge from the surface of the fluid
being emitted in various directions.
Typically, electrospinning has two stages: first, a jet of fluid material is ejected
from the tip of a hollow needle with a laminar and stable flow. In the second stage,
the jet gradually becomes thinner and more elongated and unstable, turning into
long circular spirals [6].
In the first stage, a fluid reservoir is connected to a source of potential through
a capillary. The electric charge that develops on the free surface of the fluid inter-
acts with the external electric field, ejecting a jet of uniform fluid. This jet of
material on its journey to the opposite pole, the collector, accelerates and becomes
thinner.
In most cases, the jet exhibits instability during its course, in such a way that
it forms spirals that increase in diameter with the increasing intensity of the insta-
bility caused by the approach of the collector. This instability causes a marked
reduction in the diameter of the jet, reaching up to three orders of magnitude while
traveling the short distance separating the electrodes, usually around 200 mm. An
example of the behavior of laminar flow and unsteady flow in an electrospinning
test is shown in Fig. 4.2.
4.1 The Electrospinning Technique 33
Fig. 4.2 Behavior of a fluid in electrospinning a laminar flow b unstable flow [7]
Also during its path, the fluid is subjected to radial loads that cause repulsion
and its division into small filaments in a process called scattering (splaying) [8].
These multiple and tiny filaments give rise to evaporation of the solvent and fibers
of small diameters.
The fibers obtained through electrospinning are produced mostly from solu-
tions and fiber diameter can vary with the concentration of the solution due to
the removal of the solvent. The final diameter of the jet is a result of the balance
between surface tension and electrostatic repulsion of the charges. However, con-
trol of fiber diameter is limited to a range of concentrations in which the solution
has its own characteristics for the process of electrospinning [9].
Empirical observations [9] indicate that smaller fiber diameters are obtained
using low flows of material. Experimental considerations show that the viscosity
greatly affects the diameter of the fibers. With increasing viscosity, the drop of
material to be submitted to the electric field changes from a semi-spherical shape
to a conical shape, and the length of the jet increases to a steady/laminar flow.
The diameter of the fibers increases with increased viscosity, proportionally to the
length of the jet.
The diameter of the fiber depends on the viscosity of the solution according to
Eq. 4.1, confirmed by experiments by Baumgarten [10] and He [11], where d is
the diameter of the fiber and η is the viscosity of the solution.
d ≈ η0,5 (4.1)
The diameter of the jet becomes thinner along the way to the opposite pole
due to: (i) the evaporation of the solvent and (ii) the continuous stretching of the
jet as a function of the electric field. Many authors have attempted to investi-
gate the relationship between the applied voltage and the diameter of the jet, but
there is no conclusive analytical theory in the literature [12, 13]. The experiments
by Demir et al. [14] show an increase in the diameter of the jet with increasing
applied voltage. According to these authors, in general, the final diameter of the
fibers under constant current flow depends on the applied voltage as formalized in
Eq. 4.2.
d ≈ E −0,5 (4.2)
Equation 4.2 indicates that the lower the applied voltage, the thinner the fib-
ers that are formed. However, when the applied voltage is too small, the electric
forces can’t overcome the surface tension and the jet is not issued. Thus, there is
a tension emission limit below which the fluid jet is not issued. Hendricks et al.
[15] calculated the minimum emission potential of a semi-spherical droplet sus-
pended in the air according to Eq. 4.3, where Eemission is the minimum voltage to
be applied to a jet of liquid emitted from the tip of a Taylor cone, γ is the surface
tension of the solution and r is the inner radius of the capillary.

Eemission = 300 20 · π · γ · r (4.3)
With increasing viscosity, higher electrical forces are necessary to over-
come the surface tension and viscoelastic forces, stretching the fiber. The volt-
age required to emit a jet of charged fluid from a droplet on the tip of a capillary
depends mainly on the fluid viscosity. Experiments by Demir et al. [14] show that
the voltage of the emission is proportional to the concentration of the solution.
Many experiments have shown that the viscosity has a well-established rela-
tionship with the concentration. Experiments [15, 16], indicate that the Brookfield
viscosity and concentration have a relationship that is described by Eq. 4.4 where
C is the concentration of the solution.
η ≈ C4 (4.4)
4.1.1 Jet Formation
The electrospinning experiment needs a relatively simple system. Components

include a voltage source that is capable of generate high potential differences
(>0.5 kV/cm), a counter electrode, a viscous polymer solution and a means of
pumping this solution.
While the solution is forced out of a capillary, through gravity or an external

force, there are forces acting immediately on the liquid, such as gravity, surface
tension and electrical voltages. These forces compete and balance each other to
form the Taylor cone and, depending on the equilibrium of the cone, droplets or
jets can be ejected.
The formation of a jet is crucial in the formation of nanofibers, but it depends
on several factors. The formation of the jet can be divided into four regions. The
jet starts at the base of the Taylor cone and travels as a single jet, decreasing in
diameter toward the counter electrode (ground system). At some point, the jet
experiences instabilities originating from the effect of surface charges and practi-
cally disappears to the naked eye. At this point, the jet experiences what is com-
monly called whipping instability, where the jet is accelerated, stretched and dried.
The final region is the collector region. In this region the jet and instabilities cease
and all the fibers are collected.
4.1.1.1 Region 1: The Taylor Cone
The formation of the cone occurs by a combination of charge repulsion and sur-
face tension mechanisms [17]. Since there is an electric field applied between the
needle and the counter electrode, a voltage is induced in the drop with normal and
tangential components. When the electric field and fluid flow are in such a con-
figuration that the value of the voltage exceeds the value of surface tension, they
form the Taylor cone [17]. The tangential electric field accelerates the charge car-
ried in the liquid, increasing the speed of the surrounding fluid toward the counter
electrode in an attempt to complete the circuit.
Taylor estimated that the surface tension is perfectly balanced by the normal
voltage to create a cone with an apex angle of 98.6°. It is assumed that this cone
has no material loss, and from there, scaling laws were created to predict the diam-
eter of the drop and the current as a function of fluid and flow properties [17].
4.1.1.2 Region 2: Jet
Hartman et al. [18] developed laws that link the diameter and the surface charges
from emitted fibers of a Taylor cone, according to Eqs. 4.5 and 4.6:
dj = bj · Qaj (4.5)
0,59 · I · dj
σ = (4.6)
4Q
where:
dj is the diameter of the jet
aj and bj, are constants
Q is the flow rate

I is the electric current through the jet
σ is the surface charge on the jet
Equations 4.5 and 4.6 do not apply in the case of instabilities that result in fibers
with nanoscale diameters. Without a proper control of operating conditions or fluid
properties, the product can be fibers mixed with drops, or, if the solvent evapora-
tion does not occur, the fibers collected on the counter-electrode will still be wet.
Fridrikh et al. [19] estimated a final diameter of the fiber obtained by electro-
spinning of a polymer. The final diameter of the jet is achieved when there is a bal-
ance among all the forces that contribute to stretch and strain the superficial jet.
According to the analysis of Fridrikh et al. [19], the final diameter of the jet depends
on the material flow, the electric current and the surface tension of the fluid.
For systems containing polyethylene oxide (PEO) and polyacrylic nitrile (PAN),
the charge carriers are the primary polymer [19] and some volatile solvents (water
and N, N-dimethyl formamide). When a volatile solvent is the principal charge
carrier, the charges are lost when the solvent evaporates. This causes lower charge
densities than those theoretically calculated, resulting in larger diameter fibers.
This prediction was made on condition that there is no other thinning mecha-
nism of the jet. However, it was observed that the spreading effect also occurs.
Fibers produced through this effect have 1/3 of the diameter of the primary fibers.
For fiber formation to occur, the presence of solvents with a high vapor pressure
is required. This is a challenge when using ceramic precursors such as alkoxides,
because they tend to combine with certain polymers and alcohols. Systems that use
water as a solvent also work, however, if the vapor pressure is not high enough,
there may be an excessive formation of beads (droplets trapped in the fibers). In tests
using di-ethylene glycol monoethyl-ether [20], which has a boiling point of 200 °C,
there was no fiber formation due to the lack of solvent evaporation. In these cases,
increasing the distance between the capillary and the collector can be beneficial.
To produce uniform fibers, surface tension and surface charges compete with
each other, while the viscosity also plays a very important role. The surface ten-
sion tries to minimize the specific surface area, transforming the jets into little
spheres (beads). Oppositely, the excess electric charge tends to increase the sur-
face area, which favors the formation of thinner jets. Meanwhile, the viscosity of
the polymer solution resists to rapid shape changes [21].
When the viscosity of the solution increases, the size of the beads grows, and
these beads become more cylindrical. With the decrease of charge densities, the
beads tend to disappear. Therefore, for a thin and stable jet, it is important to con-
trol the viscosity, the charge density and surface voltage.
4.1.1.3 Region 3: The Instability Region
Ejected from the Taylor cone tip, the jet remains stable up to a specific distance
to each solution and electrical configuration. Hohman et al. [22, 23] created the
broadest theory to date about the behavior of the jet and the regions of instability.
Initially, it was believed that when the jet passed through certain instability, it
divided into multiple jets of smaller magnitudes than the initial jet. High speed
photographs contradicted this theory and showed that in reality the jet whips so
fast that it resembles several jets, but is in fact only a single jet. As the jet travels
towards the counter electrode, the surface charge density changes along the jet,
resulting in different instabilities.
There are three main types of instabilities, and each can be considered as an
independent phenomenon. These areas of stability and instability compete for a dia-
gram of operation, as a phase diagram can be created for each system individually
[23]. The instability grows in intensity and varies with distance, the electric field
and the diameter of the fibers in different flows depending on the parameters of the
fluid and operating conditions. Each instability grows in intensity at different rates.
The Rayleigh-type instability is the primary mode of instability for a drop
under the influence of an electric field. It corresponds to an increase in dripping of
the fluid emitted by the capillary. This instability is axisymmetric and occurs when
the electric field or the charge density on the surface exceeds a given threshold.
The Rayleigh-type instability is usually treated as a form of non-conductive insta-
bility, because the conductivity of the medium does not play a role in this phenom-
enon. It is the surface tension that governs this instability [23].
The other instability mode is dependent on the conductivity of the fluid.
Axisymmetric conductive instabilities can be viewed as a direct competition
between the surface charge and surface tension of the fiber as it moves. Although
in the literature there are reports of formation of beads during the axisymmetric
instabilities, this seems an appropriate case to describe the phenomenon of their
formation. The fibers tend to decrease in diameter and form lumps in a certain fre-
quency which depends on surface charges. According to the literature, there is an
excess surface charge in areas with bumps and a lower surface charges density in
areas where the jet is thinner [22, 24].
The whipping instability has no axial symmetry and is responsible for the
smaller diameter of fibers produced by electrospinning. This instability is the result
of small deformations of the initially, straight loaded jet. As the fiber is deformed,
the surface charges around the circumference of the jet are distributed heteroge-
neously. A dipole moment P(z) is induced perpendicular to the jet, resulting in a
torque that localized deforms the jet. The deformation is increased as the jet moves
outward, becoming a whipping instability that leads to reduction of the diameter of
the fibers. The jet diameter decreases even more (up to 3 orders of magnitude) by
solvent evaporation. It is assumed that the decrease in diameter due to this instabil-
ity is the result of an increase in the path traveled by the jet, as a result of a com-
plex relationship between surface tension, viscosity and acceleration loads on the
surface and inside the jet by the action of an external electric field.
4.1.1.4 Region 4: Collector
The collector is the final region of the electrospinning process. It consists of an

electrode of opposite charge, through which the fibers are accelerated. Different
electrodes and different orientations, such as sheet metal, screens or rotating cylin-
ders have been used by several researchers.
A flat plate collector is the most used to collect the fibers. It may be a metal
plate such as a sheet or screen [25]. There are methods that use a rotating cylin-
der to collect the fibers [26]. A fiber spool can be obtained if the angular velocity
of the cylinder is combined with the speed of fiber emission. Usually the random
behavior of the jet whipping limits the ability of the fibers aligning completely,
causing twists and overlaps.
4.1.2 Factors Influencing Fiber Characteristics
In general, the process of electrospinning may be affected by several parameters,

among which the main ones are: characteristics of polymer viscosity and con-
ductivity of the polymer solution, surface tension, electric field, distance between
the capillary and the collector object, the form of the collector and environmental
conditions.
In practice, a mixture of the above mentioned factors can influence the proper-
ties of the fibers. The main achievements in the production of fibers by electro-
spinning are: control of the fiber diameter, fibers free of defects, control of the
surface of the fibers, aligned fibers and continuous fibers.
Several process parameters controlled the fibers diameter during the electro-
spinning process [27–29]: the viscosity of the polymer solution, the concentra-
tion of the solution, which is proportional to viscosity, and the voltage used during
electrospinning.
The non-uniform diameter fibers and defects such as beads are among the most
frequent problems (Fig. 4.3). Demir et al. [14] demonstrated the effect of temper-
ature on the uniformity of the fibers. Higher temperatures for polymer solutions
with the same concentration result in more uniform fiber diameters. A higher con-
centration of polymer solutions leads to a decrease in the number of beads. It has
been observed that the addition of salts to a polymer solution can decrease the for-
mation of beads. The reason for this has been attributed to the existence of higher
surface charge densities of the jet of the solution.
In general, when using the electrospinning process, finer fibers are acquired by
controlling parameters such as solution viscosity and concentration. The concen-
tration is a critical parameter and it should be noted that with very low concen-
trations, with very low viscosity, there may be deficiencies in the drying of the
material during the short path of the fibers through the air because of an excess in
solvent and lack of charge, causing a loss of shape of the fiber reaching the screen.
The solution must also have a sufficiently low surface tension, a high charge den-
sity and an adequate viscosity to prevent the collapse of the jet into droplets before
the solvent evaporates.
Fig. 4.3 SEM images of electrospun PS with beads, bead-on-string and fibers structure obtained
from solutions with different polymer concentration (w/v): a 5 %, b 10 %, c 20 %, d 30 %
PS/THF solutions; e 5 %, f 10 %, g 20 %, h 30 % PS/DMF solutions [30]
4.2 Electrospinning of Ceramic Fibers
Larsen et al. [31] were the first to combine electrospinning with the sol–gel
method to obtain the nanofibers made from inorganic oxides and hybrid materials
(organic and inorganic).
Several ceramic oxide fibers with diameters between 200 and 400 nm were
obtained by calcination at high temperatures of a hybrid (inorganic and polymeric
materials) obtained by electrospinning [32–35]. In these studies, it was observed
that the calcination temperature has great influence on the crystallinity of the
phases and morphology of the fibers obtained.
Nuansing et al. [36] investigated the formation of hybrid nanofibers by electro-
spinning polymer/ceramic in the form of a network. Through electrospinning of an
ethanol solution containing both polyvinylpyrrolidone (PVP) and titanium (diiso-
proproxide) bis (2,4-pentanedionate) nanofibers were formed. After heat treatment
of these fibers in air at 300–700 °C, the authors obtained titanium oxide nanofibers
with diameters between 85 and 132 nm.
In recent research, some authors obtained nanofibers of hollow ceramic nano-
tubes, with walls composed of a ceramic composite [37] (Fig. 4.4). Obtaining
nanotubes by electrospinning is possible through the use of two immiscible liq-
uids in a system of two coaxial capillaries, and subsequent selective removal of the
compound nucleus.
The ability to execute this method has been proven by Li et al. [37] in a study
where pure anatase-titania nanotubes/polymer were obtained. The presence of a
sol–gel precursor was required for the formation of a stable and coaxial jet and
the formation of hollow fibers with resistant walls. The authors emphasize that the
uniform circular cross-section of these fibers, their uniform size, and good spatial
orientation, are particularly attractive in the fabrication of devices for fluid trans-
port, as well as guides for optical signals.
Fig. 4.4 SEM image of
TiO2/PVP poly hollow
nanofiber. Reprinted with
permission from [37]
References 41
References
1. Formhals, A.: Process and apparatus for preparing artificial threads. US Patent 1,975,504
(1934)
2. Taylor, G.I.: Electrically driven jets. In: Proceedings of the Royal Society A313, pp. 453–475
(1969)
3. Sei-Hyun, L., Seok-Min, Y., Sang, J.K., Soo-Jin, P., Young-Seak, L.: Characterization of
nanoporous β-SiC fiber complex prepared by electrospinning and carbothermal reduction.
Res. Chem. Intermed. 36, 731–742 (2010)
4. Cloupeau, M., Prunet-Foch, B.: Electrostatic spraying of liquids in cone-jet mode. J.
Electrost. 22, 135–159 (1989)
5. Yarin, A.L., Koombhongse, S., Reneker, D.H.: Taylor cone and jetting from liquid droplets in
electrospinning of nanofibers. J. Appl. Phys. 90, 4836–4846 (2001)
6. Feng, J.J.: Stretching of a straight electrically charged viscoelastic jet. J. Nonnewton. Fluid
Mech. 116, 55–70 (2003)
7. Han, T., Reneker, D.H., Yarin, A.L.: Buckling of jets in electrospinning. Polymer 48,
6064–6076 (2007)
8. Azad, A.M.: Fabrication of yttria-stabilized zirconia nanofibers by electrospinning. Mater.
Lett. 60, 67–72 (2006)
9. Sigmund, W., Yuh, J., Park, H., Maneeratana, V., Pyrgiotakis, G., Daga, A., Taylor, J., Nino,
J.C.: Processing and structure relationships in electrospinning of ceramic fiber systems. J.
Am. Ceram. Soc. 89, 395–407 (2006)
10. Baumgarten, P.K.: Electrostatic spinning of acrylic microfiber. J. Colloid Interface Sci. 6,
64–94 (1971)
11. He, J.H., Wan, Y.Q., Yu, J.Y.: Application of vibration technology to polymer electrospinning.
J. Nonlinear Sci. Num. Simul. 5, 253–262 (2004)
12. Reneker, D.H., Yarin, A.L.: Electrospinning jets and polymer nanofibers. Polymer 49,
2387–2425 (2008)
13. Comini, E., Faglia, G., Sberveglieri, G., Calestani, D., Zanotti, L., Zha, M.: Tin oxide nano-
belts electrical and sensing properties. Sens. Actuators B 111, 2–6 (2005)
14. Demir, M.M., Yilgor, I., Yilgor, E., Erman, B.: Electrospinning of polyurethane fibers.
Polymer 43, 3303–3309 (2002)
15. Hendricks, C.D., Carson, R.S., Hogan, J.J., Schneider, J.M.: Photomicrography of eletrically
sprayed heavy particles. AIAA J. 2, 733–737 (1964)
16. Das, N., Halder, A.K., Sen, J.M.A., Maiti, H.S.: Sonochemically prepared tin-dioxide based
composition for methane sensor. Mater. Lett. 60, 991–994 (2006)
17. Ganan-Calvo, A.M., Barrero, A.: Current and droplet size in the electrospraying of liquid
scaling laws. J. Aerosol Sci. 28, 249–275 (1997)
18. Hartman, R.P.A., Camelot, D.M.A., Marijnissen, J.C.M.: Electrohydrodynamic atomiza-
tion in the cone-jet mode: physical modeling of the liquid cone and jet. J. Aerosol Sci. 30,
823–849 (1999)
19. Fridrikh, S.V., Yu, J.H., Brenner, M.P., Rutledge, G.C.: Controlling the fiber diameter during
electrospinning. Phys. Rev. Lett. 90(14), 1445021–1445024 (2003)
20. Fong, H., Reneker, D.H.: Beaded nanofibers formed during electrospinning. Polymer 40,
4585–4592 (1999)
21. Shin, Y.M., Brenner, M.P., Rutledge, G.C.: Electrospinning: a whipping fluid jet generates
submicron polymer fibers. Appl. Phys. Lett. 78(8), 1149–1151 (2001)
22. Hohman, M.M., Shin, M., Rutledge, G., Brenner, M.P.: Electrospinning and electrically
forced jets II application. Phys. Fluids 13(8), 2221–2236 (2001)
23. Hohman, M.M., Shin, M., Rutledge, G., Brenner, M.P.: Electrospinning and electrically
forced jets I Stability theory. Phys. Fluids 13(8), 2201–2220 (2001)
24. Shin, Y.M., Hohman, M.M., Brenner, M.P., Rutledge, G.C.: Experimental characterization of
electrospinning: the electrically forced jet and instabilities. Polymer 42, 9955–9967 (2001)
25. Zhou, F.L., Gong, R.H., Porat, I.: Polymeric Nanofibers via flat spinneret electrospinning.
Polym. Eng. Sci. 49(12), 2475–2481 (2009)
26. Errico, C., Detta, N., Puppi, D., Piras, A.M., Chiellini, F., Chiellini, E.: Polymeric nano-
structured items electrospun on a cylindrical template: a simple procedure for their removal.
Polym. Int. 60, 1162–1166 (2011)
27. Matabola, K.P., Moutloali, R.M.: The influence of electrospinning parameters on the mor-
phology and diameter of poly(vinyledene fluoride) nanofibers- effect of sodium chloride. J.
Mater. Sci. 48(16), 5475–5482 (2013)
28. Jacobs, V., Anandjiwala, R.D., Maaza, M.: Influence of electrospinning parameters on the
structural morphology and diameter of electrospun nanofibers. J. Appl. Polym. Sci. 115,
3130–3136 (2010)
29. Rodoplu, D., Mutlu, M.: Effects of electrospinning setup and process parameters on
nanofiber morphology intended for the modification of quartz crystal microbalance surfaces.
J. Eng. Fibers Fabr. 7(2), 118–123 (2012)
30. Zheng, J., Zhang, H., Zhao, Z., Han, C.C.: Construction of hierarchical structures by electro-
spinning or electrospraying. Polymer 53, 546–554 (2012)
31. Larsen, G., Velarde-Ortiz, R., Minchow, K., Barrero, A., Loscertales, I.G.: A method for
making inorganic and hybrid (organic/inorganic) fibers and vesicles with diameters in the
submicrometer and micrometer range via sol–gel chemistry and electrically forced liquid
jets. J. Am. Chem. Soc. 125, 1154–1155 (2003)
32. Choi, S.S., Lee, S.G., Im, S.S., Kim, S.H., Joo, Y.L.: Silica nanofibers from electrospinning/
sol-gel process. J. Mater. Sci. Lett. 22, 891–893 (2003)
33. Franco, P.Q., João, C.F.C., Silva, J.C., Borges, J.P.: Electrospun hydroxyapatite fibers from a
simple sol–gel system. Mater. Lett. 67(1), 233–236 (2012)
34. Tunç, T., Uslu, I., Keskin, S.: Fabrication and characterization of boron doped BaZrO3
nanofibers via anelectrospinning technique. J. Ceram. Process. Res. 12(5), 549–554 (2011)
35. Maneeratana, V., Sigmund, W.M.: Continuous hollow alumina gel fibers by direct electro-
spinning of an alkoxide-based precursor. Chem. Eng. J. 137(1), 137–143 (2008)
36. Nuansing, W., Ninmuang, S., Jarernboon, W., Maensiri, S., Seraphin, S.: Structural char-
acterization and morphology of electrospun TiO2 nanofibers. Mater. Sci. Eng. B 131(1–3),
147–155 (2006)
37. Li, D., Xia, Y.: Direct fabrication of composite and ceramic hollow nanofibers by electrospin-
ning. Nano Lett. 4(5), 933–938 (2004)
Chapter 5
CCVD Synthesis of Carbon Nanotubes
Since their discovery in 1991 by Sumio Iijima [1], carbon nanotubes (CNTs)
have generated enormous interest in the area of both fundamental and applied
research, in view of their exceptional mechanical, thermal and electronic proper-
ties [2].
The great interest in relation to CNTs is due mainly to their unique structure,
which provides a unique set of properties. The type of covalent bonds between
sp2 carbon atoms in the basal plane of graphite are the strongest of all chemical
bonds [3]. Since the CNTs are mainly comprised of a graphene sheet folded into
tubular form, it is theoretically the material with the highest mechanical resistance
to rupture [4]. CNTs also feature interesting thermal, electronic, chemical, geo-
metric properties and even great potential for practical applications. CNTs have
the potential to become the basis of a new industry of more resistant and durable
materials.
Initially the application of CNTs focused on single-wall carbon nanotube
(SWNTs). But for some applications, such as the production of composites, it
was necessary to functionalize these nanotubes to facilitate interaction with the
matrix or to dissolve them in a solvent. The functionalization process of altering
the external walls of the nanotube drastically affects its physical properties. The
presence of two or more walls in a CNT allows the external walls to undergo the
process of functionalization, while the inside preserves its structure and properties
[5]. For this reason, there is growing interest for research on multi-wall carbon
nanotubes (MWNTs).
The high mechanical strength demonstrated by CNTs is one of its main
appeals. Its addition to composite or fiber production suggests a large increase
in features such as elastic modulus, tensile strength and fracture toughness of the
matrix and in increasing the electrical conductivity of the matrix. However, there
are great difficulties in transferring individual properties of the CNT to macro-
scopic structures. Even with a significant amount of investigative work in this field
[6–9], it has not been possible to produce composites where the excellent mechan-
ical properties of CNTs were fully exploited.

44 5 CCVD Synthesis of Carbon Nanotubes
From a chemical point of view, the CNTs are more stable against corrosion
than most metals and polymers existing at room temperature and they are resist-
ant to attack by strong non-oxidizing acids, salt solutions and to degradation by
UV radiation. However, in oxidizing atmospheres, the CNTs begin to suffer severe
oxidation at temperatures above 350 °C. This problem can be avoided by the
application of protective films such as SiOx [10].
CNTs also have several potential electronic applications. The ability to form
percolating networks allows the production of very thin and transparent electrical
conductive coatings [11] to replace ITO (indium tin oxide), the main transparent
and high market value electrical conductor. In addition to their much lower cost,
these transparent films made with CNTs, are also very flexible, covering more than
a niche application. Another application for their high electrical conductivity com-
bined with their high surface area, would be to use them as electrodes in superca-
pacitors in the field of energy storage [12].
Other applications in micro and nanoelectronics are been developed with the
help of CNTs. One example is the development of sensors that are placed in situ
in concrete for the evaluation of internal porosity [13], through the use of oriented
nanotube membranes that vibrate when they are in the middle. For certain appli-
cations, the solution to this approach is the synthesis of films of aligned CNTs
[14–17], enabling the manufacture of monitors and microwave generators. This is
possible because of their ability to emit electron by field effect [18]. The appli-
cations of these films also include the development of polymeric solar cells: the
semiconducting properties of CNTs films with anisotropic morphology result in a
route for the separation of pairs and conduction electrons/holes generated by pho-
tons [19].
5.1 Carbon and Its Allotropes
Carbon is a vital component of life and is present in all forms of organic matter.
Belonging to the family of non-metals, each carbon atom has six electrons that
occupy the orbitals 1s2, 2s2 and 2p2. The mix between the last two atomic orbit-
als, with a single 2s electron and 2p 1, 2 or 3 electrons, is called hybridization spn
where n = 1, 2 or 3, depending on the number of atoms bonded [20]. The other
group IV elements such as Si and Ge exhibit primarily only sp3 hybridization.
The sp2 bonds, also called p bonds, make up the structure of graphite
(Fig. 5.1b), the most stable crystalline form of carbon, i.e., with the highest bind-
ing energy (25 eV/mol). Atoms arranged in the shape of hexagons are arranged
in successive planar structures, called graphene, usually displaced half the net-
work direction. This arrangement creates an electron redistribution induced by the
symmetry of the p orbital cycles which makes the hexagonal graphite electrically
conductive [21]. The mechanical properties, the weak van der Waals type link
between the layers, facilitate interplanar cleavage, which produces excellent lubri-
cating properties [22].
5.1 Carbon and Its Allotropes 45
Fig. 5.1 Eight allotropes of carbon: a Diamond, b Graphite, c Lonsdaleite, d C60

(Buckminsterfullerene or buckyball), e C540, f C70, g Amorphous carbon, and h single-walled
carbon nanotube or buckytube [25]
Diamond, however, is a metastable phase of carbon, with lower binding energy

(15 eV/mol) [23]. Its compact lattice has sp3 hybridization (tetrahedral structure)
that gives an extreme hardness, rather than electrical conductivity. Diamond is an
excellent insulator (band gap ~8 eV) due to σ orbitals (sp3), which, among other
properties, will provide a more cohesive and elastic modulus.
Another condensed phase of carbon, which is of particular interest in the syn-
thesis of CNTs, is so-called amorphous carbon (Fig. 5.1g). This allotrope of car-
bon contains sp2 and sp3 hybridization links and is usually an unwanted byproduct
formed during the synthesis of CNTs.
In the mid-80s, a new crystalline form of carbon was discovered [24]: fuller-
enes (Fig. 5.1e). This spherical structure has in its simplest form sixty carbon
atoms (C60) that are presented in the format of 20 hexagons and 12 pentagons.
An excess carbon atom (>60) in these molecules distorts the spherical structure of
C60, but without changing the number of pentagons.
Since 1976, studies on the thermal treatment of hydrocarbons (CVD) allowed

researchers to isolate and observe long fibers and filaments (hollow fibers), car-
bon of several micrometers in length, but with very small diameter. However,
this discovery made jointly by French and Japanese researchers [26] had a lim-
ited impact because the crystalline structure of these objects was inaccessible.
In the early 90s, another Japanese team from NEC Labs proposed the helical
structure of carbon nanocylinders (Fig. 5.1f), which was quickly confirmed by
several teams around the world [1]. In 1993, tubes with almost no thickness
(formed from a single sheet of graphene) were synthesized, isolated and ana-
lyzed [27]. These were named single-wall carbon nanotubes (SWNT) because of
their nanometer diameter.
Currently, numerous other structures related to CNTs have been cataloged,
including:
• Nano-onions [28], consisting of multiple concentric fullerenes;
• Nanohorns [29], SWNTs with a conical structure;
• Nanobuds [30], CNTs connected with fullerenes on the surface;
• Nanotoroids [31], nanotubes bent to form a toroid.
5.2 Carbon Nanotubes
Ideal CNTs can be conceptualized as a graphene sheet rolled to form a

cylinder with a few nanometers of diameter, micrometers and even inches
[32] of length, while the ends are closed by “half-fullerenes” on each side
(Fig. 5.2).
Depending on the amount of rolled sheets, the CNTs can be divided into two
categories: those with only one wall, called “single wall” (SWNT—Single-Wall
Nanotubes) or multi-wall (MWNT—Multi-Wall Carbon Nanotubes). The lat-
ter is the result of several coaxial cylinders with a distance similar to the distance
between the walls of graphene sheets that make up graphite (0.335 nm [34]).The
number of sheets or walls of MWNTs can vary widely, from two (also called
DWNT, Double-Wall Carbon Nanotubes) to dozens of walls [35, 36]. MWNTs are
usually isolated in synthesis products, while SWNTs are usually produced in the
form of bundles of nanotubes [37].
The way in which these graphene sheets are “rolled” determines the atomic
structure of the CNT, which is described in terms of chirality (helicity) of the tube,
defined by the chiral vector Ch and chiral angle θ, Fig. 5.3a. The numbers (n, m)
are integers and a1 and a2 are the unit vectors of the hexagonal lattice of the gra-
phene sheet.
The chiral angle determines the direction in which the tube winds, with limiting
cases when the chiral angle is 0° and 30°. These limiting cases are, respectively,
the zig-zag shape (0°), when n = m, and the armchair shape (30°) when m = 0.
For n ≠ m ≠ 0, the nanotube is called chiral (Fig. 5.3b).
5.2 Carbon Nanotubes 47
Fig. 5.2 The structure of single-walled (SWCNT) formed by wrapping a single sheet of grapheme

(multi-walled (MWCNT) are obtained from two or more sheets of grapheme [33]
The electronic properties of CNTs can be adjusted by selecting the index val-
ues, despite the interatomic bonds remain exactly the same. Theoretical calcula-
tions indicate that all CNTs are metallic where n = m (armchair) or where m – n
results in multiples of 3 [20]. The other CNTs are semiconductors, including all
MWNTs.
5.2.1 Carbon Nanotubes Properties
5.2.1.1 Mechanical Properties
CNTs have extraordinary mechanical properties [40–42]. It is the stiffest (high-

est modulus) and strongest (tensile specific) material known to men. The rupture
tension measured for MWNTs is 63 GPa [4], while the axial elasticity modulus is
1TPa, what make them around five times tougher than steel. Therefore, a break-
through is anticipated for the manufacture of a reinforced and light fiber that can
Fig. 5.3 a Schematic
diagram showing how a
blade or hexagonal graphene
sheet is rolled to form a
nanotube [38]. b types of
carbon nanotubes based on its
chirality (Zig-zag, chiral and
armchair nanotubes)[39]
transfer the properties of individual tubes to a composite matrix. CNTs also have
plastic deformation; they deform permanently after approximately 5 % of elastic
deformation occur [43].
Numerous methods are used to measure the mechanical properties of CNT:
observation of the deflection of a bundle of NTC by TEM [44, 45] or AFM
[46, 47], tensile test between two AFM tips, and inelastic scattering of light [48],
among others.
5.2.1.2 Electronic Properties
CNTs can be either metallic or semiconducting depending on chirality. The gap

in the case of semiconductors is in the order of 0.5 eV, depending on chirality and
diameter. Their conductivity varies between 0.1 and 100 S cm−1 for semiconduc-
tors and around 105 S cm−1 for metallic [5, 49–51].
5.2 Carbon Nanotubes 49
5.2.1.3 Electromechanical Properties
CNTs have a interesting feature of align their axis as an external field [52]
(electrical [53–55] or magnetic [56, 57]) is applied. This property is applied, for
example, for alignment during the synthesis [58] or to separate the CNTs accord-
ing to the semiconducting or metallic character [59].
5.2.1.4 Physical and Chemical Properties
CNTs are highly hydrophobic, which gives them a very low wettability to ionic
media. For dispersions in an aqueous medium, a surface functionalization [60] or
surfactants addition [61] step is usually required. Their large specific surface area
make them a possible candidate for catalyst supports in the areas of absorption and
conversion of gases. It is also possible to open the ends and insert them into mol-
ecules of fullerenes [62], metals [63, 64], etc.
5.2.1.5 Thermal Properties
CNTs are great heat conductors in the direction of their axis, but are poor ther-
mal conductors in the transverse axis. Measurements indicate thermal conductiv-
ity values between 1,000 and 6,000 Wm−1k−1 [65, 66], comparable to diamond
(2,000 Wm−1k−1). The thermal stability of carbon nanotubes is extremely high in
non-oxidizing atmospheres: MWNTs can withstand up to 2,800 °C [67].
5.3 Carbon Nanotubes Synthesis
The different production techniques of CNTs are classified into two groups
according to the temperature of synthesis: high temperature production, with tem-
peratures exceeding 3,000 °C, is characterized by the use of solid precursors with
or without the use of a catalyst material, and moderate temperature production,
between 600 and 1,200 °C, with gaseous precursors, when the use of a catalyst is
essential.
5.3.1 High Temperatures Methods
This route of synthesis consists of two main techniques [68]:

Arc Discharge An electrical discharge is produced between two graphite elec-
trodes, which heats and vaporizes the electrodes, and after, being condensed in the
form of a soot containing nanotubes.
Fig. 5.4 Illustration of a furnace for CCVD
Laser Ablation In this method, a graphite target is vaporized by laser irradiation

(continuous or pulsed) in an atmosphere of inert gas (helium or argon).
In both methods, the carbon is sublimated at high temperatures (3,000–4,000 °C)
and condensed in another region of the furnace under a partial pressure of inert gas
with a high thermal gradient. CNT growth occurs in the colder areas of the oven.
For the growth of SWNTs, a metal catalyst is required [58].
The main advantage of these types of techniques is the structural quality of
the CNTs. However, the production requires a high consumption of energy and
the CNTs obtained require purification steps and dispersion, as they generally are
highly agglomerated, forming very cohesive bundles. These methods do not pro-
vide organized CNTs or selectively grow on any surface.
5.3.2 CCVD
The catalytic chemical vapor deposition (CCVD) technique is far more developed
and has great potential to be applied industrially. This technique allows for mass
production at lower temperatures than the previously described methods and can
be adapted for continuous production [69]. This method consists of decomposing a
gas or a liquid precursor, which supplies carbon on catalytic particles (Fe, Ni, Co)
in a tube furnace at temperatures between 500 and 1,100 °C (Fig. 5.4). Besides
the classic oven, heated by electric heaters, plasma furnaces (PECVD, Plasma-
Enhanced Chemical Vapor Deposition) microwaves (microwave, MW-PECVD), or
DC (direct current, dc-PECVD) are also used.
The most accepted mechanism in the literature for the catalytic growth of
CNTS is similar to that described by Waner et al. [70], known as the VLS (vapor–
liquid–solid) method. The synthesis as a whole can be divided into three steps:
formation of catalyst nanoparticles (NP’s), carbon accumulation in the NP and
CNT growth.
5.3 Carbon Nanotubes Synthesis 51
Formation of metal catalyst nanoparticles This step depends on the type of

substrate used, whether it is in powder form, a flat substrate or without a sub-
strate. In addition to an inert gas used as carrier gas, hydrogen is also intro-
duced to keep the NP catalyst active and to reduce any oxides forming on the
metal catalyst.
The particle size is essential for the synthesis of CNTs. In general, the size of
these particles relates to the diameter of the CNTs. With an increasing diameter
of the NP’s, the consecutive increase in the diameter of the CNTs also leads to an
increased number of walls of the CNTs [71, 72].
Carbon accumulation in nanoparticles Once the NP’s are in the oven, the pre-
cursor is introduced. The reaction resulting from contact between the two follows
four distinct processes:
• Adsorption of carbon source gas molecules on the surface;
• Decomposition of the molecule into carbon and hydrogen;
• Diffusion of carbon from the sides of the NP to one of the faces parallel to the
substrate;
• Nucleation and incorporating.
The decomposition reaction is complex and depends, in addition to the precur-
sor used and the temperature, on catalyst type, gas ratios and the presence of any
other gas (such as water vapor, oxygen, other hydrocarbons, etc.), even in small
quantities. In general, hydrocarbon is decomposed into hydrogen, carbon and
other lighter hydrocarbons.
During the diffusion of carbon, at first there is a saturation of carbon in the par-
ticle, forming a metastable carbide that decomposes again in metal and more car-
bon in the carbon precipitation front. This carbon can either migrate to the upper
or lower surface of the NP (with respect to the substrate) depending on the NP/
substrate interaction, determining the growth mode of the CNT. For a strong NP/
substrate interaction, there is the anchoring of the NP: the carbon atom migrates to
the surface opposite to the substrate, promoting the growth known as “tip growth”
(the NP is at the upper end of the CNT and goes up with it). When there is a low
NP/substrate interaction, the growth is called “bottom growth” (NP is fixed at the
interface/substrate) [73, 74]. Many times the particle ends up getting stuck in the
middle of the CNT, in the center of the inner tube.
This diffusion is due to the gradients of carbon and temperature between
the surfaces where the carbon is adsorbed (with higher temperature due to the
decomposition of hydrocarbons, in general, exothermic) and the other surfaces
[75]. On the one hand, tip growth facilitates the access to the carbon particle,
but it results in incorporation of the metal inside the CNT or in its covering with
other forms of carbon. Bottom growth facilitates the growth of metal removed
from the CNT, but the strong bond with the substrate can result in early deacti-
vation of catalytic activity.
CNT growth As the carbon begins to deposit on the surface of the NP, it rear-
ranges itself in the form of hexagons, keeping two CC bonds and a CM bond
and forming a graphene sheet perpendicular to the NP. This form of core is more
favorable because it eliminates the presence of broken links on the edges of the
cluster [76].
From a kinetic point of view, there is still no consensus on which of the previ-
ous steps is limiting the growth of this cluster in a CNT. But globally, it is shown
that the process must start at an accelerated growth rate and then enter a period of
steady growth.
The growth will cease when the carbon supply is interrupted or when the
metal catalyst is deactivated, a process known as “poisoning” of the catalyst.
Some authors relate such poisoning to a reaction between the substrate and the
metal catalyst [77] or to a coat of different allotropes of carbon. As this deactiva-
tion will not occur at the same time for each particle, the reaction time will pass
through an optimal point in terms of CNT length and the formation of amor-
phous carbon.
The precursor used and the temperature are key factors for the formation
of SWNTs or MWNTs. In general, higher temperatures are better for obtaining
SWNTs, because they require more energy for their formation. For the same rea-
son, the choice of precursor is limited in this matter. Some precursors undergo
decomposition only at higher temperatures, as is the case with more stable hydro-
carbons such as methane. However, other precursors promote these non-catalytic
decomposition temperatures, making it impossible to form amorphous carbon and
SWNTs.
Temperature is also important in the defects presence. High temperatures pro-
vide more thermal energy for the formation of perfect crystal structures. This is
the main defect of the CCVD if compared to high temperatures techniques, the
synthesized CNTs have a considerable amount of defects.
Even the shape of the specimen holder inside the oven can affect the synthesis.
According to Liu et al., A semi-closed container retains the gas precursor for more
time improving the efficiency of the synthesis [78].
5.3.2.1 CNTs CCVD Substrates/Catalyst Powder
For the CNTs growth from powder form catalysts, it is used as a support an inert
and refractory oxide, and transition metals in the form of oxides, which will
generate, during the reaction, the catalyst NP. To produce a homogeneous mix-
ture between the oxide and metal oxide catalyst support, two methods are most
commonly used: solution combustion synthesis (SCS) [79] or the impregnation
method [80]. Both use inorganic salts (usually nitrates) as the catalysts.
In the impregnation method, the oxide support is impregnated with a liquid
solution containing the dissolved transition metals, which is then heated until the
complete evaporation of the solvent. In SCS, both precursor salts of the metal
oxide catalyst and support are dissolved in a solvent, usually water, along with
an organic compound that acts as fuel and complexing agent [79]. The solution
is then heated to its ignition and a mixture of oxides in the form of a powder with
high surface area is generated. The latter method has certain advantages over
impregnation, it allows to generate more homogeneous mixtures, it is faster and

can be done continuously [81].
Efficient catalysts for the synthesis of CNTs usually have a strong inter-
action between the metal catalyst and support material (wettability), a high
surface area and large pore volume. Furthermore, these surface characteris-
tics must be resistant to sintering at temperatures of growth of CNTs [82]. The
strong interaction between metal catalyst and support reduces the coagulation
of catalyst particles, reducing their average diameter. A large surface area and
a large volume of pores facilitate the synthesis of CNTs in large quantities due
to the large area available for the allocation of catalyst particles.
5.3.2.2 CCVD of CNTs on Flat Substrates
The growth of aligned and ordered CNTs can be designed through the use of
flat substrates. For this, the metal catalyst is deposited as thin film on substrates
with high-degree of planarity such as monocrystalline silicon wafers known as
wafers.
These films, in the range of few dozens of angstroms, while under the influ-
ence of temperature, coalesce to form NP’s scattered on the substrate. This is
due mainly to the decrease in total surface area of the catalyst when it passes
through a very thin film of semi-spherical particles. The high temperature pro-
vides the energy needed for the diffusion of these atoms to positions of lower
energy. Modeling the formation of these particles takes into account the fusion
of this film, even though it is below the melting point of the bulk metal [83],
since at the nanoscale the metals melting point is lower [84]. Another factor
that favors the coalescence in NP’s is the internal stress of films due to dif-
ferences in thermal expansion coefficient and lattice parameter of the metal
substrate [14].
In addition to the thermal treatment of these films, a plasma treatment can be
used to further reduce the size of the NP’s. The MW-PECVD technique induces
collision of H ions into the surface, breaking the NP’s [85].
The result of this synthesis method was first shown for MWNTs for both
PECVD [16] and CCVD [50], called nanotubes “forests”. This type of growth is
due to the high density of NP close to each other, so that the CNTs interact with
each other through van der Waals forces, “self-directing” themselves perpendicu-
larly to the substrate during growth [86].
Many parameters must be taken into account for the growth of the forests.
The goal is usually a high density of NPs with reduced diameter in order to pro-
mote a good alignment. The thickness of the layer is vital in controlling these
factors. Its increase in general results in NPs with a larger diameter and affects
the total density of particles [72, 78, 87]. Temperature also plays an important
role in these factors, with an optimal point for each system [88].
Some basic precautions should be taken for the substrate used. For the growth
of CNT forests, it is important to have a good surface flatness. This allows proper
Fig. 5.5 SEM images of CNT forests to form a continuous length web [95]
Fig. 5.6 SEM images of samples obtained by pyrolysing solutions of 2.5 % ferrocene: a and

b 800 °C, c and s 950 °C, and 5 % ferrocene: e and f 950 °C
alignment and prevents the preferentially particle deposition in some region of

the substrate during the coalescence of the film. Nevertheless, some groups pro-
duce CNT films even directly on plates of metal catalysts. In this method, the
surface is first oxidized and then reduced for the formation of the NP’s [89].
Fig. 5.7 SEM images of nanotube films grown at different temperature, a 590 °C, b 740 °C, c

850 °C, d 940 °C, for 60 min, 750 ml/min Ar/H2 flow rate and at a feed rate of 1.2 ml/h of the
solution
One of the latest advances in this field was the use of water vapor during the
synthesis. One of the limitations of this type of synthesis is the deactivation of the
catalyst due to its covering with amorphous carbon. The addition of small frac-
tions of water helps to keep the catalyst active for much longer to selectively oxi-
dize the amorphous carbon. [90–94]. CCVD assisted by water, or “super-growth”
as it is called, greatly enhances the quality of forests produced, not only increasing
their height (from micrometers to millimeters), but also reducing the amount of
impurities (Fig. 5.5).
Consequently, the density of the NTC films produced by this method increased.
For SWNTs forests, the typical density is 5.2 × 1011 CNTs/cm2, with 0.037 g/cm3
and a 3 nm diameter for SWNTs on average. Yet these forests are relatively “empty”,
containing 96 % of unfilled spaces. This ends up being important for the synthesis,
because the gaps are necessary for the diffusion of carbon to the metal catalyst [96].
However, access to the catalyst still presents a problem for large areas of synthesis
[97]. This problem can be circumvented by changing the direction of gas and water
on the sample. Yasuda et al. showed that introducing the reagents above the sample,
rather than laterally, increases the efficiency of growth [98].
In summary, many parameters must be controlled for the synthesis of CNT for-
ests, depending on the features you want to get in films such as number of walls,
height, density, etc. These features greatly alter the properties of films such as wet-
tability, electrical or thermal conductivity, field effect, etc. [72].
5.3.2.3 CCVD CNTs Without Substrate
In this method, the synthesis is done using a hydrocarbon gas or liquid, and an
organometallic liquid (usually a metallocene, M (C5H5)2), which acts as a catalyst.
Both are introduced simultaneously in the oven, where the organometallic sub-
stance decomposes forming metal catalyst particles, which react with the carbon
provided by the precursor. If the precursor is liquid, the reactants are premixed
and introduced into the pyrolysis furnace through a syringe, spray or aerosol. If
the precursor is gaseous, the organometallic substance is evaporated and carried by
a carrier gas, or bubbled directly into the liquid catalyst [99]. Thanks to the con-
tinuous feeding of catalyst throughout the synthesis, it is possible to achieve high
speeds of growth (around 50 μm min−1) [100] (Fig. 5.6).
The essential advantage of these techniques is that the synthesis is performed in
a single step, without the necessity of pre-catalyst synthesis, pre-deposition of the
catalyst, or treatments before synthesis.
Generally, the CNTs obtained through this method are presented in the form of
dense blocks (109 NTC cm−2 [69, 101]) of aligned MWNTs (Fig. 5.7). The disad-
vantage of this method is the guaranteed presence of metal catalyst in the CNTs,
since there is no substrate to retain these particles.
References
1. Iijima, S.: Helical microtubules of graphitic carbon. Nature 354(6348), 56–58 (1991)
2. Saito, R.G., Dresselhaus, M.S.: Physical properties of carbon nanotubes. Imperial College
Press, London (1999)
3. Coulson, C.A.: Valence. Oxford University Press, London (1963)
4. Yu, M.F., et al.: Strength and breaking mechanism of multiwalled carbon nanotubes under
tensile load. Science 287(5453), 637–640 (2000)
5. Ando, Y., et al.: Physical properties of multiwalled carbon nanotubes. Int. J. Inorg. Mater.
1(1), 77–82 (1999)
6. Ajayan, P.M., Schadler, L.S., Giannaris, C., Rubio, A.: Single-walled carbon nanotube-poly-
mer composites: strength and weakness. Adv. Mater. 12(10), 750–753 (2000)
7. Baughman, R.H., Zakhidov, A.A., Heer, W.A.: Carbon nanotubes—the route toward appli-
cations. Science 297(5582), 787–792 (2002)
8. Sandler, J., Shaffer, M.S.P., Prasse, T., Bauhofer, W., Schulte, K., Windle, A.H.:
Development of a dispersion process for carbon nanotubes in an epoxy matrix and the
resulting electrical properties. Polymer 40(21), 5967–5971 (1999)
9. Thostenson, E.T., Ren, Z.F., Chou, T.W.: Advances in the science and technology of car-
bon nanotubes and their composites: a review. Compos. Sci. Technol. 61(13), 1899–1912
(2001)
10. Seeger, T., Köhler, T., Frauenheim, T., Grobert, N., Terrones, M., Seifert, G., Rühle, M.:
SiO2-coated carbon nanotubes: theory and experiment. Zeitschrift Fur Metallkunde 93(5),
455–458 (2002)
11. Lima, M.D., Andrade, M.J., Skákalová V., Bergmann, C.P., Roth, S.: Dynamic percolation
of carbon nanotubes in liquid medium. J. Mater. Chem. 17(46), 4846–4853 (2007)
12. Arico, A.S., Bruce, P., Scrosati, B., Tarascon, J.M., Schalkwijk, W.: Nanostructured materi-
als for advanced energy conversion and storage devices. Nat. Mater. 4(5), 366–377 (2005)
References 57
13. Lebental, B., Bourquin, F., Caussignac, J.M., Acauan, L., Sanaur, S., Ghis, A. (2009) In-situ
non-destructive testing of cementitious materials with embedded ultrasonic transducers
made up of carbon nanotubes. In: Non-Destructive Testing in Civil Engineering
14. Chhowalla, M., Teo, K.B.K., Ducati, C., et al.: Growth process conditions of vertically
aligned carbon nanotubes using plasma enhanced chemical vapor deposition. J. Appl. Phys.
90(10), 5308–5317 (2001)
15. Maruyama, S., Einarsson, E., Murakami, Y., Edamura, T.: Growth process of vertically
aligned single-walled carbon nanotubes. Chem. Phys. Lett. 403(4–6), 320–323 (2005)
16. Ren, Z.F., Huang, Z.P., Xu, J.W., et al.: Synthesis of large arrays of well-aligned carbon
nanotubes on glass. Science 282(5391), 1105–1107 (1998)
17. Zhang, L., Tan, Y.Q., Resasco, D.E.: Controlling the growth of vertically oriented single-
walled carbon nanotubes by varying the density of Co-Mo catalyst particles. Chem. Phys.
Lett. 422(1–3), 198–203 (2006)
18. Cao, A.Y., Cia, L., Li, D., et al.: Vertical aligned carbon nanotubes grown on Au film
and reduction of threshold field in field emission. Chem. Phys. Lett. 335(3–4), 150–154
(2001)
19. Kymakis, E., Amaratunga, G.A.J.: Photovoltaic cells based on dye-sensitisation of single-
wall carbon nanotubes in a polymer matrix. Sol. Energy Mater. Sol. Cells 80(4), 465–472
(2003)
20. Dresselhaus, M.S., Dresselhaus, G., Avouris, P.: Carbon nanotubes: synthesis, structure,
properties, and applications. In: Topics in applied physics. Springer, Berlin, New York
(2001)
21. Sutton, A.P.: Electronic structure of materials. Oxford science publications. Clarendon
Press, Oxford (2004)
22. Callister Jr, W.D., Soares, S.M.S.: Ciência e engenharia de materiais uma introdução. Livros
Técnicos e Científicos, Rio de Janeiro (2008)
23. Bernier, P.E., Lefranc, S.: Le Carbone dans tous ses états. Gordon and Breach Science
Publishers, Amsterdam (1997)
24. Kroto, H.W., Heath, J.R., O’brien, S.C., Curl, R.F., Smalley, R.E.: C-60-
Buckminsterfullerene. Nature 318(6042), 162–163 (1985)
25. Ströck, M.: Eight allotropes of carbon, Wikimedia commons, viewed. http://commons.wiki
media.org/wiki/File:Eight_Allotropes_of_Carbon.png (2006). Accessed 08 August 2013
26. Oberlin, A., Endo, M., Koyama, T.: Filamentous growth of carbon through benzene decom-
position. J. Cryst. Growth 32(3), 335–349 (1976)
27. Wang, N., Tang, Z.K., Li, G.D., Chen, J.S.: Materials science-single-walled 4 angstrom car-
bon nanotube arrays. Nature 408(6808), 50–51 (2000)
28. Ugarte, D.: Onion-like graphitic particles. Carbon 33(7), 989–993 (1995)
29. Iijima Yudasakaa, S.M., Yamada, R., et al.: Nano-aggregates of single-walled graphitic car-
bon nano-horns. Chem. Phys. Lett. 309(3–4), 165–170 (1999)
30. Nasibulin, A.G., Anisimova, A.S., Pikhitsa, P.V., et al.: Investigations of nanobud formation.
Chem. Phys. Lett. 446(1–3), 109–114 (2007)
31. Liu, J., Dai, H., Hafner, J.H., et al.: Fullerene ‘crop circles’. Nature 385(6619), 780–781
(1997)
32. Zheng, L.X., O’Connell, M.J., Doorn, S.K., et al.: Ultralong single-wall carbon nanotubes.
Nat. Mater. 3(10), 673–676 (2004)
33. Da Dalt, S., Alves, A.K., Bergmann, C.P.: CNTs/TiO2 composites. In: NanoCarbon 2011:
Selected works from the Brazilian Carbon Meeting, Springer, Berlin (2012)
34. Delhaes, P.: (2001) Graphite and precursors. In: World of carbon v.1. Gordon & Breach,
Amsterdam
35. Odom, T.W., Huang, J.L., Kim, P., Lieber, C.M.: Structure and electronic properties of car-
bon nanotubes. J. Phys. Chem. B 104(13), 2794–2809 (2000)
36. Dresselhaus, M.S., Lin, Y.M., Rabin, O., et al.: Nanowires and nanotubes. Mater. Sci. Eng.
C-Biomimetic Supramol. Syst. 23(1–2), 129–140 (2003)
37. Thess, A., Lee, R., Nikolaev, P., et al.: Crystalline ropes of metallic carbon nanotubes.
Science 273(5274), 483–487 (1996)
38. Kebes: CNTnames, Wikimedia Commons. http://commons.wikimedia.org/wiki/
File:CNTnames.png (2005). Accessed 08 August 2013
39. Kalamkarov, A.L., Georgiades, A.V., Rokkam, S.K., Veedu, V.P., Ghasemi-Nejhad, M.N.:
Analytical and numerical techniques to predict carbon nanotubes properties. Int. J. Solids
Struct. 43, 6832–6854 (2006)
40. Ruoff, R.S., Lorents, D.C.: Mechanical and thermal-properties of carbon nanotubes. Carbon
33, 925–930 (1995)
41. Rafii-Tabar, H.: Computational modelling of thermo-mechanical and transport properties of
carbon nanotubes. Phys. Rep. Rev. Sect. Phys. Lett. 390, 235–452 (2004)
42. Ruoff, R.S., Qian, D., Liu, W.K.: Mechanical properties of carbon nanotubes: theoretical
predictions and experimental measurements. C.R. Phys. 4, 993–1008 (2003)
43. Qian, D., Wagner, G.J., Liu, W.K.: Mechanics of carbon nanotubes. Appl. Mech. Rev. 55(6),
495–533 (2002)
44. Treacy, M.M.J., Ebbesen, T.W., Gibson, J.M.: Exceptionally high Young’s modulus
observed for individual carbon nanotubes. Nature 381(6584), 678–680 (1996)
45. Enomoto, K., Kitakata, S., Yasuhara, T., Ohtake, N., Kuzumaki, N., Mitsuda, Y.:
Measurement of Young’s modulus of carbon nanotubes by nanoprobe manipulation in a
transmission electron microscope. Appl. Phys. Lett. 88(15), 1531151–1531153 (2006)
46. Salvetat, J.P., Bonard, J.M., Thomson, N.H., et al.: Mechanical properties of carbon nano-
tubes. Appl. Phys. A Mater. Sci. Process. 69(3), 255–260 (1999)
47. Salvetat, J.P., Briggs, G.A.D., Bonard, J.M., et al.: Elastic and shear moduli of single-walled
carbon nanotube ropes. Phys. Rev. Lett. 82(5):944–947 (1999)
48. Bassi, A.L., Beghi, M.G., Casari, C.S., et al.: Inelastic light scattering from magnetically
aligned single-walled carbon nanotubes and estimate of their two-dimensional Young’s
modulus. Diam. Relat. Mater. 12(3–7), 806–810 (2003)
49. Yang, J., Waltermire, S., Chen, Y., et al.: Contact thermal resistance between individual mul-
tiwall carbon nanotubes. Appl. Phys. Lett. 96(2), 023109-3 (2010)
50. Fan, S., Chapline, M.G., Franklin, N.R., et al.: Self-oriented regular arrays of carbon nano-
tubes and their field emission properties. Science 283(5401), 512–514 (1999)
51. Ho, Y.H., Chang, C.P., Shyu, F.L., et al.: Electronic and optical properties of double-walled
armchair carbon nanotubes. Carbon 42, 3159–3167 (2004)
52. Jones, T.B.: Electromechanics of particles. Cambridge University Press, Cambridge
(1995)
53. Dimaki, M., Boggild, P.: Dielectrophoresis of carbon nanotubes using microelectrodes: a
numerical study. Nanotechnology 15(8), 1095–1102 (2004)
54. Subramanian, A., Vikramaditya, B., Dong, L., et al.: Micro and nanorobotic assembly
Using dielectrophoresis. In: Robotics: Science and Systems. The MIT Press, Cambridge
(2005)
55. Smith, P.A., Nordquist, C.D., Jackson, T.N., et al.: Electric-field assisted assembly and
alignment of metallic nanowires. Appl. Phys. Lett. 77(9), 1399–1401 (2000)
56. Kordás, K., Mustonen, T., Tóth, G., et al.: Magnetic-field induced efficient alignment of car-
bon nanotubes in aqueous solutions. Chem. Mater. 19(4), 787–791 (2007)
57. Kimura, T., Ago, H., Tobita, M., et al.: Polymer composites of carbon nanotubes aligned by
a magnetic field. Adv. Mater. 14(19), 1380–1383 (2002)
58. Zhang, Y.G., Chang, A., Cao, J., et al.: Electric-field-directed growth of aligned single-
walled carbon nanotubes. Appl. Phys. Lett. 79(19), 3155–3157 (2001)
59. Krupke, R., Hennrich, F., Löhneysen, H.V., Kappes, M.M.: Separation of metallic from
semiconducting single-walled carbon nanotubes. Science 301(5631), 344–347 (2003)
60. Rakov, E.G.: The chemistry and application of carbons nanotubes. Usp. Khim. 70(10),
934–973 (2001)
61. Moore, V.C., Strano, M.S., Haroz, E.H., et al.: Individually suspended single-walled carbon
nanotubes in various surfactants. Nano Lett. 3(10), 1379–1382 (2003)
References 59
62. Smith, B.W., Monthioux, M., Luzzi, D.E.: Encapsulated C-60 in carbon nanotubes. Nature
396(6709), 323–324 (1998)
63. Grobert, N., Mayne, M., Terrones, M., et al.: Alloy nanowires: Invar inside carbon nano-
tubes. Chem. Commun. 5, 471–472 (2001)
64. Lv, R.T., Kanga, F., Cai, D., et al.: Long continuous FeNi nanowires inside carbon nano-
tubes: synthesis, property and application. J. Phys. Chem. Solids 69(5–6), 1213–1217
(2008)
65. Che, J.W., Çagin, T., Goddard, W.A.: Thermal conductivity of carbon nanotubes.
Nanotechnology 11(2), 65–69 (2000)
66. Hone, J., Whitney, M., Piskoti, C., Zettl, A.: Thermal conductivity of single-walled carbon
nanotubes. Phys. Rev. 59(4), R2514–R2516 (1999)
67. Jin, R., Zhou, Z.X., Mandrus, D., et al.: The effect of annealing on the electrical and thermal
transport properties of macroscopic bundles of long multi-wall carbon nanotubes. Phys. B
68. Journet, C., Bernier, P.: Production of carbon nanotubes. Appl. Phys. Α Mater. Sci. Process.
Condens. Matter 388(1–2), 326–330 (2007)
67(1), 1–9 (1998)

69. Andrews, R., Jacquesa, D., Rao, A.M., et al.: Continuous production of aligned carbon
nanotubes: a step closer to commercial realization. Chem. Phys. Lett. 303(5–6), 467–474
(1999)
70. Wagner, R.S., Ellis, W.C.: Vapor-liquid-solid mechanism of crystal growth and its applica-
tion to silicon. Trans. Metall. Soc. AIME 233(6), 1053–1064 (1965)
71. Schäffel, F., Rümmeli, M.H., Kramberger, C., et al.: Tailoring the diameter, density and
number of walls of carbon nanotubes through predefined catalyst particles. Phys. Status
Solidi A Appl. Mater. Sci. 205(6), 1382–1385 (2008)
72. Zhao, B., Futaba, D.N., Yasuda, S., et al.: Exploring advantages of diverse carbon nanotube
forests with tailored structures synthesized by supergrowth from engineered catalysts. ACS
Nano 3(1), 108–114 (2009)
73. Baker, R.T.K.: Catalytic growth of carbon filaments. Carbon 27(3), 315–323 (1989)
74. Malesevic, A., Chen, H., Hauffman, T., et al.: Study of the catalyst evolution during anneal-
ing preceding the growth of carbon nanotubes by microwave plasma-enhanced chemical
vapour deposition. Nanotechnology 18(45), 455602 (2007)
75. Klinke, C., Bonard, J.M., Kern, K.: Thermodynamic calculations on the catalytic growth of
multiwall carbon nanotubes. Phys. Rev. B 71(3), 035403 (2005)
76. Kuznetsov, V.L., Usoltseva, A.N., Chuvilin, A.L.: Thermodynamic analysis of nucleation of
carbon deposits on metal particles and its implications for the growth of carbon nanotubes.
Phys. Rev. B 64, 235401 (2001)
77. Homma, Y., Kobayashi, Y., Ogino, T.: Role of transition metal catalysts in single-walled
carbon nanotube growth in chemical vapor deposition. J. Phys. Chem. B 107(44), 12161–
12164 (2003)
78. Liu, K., Sun, Y., Chen, L., et al.: Controlled growth of super-aligned carbon nanotube arrays
for spinning continuous unidirectional sheets with tunable physical properties. Nano Lett.
8(2), 700–705 (2008)
79. Patil, K.C., Aruna, S.T., Mimani, T.: Combustion synthesis: an update. Curr. Opin. Solid
State Mater. Sci. 6(6), 507–512 (2002)
80. Liu, B.C., Lyu, S.C., Lee, T.J., et al.: Synthesis of single- and double-walled carbon nano-
tubes by catalytic decomposition of methane. Chem. Phys. Lett. 373(5–6), 475–479 (2003)
81. Lima, M.D., Dettlaff, U., Andrade, M.J., et al.: Method for continuous production of cat-
alysts for synthesis of carbon nanotubes. Phys. Status Solidi B Basic Solid State Phys.
244(11), 3930–3934 (2007)
82. Cassell, A.M., Raymakers, J.A., Kong, J., Dai, H.: Large scale CVD synthesis of single-walled
carbon nanotubes. J. Phys. Chem. B 103(31), 6484–6492 (1999)
83. Sanjabi, S., Faramarzi, A., Momen, M.H., Barber, Z.H.: Modeling of the heterogeneous
formation of Ni catalyst particles for carbon nanotube growth. J. Phys. Chem. C 113(20),
8652–8659 (2009)
84. Safaei, A., Shandiz, M.A., Sanjabi, S., Barber, Z.H.: Modelling the size effect on the melt-
ing temperature of nanoparticles, nanowires and nanofilms. J. Phys. Condens. Matter
113(20), 8652–8659 (2007)
85. Rizk, S., Assouar, B.M., Poucques, L.D., Alnot, P., Bougdira, J.: Controlled nanostructura-
tion of catalyst particles for carbon nanotubes growth. J. Phys. Chem. C 113(20), 8718–
8723 (2009)
86. Dai, H.J.: Carbon nanotubes: opportunities and challenges. Surf. Sci. 500(1–3), 218–241
(2002)
87. Signore, M.A., Rizzo, A., Rossi, R., Piscopiello, E., Di Luccio, T., Capodiecia, L.,
Dikonimos, T., Giorgi, R.: Role of iron catalyst particles density in the growth of forest-like
carbon nanotubes. Diam. Relat. Mater. 17(11), 1936–1942 (2008)
88. Yao, Y., Falk, L.K.L., Morjan, R.E., Nerushev, O.A., Campbell, E.E.B.: Synthesis of carbon
nanotube films by thermal CVD in the presence of supported catalyst particles. Part I: The
silicon substrate/nanotube film interface. J. Mater. Sci. Mater. Electr. 15(8), 533–543 (2004)
89. Karwa, M., Iqbal, Z., Mitra, S.: Scaled-up self-assembly of carbon nanotubes inside long
stainless steel tubing. Carbon 44(7), 1235–1242 (2006)
90. Hata, K., Futaba, D.N., Mizuno, K., et al.: Water-assisted highly efficient synthesis of impu-
rity-free single-walled carbon nanotubes. Science 306(5700), 1362–1364 (2005)
91. Li, Q.W., Zhang, X., DePaula, R.F., et al. (2006) Sustained growth of ultralong carbon nano-
tube arrays for fiber spinning. Adv. Mater. 18(23), 3160–3163
92. Chakrabarti, S., Nagasaka, T., Yoshikawa, Y., et al. (2006) Growth of super long aligned
brush-like carbon nanotubes. Japan. J. Appl. Phys. Part 2 Lett. Express Lett. 45(24–28),
L720–L722
93. Yun, Y.H., Shanov, V., Tu, Y., et al.: Growth mechanism of long aligned multiwall carbon
nanotube arrays by water-assisted chemical vapor deposition. J. Phys. Chem. B 110(47),
23920–23925 (2006)
94. Ago, H., Ueharab, N., Yoshihara, N., et al.: Gas analysis of the CVD process for high yield
growth of carbon nanotubes over metal-supported catalysts. Carbon 44(14), 2912–2918
(2006)
95. Sears, K., Skourtis, C., Atkinson, K., Finn, N., Humphries, W.: Focused ion beam milling
of carbon nanotube yarns to study the relationship between structure and strength. Carbon
48(15), 4450–4456 (2010)
96. Joselevich, E., Dai, H., Liu, J., Hata, K., Windle, A.H.: Carbon nanotube synthesis and
organization. Carbon Nanotubes 111, 101–164 (2008)
97. Zhong, G., Iwasaki, T., Robertson, J., Kawarada, H.: Growth kinetics of 0.5 cm vertically
aligned single-walled carbon nanotubes. J. Phys. Chem. B 111(8), 1907–1910 (2007)
98. Yasuda, S., Futaba, D.N., Yamada, T., et al.: Improved and large area single-walled carbon
nanotube forest growth by controlling the gas flow direction. ACS Nano 3(12), 4164–4170
(2009)
99. Castro, C.: Mécanismes de croissance de nanotubes de carbone alignés: relation catalyseur -
nanotube, in Laboratoire Francis PERRIN, p. 189. Université Paris Sud, Gif-sur-Yvette (2009)
100. Mayne, M., Groberta, N., Terrones, M., et al.: Pyrolytic production of aligned carbon nano-
tubes from homogeneously dispersed benzene-based aerosols. Chem. Phys. Lett. 338(2–3),
101–107 (2001)
101. Singh, C., Shaffer, M.S., Windle, A.H.: Production of controlled architectures of aligned
carbon nanotubes by an injection chemical vapour deposition method. Carbon 41(2),
359–368 (2003)
Chapter 6
Hydrothermal Synthesis
6.1 Introduction
The term hydrothermal was first used by the geologist Sir Roderick Murchison
(1792–1871) to describe the action of water at elevated temperature and pressure
leading to the formation of various rocks and minerals. Geologists used the hydro-
thermal technique in the nineteenth century in order to understand the genesis of
rocks and minerals by simulating the conditions existing under the earth’s crust.
However, materials scientists popularized the technique, particularly during 1940s,
and the commercial importance became apparent with the beginning of the syn-
thesis of large single crystals of quartz and zeolites in 1948. Since the mid-1970s
exploration of hydrothermal reactions, other than the hydrometallurgical and crys-
tal growth aspects, began in Japan, particularly with reference to ceramic powder
processing. Nowadays, the hydrothermal technique has stretched its application to
several areas of nanopowder synthesis.
The term hydrothermal usually refers to heterogeneous reactions in the pres-
ence of a solvent (aqueous or non-aqueous) under high pressure and tempera-
ture conditions to dissolve and then recrystallize materials in a closed system.
Although there is no exact lower limit for the pressure and temperature conditions,
the majority of authors fix hydrothermal synthesis at conditions above 100 °C and
above 1 atm.
Hydrothermal synthesis is also known mainly by chemists as solvothermal syn-
thesis, a boarder term meaning any chemical reaction in the presence of a solvent
in supercritical or near supercritical conditions. Likewise, there are other terms
such as glycothermal, alcothermal, ammonothermal, depending upon the type of
solvent used in such reactions. However, the purpose behind using these different
solvents in the chemical reactions is essentially to bring down the pressure and
temperature conditions.
Under hydrothermal conditions, reactions that only occur at high temperatures
can occur under fairly normal conditions. It is used to increase reaction veloci-
ties between solids, dissolve or crystallize substances, and promote phenomena

62 6 Hydrothermal Synthesis
such as doping, formation of new phases or phase separation. Under normal condi-
tions these phenomena would not show appreciable results [1–4]. Water characteris-
tics such as density, pKw, dielectric constant and viscosity markedly vary with the
employed thermodynamic conditions, and may under certain conditions approach
supercritical fluid characteristic and thereby favor the occurrence of hydrothermal
reactions.
In order to facilitate the solubilization of chemically inert materials it is often
necessary to use chemical additives called mineralizers generally represented by
an electrolyte. They modify the solubility of solids by the formation of interme-
diate compounds that usually are not present in the water in the absence of this
agent [1, 2], representing another system variable to corroborate the capability of
the method, controlling not only the chemical composition of the studied material,
but also the morphology and microstructure [2, 5, 6].
During hydrothermal synthesis one can also expect the occurrence of chemical
reactions such as: synthesis of new phases, stabilization of new complexes, crys-
tal growth, preparation of finely divided materials and microcrystallites with well-
defined size and morphology, leaching of ores in metal extraction, decomposition,
alteration, corrosion and etching.
6.2 Application
An understanding of the mineral formation in nature under elevated pressure and

temperature in the presence of water led to the development of the hydrothermal
technique. One of the first scientists to use the hydrothermal technique to produce
crystals was Schafthaul in 1845. He obtained quartz crystals upon transforma-
tion of precipitated silicic acid in a Papin’s digestor (Fig. 6.1) [7]. But, the first
successful commercial application of hydrothermal technology began with min-
eral extraction and ore beneficiation. In 1892 Karl Josef Bayer invented a method
using sodium hydroxide to leach bauxite to obtain pure aluminum hydroxide,
which could be converted to pure Al2O3 and then to pure aluminum. Similarly,
ilmenite, wolframite, cassiterite, laterites, sulphides of gold, copper, nickel, zinc,
arsenic, and antimony are treated by this process to extract the metal.
Further commercial importance of the hydrothermal technique for the synthesis
of inorganics was established soon after the synthesis of large single crystals of
quartz and zeolites in the 40s and, respectively [6], [7].
The synthesis of ceramic materials typically involves heat treatment at elevated
temperatures. Some alternatives have been widely exploited in the solution synthe-
ses that have proven to be suitable for the manufacture of advanced ceramic mate-
rials with controlled shapes and sizes [9].
Among the chemical methods in liquid phase, hydrothermal synthesis has the
advantage of being easy to implement and use at low temperatures. The hydrother-
mal process involves heating the reactants, often salts, oxides, hydroxides or metal
6.2 Application 63
Fig. 6.1 Papin’s digestor [8]
powders in an aqueous solution or suspension (when other solvents are used it is

called solvotermal) [10]. The solution or suspension is subjected to temperatures
which typically range from 80–400 °C and pressures ranging from those generated
by the expansion of the fluids subjected to the process temperatures up to 100 MPa
[11]. The produced powders have high purity, high degree of crystallinity, particle
sizes from nanometers to micrometers, narrow particle size distribution and good
stoichiometric control [12, 13].
It is a fast method that can have high productive rates, while also having the
advantage of allowing control of particle size and morphology of the crystals
through the change of process variables [12–17]. Some variables have been shown
to be of great influence on the characteristics of the powder formed: pH, minerali-
zation, reagents, concentrations, temperature and reaction time.
The work of Zhu et al. [15] study the influence of parameters such as temper-
ature, reaction time and different amount of surfactant on the formation of PbI2
under DTAB-assisted hydrothermal process. Figure 6.2 depicts the influence of the
temperature in the morphology of the products. At 100 °C large-scale submicron
belt-like structures with a width in the range of 200–500 nm and the thickness of
about 100 nm. The morphology changes with the increasing of the temperature.
At 200 °C the product was completely in the form of microtubes with the length of
nearly 1 mm. It was also observed that the wall of the tubes became thinner with
the increase in treatment temperature.
Fig. 6.2 SEM images of the PbI2 powders hydrothermally synthesized at different temperatures

for 8 h with DTAB: 100 °C (a), 120 °C (b), 140 °C (c), 160 °C (d), and 200 °C (e) [15]
When maintaining the temperature at 200 °C and the reaction time was
changed, there was also and modification in the structure (Fig. 6.3). For reaction
of 0.5 h there was the formation of uniform submicron belts with a length of about
3 μm and the presence of some irregular particles. After 8 h, uniform microtubes
were formed.
But, the factor that most changed the structure of the material was the amount
of surfactant added (Fig. 6.4). In the absence of surfactant large-scale microplates
with a diameter of about 15 μm were obtained. When the surfactant is added,
the morphology changed to microrods up to 1 μm width and a length of more
than 20 μm.
6.2 Application 65
Fig. 6.3 SEM images of the PbI2 powders hydrothermally synthesized at 200 °C for different
reaction times: 0.5 h (a), 1 h (b), 4 h (c) and 8 h (d) [15]
Various oxides of micrometer and nanometer sizes have been synthesized suc-
cessfully via hydrothermal treatment. Examples are Fe2O3, TiO2, ZrO2, SnO2,
NiO, ZnO, among others [18–23]. Hydrothermal synthesis was found to be suit-
able also for obtaining oxides such as PbTiO3, BaTiO3, PZT, CaWO4, BaWO4
[24, 25–27].
6.2.1 Hydrothermal Synthesis of Al2O3
Alpha alumina (α-Al2O3) powders can be synthesized by different high temper-

ature methods, such as the Bayer process, heat treatment of gel-based Al(OH)3,
high-temperature decomposition of aluminum containing salts, and chemical
vapor deposition (CVD) [28]. Hydrothermal synthesis is a low temperature alter-
native to the methods described above and crystallizes anhydrous materials in
many forms directly from aqueous solutions at temperatures up to 300 °C and high
pressures [29].
According to the work of Sharma et al. [30], to obtain α-Al2O3, a precursor
solution was prepared dissolving AlCl3 in water, in the presence of a surfactant
and an aqueous ammonium hydroxide solution (pH > 10). After stirring this
Fig. 6.4 SEM images of the PbI2 powders synthesized under hydrothermal condition at 120 °C
for 8 h with different amounts of DTAB: 0 mg (a), 40 mg (b), 80 mg (c), and 120 mg (d) [15]
mixture was converted into a complete gel. α-Al2O3 particles were added for seed-
ing. The gel was then subjected to hydrothermal treatment, which was carried out
at 190 °C for 1 h. The pressure inside the autoclave was the autogenous water
vapor pressure. After the hydrothermal synthesis, the maximum diameter of the
particles was 66 nm with spherical morphology and a surface area of 245 m2/g.
Lu et al. [31] synthesized alumina nanotubes via the hydrothermal technique.
For a typical synthesis, Al(NO3)3 and camphor sulfonic acid, as surfactant, were
dissolved in water. An ammonia aqueous solution was added to adjust the pH
value to 5.4. A Teflon-lined stainless steel autoclave heated to 160 °C was used
to grow the nanotubes for 24 h. A solid precipitate was collected by centrifuga-
tion, washed with ethanol and dried in air at room temperature followed by grind-
ing. The product of this synthesis exhibits a one-dimensional morphology with a
length of ∼500 nm and a diameter of ∼50 nm, and a boehmite phase.
Kim et al. [32] used an ionic liquid to produce uniform spindle-like Al2O3
using the hydrothermal method. In the typical synthesis AlCl3 and the ionic liq-
uid (1-butyl-3-dimethylimidazolium bromide) were mixed with deionized water.
Subsequently, NaOH was added into the solution and then transferred into a
stainless-steel autoclave and heated at 150 °C for 12 h. The resultant product was
collected and washed with deionized water and anhydrous ethanol for several
times until the solution was neutral. The final product was dried in a vacuum at
80 °C for 3 h.
6.2 Application 67
Fig. 6.5 TEM images of γ-AlOOH prepared at 200 °C for 24 h: a under pH = 5;

b HRTEM of sample produced under pH = 5 and SAED pattern (inset); c TEM image of sample
prepared under pH = 4; d Magnified image of Fig. 6.5c; e Magnified image of Fig. 6.5c and
SAED pattern (inset); f TEM image of sample prepared under pH = 6 (f) [33]
Yang synthesized boehmite (γ-AlOOH) nanorods using aluminum nitrate and

sodium hydroxide as starting materials. The results show that the nanorods had
regular shape with a diameter of 10–30 nm, length of 200–300 nm, when pro-
duced hydrothermically at 200–220 °C for 24 h at pH = 5. Figure 6.5 depicts the
influence of the pH in the structure of the boehmite.
6.2.2 Hydrothermal Synthesis of Zinc Oxide
ZnO is an electronic and photonic material mainly because of its band gap of
3.37 eV. It has been widely used in near-UV emission, gas sensors, transparent
conductors and piezoelectric applications [34–38]. There have been many existing
preparative techniques for this material. ZnO nanoparticles can be prepared on a

large scale at low cost by simple solution-based methods, such as chemical pre-
cipitation [39, 40], sol-gel synthesis [41], and solvothermal/hydrothermal reaction
[42–44].
Aneesh et al. synthesized ZnO nanoparticles (Fig. 6.6) using solutions of
Zn(CH3COO)2 and NaOH in methanol at pH values between 8 and 11. An auto-
clave was used at temperatures ranging from 100 to 200 °C for 6 and 12 h under
autogenous pressure. The ZnO particles have an average grain size of 7 to 16 nm
as the temperature increases from 100 to 200 °C.
Liu et al. [46] produced monodispersed ZnO nanorods using the hydrothermal
technology. Zinc nitrate and NaOH were dissolved in deionized water. The solu-
tion was mixed with ethanol and ethylenediamine. A Teflon-lined autoclave was
used at 180 °C for 20 h. The product, ZnO nanorods, was arranged in a bushlike
assembly with a diameter and length of 45.6 nm and 1.54 nm, respectively.
Huang et al. produced nanostructured ZnO using microwave hydrothermal syn-
thesis. In a typical synthesis process, Zn(NO3)2 was dissolved in deionized water.
NaOH was added to form a colloid solution. The solution was transferred into an
autoclave and treated at 140 °C for 20 min, under temperature-controlled mode
or at 3.0 MPa for 20 min under pressure-controlled mode in a MDS-6 microwave
hydrothermal system. ZnO nanostrucured forms such as rods, wires, thrusters,
dandelions and spindles were formed using different temperature and pressure
conditions. Figure 6.7 suggests a mechanism of this multi-structure formation.
The nanorods are hexagonal prisms with a typical diameter of 30 nm and length
of 100 nm. The nanowires are hexagonal shafts with a typical diameter ranging
from 10 to 30 nm and a length ranging from hundreds of nanometers to several
micrometers. The nanothruster vanes are thin slices with a typical thickness and
width of 10 and 400 nm, respectively. The nanodandelions are radial hexagonal
prisms with a typical diameter of the petals of about 10 μm (Fig. 6.8).
Fig. 6.6 TEM image of Eu-doped ZnO nanoparticles with a 1·2 at. % and b 3·78 at. % Eu
dopant concentration [45]
6.2 Application 69
Fig. 6.7 Schematic of the
shape-controlled synthesis
of ZnO nanorods via a
microwave hydrothermal
route [47]
6.2.3 Titanium Oxide
TiO2 has been employed extensively in studies of heterogeneous photocataly-

sis and has been accepted as one of the best photocatalysts for the degradation of
environmental contaminants. The process involves the absorption of a photon by
TiO2, leading to the promotion of an electron from the valence band to the con-
duction band and producing an electron hole. The electron in the conduction band
reacts with O2 available in the external system. The hole in the valence band can
react with OH− or H2O species to give origin to hydroxyl radicals. These hydroxyl
radicals initiate the photocatalytic oxidation, which destroys the organic chemical
contaminants in air, water, and soil.
There are several ways of preparing TiO2 particles [48–51]. The hydrothermal
method has many advantages, such as producing a highly homogeneous crystal-
line product, which can be obtained directly at relatively low reaction temperatures
(<150 °C). Its most important feature is that it favors a decrease in agglomeration
between particles, narrow particle size distributions, phase homogeneity, and con-
trolled particle morphology.
Fig. 6.8 FE-SEM images of the ZnO nanocrystals with different morphologies: a

nanorods (temperature = 413K , middle: HRTEM image and right: SEAD pattern), b
nanowires (temperature = 453K ) c nanothruster vanes (temperature = 393K ) d nanodandeli-
ons (temperature = 373K ) and e radial nanospindles (pressure = 3.0MPa) [47]
Tomita et al. produced TiO2 nanoparticles using the hydrothermal process.

They used metallic titanium powder dissolved in a cooled mixture of 30 % NH3
aqueous solution and 30 % H2O2. After dissolution, a hydroxycarboxylic acid
(citric acid, lactic acid, glycolic acid, malic acid, or tartaric acid) was added to the
solution. These solutions were dried at 80 °C to form a gel-like substance. Upon
further drying, the gels transform into dry powders, easily dissolved in pure water.
This aqueous solution (pH 6) was autoclaved at 200 °C for 24 h. Anatase particles
of different sizes were obtained depending on the type of hydroxycarboxylic acid
(Fig. 6.9). The anatase particles had a spherical or square shape with the lowest
size, using titanium-lactate, at 7 nm. The sample synthesized using tartrate had a
diameter of about 15 nm. Rod-like shaped rutiles were obtained using titaniumgly-
colate, with diameters from 50 to 150 nm.
Nian et al. produced single-crystalline anatase TiO2 nanorods using the hydro-
thermal technique. The TiO2 source used in their work was a commercially avail-
able TiO2 powder (P25, Degussa AG, Germany)—primary particle size of about
21 nm. P25 was mixed with a NaOH solution, followed by heat treating the mixture
at 130 °C in an autoclave for 20 h. After this treatment, the filtered sample was
washed with a HNO3 solution. The suspensions were subjected to another hydro-
thermal treatment in the autoclave at 175 °C for 48 h. The resulting slurries were
then filtered and dried at 100 °C for 3 h to give the final products. Under pH 2.2
6.2 Application 71
Fig. 6.9 TEM images of TiO2 prepared by hydrothermal treatment of 1 under the following con-
ditions: a pH 10, 200 °C for 24 h (brookite); b pH 6, 200 °C for 24 h (rutile); c pH 3, 200 °C for
24 h (rutile and anatase); d pH 6, 160 °C for 24 h (rutile and anatase) [52]
the nanoparticles produced have an average size of about 10 nm (Fig. 6.10a). By

increasing the pH value to 4.0, rodlike nanoparticles of about 20 to 60 nm were
obtained (Fig. 6.10b). At a pH of 5.6 the formation of nanorods of about 20 to
120 nm was observed (Fig. 6.10c).
Kim et al. produced mesoporous TiO2 via hydrothermal synthesis (Fig. 6.11).
In a typical experiment, a triblock copolymer was dissolved in water at 40 °C.
Sulfuric acid, titanium (IV) isopropoxide, and 2,4-pentanedione were added to the
solution.
The reaction was carried out at 55 °C for 2 h without stirring until a light yel-
low powder was obtained. The obtained material was subjected to hydrother-
mal treatment at 90 °C for 10 h without stirring. The final product particles have
well-defined spherical morphology, with a diameter range of 2–3 m. The possible
machismo of the TiO2 formation during the hydrothermal process is depicted in
Fig. 6.12.
Fig. 6.10 TEM images of
TiO2 nanoparticles prepared
from hydrothermal treatment
(at 175 °C for 48 h) of
nanotube suspensions with
pH values of a 2.2, b 4.0, and
c 5.6 [53]
6.2 Application 73
Fig. 6.11 FE-SEM image of mesoporous spherical shape TiO2 (a), magnified image of a

selected area of one particle (b). TEM image of mesoporous TiO2 (c), and magnified HR-TEM
image of nanocrystalline anatase (d) [54]
Fig. 6.12 Possible mechanism for the formation of mesoporous TiO2 particles with well-defined
spherical shapes [54]
References
1. Suchanek, W.L., Riman, R.E.: Hydrothermal synthesis of advanced ceramic powders. Adv.
Sci. Technol. 45, 184–193 (2006)
2. Eckert, J.O., Hung-Houston, C.C., Gersten, B.L., Lencka, M.M., Riman, R.E.: Kinetics and
mechanisms of hydrothermal synthesis of barium titanate. J. Am. Ceram. Soc. 79, 2929–
2939 (1996)
3. Morey, G.W., Niggli, P.: The hydrothermal formation of silicates, a review. J. Am. Chem.
Soc. 35, 1086–1130 (1913)
4. Rabenau, A.: The role of hydrothermal synthesis in preparative chemistry. Angew. Chem. 24,
1026–1040 (1985)
5. Dell’Agli, G., Colantuono, A., Mascolo, G.: The effect of mineralizers on the crystallization
of zirconia gel under hydrothermal conditions. Solid State Ionics 123, 87–94 (1999)
6. Wang, Y., Xu, G., Ren, Z., Wei, X., Weng, W., Du, P., Shen, G., Han, G.: Mineralizer-assisted
hydrothermal synthesis and characterization of bifeo3 nanoparticles. J. Am. Ceram. Soc. 90,
2615–2617 (2007)
7. Byrappa, K., Yoshimura, M.: Handbook of hydrothermal technology. William Andrew Inc,
Norwich (2001)
8. Thurston, R.H.: A history of the growth of the steam-engine. D Appleton and Company, New
York (1886)
9. Ortiz-Landeros, J., Gómez-Yáñez, C., López-Juárez, R., Dávalos-Velasco, I., Pfeiffer, H.:
Synthesis of advanced ceramics by hydrothermal crystallization and modified related meth-
ods. J. Adv. Ceram. 1(3), 204–220 (2012)
10. Byrappa, K., Adschiri, T.: Progress in crystal growth and characterization of materials.
Elsevier, Amsterdam (2007)
11. Riman, R.E., Suchanek, W.L., Lencka, M.M.: Hydrothermal crystallization of ceramics. Ann.
Chim. Sci. Mat. 27: 15–36 (2002)
12. Yoshimura, M., Byrappa, K.: Hydrothermal processing of materials: past, present and future.
J. Mater. Sci. 43, 2085–2103 (2008)
13. Schäf, O., Ghobarkar, H., Knauth, P.: Hydrothermal synthesis of nanomaterials. nanostruc-
tured materials. Electron. Mater. Sci. Technol. 8, 23–41 (2004)
14. Uchiyama, H., Shirai, Y., Kozuka, H.: Hydrothermal synthesis of flower-like SnO2 par-
ticles consisting of singlecrystalline nanorods through crystal growth in the presence of
poly(acrylic acid). RSC Adv. 2, 4839–4843 (2012)
15. Zhu, G., Hojamberdiev, M., Liu, P., Peng, J., Zhou, J., Bian, X., Huang, X.: The effects of
synthesis parameters on the formation of PbI2 particles under DTAB-assisted hydrothermal
process. Mater. Chem. Phys. 131, 64–71 (2011)
16. Zhang, W.-M., Chen, M., Jiang, Y.-Q.: Morphology dependence on anions in hydrothermal
synthesis of Co3O4. Int. Nano Lett. 3, 44 (2013)
17. Devers, E., Afanasiev, P., Jouguet, B., Vrinat, M.: Hydrothermal syntheses and catalytic prop-
erties of dispersed molybdenum sulfides. Catal. Lett. 82, 13–17 (2002)
18. Yin, C.Y., Minakshi, M., Ralph, D.E., Jiang, Z.T., Xie, Z., Guo, H.: Hydrothermal synthesis
of cubic α-Fe2O3 microparticles using glycine: Surface characterization, reaction mechanism
and electrochemical activity. J. Alloy. Compd. 509, 9821–9825 (2011)
19. Souvereyns, B., Elen, K., Dobbelaere, C., Kelchtermans, A., Peys, N., D’Haen, J., Mertens,
M., Mullens, S., Van den Rul, H., Meynen, V., Cool, P., Hardy, A., Van Bael, M.K.:
Hydrothermal synthesis of a concentrated and stable dispersion of TiO2 nanoparticles. Chem.
Eng. J. 223, 135–144 (2013)
20. Noh, H.J., Seo, D.S., Kim, H., Lee, J.K.: Synthesis and crystallization of anisotropic shaped
ZrO2 nanocrystalline powders by hydrothermal process. Mater. Lett. 57, 2425–2431 (2003)
21. Talebian, N., Jafarinezhad, F.: Morphology-controlled synthesis of SnO2 nanostructures
using hydrothermal method and their photocatalytic applications. Ceram. Int. 39(7), 8311–
8317 (2013)
References 75
22. Miao, B., Zeng, W., Lin, L., Xu, S.: Characterization and gas-sensing properties of NiO
nanowires prepared through hydrothermal method. Physica E 52, 40–45 (2013)
23. Ekthammathat, N., Thongtem, T., Phuruangrat, A., Thongtem, S.: Characterization of ZnO
flowers of hexagonal prisms with planar and hexagonal pyramid tips grown on Zn substrates
by a hydrothermalprocess. Superlattices Microstruct. 53, 195–203 (2013)
24. Gelabert, M.C., Laudise, R.A., Riman, R.E.: Phase stability, solubility and hydrothermal
crystal growth of PbTiO3. J. Cryst. Growth 197, 195–203 (1999)
25. Traianidis, M., Courtois, C., Leriche, A.: Mechanism of PZT crystallisation under hydrothermal
conditions Development of a new synthesis route. J. Eur. Ceram. Soc. 20(16), 2713–2720 (2000)
26. Sun, W., Li, C., Li, J., Liu, W.: Microwave-hydrothermal synthesis of tetragonal BaTiO3
under various conditions. Mater. Chem. Phys. 97(2–3), 481–487 (2006)
27. Lei, F., Yan, B.: Hydrothermal synthesis and luminescence of CaMO4:RE3+ (M = W, Mo;
RE = Eu, Tb) submicro-phosphors. J. Solid State Chem. 181(4), 855–862 (2008)
28. Habashi F (2003) Extractive metallurgy of aluminum. In: Totten, G.E., Mackenzie D.S.,
(eds.) Handbook of aluminum: alloy production and materials manufacturing, CRC Press
29. Deng, Y., Yang, Q., Lu, G., Hu, W.: Synthesis of γ-Al2O3 nanowires through a boehmite pre-
cursor route. Ceram. Int. 36, 1773–1777 (2010)
30. Sharma, P.K., Jilavi, M.H., Burgard, D., Nass, R., Schmidt, H.: Hydrothermal synthesis of
nanosize alpha-Al2O3 from seeded aluminum hydroxide. J. Am. Ceram. Soc. 81, 2732–2734
(1998)
31. Lu, C.L., Lv, J.G., Xu, L., Guo, X.F., Hou, W.H., Hu, Y., Huang, H.: Crystalline nanotubes of
γ-AlOOH and γ-Al2O3: hydrothermal synthesis, formation mechanism and catalytic perfor-
mance. Nanotechnology 20, 1–9 (2009)
32. Kim, T., Li, H., Lian, J., Jin, H., Ma, J., Duan, X., Yao, G., Zheng, W.: Ionic liquid-assisted
hydrothermal synthesis of γ-Al2O3 hierarchical nanostructures. Cryst. Res. Technol. 45, 767–
770 (2010)
33. Yang, Q.: The reaction conditions influence on hydrothermal synthesis of boehmite nanorods.
Inorg. Mater. 46, 953–958 (2010)
34. Xu, J., Chen, Y., Li, Y., Shen, J.: Gas sensing properties of ZnO nanorods prepared by hydro-
thermal method. J. Mater. Sci. 40, 2919–2921 (2005)
35. Pearton, S.J., Lim, W.T., Wright, J.S., Tien, L.C., Kim, H.S., Norton, D.P., Wang, H.T., Kang,
B.S., Ren, F., Jun, J., Lin, J., Osinsky, A.: ZnO and related materials for sensors and light-
emitting diodes. J. Electron. Mater. 37, 1426–1432 (2008)
36. Rani, S., Suri, P., Shishodia, P.K., Mehra, R.M.: Synthesis of nanocrystalline ZnO powder via
sol-gel route for dye-sensitized solar cells. Solar Energy Mater Solar Cells 92, 1639–1645
(2008)
37. Barreca, D., Bekermann, D., Comini, E., Devi, A., Fischer, R.A., Gasparotto, A., Maccato,
C., Sberveglieri, G., Tondello, E.: 1D ZnO nano-assemblies by plasma-CVD as chemical
sensors for flammable and toxic gases. Sens. Actuators, B 149, 1–7 (2010)
38. Cao, X., Ning, W., Li, L.D., Guo, L.: Synthesis and characterization of waxberry-like micro-
structures ZnO for biosensors. Sens. Actuators, B 129, 268–273 (2008)
39. Yamabi, S., Imai, H.: Growth conditions for wurtzite zinc oxide films in aqueous solutions. J.
Mater. Chem. 12(12), 3773–3778 (2002)
40. Vayssieres, L.: Growth of arrayed nanorods and nanowires of ZnO fromaqueous solutions.
Adv. Mater. 15(5), 464–466 (2003)
41. Golić, D.L., Branković, G., Nešić, M.P., Vojisavljević, K., Rečnik, A., Daneu, N., Bernik, S.,
Šćepanović, M., Poleti, D., Branković, Z.: Structural characterization of self-assembled ZnO
nanoparticles obtained by the sol-gel method from Zn(CH3COO)2.2H2O. Nanotechnology
22, 1–9 (2011)
42. Baruah, S., Dutta, J.: Hydrothermal growth of ZnO Nanostructures. Sci. Technol. Adv. Mater
10, 1–18 (2009)
43. Nicholas, N.J., Franks, G.V., Ducker, W.A.: The mechanism for hydrothermal growth of zinc
oxide. Cryst. Eng. Comm. 14, 1232–1240 (2012)
44. Choi, K.O., Yoon, S.H., Kim, W.S., Lee, K.H., Yang, C.M., Han, J.H., Kang, C.J., Choi, Y.J.,
Yoon, T.S.: Morphological dependence of hydrothermally synthesized ZnO nanowires on syn-
thesis temperature and molar concentration. Phys. Status Solidi A 210(7), 1448–1453 (2013)
45. Aneesh, P.M., Jayaraj, M.K.: Red luminescence from hydrothermally synthesized Eu-doped
ZnO nanoparticles under visible excitation. Bull. Mater. Sci. 33, 227–231 (2010)
46. Liu, B., Chun, H.: Hydrothermal synthesis of ZnO nanorods in the diameter regime of
50 nm. J. Am. Chem. Soc. 125, 4430–4431 (2003)
47. Huang, J., Xia, C., Cao, L., Zeng, X.: Facile microwave hydrothermal synthesis of zinc oxide
one-dimensional nanostructure with three-dimensional morphology. Mater. Sci. Eng., B 150,
187–193 (2008)
48. Dhandapani, P., Maruthamuthu, S., Rajagopal, G.: Bio-mediated synthesis of TiO2 nanopar-
ticles and its photocatalytic effect on aquatic biofilm. J. Photochem. Photobiol., B 110, 43–49
(2012)
49. Wang, M.Q., Yan, J., Cui, H.P., Du, S.G.: Low temperature preparation and characteriza-
tion of TiO2 nanoparticles coated glass beads by heterogeneous nucleation method. Mater.
Charact. 76, 39–47 (2013)
50. Ghasemi, S., Setayesh, S.R., Habibi-Yangjeh, A., Hormozi-Nezhad, M.R., Gholami, M.R.:
Assembly of CeO2–TiO2 nanoparticles prepared in room temperature ionic liquid on gra-
phene nanosheets for photocatalytic degradation of pollutants. J. Hazard. Mater. 199–200,
170–178 (2012)
51. Shen, C., Wang, Y.J., Xu, J.H., Luo, G.S.: Facile synthesis and photocatalytic properties of
TiO2 nanoparticles supported on porous glass beads. Chem. Eng. J. 209, 478–485 (2012)
52. Tomita, K., Petrykin, V., Kobayashi, M., Shiro, M., Yoshimura, M., Kakihana, M.: A water
soluble titanium complex for the selective synthesis of nanocrystalline brookite, rutile, and
anatase by a hydrothermal method. Angew. Chem. Int. Ed. 45, 2378–2381 (2006)
53. Nian, J.N., Teng, H.: Hydrothermal synthesis of single-crystalline anatase TiO2 nanorods
with nanotubes as the precursor. J Phys Chem B 110, 4193–4198 (2006)
54. Kim, D.S., Kwak, S.Y.: The hydrothermal synthesis of mesoporous TiO2 with high crystal-
linity, thermal stability, large surface area, and enhanced photocatalytic activity. Appl. Catal.
A 323, 110–118 (2007)
Chapter 7
High-Energy Milling
Nanoparticles can be produced by mechanical attrition. Such nanoparticles are

formed in a mill in which energy is used to transform course-grained materials
into nanostructured powders. The particles themselves can have a size distribution
of less than 100 nm, called a nanoparticle, or, as is common in materials milled
using mechanical attrition, the product is highly crystalline, and the crystal-
lite size after milling is between 1 and 10 nm in diameter, called nanocrystalline
materials [1].
The milling of materials has been a component of ceramic processing and
powder metallurgy industries for many years. The main objectives of milling
include mixing material or phases; particle size reduction; shape changing; solid-
state alloying and modifying such properties of materials as density, flowability,
or work hardening. Mechanical attrition began to be used in the late-1960s as a
way to mix and decrease the size of metal powders in a process called Mechanical
Alloying (MA). In the mid-1990s, several researchers were researching mechani-
cal milling to synthesize a variety of stable and meta-stable phases of all classes of
materials, from metals to ceramics and polymers.
Different terms are used in the literature to denote the processing of powder
particles in high-energy ball mills. Mechanical Alloying describes the process
where mixtures of powders, usually of different metals or alloys/compounds, are
milled together. Milling of uniform composition powders, such as pure metals,
is called Mechanical Milling (MM). Another variation of milling is Cryomilling,
where the milling operation is carried out at cryogenic temperatures, usually with
liquid nitrogen. Mechanically Activated Annealing (M2A) is a process that com-
bines mechanical alloying with isothermal annealing. For example, MA of molyb-
denum and silicon powders for 1–2 h in a planetary ball mill followed by a 2–24 h
annealing at 800 °C produced the MoSi2 phase [2].

78 7 High-Energy Milling
7.1 The High-Energy Milling Process
The fundamental principle of size reduction in mechanical attrition is the energy

applied to the sample during impacts with the milling media, usually a small ball.
The particles are trapped between two colliding balls and then compressed into
small pieces (Fig. 7.1).
The process can be understood in three steps: the first step starts with the
rearrangement and restacking of particles. Particles slide past one another with
minimum deformation and fracture, producing fine, irregularly shaped particles.
The second step involves elastic and plastic deformation of particles [4]. Cold
welding may occur between metallic particles during this stage. The third step
involves particle fracture, which results in further deformation and/or fragmenta-
tion of the particles. As fragments decrease in size, the tendency to form aggre-
gates increases, and fracture resistance increases. Particle fineness approaches a
limit as milling continues and maximum energy is expended [5].
According to Harris [6], the major factors contributing to grind limit are:
• Increasing resistance to fracture.
• Increasing cohesion between particles, with decreasing particle size causing
agglomeration.
• Coating of the grinding medium by fine particles that cushion the particles from
impact.
• Surface roughness of the grinding medium.
• Connection of large particles that protect smaller particles.
• Increasing apparent viscosity as particle size decreases.
• Decreasing internal friction as particle size decreases.
The grinding limit is demonstrated in the work of Kim et al. [5] who concluded,
after milling Fe–Co powders for 30 h, that the process reached a steady state
where the particles became homogenized in size and shape, with particle size
approaching a limit of 10 μm, and crystallite size approaching 10 nm.
Fig. 7.1 Schematic diagram showing the different forms of impact which might occur during
high-energy ball milling [3]. a Head-on impact. b Oblique impact. c Multi-ball impact
7.1 The High-Energy Milling Process 79
The major differences between conventional ball milling and high-energy ball
milling (HEBM) are:
(1) In the HEBM process the impact energy is around 1,000 times higher than
in the conventional ball milling process. The dominant events in conventional
ball milling are particle fracturing and size reduction, which in fact corre-
spond to only the first stage of the HEBM;
(2) A longer milling time is generally required for HEBM to activate and com-
plete the structural changes and chemical reactions;
(3) HEBM requires the control of the milling atmosphere and temperature, which
are crucial to create the desired structural changes or chemical reactions.
These are some of parameters that affect the final constitution of the powder when
we consider HEBM:
Type of mill: Conventional ball milling equipment cannot be used directly
to conduct any HEBM work. Specially designed ball mills with a higher milling
energy are used for HEBM purposes. Different types of milling equipment are
available for nanoparticle formation, including the vibrating mill, planetary ball
mill, high-energy rotating mill, and attritors (Fig. 7.2). They differ in capacity, effi-
ciency, and arrangements for heat transfer and particle removal. The final size is
determined by the energy input during milling, the ball-to-powder weight ratio,
and the overall temperature during milling.
For a practical example of the differences between high-energy mills it is pos-
sible to study the work of Borner and Eckert [8] who investigated the milling pro-
cess of iron powders using a SPEX milling machine and a Pulverisette, among
other mills (Fig. 7.3). The SPEX mill provides the high-energy input and leads to a
fast decrease of grain size to less than 20 nm after 4 h of milling. The Pulverisette
mill provides smaller energy impact and after 32 h of milling the grain size was
40 nm at 90 rpm, 31 nm at 180 rpm, and 20 nm at 360 rpm.
Milling container: The material used is important since the impact of the
grinding medium on the inner walls of the container may cause some material
Fig. 7.2 Types of mills: a SPEX 8000 mixer/mill (SPEX CertiPrep). b Fritsch Pulverisette P-5
four station ball mill (Gilson company). c Model 1-S attritor (Union process) [7]
Fig. 7.3 Average grain size

for Fe powders versus milling
time using different mills [8]
to be incorporated into the powder. This can contaminate the powder or alter the
chemistry of the powder.
Milling speed: the maximum speed should be just enough for the balls to fall
down from the maximum height to produce the maximum collision energy.
Milling time: This is the most important parameter in the HEBM process. The
correct milling time is the one where a steady state of fracturing and/or cold weld-
ing of the powder particles are achieved. This will depend on the type of mill used,
the intensity of milling, the ball-to-powder ratio, and the temperature of milling.
It is important to note that the level of contamination increases and some undesir-
able phases can be formed if the milling time is too long [9].
Grinding medium: The type, size and size distribution of the grinding medium
significantly influences milling effectiveness. The density of the grinding medium
should be high in order to create enough impact force on the material to be
grinded. A grinding medium of large size is interesting since it has more weight
and can transfer more impact energy to the powder particles. However, the highest
collision energy can be obtained if balls with different diameters are used.
Milling atmosphere: Controlling the atmosphere of the grinding vial is a way
to control contamination, especially in the case of metals prone to oxidation. Also,
using different gases in the atmosphere of the vial, it is possible and sometimes
desirable to produce compounds such as nitrides (when using a nitrogen atmos-
phere) [10] and hydrides (when using a hydrogen atmosphere) [11].
Process control agent: This is a lubricant or surfactant added to the powder
during milling to reduce the effect of cold welding by adsorption on the surface of
the powder particles, inhibiting agglomeration. The most common PCAs include
stearic acid, hexane, methanol, and ethanol, used in practice at a level of about
1 ± 5 wt % of the total powder charge.
7.1 The High-Energy Milling Process 81
Temperature of milling: The temperature of milling has an important effect

on the processes involving alloy phases, solutions, intermetallics, nanostructures,
or an amorphous phase, since diffusion processes are involved. The temperature of
the powders during the milling process can increase due to two main reasons: the
kinetic energy of the grinding medium and the exothermic reaction that can occur
during milling. Milling of powders at low temperatures (cryomilling) usually min-
imizes welding, probably due to the increased brittleness of the powder particles at
low temperatures [12, 13].
A major concern in HEBM processing is the amount of impurities that contam-
inate the milled powder. Contamination originates from several sources, includ-
ing: impurities from the starting powders, containers and grinding media, milling
atmosphere, and agents added to the powders. In general, the extent of the con-
tamination increases with increasing milling time and energy.
Although contamination is difficult to avoid completely, various attempts have
been made to minimize powder contamination, such as using the same material for
the container, the grinding medium and the material to me milled (with obvious
limitations for milling effectiveness) and using harder/stronger materials for the
container and grinding medium than the powder to be milled.
The atmosphere of the mill is another source of impurities, especially in the
case of oxidation-sensitive materials, such as pure metals. For example, if the mill
container is not properly sealed, the air of the atmosphere can leak into the con-
tainer and contaminate the powder.
7.2 Application of HEBM for Nanoparticle Production
Since its development in the 1960s, HEBM has been used to produce finer and
finer powders. Nowadays, several types of nanoparticles are produced cost-
effectively using HEBM.
7.2.1 Nanotubes and Nanowires
Chen and co-workers [14] have produced carbon nanotubes using HEBM. They
used graphite as precursor and milled it for about 150 h at ambient temperature,
followed by a heat treatment at 1,400 °C for 6 h in a nitrogen atmosphere. The
outer diameter of the resulting material was 20 nm. The main contaminants found
in these carbon nanotubes were iron and chromium originated from the balls and
the inner wall of the steel container.
This same group of researchers produced BN nanotubes using HEBM. As a
precursor they used high purity boron powders. The atmosphere of the mill was
filled with ammonia at 300 kPa before starting the milling process. After milling,
different types of annealing conditions were used. The heat treatment at 1,200 °C
for 6 h in NH3 atmosphere resulted in multi-walled BN nanotubes, with an

external diameter of 6 nm. Bamboo-type nanotubes were produced after heating at
1,100 °C in a N2 atmosphere from the powder milled for 50 h.
These authors also produced SiC nanowires using HEBM. A mixture of silicon
monoxide (SiO) and iron (II) phthalocyanine was milled for 100 h. The milling
was conducted in a nitrogen atmosphere at 300 kPa at room temperature. After
milling, the powder was first heated at 1,000 °C for 30 min, and then the tem-
perature was raised to 1,200 °C for 1 h. During the first annealing, cylindrical,
multiwalled CNTs with a diameter of about 15 nm were produced. When the tem-
perature was increased to 1,200 °C, SiC nanowires with a diameter of 40 nm were
obtained.
The role of HEBM on nanotube and nanowire formation could be divided into
three effects:
(1) Creation of a precursor containing nucleation structures and catalysts:
For example, HEBM of graphite powder produces a disordered and nano-
porous structure through agglomeration of nanosized particles under ball
impacts: nucleation. The contaminations from milling act as catalysts to pro-
mote nanotube formation during the subsequent annealing.
(2) Mechanical activation:
HEBM produces smaller grain sizes and higher surface areas. Both contribute
to reduce the reaction temperature and to promote higher chemical reactivity
in comparison with samples without the milling treatment.
(3) New chemical reactions:
The high-energy ball milled powders have higher chemical reactivity and new
reactions could therefore take place during the subsequent annealing, with the
formation of various nanostructures as end products. Because of the energy
generated during the HEBM process, some chemical reactions could take
place even during the ball-milling process at room temperature.
7.2.2 Ceramic Powders
A wide variety of ceramic nanopowders has been synthesized using HEBM.

Experimental works have proven that there is a limitation in the effectiveness of
HEBM to produce nanopowders. The lowest particle size obtained during the
HEBM process is estimated to be about 50–25 nm [15].
Pure ZrO2 is a material that can suffer a martensitic transformation, i.e. tetrag-
onal to monoclinic phase transformation that induces a cracking phenomenon
on cooling from the fabrication temperature [16]. The addition of dopants such
as Al2O3 and MgO are known to stabilize the tetragonal structure at room tem-
perature. Maneshian et al. concluded that HEBM can provide a positive thermo-
dynamic driving force for monoclinic to tetragonal transformation, reducing the
starting temperature of the reverse martensitic transformation. In the HEBM pro-
cess at 300 rpm they used stabilized zirconia vials and balls, a 10:1 ball to powder
7.2 Application of HEBM for Nanoparticle Production 83
ratio and Toluene as a process control agent. They milled a mixture of Alumina
powder with an average particle size of 7 μm and monoclinic zirconia powder
with a particle size of 3.5 μm. After 10 h of milling the grains had sizes ranging
from 35 to 60 nm for alumina and 25–54 nm for zirconia.
Natural minerals such as ilmenite are treated by HEBM to reduce grain diam-
eter and to change composition. In the work of Chen [17], ilmenite (FeTiO3) with
activated carbon powder as reducing agent was ball milled at room temperature
for 100, 200 and 400 h and, subsequently, its oxidation was investigated. In the
HEBM process they used hardened steel balls (8.6 and 25.4 mm in diameter) and
a stainless steel cell. The process was carried out in air and vaccum (10−2 kPa).
In the last case, air was inserted to supply sufficient oxygen to complete the oxi-
dation. After the milling process, there was no oxidation reaction and the phases
present were ilmenite (rhombohedral), amorphous carbon and small amounts of
rutile. Time, intensity, and atmosphere produced identical powders. The crystal-
lite size was reduced to less than 50 nm after 100 milling hours and remained
unchanged after 400 h.
In the work of Liu et al. [18], the sintering temperature of ZnO-based varis-
tor ceramics prepared through HEBM was correlated with the microstructure, the
density and the electrical properties. A mixture of ZnO, Bi2O3, Sb2O3, Co2O3,
Cr2O3 and MnO2 was milled in ethanol in a nylon jar using stainless steel balls
at 500 rpm, for 5, 10 and 20 h. The ratio of balls to mixed powder was 20:1. As
a result, the crystalline size of the milled powder, calculated through the Scherrer
equation, was refined to 59 nm after 20 h. The synthesized powders have better
sinterability, higher density and better electrical properties than the traditional
powders.
Covalent ceramic composite nanopowders have also been produced by HEBM.
One example is the work of Wang et al. [19] who synthesized TiB2/TiC nanocom-
posites. In their study the starting materials used were titanium powder (54 μm)
and B4C powder (particle size of 10.23 μm). A previous drying of the precursors
was undertaken to improve the milling efficiency. In the milling process they used
stainless steel jars and hardened stainless steel balls (6, 10 and 20 mm diameter).
The ball-to-powder mass ratio was 10:1. The atmosphere of the jar was flushed
with Ar gas to avoid oxidation of the powder. The milling speed was 500 rpm for
up to 48 h. As a result, the formation of TiC occurred within 24 h and only a mini-
mal amount of TiB2 was produced even after 48 h of milling. The TiB2/TiC com-
posite had a particle diameter between 30 and 50 nm.
7.2.3 Intermettalics
Intermettalics such as titanium aluminide nanopowders are also produced by

HEBM. Fang et al. [20] produced Ti-50 %Al powders by HEBM using titanium and
aluminum powders in a planetary ball mill, using an argon atmosphere and stearic
acid (1 wt %) as a process controlling agent. The process was carried out using a
stainless steel milling vial and grinding medium, under 400 rpm during 9 h. After
this period of time, round shaped particles were formed, with diameters between 20
and 40 nm. Although the results show that the desired composition was achieved,
the distribution of Ti and Al was not homogeneous in the milled composite.
Metal matrix nanocomposites based on Ni–Y2O3 powders were also obtained
using HEBM [21]. As starting powders high purity Ni and Y2O3 were used, with
particle diameters of 40 and 50 μm, respectively. The HEBM process used an
argon atmosphere, the weight ratio of the 8 mm stainless steel balls to the powder
mixture was 20:1. Speeds of 400 and 1,000 rpm were used for milling times from
3 to 240 min. After the milling process, one could observe that at 400 rpm most of
the Y2O3 particles appeared in a cubic phase with a particle size of a few hundreds
of nanometers. At 1,000 rpm the cubic-to-monoclinic phase transition of Y2O3 and
an amorphous phase could be identified.
References
1. Castro, C.L., Mitchell, B.S.: Nanoparticles from mechanical attrition. In: Baraton M.I. (ed.)
Synthesis, Functionalization and Surface Treatment of Nanoparticles, pp. 1–15. American
Scientific Publishers, Stevenson Ranch (2002)
2. Gaffet, E., Malhouroux-Gaffet, N.: Nanocrystalline MoSi2 phase formation induced by
mechanically activated annealing. J. Alloy. Compd. 205, 27–34 (1994)
3. Zhang, D.L.: Processing of advanced materials using high-energy mechanical milling. Prog.
Mater. Sci. 49, 537–560 (2004)
4. Artz, E., Dehm, G., Gumbsch, P., Kraft, O., Weiss, D.: Interface controlled plasticity in met-
als: dispersion hand thin film deformation. Prog. Mater. Sci. 46, 283–307 (2001)
5. Kim, Y.D., Chung, J.Y., Kim, J., Jeon, H.: Formation of nanocrystalline Fe–Co powders pro-
duced by mechanical alloying. Mater. Sci. Eng. A 291, 17–21 (2000)
6. Harris, C.C.: A Method for determining the parameters of the Gaudin-Meloy distribution.
Trans. Soc. Mining. Eng. 238, 17 (1967)
7. Suryanarayana, C.: Mechanical alloying and milling. Prog. Mater. Sci. 46, 1–184 (2001)
8. Borner, I., Eckert, J.: Nanostructure formation and steady-state grain size of ball-milled iron
powders. Mater. Sci. Eng. A 226–228, 541–545 (1997)
9. Suryanarayana, C.: Does a disordered γ-TiAl phase exist in mechanically alloyed Ti-Al pow-
ders. Intermetallics 3, 153–160 (1995)
10. Calka, A., Williams, J.S.: Synthesis of nitrides by mechanical alloying. Mater. Sci. Forum
88–90, 787–794 (1992)
11. Chen, Y., Williams, J.S.: Hydriding reactions induced by ball milling. Mater. Sci. Forum
225–227, 881–888 (1996)
12. Hwang, S.J., Nash, P., Dollar, M., Dymek, S.: Microstructure and mechanical properties of
mechanically alloyed NiAl. MRS Proc. 213, 661 (1990)
13. Huang, B.L., Perez, R.J., Crawford, P.J., Nutt, S.R., Lavernia, E.J.: Synthesis of nanocristal-
line Fe-B-Si. Nanostruct. Mater. 7, 57–65 (1996)
14. Chen, Y., Li, C.P., Chen, H., Chen, Y.: One-dimensional nanomaterials synthesized using
high-energy ball milling and annealing process. Sci. Technol. Adv. Mater. 7, 839–846 (2006)
15. Kong, L.B., Zhu, W., Tan, O.K.: Preparation and characterization of Pb(Zr0.52Ti0.48)O3
ceramics from high-energy ball milling powders. Mater. Lett. 42, 232–239 (2000)
16. Maneshian, M.H., Banerjee, M.K.: Reverse martensitic transformation in alumina – 15 vol %
zirconia nanostructured powder synthesized by high energy ball milling. J. Alloy. Compd. 459,
531–536 (2008)
References 85
17. Chen, Y., Hwang, T., Marsh, M., Williams, J.S.: Mechanically activated carbothermic reduction
of ilmenite. Metall. Mater. Trans. A 28A, 1115–1121 (1997)
18. Liu, H.Y., Kong, H., Ma, X.M., Shi, W.Z.: Microstructure and electrical properties of ZnO-
based varistors prepared by high-energy ball milling. J. Mater. Sci. 42, 2637–2642 (2007)
19. Wang, H., Wua, W., Sun, S., Bian, X., Tu, G.: Characterization of the structure of TiB2/TiC
nanocomposite powders fabricated by high-energy ball milling. Ceram. Int. 37, 2689–2693
(2011)
20. Fang, W.B., Li, X.W., Sun, H.F., Ding, Y.F.: Characterization of Ti-50%Al composite powder
synthesized by high energy ball milling. Trans. Nonferrous Met. Soc. China 21, s333–s337
(2011)
21. Park, J.J., Choe, H.J., Hong, S.M., Lee, M.K., Rhee, C.K.: Synthesis of Ni–Y2O3 nanocom-
posite powders by a very high speed planetary milling process: microstructural development
and refinement behavior. Powder Technol. 230, 139–144 (2012)

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Library of Congress Control Number: 2013950726

© Springer-Verlag Berlin Heidelberg 2013

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Springer is part of Springer Science+Business Media (www.springer.com)

This book contains an overview of Novel Synthesis and Characterization of

Porto Alegre, Brazil, August 2013 A. K. Alves

5 CCVD Synthesis of Carbon Nanotubes. . . . . . . . . . . . . . . . . . . . . . . . . . 43

Keywords Combustion synthesis • Spray pyrolysis • Electrospinning • CCVD

The Science of Nanomaterials is proving to be one of the most attractive and

A. Kopp Alves et al., Novel Synthesis and Characterization of Nanostructured Materials, 1

Fig. 1.1 Articles publishing survey regarding synthesis processes to obtain nanoparticles or

A way to see the importance that is given to nanostructured materials synthesis

Fig. 1.2 Articles publishing survey regarding solution combustion synthesis techniques since

Fig. 1.3 Articles publishing survey regarding the Spray-Pyrolysis technique since 2003

Fig. 1.4 Growth of the number of articles published concerning the hydrothermal synthesis

A very interesting technique to produce nanostructured materials is electro-

• Low heating temperature

The Science of Nanomaterials is proving to be one of the most attractive and

A. Kopp Alves et al., Novel Synthesis and Characterization of Nanostructured Materials, 11

Table 2.1 Some oxides prepared by combustion in solution

Table 2.2 Flame types [3]

Fig. 2.1 Smoldering flame type: the evolution of combustion reaction containing Ca(NO3)2,

Fig. 2.2 Flamming type reaction: the evolution of combustion reaction containing Ca(NO3)2,

Adiabatic flame temperature (Tad) is the maximum combustion temperature

It is a well-established fact that in combustion synthesis, the powder morphol-

The effect of atmosphere composition and properties of combustion products

A fuel is a substance capable of burning the CH bonds (electrons acceptor). An

Table 2.3 Study of the influence of fuel-oxidant ratio in obtaining ceramic oxides by SCS

2.2.6 Chemical Composition of Precursor Chemicals

The excess addition of ammonium nitrate produces an increase in combustion

A. Kopp Alves et al., Novel Synthesis and Characterization of Nanostructured Materials, 23

The tendency to seek technological miniaturization of devices is associated with

Fig. 3.1 Steps of powder production during the spray-pyrolysis

Fig. 3.2 Schematic diagram of the spray-pyrolysis film formation mechanisms

3.2.1 Atomization of Precursor Solution

Atomizing the precursor through a jet of compressed air, an ultrasonic system

3.2.3 Decomposition of the Precursor

is the deposition substrate temperature. The concentration of precursor solution

3.2.4 Influence of Spray Parameters on the Morphology

The morphology of the film is highly dependent on the substrate temperature at

4.1 The Electrospinning Technique

A. Kopp Alves et al., Novel Synthesis and Characterization of Nanostructured Materials, 31

Fig. 4.1 Schematic assembly of an electrospinning system [3]

Fig. 4.2 Behavior of a fluid in electrospinning a laminar flow b unstable flow [7]

The electrospinning experiment needs a relatively simple system. Components

While the solution is forced out of a capillary, through gravity or an external

4.1.1.1 Region 1: The Taylor Cone

Q is the flow rate

4.1.1.3 Region 3: The Instability Region

The collector is the final region of the electrospinning process. It consists of an

4.1.2 Factors Influencing Fiber Characteristics

In general, the process of electrospinning may be affected by several parameters,

4.2 Electrospinning of Ceramic Fibers

A. Kopp Alves et al., Novel Synthesis and Characterization of Nanostructured Materials, 43

5.1 Carbon and Its Allotropes

Fig. 5.1 Eight allotropes of carbon: a Diamond, b Graphite, c Lonsdaleite, d C60

Diamond, however, is a metastable phase of carbon, with lower binding energy

Since 1976, studies on the thermal treatment of hydrocarbons (CVD) allowed

Ideal CNTs can be conceptualized as a graphene sheet rolled to form a

Fig. 5.2 The structure of single-walled (SWCNT) formed by wrapping a single sheet of grapheme

5.2.1 Carbon Nanotubes Properties

2.2.6 Chemical Composition of Precursor Chemicals

3.2.1 Atomization of Precursor Solution

3.2.3 Decomposition of the Precursor

3.2.4 Influence of Spray Parameters on the Morphology

4.1 The Electrospinning Technique

4.1.1.1 Region 1: The Taylor Cone

4.1.1.3 Region 3: The Instability Region

4.1.2 Factors Influencing Fiber Characteristics

4.2 Electrospinning of Ceramic Fibers

5.1 Carbon and Its Allotropes

5.2.1 Carbon Nanotubes Properties

5.2.1.4 Physical and Chemical Properties

5.3 Carbon Nanotubes Synthesis

5.3.1 High Temperatures Methods

5.3.2.1 CNTs CCVD Substrates/Catalyst Powder

5.3.2.2 CCVD of CNTs on Flat Substrates

5.3.2.3 CCVD CNTs Without Substrate

6.2.1 Hydrothermal Synthesis of Al2O3

6.2.2 Hydrothermal Synthesis of Zinc Oxide

7.1 The High-Energy Milling Process

7.2 Application of HEBM for Nanoparticle Production

7.2.1 Nanotubes and Nanowires