Tesi Caterina Leone

HIGH PERFORMANCE
SYNTHESIS AND
PURIFICATION OF CARBON
NANOTUBES
Caterina Leone
This Ph. D. thesis has been realized with the financial support of the
Department of Chemical and Food Engineering of the University of Salerno
Unione Europea UNIVERSITÀ DEGLI
STUDI DI SALERNO
FONDO SOCIALE EUROPEO

Programma Operativo Nazionale 2000/2006
“Ricerca Scientifica, Sviluppo Tecnologico, Alta Formazione”
Regioni dell’Obiettivo 1 – Misura III.4
“Formazione superiore ed universitaria”
Department of Chemical and Food Engineering

Ph.D. Course in Chemical Engineering
(VI Cycle-New Series)
HIGH PERFORMANCE SYNTHESIS

AND PURIFICATION OF CARBON
NANOTUBES
Supervisor Ph.D. student

Prof. Paolo Ciambelli Caterina Leone
Scientific Referees
Prof. D. Sannino
Ing. M. Sarno
Ph.D. Course Coordinator

Prof. Paolo Ciambelli
To my family
Acknowledgments
Per la realizzazione di questo mio lavoro di tesi ringrazio il prof. Paolo

Ciambelli per la collaborazione, la prof. ssa Diana Sannino per il suo
contributo, l’ing. Maria Sarno che mi ha seguito con costanza e disponibilità.
Vorrei inoltre ringraziare i miei compagni di laboratorio Antonietta, Arianna,

Claudia, Elvirosa, Emma, Giovanna, Giusy, Massimo, Paola, Roberto e
Vincenzo, che hanno condiviso con me la movimentata attività di ricerca; e
insieme ai quali ho collaborato con armonia e serietà.
Ringrazio infine i miei familiari sempre presenti con il loro affetto e con la
loro attenzione.
Publications list
1. Ciambelli, P.; Sannino, D.; Sarno, M.; Leone, C. and Lafont, U.;
Effects of alumina phases and process parameters on the multiwalled carbon
nanotubes growth (2007) Diamond & Related Materials 16 1144–1149.
Effects of alumina phases and process parameters on the multiwalled carbon
nanotubes growth. 16th European Conference on Diamond, Diamond-Like
Materials, Carbon Nanotubes, and Nitrides Estoril, Portugal, September 3-8,
2006, section 5.8.36
CVD synthesis and characterization of carbon nanotubes produced on a
monolith support. XXII National Congress Italian Chemical Society, SCI
2006, Florence September 10-15, 2006, p.284.
Abstract
Carbon nanotubes, constituted by rolled up graphene sheets, have become

a popular topic of discussion, thanks to their exceptional electronic,
mechanical and thermal properties, some of which derive from the close
relation between carbon nanotubes and graphite, others from their high
aspect ratio.
Catalytic chemical vapour deposition (CCVD) is a widely employed
method to synthesise carbon nanotubes, at controlled growth level. It
requires much lower temperatures than other methods of synthesis, then it is
more suitable for large-scale production at a lower cost.
In this light, this thesis work has been focused to improve multi-wall
carbon nanotubes (MWNT) growth by means of CCVD and to explore
innovative purification methods.
The first part of investigation has been addressed to enhance catalyst
performance for the synthesis of CNT, investigating different aluminium
hydrates, hydroxides, oxides (bohemite, gibbsite, bayerite, γ-alumina) as
supports for Co and Fe metal particles.
Subsequently, a large range of operative conditions to optimize the
synthesis process on the selected “best catalyst” have been explored.
Research activity was devoted to the determination for catalytic
performances and lifetime of Co-Fe-supported gibbsite catalyst, developing
a cross monitoring of MWNT growth by gas-phase and by solid-phase. The
synthesis laboratory plant was implemented with on-line specific analysers
for the continuous examination of reactor outlet stream, while discontinuous
evaluations by means of physic-chemical characterisation of produced solid
phase, was performed at set synthesis times.
Parallel, innovative purification of as-grown CNT from by ethylene
catalytic chemical vapour deposition (CCVD) on Co/Fe-zeolite, selected
with respect to the high level of impurities, was investigated. Carbon
nanotubes impurities were dissolved by a microwave assisted system, in the
presence of inorganic acids such as HF and a HNO3/H2SO4 mixture,
founding that a much lower concentration of acids and acid immersing time
were sufficient in comparison to more conventional methods. High
performance purification permitted also functionalisation of MWNT.
On the synthesised nanotubes and on samples at a progressive
purification degree, a wide characterization approach was based on the
combined use of various techniques, such as transmission electron
microscopy (TEM) coupled with EDX analysis, field emission scanning
electron microscopy (FESEM), Raman and FT-IR Spectroscopy, X-ray
diffraction analysis, N2 adsorption-desorption analysis, quantitative
evaluations on termogravimetric (TG) and inductive coupled plasma-mass
spectrometer (ICP-MS) analyses.
High performance synthesis of MWNT arose from very high carbon and
reaction yield obtained by tuning operative parameters and catalysts
selection and optimisation. The catalyst activity was kept constant for a
longer period compared to literature previous findings. 100% selectivity to
MWNT was reached by choosing the most appropriate support and by
varying active metals amount.
Finally, a kinetic investigation of carbon nanotubes synthesis has been
performed.
Thesis outline
In chapter I, after an introduction, providing some historical background

and a brief summary of the subject matter, the structure and properties of
CNTs are reviewed in.
In Chapter II and in the appendix the most common techniques employed
for carbon nanotubes and characterisation are, in turn, discussed.
Chapter III, IV, V, VI and VII deal with the experimental part of the
thesis. The laboratory plant, for CNT synthesis is described in Chapter III.
Chapter IV reports the results obtained through different support methods
for the CNT synthesis, the choice of the best materials and report the effects
of several operating conditions on the synthesis performance.
With the aim of obtaining high performance synthesis, in terms of CNT
reaction yield and MWNTs selectivity, both catalytic activity and lifetime
have been determined: the results are reported in the Chapter V.
The experimental results of the innovative purification procedure,
obtained with the microwave apparatus in comparison with a more
conventional method, are described in Chapter VI.
Finally, the results of the kinetic investigation are summarised in Chapter
VII.
Objectives
The target of the research has been to improve performance in catalytic

synthesis and purification to obtain high quality carbon nanotubes,
considering techniques at lower costs.
To this purpose, a catalytic, chemical vapour deposition (CCVD)
technique has been used to synthesise carbon nanotubes. The objectives have
been achieved through the optimisation of the catalyst formulation, the
operative conditions for the synthesis, the purification procedure.
Collaborations
Transmission electron microscopy (TEM) analyses have been conducted

with the support of Delft Chem Tech.
Contents
3IChapter I Structure and properties of carbon nanotubes......................1
I.1Structure....................................................................................................1
I.2 Characterization of carbon nanotubes ................................................. 4
I.3 Mechanics of carbon nanotubes ............................................................ 6
I.3.1 Single-walled carbon nanotubes..........................................................6
I.3.2. Multi-walled carbon nanotubes…………………………………….. 9
I.4 Thermal and electrical properties ....................................................... 10
Chapter II: Carbon nanotubes synthesis technique...............................13
II.1 Synthesis............................................................................................... 13
II.2 Arc discharge....................................................................................... 13
II.2.1 Synthesis of SWNT........................................................................... 15
II.2.1.1 Inert gas ........................................................................................ 15
II.2.1.2 Optical plasma control.................................................................. 15
II.2.I.3 Catalyst........................................................................................... 16
II.2.I.4 Improvement of oxidation resistance........................................... 16
II.2.2 Synthesis of MWNT ......................................................................... 17

II.2.2.1 Synthesis in liquid nitrogen .......................................................... 18
II.2.2.2 Magnetic field synthesis ................................................................ 18
II.2.2.3 Plasma rotating arc discharge..................................................... 19
II.3 Laser ablation ...................................................................................... 20
II.3.1SWNT versus MWNT ....................................................................... 22
II.3.2 Large scale synthesis of SWNT ....................................................... 23
II.3.3 Ultra fast Pulses from a free electron laser (FEL)method............ 23
II.3.4 Continuous wave laser-powder method ......................................... 23
II.4 Chemical vapour deposition ............................................................... 25
II.4.1 Plasma enhanced chemical vapour deposition............................... 25
II.4.2 Thermal chemical vapour deposition ............................................. 26
II.4.3 Alcohol catalytic chemical vapour deposition……….....................27
II. 4.4 Vapour phase growth……………………………………………...28
II.4.5 Aero gel-supported chemical vapour deposition…………………29
II.4.6 CoMoCat process ............................................................................. 29
Chapter III: Experimental I:Experimental Plant..................................33
III.1 Introduction.........................................................................................33
III.2 Experimental Plant for nanotubes synthesis....................................33
Chapter IV: Experimental II Effect of alumina phases and process

parameters in the MWNT growth ............................................................37
IV.1 Introduction........................................................................................ 37
IV.2 Experimental ...................................................................................... 38
IV.2.1TG, DTG evaluation ........................................................................ 38
IV.2.2 SEM characterization..................................................................... 42
IV.2.3 Transmission electron microscopy characterization ................... 44
IV.2.4 Raman spectroscopy ....................................................................... 45
Chapter V: Experimental III On-line analysis.......................................47
V.I Introduction...........................................................................................47
V.2Experimental......................................................................................... 48
V.3 Results and discussion......................................................................... 48
V.3.1 Catalyst characterization................................................................. 48
V.3.2 On-line analysis of effluent gas...…………………………………..55
V.3.3 TG, DTG evaluation......................................................................... 61
V.3.4 SEM characterisation....................................................................... 64
V.3.5 Transmission electron microscopy characterization..................... 65
V.3.6 Raman spectroscopy......................................................................... 67
Chapter VI: Experimental IV Microwave purification and

functionalization of MWNTs......................................................................69
VI.I Introduction ........................................................................................ 69
VI.2Experimental Part .............................................................................. 70
VI.2.1 Carbon nanotubes synthesis............................................................70
VI.2.1 Purification treatment..........….………………………………......70
VI.2.3 Methods .......................................................................................... .73

VI.3 Result and discussion..........................................................................73
VI.3.1 Microscopy images.......................................................................... 73
VI.3.2 TG-DTG evaluation ....................................................................... .78
VI.3.3 ICP-MS analysis.............................................................................. 80
VI.3.4 Raman spectroscopy analysis........................................................ .81
VI.3.5 FT-IR................................................................................................ 83
VI.3.6 X-ray analysis .................................................................................. 84
VI.3.7 Surface area evaluation .................................................................. 86
VII Kinetic evaluation...............................................................................87
VII.1Introduction........................................................................................87
VII.2Experimental.......................................................................................87
VII.3 Results and discussion.......................................................................88
VII.3.1 Reaction rate...................................................................................88
VII.3.2 External and internal diffusion evaluation..................................88
VII.3.3 Kinetic study...................................................................................92
Conclusion....................................................................................................97
References.....................................................................................................99
Appendix: Investigation method ........................................................... 107
1 Electron microscopy.............................................................................. 107
1.1 Scanning electron microscopy (SEM)............................................... 108

1.2 Transmission Electron Microscopy (TEM) ..................................... 110
2 Raman spectroscopy ............................................................................. 112
2.1 Introduction ........................................................................................ 112
2.2 Raman spectra of carbon................................................................... 114
2.2.1 Raman spectra of graphite ............................................................. 114
2.2.2 Raman spectra of carbon nanotubes ............................................. 115

Figures content
Figure I.1. Schematic diagram showing how a hexagonal sheet of graphite is

‘rolled’ to form a carbon nanotube..................................................................2
Figure I.2 Illustrations of the atomic structure of (a) an armchair and (b) a
zig-zag nanotube..............................................................................................2
Figure I.3 The Stone-Wales transformation occurring in an armchair

nanotube under axial tensione.........................................................................3
Figure I.4 TEM micrograph showing the layered structure of a multiwalled

carbon nanotube...............................................................................................4
Figure I.5 Micrographs showing (a) the apparatus for tensile loading of
MWCNTs and (b) the telescoping, ‘‘sword and sheath’’ fracture behavior of
the MWCNT ..............................................................................................….5
Figure I.6 TEM micrograph and computer simulation of nanotube

buckling...........................................................................................................7
Figure I.7 Band-gap values vs. nanotube diameters define nanotubes as

metallic or semiconducting. ......................................................................... 11
Figure II.1 Experimental set-up of an arc discharge apparatus................... 14
Figure II.2 Schematic drawings of the electrode set-ups for (a) the
conventional and (b) the new arc discharge electrodes.................................16
Figure II.3 Experimental set-up of the torch arc method in open air.......... 17
Figure II.4 Schematic drawings of the arc discharge apparatus in liquid

nitrogen..........................................................................................................18
Figure II.5 Schematic diagram of the synthesis system for MWNTs in a
magnetic field. .............................................................................................. 19
Figure II.6 TEM micrograph and computer simulation of nanotube

buckling.........................................................................................................19
Figure II.7 Schematic rotating electrode system......................................... 20
Figure II.8 Schematic drawings of a laser ablation apparatus..................... 21
Figure II.9 TEM images of a bundle of SWNTs catalysed by Ni/Y (2:0.5 at.
%) mixture, produced with a continuous laser. ............................................ 22
Figure II.10 Schematic drawings of the ultra fast-pulsed laser ablation

apparatus....................................................................................................... 24
Figure II.11(Left) The principle scheme of the set-up for carbon SWNT
production by continuous wave laserpowder method (Right) HRTEM of a
SWNT-bundle cross-section..........................................................................24
Figure II.12 Schematic diagram of plasma CVD apparatus.........................26
Figure II.13 Schematic diagram of thermal CVD

apparatus........................267
Figure II.14 ACCVD experimental apparatus.………………………….....28
Figure II.16 . Experimental set-up for laser-assisted CVD ......................... 30
Figure II.17 Schematic diagram of a CoMoCat apparatus.......................... 31
Figure III.1 Experimental plant....................................................................35
Figure III.2 Uras 14 and Caldos 17 ABB analysers.....................................36
Figure IV.1 TG-DTG curves of samples obtained by supported synthesys

with: (a) bohemite; (b) gibbsite; (c) γ-alumina ; (d) bayerite. ...................... 42
Figure IV.3 SEM images of: GDl6020078 (a); GDl6030078 (b); GDl1020078
(c); GDl3020078 (d), GDl12020078 (e, f)....................................................... 44
Figure IV.4 TEM images of: BWs30100200 (a); TG residue at 510°C of

BWs30100200 (b); GDl6020078 (c); GDl3020078 (d, e)................................. 45
Figure IV.5 Raman Spectra of samples BWs30100200, TG residue at 510°C
of BWs30100200 and BWs60300200. ............................................................. 46
Figure V.I FESEM image of impregnated and dried catalyst, the inserts
show the EDX maps of the particles agglomerate in the image....................50
Figure V.2. FESEM image of catalyst after synthesis pretreatment, the

inserts show the EDX maps of the image zone.............................................51
Figure V.3 FESEM image of catalyst after synthesis and successive

oxidation of CNT, the inserts show the EDX maps of the image zone.........52
Figure V.4 TG–DTG curves of samples G5_30, G10_30, G15_30, G20_30

(a), TG–DTG curves of gibbsite after a blank test........................................54
Figure V.5: X-ray diffraction patterns of gibbsite, catalyst after

pretreatment, catalyst after synthesis, γ-Al2O3...............................................54
Figure V.6 :Raman spectrum of support (gibbsite)......................................55
Figure V.7: Profiles of C2H4, C2H2, CH4 and H2 concentrations during CNT
growth tests for samples G15_30 .................................................................56
Figure V.8: Profiles of C2H4, C2H2, CH4 and H2 concentrations during blank
test..................................................................................................................56
Figure V.9: Ethylene conversion and hydrogen yield for G5_30, G10_30...8
Figure V.10: Ethylene conversion and hydrogen yield for

G15_30,G20_30............................................................................................59
Figure V.11: Ethylene conversion and hydrogen yield for G5_30, G5_70,
and G5_140……...........................................................................................60
Figure V 12: TG–DTG curves of samples G5_30, G10_30, G15_30,

G20_30 (a), TG–DTG curves of gibbsite after a blank test
.......................................62
Figure V.13: TG–DTG curves c) of sample G5_30 taken at different heights

of the as grown bed a) A catalyst image b)...................................................63
Figure. V.14: SEM images of G5_140 and G5_30 at 500X........................64

Figure V.15 TEM images of G15_30 at low resolution a); higher resolution
b), c), d) and f). EDX analysis of a catalytic particle inside the hallow core of
a CNT e), and EDX analysis of catalytic particles covered of no-nanotubes
carbon g), evidencing Fe and Co presence....................................................66
Figure V.16 Raman spectra (514 nm excitation wavelength) of samples

prepared at different ethylene partial pressure..............................................67
Fig.V.17 Raman spectra (785 nm excitation wavelength) of G5_30, G10_30

and G20_30....................................................................................................68
Figure VI.1 TEM images of MW1(a, b) and EDX spectra of MW1(c )…..73
Figure VI.2 TEM images of MW2( a,b) and MW3 (c)................................74
Figure VI.3 TEM images of MW4 (a), MW5 (b,c), MW6 (d,e)..................75
Figure VI.4 Histogram of The inner and outer diameter of the raw and
treated materials............................................................................................76
Figure VI.5 FESEM of MW1 (a,b)..............................................................77
Figure VI.6 MW1(a), MW3(b), MW6(c)………...……….….....................79
Figure VI.7 TG-DTG curves of different samples and of MW1 at several

heating rate…………………………………………………………………81
Figure VI.8 Raman spectra (785 nm excitation wavelength) of MW1,

MW2, MW3, MW5, MW6…………………………………………………82
Figure VI.9 FTIR spectra of samples MW3 and MW6………….……….84
Figure VI.10 X-ray diffraction spectra of the raw and treated materials...85
Figure VI. 11 adsorption-desorption isotherms of N2 at 77 K for MW1,

MW2,MW3, MW5 and MW6……………………......…………….............86
Figure VII.1 Example (sample G5_30120600) of hydrogen production curve

as a function of time and determination of the global observed rate of CNT
synthesis.........................................................................................................91
Figure VII.2 Kinetic constant evaluation at 600°C, varying the amount of

catalyst at a constant feed rate, composition, pressure .................................96

Figure VII.5 Kinetic constant evaluation at 700°C, varying gas flow at
given amount of catalyst at a constant feed composition and pressure........97
Figure VII.6 Plot of the natural logarithm of growth rate against the
reciprocal of absolute temperature................................................................97
Figure A.I Signal generated when a high-energy electron beam interacts

with a thin specimen. Most signals can be detected in a SEM or
TEM.............................................................................................................107
Figure A.2 The two basic operations of a TEM: projecting the diffraction
pattern on the viewing screen (left) or projecting the image on the screen
(right). The intermediate lens selects the back focal- or the image plane of
the objective lens as its object ....................................................................111
Figure A.3 Signal generated when a high-energy electron beam interacts

with a thin specimen. Most signals can be detected in a SEM or
TEM.............................................................................................................112
Figure A.4 The two basic operations of a TEM: projecting the diffraction
the objective lens as its object ....................................................................115
Figure A.5 Polarized molecule in an electric field (left), energy diagram of

the different light scattering processes. The elastic Rayleigh scattering and
the inelastic Raman scattering (Stokes/Anti-Stokes) (right)…...................116
Figure A.6 Normalised Raman spectra of HOPG, glassy carbon, CVD

MWNT and CVD SWNT. The laser wavelength was λ = 514.5 nm (left).
The inverse crystallite size vs.the ratio of the D- and G-band; according to
(right)...........................................................................................................117
Tables content
Table IV.I Synthesis conditions with the different supports, carbon yield,
MWNT selectivity and reaction yield obtained by TG evaluation.................39
Table IV.2 Synthesis conditions with the different supports, carbon yield,
MWNT selectivity and reaction yield obtained by TG evaluation.................40
Table IV.3 Carbon yield obtained by TG evaluation for samples prepared

with different metal loading...........................................................................41
Table V.1 carbon yield, MWNT selectivity and reaction yield obtained by
TG evaluation................................................................................................61
Table V.2 ID/IG intensity ratio at two different excitation wavelength for
CNT produced at increased ethylene partial pressure and at different
times...............................................................................................................65
Table VI.1 TG residue % samples MW1, MW2, MW3, MW5, MW6............78
Table VI.2 Results of the ICP-MS analysis for the raw and treated
materials, performed with particular regards to the Co and Fe content......80
Table VI.3 Raman spectroscopy analysis: ID/IG ratio, D and G

wavenumbers for raw samples and treated materials...................................83
Table VI.4 Effects of the treatments on the nanotubes geometrical

characteristics, XRD evaluation....................................................................85
Table VII.1 External diffusion evaluation before and after syntheses........90
Table VII.2 Internal diffusion evaluation before and after synthesis.,........93
Table VII. 3 Calculated results for the reaction C2H4→2C+2H2................94

Chapter I
Structure and properties of CNT
I.1 Structure
Carbon nanotubes can be visualized as a sheet of graphite that has been

rolled into a tube. Unlike diamond, where a 3-D diamond cubic crystal
structure is formed with each carbon atom having four nearest neighbors
arranged in a tetrahedron, graphite is formed as a 2-D sheet of carbon atoms
arranged in a hexagonal array. In this case, each carbon atom has three
nearest neighbors. ‘Rolling’ sheets of graphite into cylinders forms carbon
nanotubes. The properties of nanotubes depend on the atomic arrangement
(how the sheets of graphite are ‘rolled’), the diameter and length of the
tubes, and the morphology, or nano structure. Nanotubes exist as either
single-walled or multi-walled structures; multi-walled carbon nanotubes
(MWCNTs) are simply composed of concentric single-walled carbon
nanotubes of progressive larger diameters.“Thostenson et al.(2001)”.
The atomic structure of nanotubes is described in terms of tube chirality,
or helicity, which is defined by the chiral vector, Ch, and the chiral angle, θ.
In Fig. I.1, we can visualize cutting the graphite sheet along the dotted lines
and rolling the tube so that the tip of the chiral vector touches its tail. The
chiral vector, often known as the roll-up vector, can be described by the
following equation:
r r r
C h = na1 + ma2
where the integers (n, m) are the number of steps along the ziz-zag
carbon bonds of the hexagonal lattice and a1 and a2 are unit vectors, shown
in Fig. I.1.
Chapter I
Figure I.1: Schematic diagram showing how a hexagonal sheet of graphite

is ‘rolled’ to form a carbon nanotube.
The chiral angle determines the amount of ‘twist’ in the tube. There are
two limiting cases where the chiral angle is at 0° and 30°. These limiting
cases are referred to as ziz-zag (0°) and armchair (30°) based on the
geometry of the carbon bonds around the circumference of the nanotube.
The difference in armchair and zig-zag nanotube structures is shown in Fig.
I.2.
Figure I.2: Illustrations of the atomic structure of (a) an armchair and (b) a
zig-zag nanotube.
In relation to the roll-up vector, the ziz-zag nanotube is (n, 0) and the
armchair nanotube is (n, n). The roll-up vector of the nanotube also defines
the nanotube diameter since the inter-atomic spacing of the carbon atoms is
known. The chirality of the carbon nanotube has significant implications on
its material properties. In particular, tube chirality is known to have a strong
2
impact on the electronic properties of carbon nanotubes. Graphite is

considered to be a semi-metal, but it has been shown that nanotubes can be
either metallic or semiconducting, depending on tube chirality “Dresselhaus
et al. (1996)”. Investigations on the influence of chirality on the mechanical
properties have also been reported. The analytical work of Yakobson et al.
“Yakobson et al. (1996a), Yakobson et al. (2000b)” examined the instability
of carbon nanotubes beyond linear response. Their simulations show that
carbon nanotubes are remarkably resilient, sustaining extreme strain with no
signs of brittleness or plasticity. Although the chirality has a relatively small
influence on the elastic stiffness, they concluded that the Stone-Wales
transformation, a reversible diatomic interchange where the resulting
structure is two pentagons and two heptagons in pairs, plays a key role in the
nanotube plastic deformation under tension. The Stone-Wales
transformation, shown in Fig. I.3, occurs when an armchair nanotube is
stressed in the axial direction. Nardelli et al.(1998) theorized that the Stone-
Wales transformation results in a ductile fracture for armchair nanotubes.
Figure I.3: The Stone-Wales transformation occurring in an armchair

nanotube under axial tension.
As mentioned before, fullerenes are closed, convex cages that are

composed of pentagons and hexagons. The Stone-Wales transformation
introduces a new defect into the nanotube structure, the heptagon. Heptagons
allow for concave areas within the nanotube. Thus, the heptagonal defects in
nanotubes can result in many possible equilibrium shapes. Indeed, most
nanotubes are not straight cylinders with hemispherical caps.
In addition to different tube morphologies caused by defects, carbon
nanotubes can be single walled or multi-walled structures. Fig. I.4 shows a
transmission electron microscope (TEM) image showing the nanostructure
3
Chapter I
of a multi-walled carbon nanotube where several layers of graphitic carbon

and a hollow core are evident. Multi-walled carbon nanotubes are essentially
concentric single walled tubes, where each individual tube can have different
chirality. These concentric nanotubes are held together by secondary, van
der Waals bonding. Single-walled nanotubes are essential for fundamental
investigations of the structure/property relationships in carbon nanotubes,
since the intra-tube interactions further complicate the properties of carbon
nanotubes. Indeed, both single and multi-walled nanotubes show unique
properties that can be exploited for use in composite materials.
Figure I.4: TEM micrograph showing the layered structure of a multiwalled

carbon nanotube. “Thostenson et al.(2001)”
I.2 Characterization of carbon nanotubes
Significant challenges exist in both the micromechanical characterization

of nanotubes and the modelling of the elastic and fracture behaviour at the
nano-scale. Challenges in characterization of nanotubes and their composites
include: (a) complete lack of micromechanical characterization techniques
for direct property measurement, (b) tremendous limitations on specimen
size, (c) uncertainty in data obtained from indirect measurements, and (d)
inadequacy in test specimen preparation techniques and lack of control in
nanotube alignment and distribution. In order to understand the mechanical
properties of carbon nanotubes, a number of investigators have attempted to
characterize them directly. Treacy et al.”Treacy et al. (1996)” first
investigated the elastic modulus of isolated multi-walled nanotubes
measuring, by transmission electron microscopy, the amplitude of their
intrinsic thermal vibration. The average value obtained over 11 samples was
1.8 TPa. Direct measurement of the stiffness and strength of individual,
structurally isolated multi-wall carbon nanotubes has been made with an
atomic-force microscope (AFM). Wong et al. “Wong et al.(1997)” were the
first to perform direct measurement of the stiffness and strength of
individual, structurally isolated multi-wall carbon nanotubes using atomic
force microscopy. The nanotube was pinned at one end to molybdenum
4
disulfide surfaces and load was applied to the tube by a AFM tip. The
bending force was measured as a function of displacement along the
unpinned length, and a value of 1.26 TPa was obtained for the elastic
modulus. The bending force was measured as a function of displacement
along the unpinned length, and a value of 1.26 TPa was obtained for the
elastic modulus. The average bending strength measured was 14.2_8 GPa.
Single-walled nanotubes tend to assemble in the ‘ropes’ of nanotubes.
Salvetat et al. “Salvetat et al.(1999)” measured the properties of these
nanotube bundles with the AFM. As the diameter of the tube bundles
increases, the axial and shear module decrease significantly. This suggests
slipping of the nanotubes within the bundle. Walters et al. “Walters et al.
(1999)” further investigated the elastic strain of nanotube bundles with the
AFM. On the basis of their experimental strain measurements and an
assumed elastic modulus of 1.25 TPa, they calculated a yield strength of
45±7 GPa for the nanotube ropes. Indeed, their calculated value for strength
would have been much lower if the elastic modulus of the nanotube bundle
had been decreased as a consequence of slipping within the bundle, as
suggested by Salvetat et al. “Salvetat et al. (1999).”
b
Figure I 5: Micrographs showing (a) the apparatus for tensile loading of
MWCNTs and (b) the telescoping, ‘‘sword and sheath’’ fracture behavior of
the MWCNT
5
Chapter I
Yu et al. “ Yu et al. (2000a), Yu et al. (2000b)” have investigated the

tensile loading of multi-walled nanotubes and single-walled nanotube ropes.
In their work, the nanotubes were attached between two opposing AFM tips
and loaded under tension. Their experimental set-up is shown in Fig. I.5. For
multi-walled carbon nanotubes “Yu et al.(2000b)” the outermost tube failed
followed by the pullout of the inner nanotubes. This ‘sword and sheath’
telescoping failure mechanism of multi-walled carbon nanotubes in tension
is also shown in Fig. I.5. The experimentally calculated tensile strengths of
the outermost layer ranged from 11 to 63 GPa and the elastic modulus
ranged from 270 to 950 GPa. In their subsequent investigation of single-
walled nanotube ropes Yu et al. “Yu et al.(2000a)”, assumed that only the
outermost tubes assembled in the rope carried the load during the
experiment, and they calculated tensile strengths of 13 to 52 GPa and
average elastic module of 320 to 1470 GPa. Xie et al. “Xie et al.(2000)” also
tested ropes of multi-walled nanotubes in tension. In their experiments, the
obtained tensile strength and modulus were 3.6 and 450 GPa, respectively. It
was suggested that the lower values for strength and stiffness may be a
consequence of defects in the CVD-grown nanotubes.
I.3 Mechanics of carbon nanotubes
As discussed in the previous section, nanotube deformation has been

examined experimentally “Thostenson et al.(2001)”. Recent investigations
have shown that carbon nanotubes possess remarkable mechanical
properties, such as exceptionally high elastic modulus “Treacy et al., (1996),
Wong et al.(1997)”, large elastic strain and fracture strain sustaining
capability “Falvo et al.(1997), Bower et al.(1999)”. Similar conclusions have
also been reached through some theoretical studies “Overney et al.(1993),
Lu (1997), Yakobson et al.(1997), Bernholc et al. (1998)” although very few
correlations between theoretical predictions and experimental studies have
been made. In this section we examine the mechanics of both single walled
and multi-walled nanotubes.
I.3.1 Single-walled carbon nanotubes
Theoretical studies concerning the mechanical properties of single-walled

nanotubes have been pursued extensively. Overney et al. “Overney et al.
(1993)” studied the low-frequency vibrational modes and structural rigidity
of long nanotubes consisting of 100, 200 and 400 atoms. The calculations
were based on an empirical Keating Hamiltonian with parameters
determined from first principles. A comparison of the bending stiffnesses of
single-walled nanotubes and an iridium beam was presented. The bending
stiffness of the iridium beam was deduced by using the continuum Bernoulli-
Euler theory of beam bending. Overney and his co-workers concluded that
6
the beam bending rigidity of a nanotube exceeds the highest values found in
any other presently available materials. In addition to their experimental
observations, Iijima et al. “Iijima et al., (1996)” examined response of
nanotubes under compression using molecular dynamics simulations. They
simulated the deformation properties of single- and multi-walled nanotubes
bent to large angles. Their experimental and theoretical results show that
nanotubes are remarkably flexible. The bending is completely reversible up
to angles in excess of 110°, despite the formation of complex kink shapes.
Fig. I.6 shows their numerical and experimental results, demonstrating the
exceptional resilience of carbon nanotubes under high strain. Ru “Ru et
al.(2000)” noticed that the actual bending stiffness of singlewalled
nanotubes is much lower than that given by the elastic-continuum shell
model if the commonly defined representative thickness is used. Ru
proposed the use of an effective nanotube bending stiffness as a material
parameter not related to the representative thickness. With the aid of this
concept, the elastic shell equations can be readily modified and then applied
to single-walled nanotubes. The computational results based on this concept
substantiate the results from molecular dynamics simulations.
Figure I.6: TEM micrograph and computer simulation of nanotube buckling
Vaccarini et al. “Vaccarini et al.(2000)” investigated the influence of

nanotube structure and chirality on the elastic properties in tension, bending,
and torsion. They found that the chirality had little influence on the nanotube
tensile modulus. However, the chiral tubes exhibit asymmetric torsional
behavior with respect to left and right twist, whereas the armchair and ziz-
7
Chapter I
zag tubes do not exhibit this asymmetric torsional behaviour. A relatively

comprehensive study of the elastic properties of single-walled nanotubes was
reported by Lu “Lu (1997)”. In this study, Lu adopted an empirical lattice-
dynamics model “Al-Jishi et al. (1982)” which has been successfully
adopted in calculating the phonon spectrum and elastic properties of
graphite. In this lattice-dynamics model, atomic interactions in a single
carbon layer are approximated by a sum of pair-wise harmonic potentials
between atoms. The local structure of a nanotube layer is constructed from
conformal mapping of a graphite sheet on to a cylindrical surface. Lu’s work
attempted to answer such basic questions as: (a) how do elastic properties of
nanotubes depend on the structural details, such as size and chirality? and (b)
how do elastic properties of nanotubes compare with those of graphite and
diamond?
Lu concluded that the elastic properties of nanotubes are insensitive to size
and chirality. Young’s predicted modulus (~1 TPa), shear modulus (~0.45
TPa), and bulk modulus (~0.74 TPa) are comparable to those of diamond.
Hernandez and his co-workers “Hernandez et al.(1998)” performed
calculations similar to those of Lu and found slightly higher values (~1.24
TPa) for Young’s tubes modulus. But unlike Lu, they found that elastic
modulus are sensitive to both tube diameter and structure. Besides their
unique elastic properties, the inelastic behaviour of nanotubes has also
received considerable attention. Yakobson and co-workers “Yakobson et
al.(1996), Bernholc et al. (1998)” examined the instability behaviour of
carbon nanotubes beyond linear response by using realistic many-body
Tersoff-Brenner potential and molecular dynamics simulations. Their
molecular-dynamics simulations show that carbon nanotubes, when
subjected to large deformations, reversibly switch into different
morphological patterns. Each shape change corresponds to an abrupt release
of energy and a singularity in the stress/strain curve. These transformations
are explained well by a continuum shell model. With properly chosen
parameters, their model provided a very accurate ‘roadmap’ of nanotube
behavior beyond the linear elastic regime. They also carried out molecular
dynamics simulations to single- and double-walled nanotubes of different
chirality and at different temperatures “Yakobson et al.(1997b)”.
Their simulations show that nanotubes have an extremely large breaking
strain (in the range 30–40%) with decreases according to temperature.
Yakobson “Yakobson et al.(2000c)” also applied dislocation theory to
carbon nanotubes to describe their main routes of mechanical relaxation
under tension. It was concluded that the yield strength of a nanotube depends
on its symmetry and it was believed that there exists an intra-molecular
plastic flow. Under high stress, this plastic flow corresponds to a motion of
dislocations along helical paths within the nanotube wall and causes a
stepwise necking, a well-defined new symmetry, as the domains of different
chiral symmetry are formed. As a result, both the mechanical and electronic
8
properties of carbon nanotubes are changed. The single walled nanotubes

produced by laser ablation and arc-discharge techniques have a greater
tendency to form ‘ropes’ or aligned bundles “Journet et al.(1995), Thess et
al.(1996)”. Thus, theoretical studies have been made to investigate the
mechanical properties of these nanotube bundles. Ru “Ru (2000) presented a
modified elastic-honeycomb model to study elastic buckling of nanotube
ropes under high pressure. Ru gave a simple formula for the critical pressure
as a function of nanotube Young’s modulus and wall thickness-to-radius
ratio. It was concluded that single-walled ropes are susceptible to elastic
buckling under high pressure and elastic buckling is responsible for the
pressure-induced abnormalities of vibration modes and electrical resistivity
of single walled nanotubes.
Popov et al. “Popov et al. (2000b)” studied the elastic properties of
triangular crystal lattices formed by single-walled nanotubes by using
analytical expressions based on a force constant lattice dynamics model
“Popov et al.(1999a)”. They calculated various elastic constants of nanotube
crystals for nanotube types, such as the armchair and zigzag. It was shown
that the elastic modulus, Poisson’s ratio and bulk modulus clearly exhibit a
strong dependence on the tube radius. The bulk modulus was found to have a
maximum value of 38 GPa for crystals composed of singlewalled nanotubes
with ~0.6 nm radius.
I.3.2. Multi-walled carbon nanotubes
Multi-walled nanotubes are composed of a number of concentric single

walled nanotubes held together with relatively weak van der Waals forces.
The multi-layered structure of these nanotubes further complicates the
modelling of their properties.
Ruoff and Lorents “Ruoff et al.(1995)” derived the tensile and bending
stiffness constants of ideal multi-walled nanotubes in terms of the known
elastic properties of graphite. It has been suggested that unlike the strongly
anisotropic thermal expansion in conventional carbon fibres and graphite,
the thermal expansion of carbon nanotubes is essentially isotropic. However,
the thermal conductivity of nanotubes is believed to be highly anisotropic
and its magnitude along the axial direction is perhaps higher than that of any
other material.
Lu “Lu et al.(1997)” also calculated the elastic properties of many multi-
walled nanotubes formed by single-layer tubes by means of the empirical-
lattice dynamics model. It was found that elastic properties are insensitive to
different combinations of parameters, such as chirality, tube radius and
numbers of layers, and the elastic properties are the same for all nanotubes
with a radius larger than one nm. Interlayer van der Waals interaction has a
negligible contribution to both the tensile and shear stiffness.
9
Chapter I
Govindjee and Sackman “Govindjee et al.(1999)” were the first to

examine the use of continuum mechanics to estimate the properties of multi-
walled nanotubes. They investigated the validity of the continuum approach
by using Bernoulli-Euler bending to infer the Young’s modulus. They used a
simple elastic sheet model and showed that at the nanotube scale, the
assumptions of continuum mechanics must be carefully respected in order to
obtain reasonable results. They showed the explicit dependence of ‘material
properties’ on system size when a continuum cross-section assumption was
used.
Ru “Ru et al.(2000a)” used the elastic-shell model to study the effect of
van der Waals forces on the axial buckling of a double-walled carbon
nanotube. The analysis showed that the van der Waals forces do not increase
the critical axial buckling strain of a double-walled nanotube. Ru “Ru et
al.(2000b), Ru et al.(2001c)” thereafter also proposed a multiple column
model that considers the interlayer radial displacements coupled through the
van der Waals forces. This model was used to study the effect of interlayer
displacements on column buckling. It was concluded that the effect of
interlayer displacements could not be neglected unless the van der Waals
forces are extremely strong. Kolmogorov and Crespi “Kolmogorov et
al.(2000)” investigated the interlayer interaction in two-walled nanotubes. A
registry-dependent two-body graphite potential was developed. It was
demonstrated that the tightly constrained geometry of a multi-walled
nanotube could produce an extremely smooth solid-solid interface wherein
the corrugation against sliding does not grow in relation to system size. The
energetic barrier to interlayer sliding in defect-free nanotubes containing
thousands of atoms can be comparable to that for a single unit cell of
crystalline graphite.
I.4 Thermal and electrical properties
Thermal properties including specific heat and thermal conductivity of

carbon nanotubes are determined primarily by the phonons “Cui et
al.(2000)”. A phonon is a quantum acoustic energy similar to the photon.
Phonons are a result of lattice vibrations observed in the Raman spectra
“Collins et al.(2000).”. The phonon contribution to these quantities
dominates especially at low temperatures and is due to the acoustic phonons.
The measurements of thermoelectric power of nanotube systems give direct
information for the type of carriers and conductivity mechanisms.
Theoretical and experimental results have shown the superior electrical
properties of carbon nanotubes. They can produce electric current carrying
capacity 1000 times higher than copper wires “Salvetat et al. (1999)”. For
1D systems, cylindrical surface and translational symmetry with a screw axis
could affect the electronic structures and related properties. The electronic
capabilities possessed by carbon nanotubes are seen to arise predominately
10
from interlayer interactions, rather than from interlayer interactions between

multi layers within a single carbon nanotube or between different nanotubes
“ Walters et al.(1999)”.
These optical properties have proved to be especially unique with the
capabilities of acting either as a metallic or semiconductor, which depends
on tubule diameter and chiral angle. Studies have shown that metallic
conduction can be achieved without the introduction of doping effects. For
semiconducting nanotubes the band gaps have been found to be proportional
to a fraction of the diameter and without relation to the tubule chirality
“Walters et al.(1999)”.
Figure I.7: Band-gap values vs. nanotube diameters define nanotubes as

metallic or semiconducting.
The I-tight-binding model within the zone folding scheme shows, one
third of carbon nanotubes are found to be metallic while two thirds are
semiconducting, depending on their indices “Cui et al.(2000)”. Calculations
based on the use of r and P bands, due to curvature induced mixing of these
bands, are used to predict that some metallic nanotubes are very-small-band-
gap semiconducting nanotubes “Yu et al.(2000b)” (Fig. I.7). The symmetry
of the structures basically links all the calculations in both single and multi-
wall carbon nanotubes. The electronic properties of bundles of single wall
nanotubes can be derived, assuming the intertube interactions are not strong
enough to change the band structure. Broken symmetry caused by
interactions between tubes in a bundle create a pseudogap of about 0.2 and
0.1 eV “Yu et al.(2000a)” This pseudo-gap, which is created can modify
11
Chapter I
electronic properties such as semimetal-like temperature dependence of the

electrical conductivity and a finite gap in the infrared absorption spectrum is
predicted “Cui et al.(2000)”.
12
Chapter II
Carbon nanotubes synthesis
technique
II.1 Synthesis
Since carbon nanotubes were discovered nearly a decade ago, there have
been a variety of techniques developed for their preparation.
Primary synthesis methods for single and multi-walled carbon nanotubes
include arc-discharge “Keidar et al.(2004), Lee et al (2002)”, laser ablation
“Assovskii et al.(2003)”, gas-phase catalytic growth from carbon monoxide
“Khassin et al.(1998)”, and chemical vapour deposition (CVD) of
hydrocarbons “Zhang et al.(2005), Du et al.(2005)”. In order to apply carbon
nanotubes, large quantities are required, and the scale-up limitations of the
arc discharge and laser ablation techniques would make the cost of nanotube
prohibitive. During nanotube synthesis, impurities in the form of catalyst
particles, amorphous carbon, and non-tubular fullerenes are also produced.
Thus, subsequent purification steps are required to separate the tubes. The
gas-phase processes tend to produce nanotubes with fewer impurities and are
more amenable to large-scale processing. It is considered that gas phase
techniques, such as CVD, for nanotube growth offer the greatest potential for
the scaling-up of nanotube production for the processing of composites and
applications in different fields.
In this chapter, we summarize the progress made in recent years in
growing carbon nanotubes by various methods to produce carbon nanotubes
and review some of the benefits and drawbacks of each technique.
II.2 Arc discharge
The carbon arc discharge method, initially used for producing C60
fullerenes, is the most common and perhaps easiest way to produce carbon
nanotubes as it is rather simple to undertake. However, it is a technique that
Chapter II
produces a mixture of components and requires separating nanotubes from

the soot and the catalytic metals present in the raw product.
This method creates nanotubes through arc-vaporisation of two carbon rods
placed end to end, separated by approximately 1mm, in an enclosure that is
usually filled with inert gas (helium, argon) at low pressure (between 50 and
700 mbar). Recent investigations have shown that it is also possible to create
nanotubes with the arc method in liquid nitrogen “Anazawa et al.(2002)”. A
direct current of 50 to 100 A driven by approximately 20 V creates a high
temperature discharge between the two electrodes. The discharge vaporises
one of the carbon rods and forms a small rod shaped deposit on the other
rod. Producing nanotubes in high yield depends on the uniformity of the
plasma arc and the temperature of the deposit form on the carbon electrode
“Lee et al. (2002)”
Insight into the growth mechanism is increasing and measurements have
shown that the different diameter distributions that have been found are
dependant on the mixture of helium and argon. These mixtures have
different diffusions coefficients and thermal conductivities. These properties
affect the speed with which the carbon and catalyst molecules diffuse and
cool, affecting nanotube diameter in the arc process. This implies that single-
layer tubules nucleate and grow on metal particles in different sizes
depending on the quenching rate in the plasma and it suggests that
temperature and carbon and metal catalyst densities affect the diameter
distribution of nanotubes “Lee et al. (2002)”
Depending on the preparation technique it is possible to selectively grow
SWNTs or MWNTs, as shown in Figure II.1.
Figure II.1: Experimental set-up of an arc discharge apparatus
14
Carbon nanotubes synthesis technique
II.2.1 Synthesis of SWNT
If SWNTs are to be obtained, the anode has to be doped with metal

catalyst, such as Fe, Co, Ni, Y or Mo.
A lot of elements and mixtures of elements have been tested by various
authors “Journet et al.(1998)” and it is noted that the results vary a lot, even
though they use the same elements. This is not surprising as experimental
conditions differ. The quantity and quality of the nanotubes obtained depend
on various parameters such as the metal concentration, inert gas pressure,
type of gas, current and system geometry.
Usually the diameter is in the range of 1.2 to 1.4 nm. Some ways of
improving the process of arc discharge are described below.
II.2.1.1 Inert gas

The most common problems with SWNT synthesis are that the product
contains a lot of metal catalyst, SWNTs have defects and purification is hard
to perform. On the other hand, one advantage is that the diameter can be
slightly controlled by changing thermal transfer and diffusion, hence
condensation of atomic carbon and metals between the plasma and the
vicinity of the cathode can control nanotube diameter in the arc process. This
was shown in an experiment in which different mixtures of inert gases were
used “Farhat et al.(2001a)”.
It appeared that argon, with a lower thermal conductivity and diffusion
coefficient, gave SWNTs with a smaller diameter of approximately 1.2 nm.
A linear fit of the average nanotube diameter showed a 0.2 nm diameter
decrease per 10 % increase in argon helium ratio, when nickel/yttrium was
used (C/Ni/Y was 94.8:4.2:1) as catalyst.
II.2.1.2 Optical plasma control

A second way of controlling plasma is to change the anode to cathode
distance (ACD). The ACD is adjusted in order to obtain strong visible
vortices around the cathode. This enhances anode vaporisation, which
improves nanotubes formation. Combined with controlling the argon-helium
mixture, one can simultaneously control the macroscopic and microscopic
parameters of the nanotubes formed “Farhat et al.(2001b)”.
With a nickel and yttrium catalyst (C/Ni/Y is 94.8:4.2:1) the optimum
nanotube yield was found at a pressure of 660 mbar for pure helium and 100
mbar for pure argon. The nanotube diameter ranges from 1.27 to 1.37
nanometre.
15
Chapter II
II.2.I.3 Catalyst
Since chemical vapour deposition (CVD) could give SWNTs with a
diameter of 0.6–1.2 nm, researchers tried the same catalyst as used in CVD
on arc discharge. Not all of the catalysts used appeared to give nanotubes
for both methods. But there seemed to be a correlation of diameter of
SWNTs synthesised by CVD and arc discharge. As a result, the diameter can
be controlled to a range of 0.6-1.2 nm with arc-discharge.
II.2.I.4 Improvement of oxidation resistance

There has also been progress in developing methods to improve the
oxidation resistance of the SWNTs, which is a consequence of the defects
present in nanotubes. Strong oxidation resistance is needed for the nanotubes
if they have to be used for applications such as field emission displays.
Recent research has indicated that a modified arc-discharge method using a
bowl-like cathode (see Figure II.2) decreases the defects and gives cleaner
nanotubes, and thus improves the oxidation resistance “Huang et al.(2002)”
The Raman spectrum of the newly synthesised nanotubes shows that the
nanotubes formed are cleaner and less defective compared to those
synthesised by conventional methods. The anode rod contained Ni and Y
catalyst (C /Ni/Y is 94.8:4.2:1). No information is given about the diameter
size.
Figure II.2:Schematic drawings of the electrode set-ups for (a) the

conventional and (b) the new arc discharge electrodes.
It was only recently discovered that it is possible to form MWNTs in the
open air “Takikawa et al.(2001b)”; by welding arc torch, the process was
shielded with argon gas flow.The anode and cathode were made of graphite
containing Ni and Y (Ni/Y is 4.2:1 at. %).
16
Figure II.3: Experimental set-up of the torch arc method in open air.
This method was modified for preparing SWNTs “Takikawa et al.(2001a)”
A plate target made of graphite containing Ni and Y , was fixed at the
sidewall of a water–cooled, steel based electrode. The torch arc aimed at the
edge of the target and the soot was deposited on the substrate behind the
target (see Figure II.3). The arc was operated at a direct current of 100 A.
and shielding argon gas flowed through the torch, enhancing the arc jet
formation beyond the target. Carbon nanohorns (CNHs) and bundles of
SWNT with an average diameter of 1.32 nm were found in the soot.
However, the yield was much lower than for the conventional low-pressure
arc discharge method. There are two reasons for this; first of all, because of
the open air, the lighter soot will escape into the atmosphere, secondly, the
carbon vapour might be oxidised and emitted as carbon dioxide gas. In order
to improve the yield in this method, a means for collecting soot and
developing an appropriate target are required.
This method seems to be convenient and inexpensive once the conditions
for higher yield are optimised. With a Ni/Y catalyst (Ni/Y is 3.6:0.8), SWNT
bundles and CNHs are formed. In this case the SWNTs have a diameter of
approximately 1.32 nm “Takikawa et al.(2002b)”.
II.2.2 Synthesis of MWNT
If both electrodes are graphite the main product will be MWNTs. But
next to MWNTs a lot of side products are formed such as fullerenes,
amorphous carbon, and some graphite sheets. The purification of the
MWNTs causes loss of structure and disorders the walls. Therefore,
scientists are developing ways to gain pure MWNTs in a large-scale process
without purification.Typical sizes for MWNTs are 1-3 nm for inner diameter
17
Chapter II
and approximately 10 nm for outer diameter Because no catalyst is involved

in this process, there is no need for a heavy acidic purification step. This
means the MWNT can be synthesised with few defects.
II.2.2.1 Synthesis in liquid nitrogen

One possible economical route to highly crystalline MWNTs is the arc-
discharge method in liquid nitrogen “Jung et al.(2003)”. By this route,
indeed, mass production is also possible. For this option low pressures and
expensive inert gasses are not needed (Fig. II.4).
Figure II.4:Schematic drawings of the arc discharge apparatus in liquid

nitrogen.
The content of MWNTs can be as high as 70 % of the reaction product.
Analysis with Auger spectroscopy revealed that no nitrogen was
incorporated in the MWNTs. There is a strong possibility that SWNTs can
be produced with the same apparatus under different conditions.
II.2.2.2 Magnetic field synthesis

Synthesis of MWNTs in a magnetic field “Anazawa et al. (2002)” gives
defect-free, high purity MWNTs that can be applied as nanosized electric
wires for device fabrication. In this case the arc discharge synthesis was
controlled by a magnetic field around the arc plasma (figure II.5).
18
Extremely pure graphite rods (purity > 99.999 %) were used as

electrodes. Highly pure MWNTs (purity > 95 %) were obtained without
further purification, which disorders walls of MWNTs.
Figure II.5: Schematic diagram of the synthesis system for MWNTs in a

magnetic field.
Figure II.6: SEM images of MWNTs synthesised with (a) and without (b) the
magnetic field.
II.2.2.3 Plasma rotating arc discharge

A second possible economical route to mass production of MWNTs is
synthesis by plasma rotating arc discharge technique “Lee et al.(2002)”.
19
Chapter II
The centrifugal force caused by the rotation generates turbulence and

accelerates the carbon vapour perpendicular to the anode. In addition, the
rotation distributes the micro discharges uniformly and generates stable
plasma. Consequently, it increases the plasma volume and raises the plasma
temperature.
At a rotation speed of 5000 rpm a yield of 60 % was found at a
temperature of 1025 °C without the use of a catalyst. The yield increases up
to 90% after purification if the rotation speed is increased and the
temperature is raised to 1150 °C. The diameter size was not mentioned in
this publication.
Figure II.7: Schematic rotating electrode system.

II.3 Laser ablation
In 1995, the Smalley's group “Guo et al.(1995)” at Rice University reported

the synthesis of carbon nanotubes by laser vaporisation., with the apparatus
shown in Figure II.8. A pulsed “Yudasaka et al.(1999), Eklund et al.(2002)”
or continuous “Maser et al.(1998), Bolshakov et al.(2002)” laser is used to
vaporise a graphite target in an oven at 1200 °C. The main difference
between a continuous and a pulsed laser, is that the pulsed laser demands a
much higher light intensity (100 kW/cm2 compared to 12 kW/cm2). The
oven is filled with helium or argon gas in order to keep the pressure at 500
Torr. A very hot vapour plume forms, then expands and cools rapidly. As the
vaporised species cool, small carbon molecules and atoms quickly condense
to form larger clusters, possibly including fullerenes. The catalysts also
begin to condense, but more slowly at first, and attach themselves to the
carbon clusters and prevent their closing into cage structures “Scott et
al.(2001)”. Catalysts may even open cage structures when they attach to
them. From these initial clusters, tubular molecules grow into single-wall
20
carbon nanotubes until the catalyst particles become too large, or until
conditions have cooled sufficiently that carbon no longer can diffuse through
or over the surface of the catalyst particles. It is also possible that the
particles become well coated with a carbon layer that they cannot absorb
more and the nanotube stops growing. The SWNTs formed in this case are
bundled.
There are some striking, but not exact similarities, in the comparison of
the spectral emission of excited species in laser ablation of a composite
graphite target to that of laser-irradiated C60 vapour. This suggests that
fullerenes are also produced by laser ablation of catalyst-filled graphite, as is
the case when no catalysts are included in the target. However, subsequent
laser pulses excite fullerenes to emit C2 that adsorbs on catalyst particles and
feeds SWNT growth. However, there is insufficient evidence to conclude
this with certainty “Scott et al.(2001)” Laser ablation is almost similar to arc
discharge, since the optimum background gas and catalyst mix is the same as
in the arc discharge process. This might be due to very similar reaction
conditions required, and the reactions probably occur with the same
mechanism.
Figure II.8: Schematic drawings of a laser ablation apparatus.
21
Chapter II
II.3.1 SWNT versus MWNT
The condensates obtained by laser ablation contain carbon nanotubes and

carbon nanoparticles. In the case of pure graphite electrodes, MWNTs would
be synthesised, but uniform SWNTs could be synthesised if a mixture of
graphite with Co, Ni, Fe or Y was used instead of pure graphite. SWNTs
synthesised this way exist as 'ropes', see Figure II.9 “Maser et al.(1998),
Scott et al.(2001)”.
Laser vaporisation results in a higher yield for SWNT synthesis and the
nanotubes have better properties and a narrower size distribution than
SWNTs produced by arc-discharge.
Nanotubes produced by laser ablation are purer (up to about 90 % purity)
than those produced in the arc discharge process. The Ni/Y mixture catalyst
(Ni/Y is 4.2/1) gave the best yield.
Figure II.9: TEM images of a bundle of SWNTs catalysed by Ni/Y (2:0.5 at.
%) mixture, produced with a continuous laser.
The size of the SWNTs ranges from 1-2 nm, for example the Ni/Co catalyst
with a pulsed laser at 1470 °C gives SWNTs with a diameter of 1.3-1.4 nm
“Yudasaka et al.(1999)” In case of a continuous laser at 1200 °C and Ni/Y
catalyst (Ni/Y is 2:0.5 at. %), SWNTs with an average diameter of 1.4 nm
were formed with 20-30 % yield (see FigureII.9. “Maser et al.(1998)”.
22
II.3.2 Large scale synthesis of SWNT
Because of the good quality of nanotubes produced by this method, scientists

are trying to scale up laser ablation. However the results are not yet as good
as for the arc-discharge method, but they are still promising. In the next two
sections, two of the newest developments on large-scale synthesis of SWNTs
will be discussed. The first is the ‘ultra fast pulses from a free electron laser’
“Eklund et al.(2002)” method, the second is ‘continuous wave laser-powder’
method " Bolshakov et al.(2002)”. Scaling up is possible, but the technique
is rather expensive due to the laser and the large amount of power required.
II.3.3 Ultra fast Pulses from a free electron laser (FEL)method
While usually the pulses in an Nd:YAG system have width of approximately

10 ns, in this FEL system the pulse width is ~ 400 fs. The repetition rate of
the pulse is enormously increased from 10 Hz to 75 MHz. To give the beam
the same amount of energy as the pulse in an Nd:YAG system, the pulse has
to be focused. The intensity of the laser bundle behind the lens reaches ~5 x
10 “Damnjanovic et al.(1999)” W/cm2, which is about 1000 times greater
than in Nd:YAG systems. “Eklund et al.(2002)”.
A jet of preheated (1000 °C) argon through a nozzle tip is situated close
to the rotating graphite target, which contains the catalyst. The argon gas
deflects the ablation plume approximately 90° away from the incident FEL
beam direction, clearing away the carbon vapour from the region in front of
the target. The produced SWNT soot is collected in a cold finger. This
process can be seen in Figure II.10. The yield is 1,5 g/h, which is at 20 % of
the maximum power of the not yet upgraded FEL. If the FEL is upgraded to
full power and is working at 100 % power, a yield of 45 g/h could be
reached since the yield was not limited by the laser power.
Using this method the maximum achievable yield with the current lasers
is 45 g/h, with a NiCo or NiY catalyst, in an argon atmosphere at 1000 °C
and a wavelength of ~3000 nm. The SWNTs produced in bundles of 8-200
nm and a length of 5-20 microns has a diameter range 1-1.4 nm. “Eklund et
al.(2002)”
II.3.4 Continuous wave laser-powder method
This method is a novel continuous, highly productive laser-powder method

of SWNT synthesis based on the laser ablation of mixed graphite and
metallic catalyst powders by a 2-kW continuous wave CO2 laser in an argon
or nitrogen stream. Because of the introduction of micron-size particle
powders, thermal conductivity losses are significantly decreased compared
to laser heating of the bulk solid targets in known laser techniques. As a
result, more effective utilisation of the absorbed laser power for material
23
Chapter II
evaporation was achieved. The set-up of the laser apparatus is shown in

Figure II.11 “Bolshakov et al.(2002)”.
Figure II.10: Schematic drawings of the ultra fast-pulsed laser ablation

apparatus.
Figure II.11: (Left) The principle scheme of the set-up for carbon SWNT
production by continuous wave laser powder method (Right) HRTEM of a
SWNT-bundle cross-section.
24
II.4 Chemical vapour deposition
Chemical vapour deposition (CVD) synthesis is achieved by putting a

carbon source in the gas phase and using an energy source, such as a plasma
or a resistively heated coil, to transfer energy to a gaseous carbon molecule.
Commonly used gaseous carbon sources include methane, carbon monoxide
and acetylene. The energy source is used to “crack” the molecule into
reactive atomic carbon. Then, the carbon diffuses towards the supported
metal catalyst (usually a first row transition metal such as Ni, Fe or Co)
Carbon nanotubes are formed if the proper parameters are maintained.
Excellent alignment, as well as positional control on nanometre scale, can be
achieved by using CVD. Control of the diameter, as well as the growth rate
of the nanotubes can also be maintained. The appropriate metal catalyst can
preferentially grow single rather than multi-walled nanotubes “Sinnot et
al.(1999)”.
CVD carbon nanotube synthesis is essentially a two-step process consisting
of a catalyst preparation step followed by the actual synthesis of the
nanotube. The catalyst is generally prepared by sputtering a transition metal
onto a substrate and then using either chemical etching or thermal annealing
to induce catalyst particle nucleation. Thermal annealing results in cluster
formation on the substrate, from which the nanotubes will grow. Ammonia
may be used as the etchant “Ren et al.(1998a), Ren et al.(1999b), Yudasaka
et al.(1995a), Yudasaka et al.(1997b)”. The temperatures for the synthesis of
nanotubes by CVD are generally within the 650–900 °C range “Ren et
al.(1998a), Ren et al.(1999b), Yudasaka et al.(1995a), Yudasaka et
al.(1997b)”. Typical yields for CVD are approximately 30%. These are the
basic principles of the CVD process. In the last decade, different techniques
for the carbon nanotubes synthesis with CVD have been developed, such as
plasma enhanced CVD, thermal chemical CVD, alcohol catalytic CVD,
vapour phase growth, aero gel-supported CVD and laser assisted.
II.4.1 Plasma enhanced chemical vapour deposition
The plasma enhanced CVD method generates a glow discharge in a

chamber or a reaction furnace by means of high frequency voltage being
applied to both electrodes. Figure II.12 shows a schematic diagram of a
typical plasma CVD apparatus with a parallel plate electrode structure.
A substrate is placed on the earthed electrode. In order to form a uniform
film, the reaction gas is supplied from the opposite plate. Catalytic metals,
such as Fe, Ni and Co, are used typically on Si, SiO2, or glass substrates
using thermal CVD or sputtering. After nanoscopic fine metal particles are
formed, carbon nanotubes will be grown on the metal particles on the
substrate by the glow discharge generated from high frequency power.
25
Chapter II
Figure II.12: Schematic diagram of plasma CVD apparatus.
A carbon containing reaction gas, such as C2H2, CH4, C2H4, C2H6, CO is

supplied to the chamber during the discharge “Chen et al.(2002)”.
The catalyst has a strong effect on the nanotube diameter, growth rate,
wall thickness, morphology and microstructure. Ni seems to be the most
suitable pure-metal catalyst for the growth of aligned multiwalled carbon
nanotubes (MWNTs) “Huang et al.(2002)”. The diameter of the MWNTs is
approximately 15 nm. The highest yield of carbon nanotubes achieved was
about 50% and was obtained at relatively low temperatures (below 330° C)
“Chen et al.(2002)”
II.4.2 Thermal chemical vapour deposition
In this method Fe, Ni, Co or an alloy of the three catalytic metals is

initially deposited on a substrate. After the substrate is etched in a diluted HF
solution with distilled water, the specimen is placed in a quartz boat. The
boat is positioned in a CVD reaction furnace, and nanometre-sized catalytic
metal particles are formed after an additional etching of the catalytic metal
film using NH3 gas at a temperature of 750 to 1050°°C. As carbon nanotubes
are grown on these fine catalytic metal particles in CVD synthesis, forming
these fine catalytic metal particles is the most important process. Figure II.13
shows a schematic diagram of thermal CVD apparatus in the synthesis of
carbon nanotubes.
26
Figure II.13: Schematic diagram of thermal CVD apparatus.
When growing carbon nanotubes on a Fe catalytic film by thermal CVD,

the diameter range of the carbon nanotubes depends on the thickness of the
catalytic film. By using a thickness of 13 nm, the diameter distribution lies
between 30 and 40 nm. When a thickness of 27 nm is used, the diameter
range is between 100 and 200 nm. The carbon nanotubes formed are
multiwalled “Park et al.(2002)”.
II.4.3 Alcohol catalytic chemical vapour deposition
Alcohol catalytic CVD (ACCVD) is a technique that is being intensively

developed for the possibility of large-scale production of high quality single
wall nanotubes SWNTs at low cost. In this technique, evaporated alcohols,
methanol and ethanol, are been utilised over iron and cobalt catalytic metal
particles supported in zeolite. CNT generation is observed at a relatively low
minimum temperature of about 550 °C. It seems that hydroxyl radicals,
coming from reacting alcohol to catalytic metal particles, remove carbon
atoms with dangling bonds, which are obstacles in creating high-purity
SWNTs. The diameter of the SWNTs is about 1 nm. Figure II.14 shows the
ACCVD experimental apparatus.
The lower reaction temperature and the high-purity material obtained by
ACCVD technique guarantee the possibility of scaling production up at low
cost. Furthermore, the reaction temperature, which is lower than 600 °C,
ensures that this technique is easily applicable for the direct growth of
SWNTs on semiconductor devices already patterned with aluminium
“Maruyama et al.(2003)”.
27
Chapter II
Figure II.14: ACCVD experimental apparatus.
II. 4.4 Vapour phase growth
Vapour phase growth is a synthesis method of carbon nanotubes, directly

supplying reaction gas and catalytic metal in the chamber without a substrate
“Lee et al.(2002)”.
Figure II.15 shows a schematic diagram of a vapour phase growth
apparatus. Two furnaces are placed in the reaction chamber. Ferrocene is
used as catalyst. In the first furnace, vaporisation of catalytic carbon is
maintained at a relatively low temperature. Fine catalytic particles are
formed and when they reach the second furnace, decomposed carbon is
absorbed and diffused to the catalytic metal particles. Here, the growth of
carbon nanotubes occurs The diameter of the carbon nanotubes by using the
vapour phase growth are in the range of 2 – 4 nm for SWNTs “Ge et
al.(1994)” and between 70 and 100 nm for MWNTs “Lee et al.(2002)”.
Figure II.15: Schematic diagram of a vapour phase growth apparatus
28
II.4.5 Aero gel-supported chemical vapour deposition
In this method SWNTs are synthesised by the disintegration of carbon

monoxide on an aero gel-supported Fe/Mo catalyst. There are many
important factors that affect the yield and quality of SWNTs, including the
surface area of the supporting material, reaction temperature and feeding
gas. Because of the high surface area, the porosity and ultra-light density of
the aero gels, the productivity of the catalyst is much higher than in other
methods “Su et al.(2000)” . After a simple acidic treatment and oxidation
process high purity (>99%) SWNTs can be obtained.
When using CO as the feeding gas the yield of the nanotubes is lower but
the overall purity of the materials is very good. The diameter distribution of
the nanotubes is between 1.0 nm and 1.5 nm. The optimal reaction
temperature is approximately 860 °C.
In laser-assisted thermal CVD (LCVD) a medium power, continuous wave
CO2 laser, which was perpendicularly directed onto a substrate, pyrolyses
sensitised mixtures of Fe(CO)5 vapour and acetylene in a flow reactor. The
carbon nanotubes are formed by the catalysing action of the very small iron
particles. Figure II.16 shows the experimental set-up for laser-assisted CVD
“Alexandrescu et al.(2003)”.
By using a reactant gas mixture of iron pentacarbonyl vapour, ethylene
and acetylene both single- and multi-walled carbon nanotubes are produced.
Silica is used as substrate. The diameters of the SWNTs range from 0.7 to
2.5 nm. The diameter range of the MWNTs is 30 to 80 nm . “Alexandrescu
et al.(2003)”.
II.4.6 CoMoCat process
In this method, SWNTs are grown by CO disproportionateness at 700 – 950

°C. The technique is based on a unique Co-Mo catalyst formulation that
inhibits the sintering of Co particles and therefore inhibits the formation of
undesired forms of carbon that lower the selectivity. During the SWNT
reaction, cobalt is progressively reduced from the oxidic state to the metallic
form. Simultaneously, molybdenum is converted to the carbidic form
(Mo2C). Co acts as the active species in the activation of CO, while the role
of the Mo is possibly dual.
29
Chapter II
Figure II.16: Experimental set-up for laser-assisted CVD
It would stabilise Co as a well-dispersed Co2+ avoiding its reduction and

would act as a carbon reservoir to moderate the growth of carbon inhibiting
the formation of undesirable forms of carbon “Bachilo et al. (2003)”. It has
been found that one of the critical conditions for an effective reactor
operation is that the space velocity has to be high enough to keep the CO
conversion as low as possible. Figure II.17 shows a fluidised bed reactor for
a CoMoCat process. The most important advantage of fluidised bed reactors
is that they permit continuous addition and removal of solid particles from
the reactor, without stopping the operation.
This method can be scaled-up without losses in SWNT quality. By
varying the operation conditions, SWNTs can be produced with different
diameter ranges. The CoMoCat catalyst has a high selectivity towards
SWNTs, namely 80 – 90 %.
30
Figure II.17: Schematic diagram of a CoMoCat apparatus
31
Chapter III
Experimental I
Experimental Plant
III.1 Introduction
To study carbon nanotubes catalytic growth a semi-continuous

experimental plant was implemented and set up to allow the continuous
analysis of gaseous streams containing the carbon source. In the difference
from literature, a vertical quartz micro-reactor where a catalytic fixed bed is
crossed by reaction feed was employed. Continuous analysis of gaseous
streams, realised with NDIR continuous analysers, permitted to perform
carbon mass balance, to evaluate hydrocarbons conversion, the presence of
by-products, catalysts performances and lifetime.
III.2 Experimental Plant for nanotubes synthesis
A diagram of the experimental plant for CNT syntheses is shown in Fig

III.1. It consists of three sections:
feed section
reaction section
analysis section
All the gas pipes (¼’’ ed) are of Teflon, connections are made with
Swagelok union and two, three and four way Nupro valves. All the
connections are in stainless steel to avoid any corrosion due to the presence
of water in the reaction products.
The feed section allows the feeding of the carbon source using N2 as the
carrier gas. For each gas a mass flow controller (MFC) was used, in order to
assure a constant flow rate. Each gas came from cylinders (SOL SPA) with a
high purity degree.
Chapter III
Brooks measured flow controller (MFC) are used, able to operate with a
maximum pressure drop of 3 atm.
The working principle of the MFC is heat transport: the temperature
difference in a capillary, where a part of the gas is split, it is measured. This
temperature difference is proportional to the amount of heat adsorbed by the
mass gas for the equation:
ΔT = K • Cp • Φm
where:
ΔT = temperature difference.
Cp = specific heat of the gas.
K = dimensional constant.
Φm = mass flow.
The instrument’s temperature detector produces an electrical signal from
0 to 5 V (c.c.); this signal is sent to the control unit (MFC C.U.) which
converts the signal in volumetric flow. This control unit allows the mass
flow of the gases to be regulated.
The reaction section allows the preparation of carbon nanotubes in a
reactor, consisting of a quartz tube of 300 mm length and 16 mm internal
diameter. A portion of the reactor, placed in a vertical furnace, was filled
with a thin layer of catalyst particles. An external quartz tube, internal
diametre 35 mm, permitted the preheating of the reactants stream. In order to
measure the temperature inside the reactor, a thermocouple is placed on a 4
mm internal diameter quartz shield, coaxial to the reactor. The reactor is set
in a vertical electrically heated oven. The oven temperature and the control
parameters are adjusted by a temperature programmer-controller, connected
to a type K thermocouple located inside the reactor. A temperature reader
connected to a second thermocouple measures the temperature of the
catalytic bed inside the reactor.
In the reaction section a system of valves allows the reactants to go to the
reactor, and the products to the analysis section, or, in the bypass position,
the reactants to the analysis section to verify the reactant composition. In
bypass mode an independent line is used to send air or nitrogen to the reactor
for the thermal pretreatment of the catalysts, or to wash the reactor.
For catalytic test in the presence of water, vapour is added into the
reactants by a glass saturator closed with a porous set immersed in distilled
H2O. He is sent to the reactor through the saturator, and by changing
temperature and He flow, it is possible to obtain different concentrations in
the reaction feed.
In the analysis section continuous analysers (ABB) Fig. III.2 mean that
C2H4, C2H2, CH4 (URAS 14) and H2 (Caldos 17) concentrations in the
effluent stream on line during the reaction can be monitored.
The URAS 14 (Infrared analyser module) uses a NDIR absorption
process, which is based on resonance absorption at the characteristic
vibration rotation spectrum bands of non-elemental gases in the middle
34
Experimental I – Experimental plant
infrared range. Because of their bipolar moment, the gas molecules interact
with infrared emissions. The photometer is characterized by high stability
and selectivity.
The analyzer has gas-filled opto-pneumatic detectors which have been
optimized for each application. This enables higher sensitivity, a wider range
of sample components and reduced cross-sensitivity to interfering
components. Detector filling corresponds to the gas being measured.
This means that the detector provides optimal sensitivity and high
selectivity for the component of interest. Calibration is possible via the
internal calibration cells which do not require expensive bottled test gas
mixtures. This greatly reduces operation and maintenance costs.
BYPASS
M.F.C
He
ANALYZERS
C2H4/He
C2H2/He
C2H4
CH4/He
VENT C2H2
H2
T.C
o OO
Oo o
1 2 oOOo
o O o
3 4 CH4
MFC control unit H2 O N2/ Air H2

COMPUTER
Figure III.1: Experimental plant

The Thermal conductivity analyzer module Caldos 17 exploits the
varying thermal conductivities of different gases. Measurement is carried out
by means of a silicon sensor that allows especially rapid measurement and
extremely small measuring ranges.
35
Chapter III
Figure III.2: Uras 14 and Caldos 17 ABB analysers
36
Chapter IV
Experimental II
Effect of alumina phases and
process parameters in the
MWNT growth
IV.1 Introduction
The CCVD of hydrocarbons over supported metal catalysts is an effective

way to synthesise carbon nanotubes.
The peculiar ability of metals to promote the CNT growth is related to their
catalytic activity for the decomposition of the carbon feedstock (typically a
hydrocarbon), that precedes the CNT growth “Ebbesen et al.(1992),
Ciambelli et al.(2005), Kumar et al.(2005), Das et al.(2006), Yudasaka et
al.(1995), Li et al.(2005)”. The role of the support material is to disperse the
active phase, provide the porous structure, prevent sintering, improve
mechanical strength and promote catalysis. Although these properties have
been partially investigated their influence is not yet clear “Dupuis et
al.(2005)”, since the active phase can yield completely different results upon
CCVD when supported on different materials.
Alumina and aluminium hydroxides have been recently reported as very
effective catalytic supports for CNT preparation “Nagaraju et al.(2002),
Kathyayini et al.(2006), Buang et al.(2006), Aghababazadeh et al.(2006),
Kibria et al.(2001)”.
In this perspective, different aluminium hydroxides have been investigated
as supports of Co, Fe for the synthesis of CNT, to find out the most effective
catalyst and to investigate the influence of the support nature on the catalyst
activity. CNT characterization by thermogravimetry, Raman spectroscopy,
scanning and transmission electron microscopy, has been performed. Very
high CNT selectivity at high carbon and reaction yields has been obtained
with gibbsite and bayerite.
Chapter IV
IV.2 Experimental
Co, Fe catalysts (2.5 wt.% of each metal) were prepared by dry (D) or
wet (W) impregnation with cobalt acetate and iron acetate solution of (Ba)
bayerite (α-Al(OH)3), (B) boehmite (γ-AlO(OH)), (G) gibbsite (γ-Al(OH)3)
and for comparison (γA) γ-alumina (γ-Al2O3). The samples were
successively dried at 393 K for 20 or 720 min. For CNT synthesis, a mixture
of ethylene in helium (10% v/v) was fed to a continuous flow microreactor
for 10, 30, 60 and 120 min. The gas flow rate was 78 or 200 (stp) cm3 /min,
the catalyst mass 100, 200, 250 or 300 mg.
Gradual heating and fast heating were used as procedures for catalysts
preheating. The composite samples obtained from the synthesis are
denominated as indicated in Table IV.1.
In gradual heating (GH): reactor temperature increases from 298 K up to
973 K (10 K/min) under helium flow, then reaction gas is introduced for 10,
30, 60 and/or 120 min.
In fast heating (FH) reactor temperature is kept constant at 298 K for 4
min and at 973 K for 6 min under helium flow. Four reaction times were set:
10, 30, 60 and/or 120 min.
The composite samples obtained from the synthesis are denominated as
indicated in Table IV.1.
Thermogravimetric analysis (TG–DTG) at 10 K/min heating rate in
flowing air was performed with a SDTQ 500 Analyser (TA Instruments).
Scanning electron microscopy (SEM) pictures were obtained with a LEO
420 microscope.
Transmission electron microscopy (TEM) images were performed using a
Philips CM30T electron microscopy with a LaB6 filament as source of
electrons operated at 300 kV. Raman spectra were obtained at room
temperature with a microRaman spectrometer Renishaw inVia (514 nm
excitation wavelength).
IV.2.1 TG, DTG evaluation
Deposited carbon yield, reaction yield and CNT selectivity (Tab.IV.2)

were calculated “Ciambelli et al.(2004b), (2005c)” with the help of TG-
DTG curves reported in Fig.IV.1. In fact, in air flow, carbon combustion
occurs in the range 350-700°C. The TG oxidation profiles show mainly two
weight losses: the first due to amorphous carbon, that burns at lower
temperature, the second attributed to CNT combustion.
In particular, carbon deposit yield and reaction yield were calculated:
mcd
% carbon deposit yield = 100 x (1)
mcat
where mcat is the dry catalyst weight and mcd the deposited carbon mass.
38
Experimental II
The amount of deposited carbon was evaluated as the weight loss in the
temperature range where carbon burns in air, and mcat is the weight left at
800 °C.
mcd
% reaction yield = 100 x (2)
mci
where mcd is the deposited carbon mass (TG evaluated) and mci the mass of
fed carbon.
MWNT selectivity=100·m2 / (m2+m1) (3)
where m1 and m2 are respectively the mass loss in the first and second
oxidation steps during TG experiments. The amounts m1 and m2 were
evaluated by fitting the DTG profiles with two Gaussian curves centred on
the DTG peaks and measuring the areas under the curves, that are
proportional to the mass losses. For the TG experiments, 5 mg of reaction
product was used.
Table IV.I: Synthesis conditions with the different supports, carbon yield,
MWNT selectivity and reaction yield obtained by TG evaluation.
Sample Catalyst Drying time Reaction Catalyst Feed
preparationa (min)d time mass flow
- Reaction (min) (mg) (Ncc/min)
pretreatment
(b) (c)
BWs30100200 W-GH S 30 100 200

BWs60100200 W-GH S 60 100 200
BWs30200200 W-GH S 30 200 200
BWs60200200 W-GH S 60 200 200
BDl60200200 D-GH L 60 200 200
BWs6020078 W-GH S 60 200 78
BDl6020078 D-FH L 60 200 78
BWs60300200e W-GH S 30 300 200
GDl6010078 D-FH L 60 100 78
GDl6020078 D-FH l 60 200 78
GDl6025078 D-FH l 60 200 78
GDl6030078 D-FH l 60 300 78
GDl1020078 D-FH l 10 200 78
GDl3020078 D-FH l 30 200 78
GDl12020078 D-FH l 120 200 78
GDl60200200 D-FH l 60 200 200
GWs60200200 W-GH s 60 200 200
BaDl6020078 D-FH l 60 200 85
BaWs6020078 W-GH s 60 200 200
γADl6020078 D-FH l 60 200 85
γADl60200200 D-FH l 60 200 200
γAWs60200200 W-GH s 60 200 200
a) Wet impregnation (W); Dry impregnation (D).
b) Gradual heating (GH):
c) Fast heating (FH)
d) 15 min drying catalyst time (s), 720 min drying catalyst time (l).
e) BWs60300200 has been prepared by adding water 10% v/v to the feed flow.
39
Chapter IV
Table IV.2: Synthesis conditions with the different supports, carbon

yield, MWNT selectivity and reaction yield obtained by TG evaluation
Sample Carbon yield (%) MWNT Reaction
Selectivity Yield
(%) (eq.3) (%) (eq.2)
BWs30100200 66,7 61,6 7,8
BWs60100200 86,0 65,8 5,0
BWs30200200 116,9 69,1 27,3
BWs60200200 252,6 73,5 29,5
BDl60200200 89,4 61,1 10,4
BWs6020078 135,2 68,8 40,4
BDl6020078 40.3 39.2 12,1
BWs60300200e 71.0 - 12.4
GDl6010078 189.9 ~ 100 24.6
GDl6020078 278.4 ~ 100 72.2
GDl6025078 226.5 ~ 100 73.4
GDl6030078 190.4 ~ 100 74.0
GDl1020078 47.8 ~ 100 74.3
GDl3020078 150 ~ 100 77.8
GDl12020078 282.1 ~ 100 36.6
GDl60200200 163.2 ~ 100 16.5
GWs60200200 105 ~ 100 10.6
BaDl6020078 260.1 ~ 100 69.3
BaWs6020078 107.2 ~ 100 11.7
γADl6020078 71.8 29.7 25.8
γADl60200200 79.5 30.5 11.1
γAWs60200200 34.5 53.8 4.8
For the different prepared catalysts results are summarised in Table IV.2.
Boehmite samples. For B samples obtained on wet impregnated catalyst
(BWs) both carbon yield and CNT selectivity increase by increasing catalyst
mass and synthesis time, while reaction yield decreases. Larger catalyst mass
gives higher CNT selectivity, due to better use of hydrocarbon fed, that
lowers its partial pressure and homogeneous reaction rate. CNT selectivity
increases with time as result of decreased amorphous carbon deposition rate.
Reaction yield decrease is likely due to higher hydrocarbon decomposition
rate than CNT growing rate.
Sample BWs60300200, obtained by adding water 10% v/v in the gas
stream, showing a single DTG peak at low temperature (Fig.IV.1a-insert),
has been used as a carbon sample material which doesn't contains nanotubes.
Gibbsite samples. Carbon oxidation occurs in a single loss step
(Fig.IV.1b). The DTG peaks are sharper and shifted to higher temperatures
compared to B samples, due to the high purity and quality of CNTs. The
reaction yield (Tab.IV.1) is higher than for B samples. Increasing of reaction
time results in enhanced carbon yield and higher degree of graphitization,
which could be explained by up-shifted DTG peak temperature. A reaction
time of 120 minutes causes abrupt reduction of reaction yield, indicating
decreased catalytic activity.
Moreover in table IV.2 we can observe that the carbon yield was higher
at a catalyst mass of 200 mg while it was reduced by further mass increase.
40
Experimental II
Bayerite samples. Very good performances are given by bayerite

supported syntheses showing similar yields and selectivity to those obtained
with gibbsite supported ones. TG results (Fig. IV.1c) and Raman spectra (not
reported) of Ba samples indicate a CNT purity quite equivalent to G
samples.
Г-alumina samples. Performances comparison and characterization of the
reaction products show that aluminum hydroxides are better supports than
aluminum oxide for CNT CCVD.
The higher performances of catalyst based on aluminium hydroxides are
probably due to the effective interaction of the -OH rich surface with metal
particles precursor during preparation phase that enhances the grafting of
metal particles to the support surface, after catalyst pretreatment.
The comparison of the results relevant to gibbsite and boehmite (Table
IV.1) indicates that starting from gibbsite, longer catalyst drying time, dry
impregnation and fast heating are preferable operating conditions.
However, for boehmite the best operating conditions are wet
impregnation of the support, a short catalyst drying time and gradual heating
reaction pretreatment. These different conditions are clear evidence of the
role of support in the catalyst for CNT synthesis. Further work is necessary
to confirm the promising performance of bayerite.
A further observation is that all hydroxides are transformed to oxides
under CNT synthesis conditions. A systematic investigation of the three
catalytic systems is currently in progress. Our syntheses, obtained through
gibbsite and bayerite supported Co and Fe, exhibit high values of carbon and
reaction yield, in particular considering the use of less reactive ethylene as
carbon source in comparison to aluminium hydroxide Co and Fe supported
synthesis under acetylene flow “Nagaraju et al.(2002), Kathyayini et
al.(2006)”. In scientific publications there are several examples of CVD
CNT synthesis on similar catalysts “Kumar et al.(2005), Das et al.(2006),
Yudasaka et al.(1995), Li et al.(2005), Dupuis et al.(2005), Nagaraju et
al.(2002), Kathyayini et al.(2006)”, also characterized by high carbon
nanotubes yield.
However, a comparison between the different results is not immediate
because they were obtained with different carbon feedstocks, metal loadings,
synthesis temperatures, reaction times, etc.
The comparison of the results relevant to gibbsite impregnated with
different metals loading is reported in Table IV.3.
Table IV.3: Carbon yield obtained by TG evaluation for samples prepared

with different metal loading.
sample T (°C) % Fe % Co Carbon
yield (%)
GDl30200781 700 2.5 0 1
GDl30200782 700 2.5 2.5 150
GDl30200784 700 5 5 35
41
Chapter IV
GDl30200782 catalyts, at 2.5 wt% of iron and 2.5 wt% of cobalt, results in
the highest carbon yield.
IV.2.2 SEM characterization
SEM images show the morphology of the tubes, allowing to measure

their geometric characteristics.
BWs30100200 (Fig.IV.2a) is mostly constituted of CNT bundles.
Moreover, the surface of some boehmite particles is covered by a small
number of CNT and not by bundles (areas in Fig.IV.4a indicated by arrows),
suggesting a partial lack of uniformity of boehmite impregnation, which
cause also the deposition of amorphous carbon, as indicated by oxidation
Figure IV.1: TG-DTG curves of samples obtained by supported synthesys

with: (a) bohemite; (b) gibbsite; (c) γ-alumina; (d) bayerite.
profiles in TG tests. Increasing reaction time and catalyst mass longer
CNT bundles were obtained.
The image of BWs60200200 (Fig.IV.2d) shows catalyst particles,
indicated by arrows, located at the end of the nanotubes, indicating a weak
interaction between active phase and boehmite. On BWs60300200 (Fig.IV.2c)
no CNT were observed, in agreement with TG results.
42
Experimental II
Figure IV.2: SEM images of: BWs30100200 (a, b); BWs60300200 (c);
BWs60200200 (d).
Fig.IV.3 of G samples shows CNT homogeneously distributed; nanotubes
bundles starting from the catalyst are grown in the direction of gas flow.
Catalyst particles (support + metals) are not visible. Higher resolution
SEM images give evidence of the bundles organisation, consisting in a dense
network of tangled carbon nanotubes. Increasing catalyst mass from 100 to
200 mg the bundle length increase up to 100 μm. A further mass increase
until to 300 mg doesn’t lead to longer carbon nanotubes bundles.
By comparing SEM images of Fig.IV.3c and Fig.IV.3d we can observe
that starting from 10 min, a further increase of reaction time results in longer
carbon nanotubes, while reaction time longer than 60 min determines only a
small increase in the nanotubes length (Fig.IV.3e). The observed formation
of a few agglomerates of carbon comes from homogeneous decomposition
(Fig.IV.3f).
The coiled morphology of the ends of nanotubes bundle, suggests a
different catalyst deactivation mechanism .
Samples from bayerite show similar morphology observed on samples
from gibbsite. By contrast γ-alumina doesn’t exhibit CNT bundles.
43
Chapter IV
IV.2.3 Transmission electron microscopy characterization
Fig.IV.4a shows a typical TEM picture of BWs30100200. Nanotubes with

a diameter ranging from 9 to 23 nm are visible together with amorphous
carbon indicated by white arrows.
Figure IV.3: SEM images of: GDl6020078 (a); GDl6030078 (b); GDl1020078
(c); GDl3020078 (d), GDl12020078 (e, f).
If we compare Fig.IV.4a and Fig.IV.4b relevant to a TG residue collected
at an intermediate temperature between the two DTG peaks, we can notice
that the amorphous carbon areas, observed in the first image, are absent in
the second picture, giving experimental support to the attribution of the two
44
Experimental II
weight loss steps of TG curves. GDl6020078 and GDl3020078 are shown in

Fig.IV.4c and Fig.IV.4d, 4e respectively. The tube have an entangled
structure, a small number of catalytic particles are present in the hallow core
of the nanotubes. The external diameter of GDl6020078 is in the range 9-22
nm, while the internal diameter varies from 5 to 10 nm. Nanotubes
synthesised in shorter time show a reduced outer diameter in the range 6-16
nm, as previously observed “ Ciambelli et al. (2005)”.
Figure IV.4: TEM images of: BWs30100200 (a); TG residue at 510°C of

BWs30100200 (b); GDl6020078 (c); GDl3020078 (d, e).
IV.2.4 Raman spectroscopy
Raman spectra of BW and GD samples show the typical D, G, 2×D peaks,

centred at 1364, 1594 and 2702 cm-1, respectively. The intense G peak
indicates the presence of crystalline graphite carbon, while the D peak can be
attributed to amorphous carbon, defects in curved graphene sheet and finite
size of tubes crystalline domains. The 2×D peak, which is indicative of a
clean sample “Chuang et al.(2004)”, appears at the position of doubling
frequency of the D-line peak. The Raman spectra support the findings from
TG analysis, as shown for example in Fig.IV.5: the ID/IG intensity ratio, a
measure of disorder amount, decreases with catalyst mass increase and
reaction time from 1 (BWs30100200) to 0.74 (BWs60200200), due to the CNT
selectivity increase (Table IV.1). Moreover, after TG stopped at 510°C (i.e.,
after amorphous carbon burning) BWs30100200 has an ID/IG ratio of 0.67.
BWs60300200, that burns at low temperature, and shows (Fig.IV.5) ID/IG = 1,
without the 2×D band “Chuang et al. (2004)” and a down-shift of D-line
45
Chapter IV
together with an up-shift of G band “Jawhari et al.(1995)”, indicating a low

crystalline quality carbon (see TableIV.3 and selectivity).
The ID/IG intensity ratio of G samples is very similar (~0.8) for all
samples and not affected by changes in synthesis time and catalyst mass,
confirming the TG-DTG evaluations.
Figure IV.5: Raman Spectra of samples BWs30100200, TG residue at 510°C

of BWs30100200 and BWs60300200.
46
Chapter V
Experimental III
On-line analysis
V.1 Introduction
The most of literature on chemical vapour deposition (CCVD) method for

synthesis of CNT was devoted to investigate catalyst composition and
carbon sources, while few paper deal with operating conditions of CNT
synthesis reactor. Many efforts have been dedicated to understand the best
active phases, support, carbon precursor, flow rates, operative conditions,
but in-situ diagnostic for CNT growth remains difficult to implement in a
CVD reaction owing high temperatures and reactive atmospheres.
To explore CNT kinetics growth a common method is to track the CNT
weight or height at specific time. Several limitations are due to changing of
growth rate during the time so only an average growth rate can be evaluated.
In addition, overall kinetics arises also from transport effects, and must be
taken into account for kinetics parameters calculations.
Horizontal furnaces, with catalyst bed placed in quartz boat is the more
diffused configuration for scientific investigations, but suffers of diffusive
limitations, both longitudinal, along the reactor axes, and vertical, diffusion
into the bed height “Gommes et al.(2004)”.
With the aim to optimise the process, a large range of operative
conditions have been explored in a more “classic” fixed bed with an
orthogonal gas flow. Particular attention has been devoted to parameters
such as catalytic activity and the lifetime of Co-Fe-supported gibbsite, which
emerged as high promising catalyst “Ciambelli et al.(2007)”, for the
synthesis of MWNTs, by monitoring the effluent stream with handy and by
the immediate response on-line ABB analysers.
This system permits that the rection rate could be inferred from exhaust
gas composition. Very high carbon and reaction yield have been obtained.
Catalyst activity by employing a fixed bed with an orthogonal gas flow, was
Chapter V
higher and more stable for longer period as compared with previous
published works “Ago et al., (2006); Pirard et al., (2007)”.
On the nanotubes produced, a characterisation to correlate their properties
with the reactor operative conditions was also performed and showed that
our system results in high quality carbon nanotubes being obtained.
V.2 Experimental
The syntheses were performed in the experimental plant described in

Chapter IV, equipped also with the on-line ABB analysers that permit the
monitoring of C2H4, C2H2, CH4 and H2 concentrations in the effluent stream
on line during the reaction. Co, Fe catalysts (2.5 wt% of each metal) were
prepared by dry impregnation with a cobalt acetate and iron acetate solution
of gibbsite (γ-Al(OH)3). The catalyst was dried at 393 K for 720 min, and
preheated before synthesis at 70 K/min up to 973 K under N2 flow. For the
CNT synthesis a mixture of ethylene in nitrogen was fed to a continuous
flow microreactor at 923-973-1023 K. Runtime of 30 min was chosen
because the absence of side-reactions, longer times also have been explored.
Gas flow rate ad catalyst mass were kept constant (120 (stp)cm3/min and
400 mg), different percentage of the hydrocarbon (5% v/v, 10% v/v, 15%
v/v, 20% v/v) were tested. In the following, samples were named GX_Y
where X is ethylene concentration (volume percentage) and Y synthesis
time. Gas flow rates were controlled by calibrated Brooks mass flow
controllers.
Thermogravimetric analysis (TG-DTG) at 10 K/min heating rate in
flowing air was performed with a SDTQ 500 Analyser (TA Instruments).
Scanning electron microscopy (SEM) pictures were obtained with a LEO
1525 microscope equipped with EDX analysis. Transmission electron
microscopy (TEM) images were performed using a Philips CM30T electron
microscopy with a LaB6 filament as source of electrons operated at 300 KV.
Raman spectra were obtained at room temperature with a microRaman
spectrometer Renishaw inVia (514-785 nm excitation wavelength).
V.3 Results and discussion
V.3.1 Catalyst characterisation
Field Emission Scanning Electron microscopy (FESEM) equipped with

EDX analysis, X-ray diffraction, Thermogravimetrical and Raman
Spectroscopy analyses were used for the characterisation of catalyst and
support.
FESEM images permit to evaluate the morphology of the catalyst at
different preparation stages, particles dimensions and state of aggregation.
48
Experimental III
The EDX maps give information about the metals disposition both
topographically and quantitatively. Fig. V.1 shows the as prepared catalyst
constituted of agglomerates of flat and faceted particles of gibbsite with a
mean size in the range 1-6 μm, with metals distributed on the support,
mainly near the contact surfaces of gibbisite grains in the aggregate. Fig.V.2
shows the homogeneous distribution of the metals on the support after the
catalyst pretreatment, at higher magnification, not showed here, low amount
of big metals particles can be observed on the support surfaces.
In Fig.V.3 the catalyst after a synthesis and successive oxidation of the
produced nanotube can be observed, a random distribution of the metals
either on the support and on the surrounding area is visible.
Metal particles appear to be removed from both nanotubes hollow core
and support by oxidation treatment. In particular, Fe particles are more
homogeneously distributed than Co, instead concentrated in few image
zones, and in lower amount.
This result suggests that part of Co is dispersed with dimensions smaller
with respect to SEM-EDX sensitivity. EDX quantitative analysis, of the
catalysts after drying, shows that the metals concentration in the first 1-2 μm
(penetration depth of the probe used for EDX measurements) of the support
exceed the 2.5 wt%, chosen for impregnation, resulting equal to 12% for Fe
and 16% for Co, indicating a metals concentration gradient along the support
particles body and location of metals on the surface.
Furthermore, the evidence of the higher concentration of Co suggests
high dispersion or a deeper penetration of Fe. At the end of the pretreatment
the concentration of the two metal in the first micrometers of the support
porosity results slightly increased, remaining substantially unmodified the
relative proportions.
49
Chapter V
Figure V.1: FESEM image of impregnated and dried catalyst, the inserts
show the EDX maps of the particles agglomerate in the image.
50
Experimental III
Figure V.2: FESEM image of catalyst after synthesis pretreatment, the

inserts show the EDX maps of the image zone.
51
Chapter V
Figure V.3: FESEM image of catalyst after synthesis and successive

oxidation of CNT, the inserts show the EDX maps of the image zone.
52
Experimental III
The results of the TG-DTG analysis performed in helium on the gibbsite

supports were shown in Fig. V.4. The total mass loss observed on TG curve
in the temperature range 220-820 °C was 34.2 %, this value is in agreement
with the theoretical value 34.6 % for the reaction (1). The dehydration of the
sample was characterized by three weight loss with DTG peaks at 228, 285
and 493 °C.
Al(OH)31/2Al2O3+3/2H2O (1)
These peaks were interpreted by several authors “Balek et al. (2003)” who
agree on the general interpretation. For instance, the first peak is usually
considered to correspond to a partial transformation of gibbsite into
boehmite, according to the Scheme (2) given by Mackenzie:
Al(OH)3χ-Al2O3+γ-AlO(OH) (2)
This first DTG peak corresponds to a mass loss of ~7.4 % (TG curve in
Fig. V.4). The second, more intense DTG peak at 285 °C, was accompanied
by a mass loss of ~22.1 %.
A further mass loss of ~5.1 % was completed at 820 °C and corresponds
to the total dehydration of boehmite and formation of a second type of
anhydrous aluminium oxide.
The latter dehydration step can be formally expressed by the chemical

reaction (3).
AlO(OH)1/2Al2O3+1/2H2O (3)
This residual transformation is reflected by the weight loss with DTG

peaks at 493 °C.
Figure V.5 reports the X-ray diffraction spectra of gibbsite support and
catalyst at different steps of CNT synthesis. Catalyst after impregnation and
drying kept the spectrum of γ-Al(OH)3, no Fe and Co are visible, after
pretreatment the appearance of γ-Al2O3 is registered even if the spectrum
shows also reflection of boehmite and probably of θ-Al2O3. Finally the
catalyst after synthesis is essentially γ-Al2O3 with a certain quantity of
residual AlO(OH).
Typical Raman bands of gibbsite is showed, in the low-wavenumber
region, between 200-1200 cm-1, “Ruan et al. (2001)” in Fig.V.6. Hydroxyl
deformation modes of gibbsite are observed in the range 916-1051 cm-1.
Major bands in the low-wavenumber Raman Spectrum of gibbsite are found
at 1019, 893, 812, 710, 568, 539, 506, 429, 395, 381, 324, 306, 255, and 242
cm-1. The bands with greatest intensity are at 568, 539 and 323 cm-1. The 568
and 539 cm-1 bands are attributed to Al-O-Al deformation and the 323 cm-1
band with a shoulder at 306 cm-1 is ascribed to Al-O stretching vibrations.
53
Chapter V
Figure V.4: TG-DTG curves obtained under helium flow of gibbsite
Figure V.5: X-ray diffraction patterns of gibbsite, catalyst after

pretreatment, catalyst after synthesis, γ-Al2O3.
54
Experimental III
Figure V.6: Raman spectrum of support (gibbsite)
V.3.2 On-line analysis of effluent gas
A typical example of the profiles of C2H4, C2H2, CH4 and H2

concentrations during CNT growth tests was shown in Fig. V.7, for 30 min
synthesised samples at 700°C and 15% v/v of ethylene.
We can distinguish almost four zones:
(1) In this phase we prepare and stabilize the reaction stream, the reaction
gas was feed to the analysers, all the profiles are closed on zero except for
the initial ethylene concentration that is 15% v/v.
(2) the reaction starts, we first can observe that all the profiles come to
zero for the short period of time necessary to get the gas to the reactor,
through the same and then return to the analysis;
(3) after about 10 min the ethylene concentration stabilizes on the 0.25%
and, in correspondence, the hydrogen concentration in the effluent stream
shows an opposite trend: it starts to increase at the beginning of reaction
reaching the 24% v/v. No significant CH4 and C2H4 traces are observed
during the entire running time, at the chosen temperature;
(4) the reaction is stopped, all the profiles return on phase 1 values.
The similar behaviour is shown by G5_30, G10_30 and G20_30 for
which in particular the final concentration of ethylene is lower than the 5%
of the initial one. Hydrogen concentration reaches a plateau except in the
case of G20_30, after 18 min starts to decrease slowly.
Blank measurements have been performed in order to take into account
the behaviour of the feed in the syntheses operative conditions in the absence
of the catalyst, by recoding the evolution of the exhaust gas composition
from the feed gas composition. The tests have been performed with an empty
reactor, in the presence of a filling consisting of non-impregnated gibbsite,
55
Chapter V
Figure V.7: Profiles of C2H4, C2H2, CH4 and H2 concentrations during CNT
growth tests for samples G15_30
Figure V.8: Profiles of C2H4, C2H2, CH4 and H2 concentrations duringblank

test.
56
Experimental III
for all cases, the results are shown in Fig. V.8, and the reactor and filling
result light grey in colour.
It is visible that a weak homogeneous ethylene decomposition occurs, with
formation of pyrolitic carbon, hydrogen and methane. The phenomenon
amount depends on the hydrocarbon partial pressure, but it’s of low extent,
C2H4 conversion was stable at about 6%.
In Figure V.13 b is reported the results of TG-DTGanalysis, performed
on gibbsite coming from a blank test analysis: the oxidation of the carbon
happens in a one loss step centred at 595°C, long before the temperature of
CNT combustion (see Fig. V.13a TG-DTG section below), suggesting that in
the blank measurement the homogeneous decomposition of ethylene leads to
the formation of non-CNT carbon, the hypothesis has confirmed by SEM
observation.
The ethylene conversion and hydrogen yield have been calculated by
considering the ethylene conversion to carbon and hydrogen as the main
reaction:
C2H4 → 2 C + 2 H2
In relation to this reaction and initial feed composition, expansion volume

factor εC2H4 can be calculated. Ethylene conversion and hydrogen yield can
be expressed as:
C
1 − 0C 2 H 4
C C 2H 4 (1 + ε C 2 H 4 xC 2 H 4 ) ∗ C H 2
X C 2H 4 = ; RH 2 =
ε *C 2CC0 2 H 4
1 + C 2 H 40 C 2 H 4
C C 2H 4
where C means concentration and apex 0 is referred to initial one.

The agreement between C2H4 conversion and H2 yield curves (Fig.V.9,
Fig.V.10) validates the previous hypotheses. Ethylene conversion reaches a
plateau, after the first synthesis minutes, at higher values as the ethylene
content in the reactor feed increases, from 0.9 of G5_30 to 0.97 of G20_30.
A particular phenomenon is observed for G20_30 after 18 min of synthesis
the curves slightly deverge, suggesting the occurrence of other reactions
than the production of H2 and C. For G5_70 we observe the same
phenomenon even if at longer time and in a lower measure. At further time
increases a deactivation phenomenon starts (Figure V.11).
57
Chapter V
Figure V.9: Ethylene conversion and hydrogen yield for G5_30, G10_30.
58
Experimental III
Figure V.10: Ethylene conversion and hydrogen yield for G15_30, G20_30.
59
Chapter V
100
90
80
X_C2H4, R_H2 (%)

70
60
X_C2H4
50
R_H2
40
30
20
10
0
0 5 10 15 20 25 30 35
time (min)
100
90
80
X_C2H4, R_H2 (%)
70
60
50 X_C2H4
40 R_H2
30
20
10
0
0 10 20 30 40 50 60 70 80
time (min)
100
90
X_C2H4, R_H2, (%)
80
70
60
50
X_C2H4
40 R_H2
30
20
10
0
0 20 40 60 80 100 120 140 160
time ( min)
Figure V.11: Ethylene conversion and hydrogen yield for G5_30, G5_70,
and G5_140
60
Experimental III
V.3.3 TG, DTG evaluation
Carbon oxidation occurs in a single loss step (Fig.V.13a) and in the same
temperature range for all the samples. Different carbon contents are
observed; the higher the hydrocarbon content in the reactor feed, the higher
the carbon content observed. To compare results from different syntheses,
deposited carbon yield and reaction yield (Tab.VI.1) were calculated
“Ciambelli et al.(2004a), (2004b)” with the help of TG-DTG curves of
Fig.VI.12.
In particular, carbon deposit yield and reaction yield were calculated:
mcd
% carbon deposit yield = 100 x (1)
mcat
mcd
% reaction yield = 100 x (2)
mci
where mcat is the weight of the dry catalyst, mcd the deposited carbon
mass and mci the mass of fed carbon.
The amount of deposited carbon was evaluated as the weight loss in the
temperature range were carbon burns in air, and mcat is the weight left at
800°C.
For comparison reaction yield was also evaluated on the base of on-line
analysis results, as the ratio between the area representative of all ethylene
fed and that of converted ethylene (see Table V.1 also).
The increase of ethylene partial pressure in the feed is followed by an
ethylene conversion increase, which means, at the same catalyst mass, an
increase of the reaction yield and a more than proportional increase in the
deposited carbon yield. Reaction yield values evaluated by TG-DTG are in
keeping with on-line analyses.
Table V.1: carbon yield, MWNT selectivity and reaction yield obtained by
TG evaluation.
Sample Carbon Reaction yield Reaction yield % MWNT

yield % % evaluated on the selectivity
(TG-DTG base H2 yield
evaluation) (on-line analysis)
G5_30 66 89 86 ~100
G10_30 134 90 89 ~100
G15_30 212 95 96 ~100
G20_30 268 90 91 ~100
61
Chapter V
Finally in Fig.V.12 the results of a TG and DTG analysis performed on G5-

30 taken in different reactor zones are shown and we can see that the TG and
DTG curves are similar and generally overlap indicating that the carbon
nanotubes mass is uniform.
Figure V.12: TG–DTG curves c) of sample G5_30 taken at different heights

of the as grown bed a). A catalyst image b).
62
Experimental III
Weight
(%)
Figure V.13: TG–DTG curves of samples G5_30, G10_30, G15_30,

G20_30, G5_140 (a), TG–DTG curves of carbon-gibbsite composite
obtained as blank reference.(b).
63
Chapter V
V.3.4 SEM characterisation
SEM images show the morphology of the tubes, allowing their geometric
characteristics to be measured “Ciambelli et al.(2006)”. Fig. V.14 shows
homogeneously distributed CNTs as nanotubes bundles starting from the
catalyst (support+metals). Increasing synthesis time increases bundle length,
as also observed increasing the ethylene partial pressure in feed gas: longer
bundle are obtained as increases the amount of deposited carbon.
Figure V.14: SEM images of G5_140 and G5_30 at 500 X.
64
Experimental III
Table V.2: ID/IG intensity ratio at two different excitation wavelength for
CNT produced at increased ethylene partial pressure and at different times
Sample 514 nm 785 nm
ID/IG ID/IG
G5_30 0.73 2.07
G10_30 0.74 2.10
G15_30 0.83 2.12
G20_30 0.93 2.13
G5_140 0.65 1.95
V.3.5 Transmission electron microscopy characterization
Figure V.15a shows a typical TEM picture of G15_30, at low magnification,

evidencing the bundle length as started from particles of catalyst (support +
metals, shown as black spots in the figure). At higher magnification, a
bundle organisation is observed (Fig V. 15a insert), the tubes have an
entangled structure suggesting that length is higher than that of the bundle
(estimated by SEM picture). TEM image of Fig. V.15b evidences the
absence of catalytic particles in a wide range of observation, permitting to
evaluate CNT external diameter ranging from 9 to 23 nm. Catalytic particles,
present inside the tubes (FigV. 15d) and constituted of Co and Fe, as
confirmed by EDX analysis (Fig. V.15e), are visible near the alumina
crystals, suggesting a basal CNT growth (FigV. 15c). The contribution of Co
in the particle entrapped in MWNT core is higher than that of Fe
(Fig.V.15e). An opposite metals contribution can be observed for the metal
particles located into carbon shells of FigV.15f, of dimensions quite larger
with respect to the previous evidenced. This may be suppose a clustering
phenomenon already commented in the section regarding the catalyst
characterization, but strong different in relative amount of metals is evinced
by EDX analysis in FigV. 15g, where higher amount of Fe than Co results.
The role of the support is to disperse the active phase, provide the porous
structure, prevent sintering, different metals giving different results in terms
of CNT quality but principally quantity. The pretreatment phase is the
activation phase, in which catalyst size is determined. Phenomenon of
sintering could lead to non-active metals particles because of larger size. Our
idea is that the metals particles composition located on the surface is crucial
in to determine the promotion of CNT growth. From the greater and Fe-
enriched particles no-CNT growth starts, according to the consideration that
iron is very active in the hydrocarbon decomposition but not equally
selective in the nanotubes growth.
65
Chapter V
Figure V.15: TEM images of G15_30 low resolution a); higher resolution
b), c), d) and f). EDX analysis of a catalytic particle inside the hallow core
of a CNT e), and EDX analysis of catalytic particles covered of no-
nanotubes carbon g), evidencing Fe and Co presence.
66
Experimental III
V.3.6 Raman spectroscopy
Raman spectra, obtained with 514 nm and 785 nm laser wavelength, are
shown in Fig. V.16 and V.17. Typical D and G bands, that indicate the
presence of crystalline graphite carbon and defects, respectively “Ciambelli
et al., (2007)” are observed with both excitation wavelength, depending in
intensity and position on the laser excitation energy.
The values of ID/IG intensity ratio, that is a measure of disordered amount,
for CNT produced at different ethylene feed partial pressure and at different
times are reported in Table V.2. It can be clearly observed that the 514 nm
excitation wavelength is more sensible to samples differences than 785 nm,
on the other hand the intensity ratio values are higher with 785 nm because
the defect and disorder bands are more enhanced. The ID/IG ratio slightly
increases as the ethylene concentration in feed rises. The degree of
crystallinity of samples produced at a higher carbon deposition rate is lower.
The increase of synthesis time results in a higher order probably due to
longer permanence at high temperature, causing the decrease of walls
defects.
Figure V.16: Raman spectra (514 nm excitation wavelength) of samples

prepared at different ethylene partial pressure.
67
Chapter V
Figure V.17: Raman spectra (785 nm excitation wavelength) of G5_30,

G10_30 and G20_30
68
Chapter VI
Experimental IV
Microwave purification and
functionalisation of MWNTs
VI.1 Introduction
Recently multiwall (MWNT) and single wall carbon nanotubes (SWNT)

have attracted very great attention thanks to their structural, mechanical
“Treacy et al. (1996), Lourier et al.(1998), Jin et al.(2001)”and electronic
properties “Tukaba et al. (1995), Tanaka et al.(1992)” and related potential
technological applications “Robertson et al.(1992), Ajayan et al.(1993)”.
For their preparation, “Ivanov et al.(1994), Li et al.(1996), Maurin et
al.(2001), Zhang et al.(1999), Mukhopadhyay et al.(1999), Maruyama et
al.(2002), Sinha et al.(2000), Ciambelli et al.(2004a), Ciambelli et
al.(2004b), Ciambelli et al.(2005c)” CCVD of hydrocarbons over supported
metal catalysts has been extensively studied, because of the relatively lower
growth temperatures (600-800°C) than those required by thermal methods
such as arc discharge “Ebbesen et al.(1992)” or laser ablation “Yudasaka et
al.(1999)”, as has the possibility to control inner diameter and length of
nanotubes.
The grown CNTs, produced by these methods, contain impurities, such as
disordered carbon and catalysts. The amount of impurities prevents the use
of the as-prepared materials for many scientific investigations and
applications. Therefore, a great challenge remains in the control of their
fabrication and purification before carbon nanotubes can be used for
technological applications.
Recently, many purified methods have been investigated and have been
used successfully to remove impurities. One of the effective purification
methods reported by Tsang et al. “Tsang et al. (1993)” was oxidation in air
Chapter VI
at 750°C. Successive researchers “Ebbesen et al,(1997), Tohji et al.(1997)”

adopted thermal annealing and similar thermal oxidation methods to purify
CNTs but with low yield. Shelimov et al. “Shelimov et al.(1998)” proposed
a method to purify SWNT by ultrasonically-assisted filtration, amorphous
carbon, crystalline carbon impurities and metal particles are removed by
means of these process. The process generates SWNT material with purity
above 90% and yields of 30-70%. A two-step process of thermal annealing
in air and acid treatment, was proposed by Moon et al. “Moon et al.(2001)”
was used to purify SWNT. Today, most of the purification methods are
based on or include steps involving oxidising attacks using various mineral
acids such as HCl, HNO3, H2SO4 for the elimination of impurities “Rinzler
et al.(1998), Liu et al., Chen et al.(2002), Dujardin, et al.(1998), Tohji et
al.(1996), Saito et al.(1999), Bandow et al.(1998), Dillon et al.(1999),
Vacarini et al.(1999), Umek et al. (2000), Chen et al.(2004)”. Rinzler at al.
“Rinzler et al.(1998) were the first to describe an acid procedure to purify
SWNTs on a large scale. Liu et al. “Liu et al.(1998)” reported the use of a
mixture of concentrated H2SO4/HNO3 to cut the highly tangled long ropes of
SWNTs into short, opened ended pipes, and thus produced many carboxylic
acid group ends.
Recently, microwave-assisted heating has received much attention
because of its high sample throughput, small reagent volume, and reliable
control of temperature and pressure “Chen et al.(2004), Ko et al.(2005)”.
Recently a microwave assisted functionalisation of SWNTs has been
reported.
Here we report the synthesis of MWNTs by ethylene decomposition over
Co-Fe modified NaY zeolite, and their purification and –COOH
functionalisation, by acidic treatment steps. A microwave-assisted digestion
system, used for the first time in presence of a very low amount of inorganic
acids such as HF, HNO3/H2SO4 mixture, was used in comparison to a
conventional procedure to purify and functionalise nanotubes.
A wide characterization approach based on the combined use of various
techniques such as transmission electron microscopy (TEM) combined with
EDX analysis, field emission scanning electron microscopy (FESEM),
Raman and FT-IR Spectroscopy, X-ray diffraction analysis, N2 adsorption-
desorption analysis, supported by quantitative evaluation based on TG and
ICP-MS analysis, on samples at progressive purification degree, have been
performed.
VI.2 Experimental Part
VI.2.1 Carbon nanotubes synthesis
The nanotubes used in this work have been synthesised by ethylene

catalytic chemical vapour deposition (CCVD) on Co/Fe-modified NaY
70
Experimental IV
powders. Catalyst samples were prepared by wet impregnation of the support

powder with a cobalt acetate (2.5 wt%) and iron acetate (2.5 wt%) ethanol
solution and dried at 140°C for 12 h. Ethylene pyrolysis was carried out in a
continuous flow micro-reactor fed by ethylene-helium gas mixture. The
micro-reactor is a quartz tube (16 mm internal diameter, 300 mm length), a
portion of which is filled with about 400 mg of catalyst. An external coaxial
quartz tube (35 mm internal diameter) allows the reactant stream to be
preheated. The temperature of catalyst bed is measured with a K
thermocouple located inside a third coaxial quartz tube (4 mm internal
diameter). The reactor is heated by an electrical oven, whose temperature is
controlled by a temperature programmer-controller (Eurotherm 2408).
Cylinder gases (99.998 pure ethylene and 99.9990 pure helium) were
mixed to give the ethylene in the helium stream to feed the reactor. For each
gas a mass flow controller (MFC) was used, in order to assure a constant
flow rate. The reactor temperature was increased from 25°C up to 600°C
(10°C/min) under helium flow and then 250 cm3/min flow rate of 10%
ethylene in helium was introduced in the reactor for 60 min. After this time,
the ethylene-helium flow was stopped and the reactor was cooled to room
temperature under a helium flow, recovering sample MW1.
The yield of deposited carbon and the reaction yield were calculated,
respectively, as indicated in equation 1 and equation 2 in chapter V.
VI.2. 2 Purification treatment
To compare the effects of a microwave digestion and a more

conventional purification procedure, the latter were conducted
simultaneously.
(i) A) The catalyst support was removed by acidic treatment in
concentrated HF (46% aqueous solution) 10 ml, in presence of 50 mg of
MW1. The solid residue was washed with distilled water, filtered and finally
dried at 120°C for 12 h, obtaining sample MW2. B) After that, 50 mg of
MW2 were treated in a low power sonic bath in 50 ml of concentrated
H2SO4 98% / HNO 365%, 3:1 mixture at 40°C. After 20 min the suspension
was diluted with distilled water and filtered on a 0.1 Millipore polycarbonate
membrane. The solid was washed with an NaOH solution to remove the
carbonaceous waste and then with HCl solution to establish carboxylic
groups attached to the nanotubes. C) Finally, a thick paper-like material was
peeled form the filter membrane and dried at 120°C overnight. Then, the
sample was suspended in a mixture 4:1 of H2SO498% and H2O230% and
stirred for 30 min at 70°C (etching treatment), to remove wastes aggregate
on the tube walls, not completely dissolved during the previous washes on
the membrane. The mixture, cooled until room temperature, was washed,
filtered and finally dried at 120°C for 12 h, samples MW3.
71
Chapter VI
(ii) To purify and functionalise MW1, acidic treatments in a closed-

vessel microwave apparatus was used. In the operative conditions the
evaporation of the acidic reagents produces high-pressure and simulates
reflux conditions A) MW1 (50 mg) were placed in 100 ml Teflon digestion
tube with 0.5 ml of HF, with a temperature increase of 25-160°C followed
by a 15 min isothermal step, obtaining samples MW4. Sample MW1 was
also submitted to the same procedure but with 1 ml of HF obtaining sample
MW5. B) Then MW5 (50 mg) was sonicated in low power deionised water
sonic bath for 20 min and subsequently microwave treated in a 1 ml of
concentrated H2SO4/HNO3, 3:1 mixture, form 25 to 160 °C followed by 10
min isothermal step. The recovered powder was then submitted to the same
procedure reported above for the preparation of MW3, obtaining sample
MW6.
VI.2.3 Methods
Microwave treatments using chemical reagents were accomplished by

placing the samples in closed vessels inside a commercial oven. The
microwave device (Ethos Plus from Milestone) was equipped with a Teflon
cavity and a removable 14-position sample carousel.
Transmission electron microscopy (TEM) images were obtained with a
Jeol 1200 EX2 microscope. The preparation of samples for TEM observation
involved sonication in ethanol for 2-5 minutes and deposition of the sample
on a carbon grid.
Field emission scanning electron microscopy (FESEM) pictures were
obtained with a LEO 1525 microscope. The samples were covered with a
250 Å thick gold film using a sputter coater (Agar mod. 108 A).
Thermogravimetric analysis (TG-DTG) was performed with a
Thermogravimetric Analyser SDTQ 500 TA with 0.2-10 K/min heating rate,
under flowing air.
ICP-MS analyses were obtained with an ICP-MS Agilent 7500ce
instrument.
Raman spectra, were obtained at room temperature, with a microRaman
spectrometer Renishaw inVia with 785 nm excitation wavelength (laser
power 30mW).
The infrared spectra were obtained at room temperature by using an FTIR
Nexus Thermo Nicolet (32 scans collected). Powdered materials (100mg, 0.5
wt.% of CNT in KBr) were pelleted (pressure 2•104 kgcm-2) in self-
supporting disks of 0.1–0.2 mm.
XRD measurements were performed with a Bruker D8 X-ray
diffractometer using CuKα radiation, in the range 20-30° 2 θ.
Surface area and porosity characterisation was obtained by N2
adsorption-desorption at 77 K with a Thermoquest Sorptomatic 1900.
72
Experimental IV
Powder samples were out-gassed in He flow at 523 K for 6 h before

measurements.
VI.3 Results and discussion
VI.3.1 Microscopy images
c
Figure VI.1: TEM images of MW1(a, b )and EDX spectra of MW1(c )
Typical TEM images of raw materials are shown in Fig. VI.1a and VI.1b.
A zeolite crystal is clearly observed in Fig. VI.1a, catalytic particles on
the surface of the crystal and inside the hallow core of carbon nanotubes are
also visible. EDX analysis (Fig. VI.1) shows the presence of Co and Fe
metals, Si and Al are detected, as large quantities of carbon. Some metallic
73
Chapter VI
particles, as confirmed by the EDX analysis (Fig. VI.1 c), of greater

dimension (size ~ 100 nm), covered of amorphous carbon are also observed
(Fig. VI.1b).
After support dissolution (Fig. VI.2a) zeolite crystals are no longer
visible, however some catalytic particles can still be observed in the sample
especially in the carbon nanotubes hallow core. MW2 is constituted of
MWNTs, and by means of a high resolution TEM image (Fig. VI.2b) we can
observe the different walls that constitute the thickness of the tubes. The
tubes, are characterised by a good level of order even if the synthesis
temperature (600°C) is relatively high. Purified MWNTs are obtained at the
end of all conventional purification steps (Fig. VI.2c).
Figure VI.2: TEM images of MW2( a,b) and MW3 (c)
74
Experimental IV
Figure VI.3: TEM images of MW4 (a),MW5 (b,c), MW6 (d,e)
75
Chapter VI
Figure VI.4: Histogram of the inner and outer diameter of the raw and
treated materials
76
Experimental IV
Zeolite residue are still present in sample MW4 (Fig. VI.3a), but are
absent in MW5 (Fig. VI.3b and VI.3c). Purified MWNTs, as a result of the
microwave digestion treatment, are obtained (Fig. VI.3d).
By TEM observation, performing a comparison between MW6 (Fig.
VI.3e), MW5 (Fig.VI.3c) and MW2 (Fig. VI.2b), we can observe that
additional damages introduced by the microwave treatments are not evident.
The inner and outer diameter of the raw and treated materials have been
measured for high resolution TEM pictures to follow the evolution of the
tube thickness under treatments. At least 200 nanotubes per sample were
taken into account, the corresponding histograms are reported in Fig.VI.4. In
general, a smaller inner diameter means a smaller outer diameter. The inner
diameter distributions are dominated by two main peaks at 4±0.5 and 6± 0.5
nm for both raw and treated materials. The number of tubes with 4 nm inner
diameter is lower than 6 nm for sample MW1, MW2 and MW5, on the
contrary for MW3 and MW6. These last samples show in addition small
contributions at 1 and 2 nm. The evolution of the outer diameter distribution
clearly shows a downshift of about 2 nm for samples MW3 and MW6.
It is known that treating SWNTs containing materials in sulphuric/nitric
mixtures, determines an increase of the content of disordered carbon, caused
by the partial destruction of SWNTs as well as the formation of defects in
SWNTs bundles “Nagasawa et al.(2000), Martinez et al., (2003)”.
The observed effects on the wall thickness of MW3 and MW6 samples
can be attributed to the sulphuric/nitric acid attack, that followed by the
etching treatment in H2O2 and H2SO4 “Liu et al. (1998)” results in thinner
carbon nanotubes. The effect seems to be more pronounced on the outer than
on the inner tubes diameter likely due to the sometimes less defined structure
of the outer tubes walls.
Figure VI.5: FESEM images MW1 (a,b)

Figure VI.5a shows a typical FESEM picture of sample MW1, revealing
the nanotubes morphology with their bundle organization. The MW1 tubes
77
Chapter VI
at higher resolution are shown in Figure VI.5b, some catalytic particles are
observed , indicated by the white arrows.
FESEM images of MW3 and MW6 (Fig. VI.6b and VI.6c respectively)
show MWNTs more tangled with one another than the un-purified sample
(Fig. VI.6a), the higher presence of nanotube ends suggests shorter carbon
nanotubes.
VI.3.2 TG-DTG evaluation
The amount of deposited carbon was also evaluated from the results of
flow air TGA of the composite material, as the weight loss in the range of
temperature where carbon burns in air, divided by the weight left at 700°C
(which is the weight of the catalyst) amount found was 30.1%.
Air flow TG-DTG curves, recovered at 10°C/min in the range 25-700°C
are reported in Fig. VI.7a. The oxidation profile of MW1 shows one weight
loss centred at 470°C. We have performed thermo-gravimetric analyses on
this sample at a decreasing heating rate (see Fig. VI.7b) with the aim of
proving the presence of several carbon species at different degree of order
“Ciambelli et al.,(2005)”. We have found that, as the heating rate decreases,
oxidation takes place at lower temperature, showing a quite symmetric, DTG
peak. The MW2 TG profile is characterised by a small residue (being NaY
dissolved), whose onset temperature is equal to 468°C. MW2 DTG curve
shows one step loss, with a DTG peak temperature of 544°C, up-shifted with
respect to MW1 DTG maximum, probably due to the lower metal content
(see ICP-MS section), as metals can catalyse carbon oxidation “Ciambelli et
al (2005)”.
The oxidation of the purified MW3 takes place in the range 576-640°C
at higher temperatures than MW2, and shows a very small residue, and a
narrow DTG profile probably due to its very low metal content.
MW5 oxidation seems to occur in at least two main distinct but not well
separated steps. DTG curve shows a broad peak in the range 465-630°C. The
MW2 and MW5 onset temperature of oxidation is almost the same, while the
MW5 offset up-shifted results indicating the presence of a higher purity
carbon nanotubes fraction.
Table VI.1: TG residue % samples MW1, MW2, MW3, MW5, MW6
Sample Residue [%]
MW1 65.3
MW2 5.3
MW3 2.5
MW5 4.9
MW6 1.2
78
Experimental IV
Figure VI.6: FESEM of MW1(a),MW3(b),MW6(c)
79
Chapter VI
MW6 oxidation starts at the same temperature as that of MW3, the offset
temperature of combustion resulting slightly higher, as observed for the
comparison between MW2 and MW5.
These effects can be attributed to the efficiency of the microwave
treatments in removing different metals in comparison to more conventional
ones.
VI.3.3 ICP-MS analysis
Detailed information about the metals content from ICP-MS analysis for
the raw and treated materials, performed with particular attention to the Co
and Fe content, are listed in Table VI.2. In the table, the values directly
measured are marked with an asterisk. The weight of cobalt and iron,
reported in the 4th and 6th column of the table are obtained by applying the
evaluated percentages of Co and Fe to the starting weight of the raw sample
(425 mg) and the remaining weights of the treated samples reported in the
2nd column.
As can be seen, the HF treatment results in an increase of the Co and Fe
percentages as a consequence of the zeolite removal, while the total
milligrams of these metals result reduced (see Table VI.2), indicating that
HF treatment is able to reduce the initial metals content.
The successive treatments determine a further reduction of the metals
content, that reaches values which are very low for both MW3 and MW6.
The acidic treatments lead to a considerable reduction of the metal content
(above 96% of the metal particles are removed). This is accomplished by a
reduction of the carbon material (see the weight values reported in the 2nd
column of the Table VI.2). Starting from these values we can evaluate the
effective MWNTs yield, obtained as a ratio between the carbon mass
measured and the initial catalyst weight, that results about 26% for MW3
and slightly lower for MW6.
Table VI.2: Results of the ICP-MS analysis for the raw and treated
materials, performed with particular regards to the Co and Fe content.
Sample Weight* Co content Fe content
[mg] [wt %]* [mg] [wt %]* [mg]
MW1 425 2.38 10.11 2.37 10.07
MW2 110 3.59 3.95 3.23 3.55
MW3 85 0.50 0.43 0.36 0.31
MW5 102 3.62 3.69 2.07 2.11
MW6 77 0.45 0.35 0.24 0.18
*Values directly measured
The cobalt and iron weight are obtained by applying the wt% values to the starting weight
of the raw sample or to the remaining weights of the treated samples.
80
Experimental IV
Figure VI.7: TG-DTG curves of different samples and of MW1 at several

heating rate.
The reduction of carbon content is mainly related to the removal of
defect-containig MWNTs walls, and less to an original non-nanotubes
carbon content, which is very low as shown by TEM images. This
conclusion is confirmed by the evolution of the tube walls as determined by
HRTEM and XRD analysis, that indicate a reduction of the thickness of the
tubes.
81
Chapter VI
Starting from MW1 Co and Fe content we can estimate that the percentage
of metals, on the original catalyst and by ICP-MS evaluation, is quite closed
on the metals weight involved in the impregnation.
VI.3.4 Raman spectroscopy analysis.
We employed Raman spectroscopy to evaluate the effects of the different

treatments on carbon nanotubes structural characteristics at different levels
of treatment.
The MWNTs Raman spectra in the range 1000-2000 cm-1 are dominated
by two Raman lines localized at ~ 1590 cm-1 (G-line) due to the in-plane
vibration of the C-C bonds, and at ~ 1300 cm-1 (D line) attributed to disorder
induced by defects and curvature in the nanotube lattice.
Figure VI.8: Raman spectra (785 nm excitation wavelength) of MW1, MW2,

MW3, MW5, MW6
82
Experimental IV
Intensity and position of the D line is linear dependent on the laser

excitation energy “Hiura et al. (1993), Brown et al. (2001)”. Together, these
bands can be used to evaluate the measure of any carbon-containing defects
“Kinloch et al.(2003), Wu et al.(2005), Ko et al.(2004).
Table VI.3: Raman Spectroscopy analysis: ID/IG ratio, D and G

wavenumbers for raw samples and treated materials
Sample ID/IG D (cm-1) G (cm-1)
MW1 1.87 1308.5 1597.9
MW2 1.86 1308.7 1597.9
MW3 1.90 1310.6 1602.5
MW5 1.88 1310.1 1596.9
MW6 1.91 1311.4 1601.7
Comparing the ID/IG ratios of the samples at different levels of treatment,

both in the conventional and in the microwave assisted procedure, we can
observe that the HF treatment doesn’t lead to an increase of the carbon
nanotubes defect. No great difference can be observed between the ID/IG
ratio of the samples at different degree of purity (Tab. VI.3). The small up-
shift of the MW3 and MW6 G lines, indicating a shortening of the C-C
bonds, is probably due to an acid intercalation “Nagasawa et al.(2000),
Martinez et al.(2003)” .
VI.3.5 FT-IR
It is known that treatment in a mixture of HNO3 and H2SO4 introduces

chemical functionality on MWNTs ends and surface “Liu et al.(1998), Saito
et al.(2002)”.
In order to investigate the effect of the acidic treatment on the MWNTs,
FTIR analysis was performed. Figure VI.9 reports the FTIR spectra of
samples MW3 and MW6, in the range 1000-2000 cm-1.
The spectra show C=O stretching modes in the range 1580-1750 cm-1 that
prove the presence of carboxyl groups.
The bands at 1380 cm-1 and in the range 1000-1280 cm-1 are assigned to
nitrate and sulphate vibration modes, respectively.
83
Chapter VI
Figure VI.9: FTIR spectra of samples MW3 and MW6

VI.3.6 X-ray analysis
X-ray diffraction spectra of the raw and treated materials are shown in
Fig. VI.10, in the 2 θ range 20-30°, with the aim to evidence the (002)
diffraction peak. This peak allows the evaluate the tube characteristics as the
spacing between two adjacent walls of carbon nanotubes depends on the tube
curvature “Ciambelli et al.(2004a), Ciambelli et al.(2005b)”. By combining
XRD and HRTEM analysis of carbon nanotubes Kiang et al. “Kinag et
al.(1998)” have found that the (002) reflection peak shifts from 26.60° for
graphite (inter-shell spacing of 0.335 nm) to 26.18°-22.77° for carbon
nanotubes, corresponding respectively to 0.34-0.39 spacing. By best fitting
of HRTEM data they obtained an empirical equation:
d 002 = 0.34 + 0.1e −D / 2 for 0<D<10 (1)
where D is the inner diameter of the tubes in nm. By increasing the tube
diameter to D=10 nm the intershell spacing decreases to 0.344 nm, i.e. the
spacing of turbo-stratic carbon. The increase of the d002 spacing is physically
reasonable for tube diameters D<10 nm.
We have determined the minimum number of Gaussian curves that fit our
dates, thus discovering that two curves are able to give the best fit (see Table
VI.4, column 2 and 3), corresponding to the inter-wall distances reported in
84
Experimental IV
Table VI.4, column 4 and 5, i.e. (Eq. 1) and to inner tube diameters of about
4 and 6 nm (column 6 and 7), in keeping with the inner diameters evaluated
by HRTEM (see the distribution histograms reported in Fig. VI.4).
By applying the Scherrer equation “ Ciambelli et al. (2005b)” to the d002
diffraction peak:
L a = 0.9λ / B cos ϑ (2)
where La is the thickness of the tubes, λ the X-ray wavelength, B the peak
half-maximum width and θ the Bragg angle, the average values of tube
thickness were calculated and reported in Tab. VI.4 (column 8 and 9). The
values are very close to those of tube thickness measured by HRTEM
images.
Figure VI.10: X-ray diffraction spectra of the raw and treated materials
Table VI.4: Effects of the treatments on the nanotubes geometrical

characteristics, XRD evaluation
Sample 2θ peak d Internal Tubes Outer
Bragg’s law diameter D thickness diameter
-
nλ=2dsen(θ) d002=0.34+0.1e Scherrer [nm]
D/2
[nm] equation
0<D≤10 nm L=0.9λ/Bcos(θ)
[nm] [nm]
MW2 25.27 25.86 3.522 3.443 4.21 6.30 4.80 6.23 13.80 18.76
MW3 25.25 25.83 3.525 3.447 4.16 6.12 4.29 5.04 12.74 16.20
MW5 25.20 25.87 3.532 3.442 4.06 6.36 4.79 5.83 13.65 18.02
MW6 25.17 25.88 3.536 3.440 3.99 6.42 3.54 4.53 11.08 15.49
85
Chapter VI
VI.3.7 Surface area evaluation
In Fig. VI.11 we show the adsorption-desorption isotherms of N2 at 77 K

for the different samples. The isotherms are of type IV of BET classification.
Surface area (SA) obtained by BET evaluation is higher for a produced
sample, as a consequence of its zeolite content. The SA of MW3 is higher
than that of MW2, likely due to the combined effect of the dissolution of
metal particles opening tube ends and the reduction of the tube thickness.
MW6 have a surface area greater than sample MW5 too, the highest value of
MW6 surface area being due to the smaller diameter of nanotubes.
The particular of Fig. VI.11 shows the isotherms in the range 0-0.5 P/Po
to emphasize the micro-porous region. MW1 shows an higher micropore
content, likely due to microporosity of zeolite. All samples show a small
contribution to pore volume from micropores, likely due to tube envelope.
Figure VI.11: adsorption-desorption isotherms of N2 at 77 K for MW1,

MW2,MW3, MW5 and MW6.
86
Chapter VII
Kinetic evaluation
VII.1 Introduction
Kinetic studies of CNT have been conducted for different growth

methods. The reaction rates anyway decrease more or less with time. With a
remote-plasma-assisted CVD, diffusion-limited growth kinetics lacking
catalyst poisoning was proposed for unpatterned growth of vertical aligned
mats SWNTs, proven by the analyzing time evolution of mats height.
“Zhong et al.(2007)”.
Other papers deals with CNT growth mechanism, based on the theoretical
diffusion-precipitation mechanism, considering three main steps, CNT
nucleation, growth and deactivation of the catalyst. The proposed kinetic
model described the evolution of the CNT growth as a function of two
diffusion and two deactivation parameters “Kim et al.(2005), Perez-Cabero,
et al.(2004)”.
As pointed out previously, CNT weight or height at specific time allows
to evaluate only average growth rates. Only in “Gommes et al. (2004), Pirard
et al. (2007)” a detailed kinetic evaluation has been reported monitoring
synthesis exhaust gases continuously. For their experiments they used a
reactor where the catalyst, in thin layer, is deposited on the surface of a
quartz shuttle near the walls. In this case, the presence of diffusive effects
along and within the catalytic bed must be taken into account.
Here, we report a careful evaluation of kinetic parameters from the
reaction rate of carbon nanotubes synthesis using continuous off-gas
analyses in a catalyst fixed bed crossed orthogonally by reaction stream. The
system allows to work in the absence of diffusion phenomena in a wide
range of reactor operating conditions.
Chapter VII
VII.2 Experimental
Co, Fe catalysts (2.5 wt% of each metal) were prepared by dry

impregnation with cobalt acetate and iron acetate solution of gibbsite (γ-
Al(OH)3) “ Ciambelli et al.(2007d)”. The catalyst was dried at 393 K for 720
min, and preheated before synthesis at 70 K/min up to synthesis temperature
under N2 flow.
Ethylene CCVD was carried out in a continuous flow micro-reactor fed
by ethylene–nitrogen gas mixture. The micro-reactor was a quartz tube
(20mm internal diameter, 300mm length), a portion of which was filled with
catalyst particles. An external coaxial quartz tube (35mm internal diameter)
allowed the reactant stream to be preheated. The temperature of catalyst bed
was measured with a K thermocouple located inside a third coaxial quartz
tube (3mm internal diameter). The reactor was heated by an electrical oven,
whose temperature is controlled by a temperature programmer–controller
(Eurotherm 2408). Cylinder gases (99.998 pure ethylene and 99.9980 pure
nitrogen) were mixed to obtain the ethylene nitrogen stream to feed the
reactor. Constant flow rate of each gas was provided by mass flow
controller. The reactor temperature was increased from 298K up to 923-973-
1023 K, with a running-time of 30 min. Gas flow rate ad catalyst mass
varied: 120, 160 and 200 (stp)cm3/min and 200-400-600 mg were
respectively explored, different percentage of the hydrocarbon (5%, 10%
v/v, 15% v/v, 20% v/v) were tested. In the following, samples were named
GX_YAB where X is the volume percentage of ethylene, Y synthesis time, A
gas flow rate and B the catalyst mass. Continuous analysers (ABB) to
evaluate C2H4, C2H2, CH4 and H2 concentrations in the influent stream on
line during the reaction (see Chapter V) were employed.
VII.3 Results and discussion
VII.3.1 Reaction rate
Initial reaction rates at different operative condition have been calculated

by the slope at zero time of hydrogen production rate and it has been verified
that it is the same as the reaction rate calculated from the ethylene
consumption curves.
Hydrogen production rate is related to ethylene consumption by the
relation:
d [C 2 H 4 ] 1 d [ H 2 ]
r=− = (1)
dt 2 dt
88
Kinetic evaluation
VII.3.2 External and internal diffusion evaluation
With the aim of evaluating the influence of the external diffusion, we

consider the transfer of reactants from the bulk fluid phase to the external
surface of the catalyst as described by the film model:
robserved = k m am (cb − cs ) (2)
where km is the mass transfer coefficient, am the outer specific particle

area, cb and cs the bulk and the surface concentration of the reactant
respectively. To evaluate if the external transport affects the global reaction
rate we will calculate (cb-cs). If this difference will be negligible we could
conclude that cs approaches cb and reaction rate isn’t limited by any external
diffusion.
Figure VII.1: Example (sample G5_30120600) of hydrogen production curve

as a function of time and determination of the initial observed rate of CNT
synthesis
Average transport coefficients between the bulk stream and particle

surface can be correlated in terms of dimensionless groups which
characterize the flow conditions. For mass transfer the Sherwood number
k m ρ / G is an empirical function of the Reynolds number doG / μ , and the
Schmidt number μ / Dρ . It is commonly practice to correlate experimental
data in terms of j-factor which are defined as the following functions of the
Sherwood and Schmidt numbers:
89
Chapter VII
k m ρ am μ 2 / 3
jD = ( )( ) (3)
G at ρD
the ratio am / at allows for the possibility that the effective mass-transfer area,
am, may be less than the total external area, at, of the particles. D is molecular
diffusivity and is defined by “Fuller et al. (1966)”
1 1 0 .5
( + )
M1 M 2
D = D12 = 0.1013 ⋅ T 1.75 (4)
P[(∑ v1 ) + (∑ v2 ) ]2
1/ 3 1/ 3
where D12 is the diffusion coefficient of compound 1 in 2 in m2/s; T is the

temperature in K; P is the pressure in Pa; M1 and M2, v1 and v2 the molecular
weight and the molar volumes of compounds 1 and 2.
For Reynolds number in the range 0.01-50 (Perry Seven Edition, sec.5)
the jD factor can be correlated with Reynolds number by:
−0.51
j D = 0.91 ⋅ψ (d p G / μ ) (5)
Where ψ is the shape factor equal to 1 for particle, 0.91 for spheres and
0.81 for cylinders.The results of this evaluation are reported in Table VII.1;
the relatively small values of (cb-cs), observed in all the examples, indicate
that the external diffusion resistance is not significant. Since the system
volume is in evolution, increasing as carbon deposit increases and enhancing
particles size, the evaluation performed on the systems at the syntheses end
is also reported in Table VII.1.
Diffusion within the porous catalyst particles can also affect the overall
rate. Internal mass transfer limitations result in concentration gradients
inside the catalyst particles.
When an heterogeneous catalytic reaction is strongly influenced by internal
mass transfer, the apparent activation energy will tend to be one-half of the
intrinsic activation energy and the apparent reaction order will tend to be one
half of the real reaction order (for single reactant reactions and bulk
diffusion in the pores) “Satterfield, 1970.”
To test to what degree a reaction is influenced by internal diffusion the
dimensionless number Thiele modulus relates the intrinsic kinetics to the
maximum effective rate of internal diffusion:
kρe 2 0.5
MT = ( ) (6)
De
where k is the kinetic constant per unit volume of the catalyst, ρ equal to
2.35 gcat/cm3 and e are respectively density and size of the particles for the
90
Kinetic evaluation
calculation e=0.015 cm has been used. Finally De is the effective diffusivity
that is, the base of a random pore model, defined by:
ε μ2 (1 + 3ε M )
De = DM ε M2 + Dμ (7)
1− εM
1 1 1
= + (8)
DM D 12 ( Dk ) M
1 1 1
= + (9)
Dμ D 12 ( Dk ) μ
T
Dk = 9.7 ⋅ 103 a( ) (10)
M
Table VII.1: External diffusion evaluation before and after syntheses

After
Before synthesis
synthesis
μ ρ Re Sc JD (cb-cs)/cb (cb-cs)/cb
3
kg/msec kg/m
T=600°C
G5_30120200 7,418E-07 7,178E-07
G5_30120400 4,870E-07 4,569E-07
G5_30120600 3,5E-05 3,9E-01 5.4E-02 3,9E-01 2.1E-01 7,268E-07 6,443E-07
G10_30120400 5,714E-07 5,207E-07
G15_30120400 4,930E-07 4,257E-07
T=650°C
G5_30120200 2,532E-06 2,187E-06
G5_30120400 2,460E-06 2,023E-06
G5_30120600 3,8E-05 3,7E-01 4.6E-02 4,2E-01 1.9E-01 2,114E-06 1,664E-06
G10_30120400 2,707E-06 2,130E-06
G15_30120400 2,428E-06 1,871E-06
T=700°C
G5_30120200 1,223E-05 9,241E-06
G5_30120400 4.1E-02 1.8E-01 8,048E-06 5,651E-06
G5_30120600 6,152E-06 4,053E-06
G5_30160400 4,1E-05 3,5E-01 5.5E-02 4,3E-01 2.1E-01 7,042E-06 4,945E-06
G5_30200400 6.8E-02 2.3E-01 6,318E-06 4,437E-06
G10_30120400 8,048E-06 5,468E-06
4.1E-02 1.8E-01
G15_30120400 8,584E-06 5,655E-06
91
Chapter VII
where εM and εμ used values are 0.3 and 0.34 respectively, and the pore
radius a are equal to 1000 Å and 14 Å for macro and micro void regions. No
tortuosity factor, that is an adjustable parameter, is involved in the model.
However, besides the DamköhlerII and Carberry numbers, the Weisz
modulus is often more applicable since it relates the observed rate of
reaction to the rate of internal mass transfer (Emig & Dittmeyer, 1997)
rρe 2
M W = M T2ε = (11)
DeCS
where r is the observed reaction rate and Cs is the ethylene concentration on

the catalytic bed and is calculated dividing ethylene molar fraction in the fed
gas by the molar volume providing by the perfect law. The results of this
evaluation, at the starting point and at the end of the syntheses considering
the change in density and size of the particles and εM equal to 0.2 are
reported in Table VII.2.
Maximum calculated value are 0.13 implying no diffusional internal
effects.
Furthermore, the observation that for a given amount of catalyst, and for
a given composition of the feed gas, the initial reaction rate stays constant,
changing the flow shows that the feed is not a factor limiting the reaction
rate (see Table VII.2).
VII.3.3 Kinetic study
To treat the laboratory kinetics data, considering that our conversions

represent integral reactor results and assuming plug-flow behaviour, the
following expression can be integrated:
rdW = FA0 dx (12)
where:
r= observed rate of reaction
W= mass of catalyst
FA0=feed rate of reactant
x= conversion of reactant.
By supposing a first order kinetic for the intrinsic reaction rate at the
catalyst site, we have calculated the values of k, in several operative
conditions, following the standard procedure. We have changed either the
amount of catalyst for a given feed rate either the feed rate for a given
amount of catalyst at a constant feed composition, pressure and temperature.
The values of k are reported in Table VII.3. If the form of the intrinsic
reaction rate is satisfactory, k should be constant at a given pressure. The
values of k in Table VII.3 are about constant at each temperature and do not
92
Kinetic evaluation
show a definite trend and therefore the first order mechanism can interpret
the kinetic data.
Developing the expression (13) we obtain:
W
( RTC b Q)k = −[(1 + ε ) ln(1 − x) + εx] (13)
FA 0
where:
R= ideal gas constant
T= temperature
Cb= bulk concentration
Q= volumetric flow
ε= expansion volume factor
Table VII.2: Internal diffusion evaluation before and after syntheses

Before After
synthesis Synthesis
r Μω Μω ρ e
3
moli/secgcat g/cm cm
T=600°C
G5_30120200 1,98E-06 0,010 0,003 1,000 0,016
G5_30120400 1,30E-06 0,006 0,002 0,980 0,017
G5_30120600 1,94E-06 0,010 0,004 0,970 0,019
G10_30120400 3,40E-06 0,005 0,005 0,940 0,023
G15_30120400 4,40E-06 0,004 0,005 0,890 0,027
T=650°c
G5_30120200 6,30E-06 0,028 0,013 0,850 0,020
G5_30120400 6,12E-06 0,027 0,015 0,840 0,022
G5_30120600 5,26E-06 0,023 0,015 0,830 0,024
G10_30120400 1,42E-05 0,021 0,025 0,800 0,028
G15_30120400 1,91E-05 0,019 0,035 0,750 0,036
T=700°c
G5_30120200 2,85E-05 0,114 0,086 0,790 0,026
G5_30120400 1,85E-05 0,075 0,074 0,780 0,030
G5_30120600 1,43E-05 0,057 0,071 0,760 0,034
G5_30160400 1,90E-05 0,076 0,075 0,780 0,030
G5_30200400 1,91E-05 0,076 0,076 0,780 0,030
G10_30120400 3,75E-05 0,056 0,098 0,710 0,036
G15_30120400 6,00E-05 0,060 0,134 0,670 0,042
93
Chapter VII
Table VII.3: Calculated results for the reaction C2H4→2C+2H2

F W K X
moli/sec g moli/(secgcatatm)
T=600°C
G5_30120200 1,253E-06 0,2 2,1E-05 1,4E-01

G5_30120400 1,253E-06 0,4 1,8E-05 2,3E-01
G5_30120600 1,253E-06 0,6 1,9E-05 3,3E-01
T=650°C
G5_30120200 1,253E-06 0,2 6,2E-05 3,7E-01

G5_30120400 1,253E-06 0,4 6,3E-05 6,1E-01
G5_30120600 1,253E-06 0,6 6,2E-05 7,5E-01
T=700°C
G5_30120200 1,253E-06 0,2 1,5E-04 6,9E-01

G5_30120400 1,253E-06 0,4 1,6E-04 9,1E-01
G5_30120600 1,253E-06 0,6 1,5E-04 9,7E-01
G5_30160400 1,670E-06 0,4 1,4E-04 8,1E-01
G5_30200400 2,088E-06 0,4 1,5E-04 7,5E-01
Figure VII.2: Kinetic constant evaluation at 600°C, varying the amount of

catalyst, at a constant feed rate and composition, pressure and temperature.
94
Kinetic evaluation

catalyst, at a constant feed rate, composition and pressure.

catalyst, at a constant feed rate, composition, and pressure
Figure VII.5: Kinetic constant evaluation at 700°C, varying gas flow at

given amount of catalyst at a constant feed composition and pressure.
95
Chapter VII
Figure VII.6: Plot of the natural logarithm of the kinetic constant against
the reciprocal of absolute temperature.
The members in brackets must be proportional, k being the proportional

factor, and by plotting these two members (see Figures VII.2, VII.3, VII.4
and VII.5) a linear relation is evident, further confirmation of the first order
kinetic hypothesis, allowing the calculation of k values at different
temperature.
To evaluate the frequency factor A0 and the activation energy Ea ( k = Ao exp
(-Ea/RT) ), in Figure VII.6 the graph that shows the ln k ~1000/T for three
different temperatures is reported. The activation energy results equal to 147
KJ/mole, in agreement with other reported values “Pirard et al, (2007), Liu
et al.(2005)”.
96
Conclusion
High performance catalytic synthesis and purification of carbon

nanotubes have been obtained. Low costs and high quality nanotubes have
been synthesised by catalytic chemical vapour deposition (CCVD)
technique. The objectives have been reached through the optimisation of the:
catalyst, synthesis operative conditions, selection of reaction system and
purification procedure.
Different aluminium hydroxides have been investigated as catalyst
support for Co and Fe in the CCVD synthesis of CNT. We have found that
the effectiveness of the method mainly depends on the surface properties of
the support through interaction with the precursor of active metal phases.
Drying time before the synthesis and aging time also affect the catalyst
activity. CNT selectivity depends both on support and operating conditions.
Very high carbon and reaction yields, and CNT selectivity have been
obtained with gibbsite and bayerite. CNT bundles grown on gibbsite and
bayerite show coiled ends, suggesting a different catalyst deactivation
mechanism. In addition, catalyst particles located at the end of the nanotubes
have been observed in samples obtained by Co-Fe modified boehmite,
indicating a weaker interaction between active phases and boehmite support.
On Co-Fe modified gibbsite, MWNT have been selectively synthesised
by CCVD of ethylene, continually monitoring the activity and lifetime of the
catalyst by the help of on-line ABB analysers. Very high carbon and reaction
yield are obtained, catalyst activity keeps constant for very long time. A
CNT characterisation to correlate the tube properties with the reactor
operative conditions was also performed. A kinetic investigation of the
CNTs growth has been also performed by the help of on-line analysers
allowing to infer the reaction rate from the exhaust gas composition
measurements.
A purification and contemporaneously –COOH functionalisation of
MWNTs by acidic treatment steps has been performed. A microwave-
assisted digestion system, in presence of a very low amount of inorganic
Conclusion
acids such as HF, HNO3/H2SO4 mixture, was used in comparison with a

conventional procedure to purify and functionalise nanotubes. The
conventional method is able to dissolve the impurities from MWNTs, but a
couple days are required to purify and then functionalised MWNTs. A
closed-vessel microwave system, in presence of inorganic acids such as HF
and HNO3/H2SO4 mixture, can rapidly absorb microwave heat and energy
and dissolve nanotubes impurities, without agitation, determining also a
MWNTs –COOH functionalisation. Lower concentration of acids and acid
immersing time are available to retain carbon nanotubes characteristics.
98
References
• Aghababazadeh, R.; Mirhabibi, A.R.; Ghanbari, H.; Chizari, K.;

Brydson, R.M. and Brown, A.P. (2006) J. Phys.: Conf. Ser, 26, 135-
138.
• Ago, H.; Uehara, N.; Yoshihara, N.; Tsuji, M.; Yumura, M.;
Tomonaga, N. and Setoguchi ,T. (2006) Carbon, 44, 2912
• Ajayan, P.M and Iijima, S. (1993) Nature, 361, 333
• Alexandrescu, R.; Crunteanu, A.; Morjan, R.E.; Morjan, I.;
Rohmund, F.; Falk, L. K. L.; Ledoux, G. and Huisken, F. (2003)
Infrared Physics & Technology, 44, 43
• Al-Jishi, R. and Dresselhaus, G. (1982) Physical Review B, 26,
4514.
• Alvarez, L.; Righi, A.; Guillard, T.; Rols, S.; Anglaret, E.; Laplaze,
D. and Sauvajol, J.L. (2000), Chemical Physics Letters, 326, 186.
• Anazawa, K.; Shimotani, K.; Manabe, C.; Watanabe, H. and
Shimizu, M. (2002) Applied Physics Letters, 81, 739.
• Assovskii, I. G. and Kozlov, G.I.(2003) Doklady Physical
Chemistry; 388, 13.
• Bachilo, S.M.; Balzano, L.; Herrera, J.E.; Pompeo, F.; Resasco, D.E.
and Weisman R.B.(2003) Journal of the American Chemical
Society., 125, 11186.
• Bacsa, W.S. and Rousset, A. (2002) J. Am. Ceram. Soc., 85, 2666.
• Balek1, V.; Ubrt, J.; Rouquerol, J.; Llewellyn, P.; Zeleòák,I, .V.
Bountsewa, M.; Beckman, I. N. and Györyová, K. (2003) Journal of
Thermal Analysis and Calorimetry, 71, 773.
• Bandow, S.; Asaka, S.; Zhao, X. and Ando Y. (1998) Applied
Physics A, 67, 23.
• Bernholc, J.; Brabec, C.J; Nardelli, M.; Maiti, A.; Roland, C. and
Yakobson, B.I. (1998) ,Applied Physics A, 67, 39.
• Bethge, H. and Heydenreich, J. (1987) Electron Microscopy in Solid
State Physics, Elsevier (Amsterdam, Oxford, New York)
References
• Bolshakov, A. P.; Uglov, S. A.; Saveliev, A. V.; Konov, V. I.;

Gorbunov, A. A.; Pompe, W. and Graff, A. (2002) Diamond and
Related Materials, 11, 927.
• Bower, C.; Rosen, R.; Jin, L.; Han, J. and Zhou, O.(1999) Applied
Physics Letters,74, 3317.
• Brown, S. D. M.; Jorio, A.; Dresselhaus, M. S. and Dresselhaus, G.
(2001) Physical Review B, 64, 0734031
• Buang, N.A.; Abd. Majid, Z.; Sulaiman, Y.; Sanip, S.M. and Ismail,
A.F (2006) Journal of Porous Material, 13, 331
• Cardona, M. and Merlin, R. (1983) Light Scattering in Solids I,
Springer-Verlag, Berlin, Heidelberg, New York.
• Chen, C.; Chen, M.; Leu, F.; Hsu, S.; Wang, S.; Shi, S. and Chen, C.
(2004) Diamond and Related Materials ,13, 1182-1186
• Chen, M.; Chen, C. M. and Chen, C. F. (2002) Journal of Materials
Science, 37, 3561.
• Chen, X. H.; Chen, C. S.; Chen, Q.; Cheng, F. Q.; Zhang, G. and
Chen, Z. Z. (2002) Material Letters, 57, 734
• Ciambelli, P.; Sannino, D.; Sarno, M. and Nagy, J.B. (2004a)
Advanced Engeneering Materials, 6, 804.
• Ciambelli, P.; Sannino, D.; Sarno, M.; Fonseca, A. and Nagy, J.B.
(2004b) Journal of Nanoscience and Nanotechnology, 4, 779-787.
• Ciambelli, P.; Sannino, D.; Sarno, M.; Fonseca, A. and Nagy J. B.
(2005c) Carbon, 43, 631.
• Ciambelli, P.; Sannino, D.; Sarno, M.; Leone, C. and Lafont, U.
(2007d) Diamond and Related Materials, 16, 1144.
• Collins, P.G. and Avouris, P. (2000). Scientific American , 283, 62.
• Cui, H.; Zhou, O. and Stoner, B.R. (2000) Journal of Applied
Physics; 88, 6072.
• Costa, P.; Friedrichs, S.; Sloan, J.; Green, M. L.H. (2004) Carbon,
42, 2527-2533.
• Das, N.; Dalai, A.; Soltan Mohammadzadeh, J.S. and Adjaye, J.
(2006) Carbon, 44, 2236.
• Dasgupta,, K.; Venugopalan, R. and Sathiyamoorthy, D. (2007)
Materials Letters , 61, 4496.
• De la Chapelle, M. L.; Lefrant, S.; Journet, C.; Maser, W.; Bernier,
P. and Loiseau, A. (1998) Carbon, 36, 705.
• Dillon A C.; Gennett, T.; Jones, K. M.; Alleman, J. L.; Parilla, A.
and Heben M J (1999) Adv. Mater., 103, 2492
• Dresselhaus, M.S. and Eklund, P.C (2000b), Advances in Physics,
49, 705.
• Dresselhaus, M.S.; Dresselhaus, G. and Eklund, P.C.(1996a) Science
of fullerenes and carbon nanotube, Academic Press, San Diego
• Du, C. and Pan, N. (2005) Materials Letters, 59, 1678
100
References
• Dujardin, E.; Ebbesen, T. W.; Krishnan, A. and Treacy, M. M. J.

(1998), Adv. Mater., 10, 611.
• Dupuis, A.C. (2005) Progress Mater. Sci., 50, 929.
• Ebbesen, T. Y.; Ajayan, P.M.; Hiura, H. and Tanagaki,K. (1994)
Nature ,367, 519
• Ebbesen, T.W. and Ajayan, P.M. (1992) Nature, 358, 220.
• Eklund, P. C.; Pradhan, B.K.; Kim, U.J.; Xiong, Q.; Fischer, J.E.;
Friedman, A.D.; Holloway, B.C.; Jordan, K. and Smith, M.W.(2002)
Nano Letters, 2, 561.
• Emmenegger, C.; Bonard, J.-M.; Mauron, P.; Sudan, P.; Lepora, A.;
Grobety, B.; Züttel, A. and Schlapbach, L.(2005) Carbon, 41, 539.
• Falvo, M.R.; Clary, G.J.; Taylor, R.M:; Chi, V.; Brooks, F.P. and
Washburn, S.(1997) Nature, 389, 582.
• Farhat, S.; Hinkov, I.; Chapelle, D. I.; Fan, S. S.; Li, G. H. and Scott,
C. D. (2001) NASA, Conference Publication
• Farhat, S.; La Chapelle, M.L.; Loiseau, A.; Scott, C.D.; Lefrant, S.;
Journet, C. and Bernier, P.(2001) Journal of Chemical Physics, 115,
6752.
• Fazle Kibria, A.K.M.; Mo, Y.H. and Nahm, K.S. (2001) Catal.
Letters,71, 229.
• Ferraro, J.R. and Nakamoto, K. (1994.) Introductory Raman
Spectroscopy, Academic Press (Boston, San Diego, New York,
London, Sydney,Tokyo, Toronto)
• Fuller et al.(1966) Perry’s Chemical Engineers’ Handbook,
McGrawHill , New York pag. 2-370
• Ge, M. and Sattler, K. (1994) Applied Physics Letters, 64, 710.
• Gommes, C.; Blacher, S.; Bossuot, Ch.; Marchot, P.; Nagy, J.B. and
Pirard, J.-P. (2004) Carbon, 42, 1473.
• Guo, T.; Nikolaev, P.; Thess, A.; Colbert, D. T. and Smalley, R. E.
(1995) Chemical Physics Letters , 243, 49.
• Hernandez, E.; Goze, C.; Bernier, P. and Rubio, A.(1998) Phys. Rev.
Lett., 80, 4502.
• Herrera, J.; Balzano, L.; Pompeo, F. and Resasco, D., (2003)
Journal of Nanoscience and Nanotechnology, 3, 133.
• Hiura, H.; Ebbesen, W. and Tanigaki, T.W (1993) Chemical Physics
Letters, 202, 509.
• Huang, H. J.; Marie, J.; Kajiura, H. and Ata, M. (2002) Nano
Letters, 2, 1117.
• Huang, Z. P.; Wang, D. Z.; Wen, J. G.; Sennett, M.; Gibson, H. and
Ren, Z.F.(2002) Applied Physics A Materials Science & Processing,
74, 387.
• Huong, P.V. and Cavagnat, R. (1995) Phys. Rev. B ,51, 10048.
101
References
• Iijima, S.; Brabec, C.; Maiti, A. and Bernholc, J.(1996) J. of Chem.

Phys., 104, 2089.
• Ivanov, V.; Nagy ,J.B.; Lambin, P.; Lucas, A.; Zhang, X.B.; Zhang,
X.F. et al. (1994) Chemical Physics Letters, 223,329.
• Jawhari, T.; Roid, A. and Casado, J. (1995) Carbon ,33, 1561.
• Jin, Z.; Pramoda, K. P.; Xu, G. and Gob, H. (2001) Chemical
Physics Letters, 337, 1212.
• Journet, C. and Bernier, P.(1998b) Applied Physics A-Materials
Science & Processing, 67, 1.
• Journet, C.; Maser, W.K.; Bernier, P. Loiseau, A. de la Chapelle,
M.L. Lefrant, S. et al. (1997a) Nature ,388, 756.
• Kathyayini, H.; Willems, I.; Fonseca, A.; Nagy, J.B. and Nagaraju,
N. (2006) Cat.Commun., 7, 140.
• Keidar, M. and Waas, A. M.(2004) Nanotechnology, 15, 1571
• Khassin, A.A.; Yurieva, T.M.; Zaikovskii, V.I. and Parmon,
V.N.(1998) Reaction Kinetics and Catalysis Letters, 64, 63
• Kinag, C.H.; Endo, M.; Ajayan, P.M.; Dresselhaus, G. and
Dresselhaus, M.S. Phys. Rev. Lett. (1998), 81, 1869.
• Kinloch, I. A.; Chen, G. Z.; Howes, J.; Boothroyd, C.; Singh, C.;
Fray, D. J. and Windle, A. H. (2003) Carbon, 41 ,1127
• Ko, C. J.; Lee, C. Y.; Ko, F. H.; Chen, H.L. and Chu, T. C. (2004)
Microelectron Eng ,570, 73.
• Ko, F.H.; Lee, C-Y.; Ko, C-J. and Chu, T.C. (2005) Carbon ,43,
727
• Kolmogorov, A. N. and Crespi, V.H. (2000) Phys. Rev. Lett., 85,
4727
• Kumar, M. and Ando, Y. (2005) Carbon ,43, 533.
• Lee, C.J.; Lyu, S.C.; Kim, H. W.; Park, C. Y. and Yang, C. W.
(2002a) Chemical Physics Letters, 359, 109.
• Lee, S. J.; Baik, H. K.; Yoo, J. and Han, J.H. (2002b) Diamond and
Related Materials, 11, 914-917.
• Li, W.Z.; Xie, S.S.; Qian, L.X.; Chan, B.H.; Zou, B.S.; Zhou, W.Y,
et al. (1996) Science; 274, 1701.
• Li, Y.; Zhang, X.; Luo, J.; Huang, W.; Cheng, J.; Luo, Z.; Li, T.;
Liu, F.; Xu, G.; Ke, X.; Li, L. and Geise, J. (2004) Nanotechnology,
15, 1645.
• Liu, J.; Rinzler, A. G.; Dai, H.; Hafner, J. H.; Bradley, R. K.; Bou, P.
J.; Lu, A.; Iverson, T.; Shelimov, K.; Huffman, C. B.; Rodriguez-
Macias, F.; Shon, Y-S.; Randall, T.; Colbert, D. T. and Smalley, R.
E. (1998) Science ,280, 1253
• Liu, K.; Jiang, K.L.; Feng, C.; Chen, Z. and Fan, S.S. (2005)
Carbon, 43, 2850.
102
References
• Lourier, O. and Wagner, H. D. (1998) J. Mater Res. 13, 2418

• Lu, J.P. (1997) J. of the Phys. and Chem. of Sol., 58, 1649–1652.
• Martínez, M T; Callejas, M A; Benito, A. M; Cochet, M; Seeger, T;
Ansón, A; Schreiber, J. et al. (2003) Nanotechnology ,14 , 691-695
• Maruyama, S.; Kajima, R.; Miyauchi, Y.; Chiashi, S. and Kohno, M.
(2002) Chemical Physics Letters, 360, 229.
• Maruyama, S.; Chiashi, S. and Miyauch, Y. Proc.of the 6thThermal
Engineering Joint Conference, March 16-20, 2003, Hawaii (Hawaii
Island)
• Maser, W. K.; Munoz, E.; Benito, A. M.; Martinez, M. T.; de la
Fuente, G. F.; Maniette, Y.; Anglaret, E. and Sauvajol, J. L. (1998)
Chemical Physics Letters, 292, 587-593.
• Maurin, G.; Tepanek, I.; Bernier, P.; Colomer, J.F.; Nagy, J.B. and
Henn, F. (2001) Carbon; 39,1273
• Moon, J.M.; An, K.H.; Lee,Y.H.; Park,Y.S.; Bae, D.J.and Park,
G.S.(2001) J. Phys. Chem. B ,105 ,5677.
• Mukhopadhyay, K.; Kosho, A.; Sugai, T.; Tanaka, N.; Shinohara,
H.; Zonya, Z. et al. (1999) Chemical Physics Letters, 303, 117–124.
• Nagaraju, N.; Fonseca, A.; Konya, Z. And Nagy, J.B. (2002) J. Mol.
Catal., A Chem., 181, 57.-62
• Nagasawa, S.; Yudasaka, M.; Hirahara, K.; Ichihashi, T.and Iijima,
S (2000) Chemical Physics Letters, 328, 374-380
• Nardelli, M.B.; Yakobson, B.I. and Bernholc, J.(1998) Physical
Review Letters,81, 4656–4659.
• Overney, G.; Zhong, W. and Tomanek, D. (1993) Zeitschrift Fur
Physik D-Atoms Molecules and Clusters, 27, 93–96.
• Park, J. B.; Choi, G. S.; Cho, Y. S.; Hong, S. Y.; Kim, D.; Choi, S.
Y.; Lee, J. H. and Cho, K. I.(2002) J. of Crystal Growth, 244, 211-
217
• Perez-Cabero, M.; Romeo, E.; Royo ,C.; Monzón, A.; Guerrero-
Ruiz, A. and Rodriguez_Ramos, I. (2004) J. Of Catal., 224, 197.
• Pirard, S.; Douven, S.; Bossuot, C.; Heyen, G. and Pirard, J.P.
(2007) Carbon, 45, 1167-1175.
• Popov, V.N.; Van Doren, V.E. and Balkanski, (2000b)M. Solid
State Communications ,114,395.
• Popov,V.N.; VanDoren, V.E. and Balkanski, M. (1999a) Physical
Review B, 59, 8355.
• Ren, Z. F.; Huang, Z. P.; Wang, D. Z.; Wen, J. G.; Xu, J. W.; Wang,
J. H.; Calvet, L. E.; Chen, J.; Klemic, J. F. and Reed, M. A.(1999b)
Applied Physics Letters, 75, 1086-1088.
• Ren, Z. F.; Huang, Z. P.; Xu, J. W.; Wang, J. H.; Bush, P.; Siegel,
M. P. and Provencio, P. N. (1998a) Science , 282, 1105-1107
103
References
• Rinzler, G.; Liu, J.; Dai, H.; Nikolaev, P.; Huffman, C. B.;
Rodriguez-Macias, F. J.; Boul, P. J.; Lu, A. H.; Heymann, D;
Colbert, D. T.; Lee, R. S.; Fischer, J. E.; Rao, A. M.; Eklund, P. C.
and Smalley, R. E. (1998) Appl. Phys. A, 67, 29-37
• Robertson, D.H.; Brenner, D.W. and Mintmire, J.W. (1992) Phys.
Rev. B;45, 12592-12595
• Ru, C.Q. (2000b) Phys. Rev. B, 62, 16962–16967.
• Ru, C.Q. (2000a) Physical Review B,62, 9973–9976..
• Ru, C.Q. (2001b) J. of Appl Phys.,89,3426–3433
• Ruan, H. D.; Frost, R.L. and Kloprogge, J.T. (2001) J of raman
spectroscopy, 32, 745,
• Ruoff, R.S. and Lorents, D.C. (1995) Carbon ,33,925–930.
• Saito, T.; Matsushige, K. and Tanaka, K. (2002) Physica B ,323,
280-283
• Saito, Y.; Mizushima, R.; Tanaka, T.; Tohji, K.; Uchida, K.;
Yumura, M. and Uemura, S. (1999) Fullerene Sci. Technol., 7 ,653
• Salvetat, J.P.; Briggs, G.A.D.; Bonard, J.M.; Bacsa, R.R.; Kulik,
A.J. and Stõckli., T. (1999) Physical Review Letters, 82, 944–947.
• Satterfield, C. N. (1970) Mass Transfer in Heterogeneous Catalysis.
Cambridge, Mass.: The MIT Press, p.138
• Schrader, B. (1995) Infrared and Raman Spectroscopy, VCH
(Weinheim, New York, Basel, Cambridge, Tokyo)
• Scott, C. D.; Arepalli, S.; Nikolaev, P. and Smalley, R.E.(2001)
Applied Physics A: Materials Science & Processing, 72, 573-580.
• Shelimov, K. B.; Esenaliev, R. O.; Rizler, A. G.; Huffman, C. B.and
Smalley, R. E. (1998) Chemical Physics Letters, 282, 429\
• Sinha, A.K.; Hwang, D.W. and Hwang, L.P. (2000) J. Chemical
Physics Letters; 332, 455–460.
• Sinnot, S. B.; Andrews, R.; Qian, D.; Rao, A. M.; Mao, Z.; Dickey,
E. C. and Derbyshire, F. (1999) J.Chemical Physics Letters, 315, 25-
30
• Su, M.; Zheng, B. and Liu, J. (2000) J.Chemical Physics Letters,
322, 321-326.
• Takikawa, H.; Ikeda, M.; Hirahara, K.; Hibi, Y.; Tao, Y.; Ruiz, P.A.;
Sakakibara, T.; Itoh, S. and Iijima, S.(2002b) Physica B: Condensed
Matter , 323, 277-279.
• Takikawa, H.; Tao, Y.; Hibi, Y.; Miyano, R.; Sakakibara, T.; Ando,
Y.; Ito, S.; Hirahara, K. and Iijima, S. (2001a) AIP Conference
Proceedings, 590, 31-34.
• Tanaka, K.; Okahara, K.; Okada, M. and Yamabe, T. (1992). Chem.
Phys. Lett.;191,469-472.
• Thess, A.; Lee, R.; Nikolaev, P.; Dai, H.; Petit, J.; Robert, P. et
al.(1996) Science, 273, 483–487.
104
References
• Thostenson, E.T.; Ren, Z. and Chou, T.W. (2001) Composites

Science and Technology, 61, 1899-1912
• Tohji, K.; Goto, T.; Takahashi, H.; Shinoda, Y.; Shimizu, N.;
Jeyadevan, B.; Matsuoka, I.; Saito, Y.; Kasuya, A.; Ohsuna, T.;
Hiraga, K. and Nishina Y (1996) Nature ,383, 679
• Tohji, K.; Takahashi, H.; Shinoda, Y.; Shimizu, N.; Jeyadevan, B.
and Matsuoka, I et al. (1997) J. Phys. Chem B, 101, 365
• Treacy, M.M.J.; Ebbesen, T.W.and Gibson, T.M. (1996) Nature,
381, 680–687.
• Tsang, S. C.; Harris, P. J. F. and Green, M.L.H (1993) Nature ,362,
520-522
• Tukaba, K.; Katagiri, M.; Kubo, M.; Vetrivel, R. and Miyamoto A.
(1995) Molecular Microporous Mater., 3, 449-455
• Umek, P.; Hassanien, A.; Tokumoto, M. and Mihailovic, D. (2000)
Carbon ,38 ,1723
• Vaccarini ,L.; Goze, C.; Aznar, R.; Micholet, V.; Journet, C. and
Bernier, P.(1999a), Synth. Met. ,103, 2492
• Vaccarini, L.; Goze, C.; Henrard, L.; Hernandez, E.; Bernier, P.and
Rubio, A. (2000b) Carbon, 38, 1681–1690.
• Venkateswaran, U.D.; Rao, A.M.; Richter, E.; Menon, M.; Rinzler,
A.; Smalley, R.E.and Eklund, P.C. (1999),Phys. Rev. B ,59, 10928
• Walters, D.A.; Ericson, L.M.; Casavant, M.J.; Liu, J.; Colbert, D.T.
and Smith, K.A.(1999) Appl. Phys. Lett., 74, 3803–3805.
• Williams, D.B. and Carter, C.B. (1996) Transmission Electron
Microscopy; BasicsI, Plenum Press (New York, London)
• Wong ,E.W.; Sheehan, P.E.; Lieber, C.M. (1997) Science,277,
1971–1975.
• Wu, T. M.; Lin, Y. W. and Liao, C. S. (2005) Carbon, 43, 734-740
• Xie, S.; Li, W.; Pan, Z.; Chang, B. and Sun, L. (2000) J. of Phys.
and Chem. of Sol.,61, 1153–1158.
• Yacaman, M.J.; Yoshida, M.M.; Rendon, L.; Santiesteban, J.G.
(1993) Applied Physics Letters, 62, 202-204
• Yakobson, B.I.; Brabec, C.J. and Bernholc, J. (1996a) Physical
Review Letters; 76, 2511–2514.
• Yakobson, B.I.; Campbell, M.P.; Brabec, C.J. and Bernholc, J.
(1997b) Comput. Mat. Sc. ,8, 341–348.
• Yakobson, B.I. and Samsonidze, G. (2000c) Carbon,38, 1675–1680.
• Yu, M.F.; Lourie, O.; Dyer, M.; Moloni, K. and Kelly, T.(2000b)
Science,287, 637–640.
• Yu, M.F.; Files, B.S.; Arepalli, S. and Ruoff, R.S.(2000a) Phys.
Rev.Lett.,84, 5552–5555.
• Yudasaka, M.; Kikuchi, R.; Matsui, T.; Ohki, Y.; Yoshimura, S. and
Ota, E. (1995a) Applied Physics Letters, 67, 2477-2479
105
References
• Yudasaka, M.; Kikuchi, R.; Ohki, Y.; Ota, E. and Yoshimura, S.

(1997b) Applied Physics Letters, 70, 1817-1818.
• Yudasaka, M.; Kokai, F.; Takahashi, K.; Yamada, R.; Sensui, N.;
Ichihashi, T. et al. (1999c) , Journal of Physical Chemistry B 103,
3576-3581
• Yudasaka, M.; Yamada, R.; Sensui, N.; Wilkins, T.; Ichihashi, T.
and Iijima, S. (1999) Journal of Physical Chemistry B, 103 , 6224-
6229.
• Zhang, A.; Li, C.; Bao, S. And Xu, Q. (1999) Micropor Mesopor
Mater.,29, 383
• Zhang, Z.; Zhao, Y. and Zhou, Y.(2005) Tsinghua Science &
Technology, 10, 741
• Zheng, B.; Li, Y. and Liu, J. (2002) Applied Physics A: Materials
Science & Processing,74, 345-348.
• Zhong, G.; Iwasaki, T.; Robertson, J. and Kawarada, H. (2007) J.
Phys. Chem. B, 111, 1907
106
Appendix
Investigation method
1 Electron microscopy
When a high-energy (~keV) electron beam interacts with a specimen then

a wide range of secondary signals are formed which can give interesting
information about the sample (Fig. A.1). In a scanning electron microscope
(SEM) the secondary electrons (SE), backscattered electrons (BSE) and
characteristic X-rays are mainly analysed (EDX). If the sample is thin
enough, the elastically scattered electrons can be investigated in a
transmission electron microscope (TEM).
Figure A.I: Signal generated when a high-energy electron beam interacts

with a thin specimen. Most signals can be detected in a SEM or TEM.
Appendix
1.1 Scanning electron microscopy (SEM)
Scanning electron microscopy is used to inspect topographies of

specimens at very high magnifications using a piece of equipment called the
scanning electron microscope. SEM magnifications can go to more than
300,000 X but most semiconductor manufacturing applications require
magnifications of less than 3,000 X only. SEM inspection is often used in
the analysis of die/package cracks and fracture surfaces, bond failures, and
physical defects on the die or package surface.
During SEM inspection, a beam of electrons is focused on a spot volume
of the specimen, resulting in the transfer of energy to the spot. These
bombarding electrons, also referred to as primary electrons, dislodge
electrons from the specimen itself. The dislodged electrons, also known as
secondary electrons, are attracted and collected by a positively biased grid
or detector, and then translated into a signal.
To produce the SEM image, the electron beam is swept across the area
being inspected, producing many signals. These signals are then amplified,
analyzed, and translated into images of the topography being inspected.
Finally, the image is shown on a CRT.
The energy of the primary electrons determines the quantity of the
secondary electrons collected during inspection. The emission of secondary
electrons from the specimen increases as the energy of the primary electron
beam increases, until a certain limit is reached. Beyond this limit, the
collected secondary electrons diminish as the energy of the primary beam is
increased, because the primary beam is already activating electrons deep
below the surface of the specimen. Electrons coming from such depths
usually recombine before reaching the surface for emission.
If the electrons are scattered inelastically then they are scattered at the
electrons of the target material. Compared to impacts with the nucleus of the
atom, the change in direction of the electrons can be neglected provided the
electron energy is not too low. The electrons continuously lose their energy
through the interaction with the electrons of the target. The loss in energy dE
per distance ds can be described by the Bethe equation (Bethge, 1987):
(1)
where N is the number of atoms, Z the atomic number of the target

material, J the ionisation energy of the target and E the Energy of the
incident electron. Through this interaction the excited secondary electrons
can escape the outermost layer of the target material and can be detected.
Apart from secondary electrons, the primary electron beam results in the
emission of backscattered (or reflected) electrons from the specimen.
Backscattered electrons possess more energy than secondary electrons, and
108
have a definite direction. As such, they can not be collected by a secondary

electron detector, unless the detector is directly in their path of travel. All
emissions above 50 eV are considered to be backscattered electrons.
Backscattered electron imaging is useful in distinguishing one material
from another, since the yield of the collected backscattered electrons
increases monotonically with the specimen's atomic number. Backscatter
imaging can distinguish elements with atomic number differences of at least
3, i.e., materials with atomic number differences of at least 3 would be
contrasted well against on the image.
The energy loss of elastically back-scattered electrons on the target
nucleus can be neglected because of the large mass difference of electrons
and target nucleus. Considering the screening of the nuclear charge by the
electron shells, the angular scattering of electrons by the coulomb field of the
atomic nucleus can be described by the screened Rutherford scattering cross-
section:
(2)
where θ is the scattering angle, Ω is the solid angle and θ0 the screening
angle given by the ratio of the reduced wave length of the electron λ/2π and
the radius of the nucleus. The probability for a scattering at a small angle is
much higher than for large angles.
The different properties of the secondary and backscattered electrons are
taken advantage of in the SEM. Since the energy of the secondary electrons
is low they are attracted with a positively charged grid on the SE-detector.
The different properties of the secondary and backscattered electrons are
taken advantage of in the SEM. Since the energy of the secondary electrons
is low they are attracted with a positively charged grid on the SE-detector.
The energy of the backscattered electrons is too big to be attracted by the
grid. The secondary electrons give particularly topographic information
aboutthe sample.
The energy of the backscattered electrons is high enough to create
electron-hole pairs in a semiconductor detector. They give information about
the chemical composition of the target material because of the Z2
dependence of the cross section.
A SEM may be equipped with an EDX analysis system to enable it to
perform compositional analysis on specimens. EDX analysis is useful in
identifying materials and contaminants, as well as estimating their relative
concentrations on the surface of the specimen.
109
Appendix
1.2 Transmission Electron Microscopy (TEM)
Transmission Electron Microscopy (TEM) is a technique used for

analyzing the morphology, crystallographic structure, and even composition
of a specimen. TEM provides a much higher spatial resolution than SEM,
and can facilitate the analysis of features at atomic scale (in the range of a
few nanometers) using electron beam energies in the range of 60 to 350 keV.
Unlike the SEM which relies on dislodged or reflected electrons from the
specimen to form an image, the TEM collects the electrons that are
transmitted through the specimen. Like the SEM, a TEM uses an electron
gun to produce the primary beam of electrons that will be focused by lenses
and apertures into a very thin, coherent beam.
This beam is then controlled to strike the specimen. A portion of this
beam gets transmitted to the other side of the specimen, is collected, and
processed to form the image.
The operation of the objective lens allows the imaging of the object in the
corresponding image plain by focusing of electrons starting from different
directions, from individual object points to the corresponding image points
(Fig.A.2). Additionally in the back focal plane of the objective all those
electrons are focused to one point, which started in the same direction from
any point in the object (Fig. 2) leading to the diffraction pattern of the object.
A bright field image contrast can be obtained by arranging a contrast
aperture in the back focal plain in order to eliminate all electrons, which are
scattered and diffracted, respectively into large angles. Depending on the
setting of the intermediate lens one may image either the back focal plane or
the image plane of the objective lens in the image plane of the projector lens.
Thus one obtains either the diffraction pattern or the image of the specimen
on the viewing screen.
The relation between the accelerating voltage U and the electron velocity
v is given by:
(3)
where m0 is the rest mass of the electron and c the velocity of light in
vacuum.
The wavelength λ attributed to an electron with velocity v is given by the
de Broglies relation:
(4)
110
where h is Planck’s constant. An electron with a kinetic energy of Ekin =

100 keV has a velocity v of ≈ 55% light velocity and a wavelength of λ = 3.7
pm.
The contrast in TEM arises mainly from the elastic scattering process.
The inelastically scattered electrons are not focused in the image plane
because of the chromatic aberration of the objective lens.
For crystalline materials, the specimen diffracts the incident electron
beam, producing local diffraction intensity variations that can be translated
into contrast to form an image. For amorphous materials, contrast is
achieved by variations in electron scattering as the electrons traverse the
chemical and physical differences within the specimen. The greatest
consideration when performing TEM analysis is sample preparation. The
quality of sample preparation contributes greatly to whether the micrograph
will be good or not, so analysts are required to exercise the necessary
diligence in preparing the sample for TEM analysis.
Figure A.2: The two basic operations of a TEM: projecting the diffraction
the objective lens as its object.
111
Appendix
2 Raman spectroscopy
2.1 Introduction
If a light quantum hν0 hits e.g. a molecule it is scattered with a high

probability elastically with the energy hν0 in the so-called Rayleigh
scattering process (Fig..A.3). With a much lower probability (~10-5) it is
scattered inelastically with an energy hν0±hνs in the Raman scattering
process in which the vibrational energy hνs is exchanged. According to the
Botzmann’s law most molecules are in their vibrational ground state at
ambient temperature.
Therefore the Raman process that transfers energy to the molecule and
leaves a quantum with lower energy hν0-hνs has a higher probability than the
reverse process. The corresponding Raman lines are called Stokes and anti-
Stokes lines, respectively “Schrader (1995)”:
Figure A.3: Polarized molecule in an electric field (left), energy diagram of

the different light scattering processes. The elastic Rayleigh scattering and
the inelastic Raman scattering (Stokes/Anti-Stokes) (right)
In the classical theory the Raman scattering is explained as follows: If a
diatomic molecule is irradiated with an alternative electric field E:
E(t)=E0cos(2πν0t) (5)
an electric dipole moment P is induced:
P =α Ε (6)
where α is the polarisability (in general a tensor). If the molecule vibrates
with a frequency νs, the nuclear displacement is written as
(7)
112
For a small amplitude of vibration, α is a linear function of q:
(8)
where α0 corresponds to the polarisability at the equilibrium position. By

combining the equations we get “Ferraro et al. (1994)”:
(9)
The first term corresponds to an oscillation of a dipole with frequency ν0

(Rayleigh scattering), the second and third term corresponds to the Raman
scattering with frequency ν0+νs (anti-Strokes) and ν0-νs (Strokes). A
vibration is only Raman active when (∂α/∂q)0 is not zero. The classical
equation does not describe the intensities of the Stokes and anti-Stokes lines.
The intensity ratio of the anti-Stokes and Stokes lines of a Raman active
vibration νs is given by “Huong et al.(1995)”:
(10)
where T is the specimen Temperature. For crystals the polarizability α is

replaced by the susceptibility tensor χ:
P = ε0 χE (11)
Whether a vibration is Raman active or not is determined by the

symmetry of the crystal described in group theory. When the frequency of
the incident radiation approaches an electronic transition frequency
(electronic level r in Fig. A.4), the intensity of the Raman bands is strongly
enhanced.
Raman spectra obtained with exciting frequencies close to absorption
bands are called resonance Raman spectra.
For crystals transparent to the incident and scattered light the
conservation of energy and momentum can be written as “ Cardona et
al.(1983)”:
(12)
(13)
113
Appendix
where νs and qs are the frequency and wave vector of a crystal excitation.
For typical light scattering experiments in or near the visible, the range of
scattering wave vectors is 0≤k≤106 cm-1. For first-order scattering processes
the accessible range |qs|, is small compared to a reciprocal lattice vector. In
high order processes the range of the individual wave vectors of the
excitation. For typical light scattering experiments in or near the visible the
range of scattering wave vectors is 0≤k≤106 cm-1. For first-order scattering
processes the accessible range |qs|, is small compared to a reciprocal lattice
vector. In high order processes the range of the individual wave vectors o e
excitation can be from zero to a reciprocal lattice vector since k = Σqi .
Under this conditions (metals and small gap semiconductors that are
opaque to the light) k0 and k1 are complex.
In the following cases the wave vector conservation (13) breaks down:
1) The scattering medium has no translation symmetry i.e. in crystals
with defects, solid solutions and in amorphous solids. The absence of
translation symmetry allows scattering by modes with qs ≠ k.
2) The scattering volume is small. In this case light scattering is due to
excitations with wave vectors in a range Δq ≈2π/d where d is a characteristic
length in the scattering volume.
3) The incident and scattered waves are damped inside the scattering
volume.
Under this conditions (metals and small gap semiconductors that are
opaque to the light) k0 and k1 are complex.
2.2 Raman spectra of carbon
2.2.1 Raman spectra of graphite

Among the six vibrational modes in graphite only the two E2g vibrational
modes are Raman active. The E2g1 mode is at 42 cm-1 and the E2g2 mode at
1582 cm-1. The first order Raman spectrum of HOPG is shown in Fig. A.4
(left). The E2g2 mode is also called “G-band”, whereas G means graphite.
The peak around 1350 cm-1 is the so-called “D-band”(disorder). In perfect
graphite this mode is forbidden and becomes only active in presence of
disorder where the wave vector conservation (equation 13) breaks down and
other modes become active. The ratio of the integrated D-and G-band is
inversely proportional to the crystallite size of graphite (Fig. A.4 (right)). For
glassy carbon the D-band is very intense due to the high disorder in this
material.
114
Figure A.4: Normalised raman spectra of HOPG, glassy carbon, CVD

MWNT and CVD SWNT. The laser wavelength was λ = 514.5 nm (left). The
inverse crystallite size vs.the ratio of the D- and G-band; according to
(right).
2.2.2 Raman spectra of nanotubes
Among the 6N calculated phonon dispersion relations for SWNT only a

few modes are Raman or infrared active. The number of the Raman- (A1g,
E1g, E2g symmetries) and IR-active (A2u, E1u symmetries) modes for SWNT
can be predicted by group theory. The number of Raman and IR active
modes do not depend on the nanotube diameter and chirality. There are only
15 to 16 Raman active modes and 6 to 9 IR-active modes.There are only six
or seven intense Raman-active modes for any nanotube chirality. Some
Raman modes for a (10, 10) SWNT are displayed in Fig. A.5. The A1g mode,
which occurs at about 165 cm-1 for an isolated (10, 10) nanotube, is strongly
dependant on the nanotube diameter, while the modes near 1580 cm-1 are
not. The power law predicted for the A1g radial breathing mode frequency ω0
RBM (dt) for an isolated SWNT valid in the range 0.6 nm ≤ dt ≤1.4 nm is
“Dresselhaus et al (2000b)”:
where ω0 (10,10) = 169 cm-1 and d(10,10) = 1.375 nm are the mode
frequency and diameter of an isolated (10, 10) armchair nanotube. When the
SWNTs are in bundles, inter-tube interactions (Van der Waals) become
115
Appendix
important and the dispersion relation for the diameter dependence of the
radial breathing mode is
(15)
where ω0RBM (dt) is given by equation (13) and ΔωRBM is a frequency upshift
which is constant for nanotube diameters near a (10, 10) tube. Some typical
values are ΔωRBM = 14 cm-1 “Venkateswaran et al.(1999)”, 6.5 cm-1 “Alvarez
et al.(2000)” and 6 cm-1 “Alvarez et al.(2000)”.One-dimensional quantum
effects are observed in the Raman spectra of SWNT through the resonant
Raman enhancement effect in nanotubes between incident or scattered
photons and the electronic transitions between the Van Hove singularities in
the 1D density of states in the valence and conduction bands. This resonant
effect can be seen experimentally by measuring spectra with different laser
excitation energies (Fig. A.6). An example of a spectrum of CVD SWNT
synthesised in the fluidised-bed is shown in Fig. 4. The CVD MWNT shown
in Fig. A.4 have a strong peak at 1576cm-1 that is strongly shifted down
relative to the 1582 cm-1 mode observed for HOPG.
This downshift is also reported in the first Raman study of MWNT “Hiura et
al.(1993)”. A second weaker mode is found at 1348 cm-1.
Figure A.5: Atomic displacements of calculated Raman modes, frequencies

and symmetries of a (10, 10) nanotube. Only one displacement of the two
doubly degenerate E1g and E2g modes are shown
116
Figure A.6: Raman spectra for purified SWNTs exited at five different laser
excitation wavelengths. 1320 nm → 0.94 eV; 1064 nm → 1.17 eV; 780 nm
→ 1.58 eV; 647.1 nm → 1.92 eV; 514.5 nm → 2.41 eV.
117

Tesi Caterina Leone

Загружено:

Сведения о документе

Оригинальное название

Авторское право

Доступные форматы

Поделиться этим документом

Поделиться или встроить документ

Параметры публикации

Этот документ был вам полезен?

Это неприемлемый материал?

Авторское право:

Доступные форматы

Tesi Caterina Leone

Загружено:

Авторское право:

Доступные форматы

HIGH PERFORMANCE

FONDO SOCIALE EUROPEO

Department of Chemical and Food Engineering

HIGH PERFORMANCE SYNTHESIS

Supervisor Ph.D. student

Ph.D. Course Coordinator

Per la realizzazione di questo mio lavoro di tesi ringrazio il prof. Paolo

Vorrei inoltre ringraziare i miei compagni di laboratorio Antonietta, Arianna,

Carbon nanotubes, constituted by rolled up graphene sheets, have become

In chapter I, after an introduction, providing some historical background

The target of the research has been to improve performance in catalytic

Transmission electron microscopy (TEM) analyses have been conducted

3IChapter I Structure and properties of carbon nanotubes......................1

I.2 Characterization of carbon nanotubes ................................................. 4

I.3 Mechanics of carbon nanotubes ............................................................ 6

I.3.1 Single-walled carbon nanotubes..........................................................6

I.3.2. Multi-walled carbon nanotubes…………………………………….. 9

I.4 Thermal and electrical properties ....................................................... 10

Chapter II: Carbon nanotubes synthesis technique...............................13

II.2 Arc discharge....................................................................................... 13

II.2.1 Synthesis of SWNT........................................................................... 15

II.2.1.1 Inert gas ........................................................................................ 15

II.2.1.2 Optical plasma control.................................................................. 15

II.2.I.4 Improvement of oxidation resistance........................................... 16

II.2.2 Synthesis of MWNT ......................................................................... 17

II.2.2.2 Magnetic field synthesis ................................................................ 18

II.2.2.3 Plasma rotating arc discharge..................................................... 19

II.3 Laser ablation ...................................................................................... 20

II.3.1SWNT versus MWNT ....................................................................... 22

II.3.2 Large scale synthesis of SWNT ....................................................... 23

II.3.3 Ultra fast Pulses from a free electron laser (FEL)method............ 23

II.3.4 Continuous wave laser-powder method ......................................... 23

II.4 Chemical vapour deposition ............................................................... 25

II.4.1 Plasma enhanced chemical vapour deposition............................... 25

II.4.2 Thermal chemical vapour deposition ............................................. 26

II.4.3 Alcohol catalytic chemical vapour deposition……….....................27

II. 4.4 Vapour phase growth……………………………………………...28

II.4.5 Aero gel-supported chemical vapour deposition…………………29

II.4.6 CoMoCat process ............................................................................. 29

Chapter III: Experimental I:Experimental Plant..................................33

III.2 Experimental Plant for nanotubes synthesis....................................33

Chapter IV: Experimental II Effect of alumina phases and process

IV.2.1TG, DTG evaluation ........................................................................ 38

IV.2.2 SEM characterization..................................................................... 42

IV.2.3 Transmission electron microscopy characterization ................... 44

IV.2.4 Raman spectroscopy ....................................................................... 45

Chapter V: Experimental III On-line analysis.......................................47

V.3 Results and discussion......................................................................... 48

V.3.1 Catalyst characterization................................................................. 48

V.3.2 On-line analysis of effluent gas...…………………………………..55

V.3.3 TG, DTG evaluation......................................................................... 61

V.3.4 SEM characterisation....................................................................... 64

V.3.5 Transmission electron microscopy characterization..................... 65

V.3.6 Raman spectroscopy......................................................................... 67

Chapter VI: Experimental IV Microwave purification and

VI.I Introduction ........................................................................................ 69

VI.2Experimental Part .............................................................................. 70

VI.2.1 Carbon nanotubes synthesis............................................................70

VI.2.1 Purification treatment..........….………………………………......70

VI.2.3 Methods .......................................................................................... .73

VI.3.1 Microscopy images.......................................................................... 73

VI.3.2 TG-DTG evaluation ....................................................................... .78

VI.3.3 ICP-MS analysis.............................................................................. 80