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ENEA-UTAPRAD, C.R. Frascati, via E. Fermi 45, 00044 Frascati, Roma, Italy
ENEA-UTTMAT, C.R. Casaccia, via Anguillarese 301, 00123 Roma, Italy
c
NILPRP, Lasers Department, 409 Atomistilor, 077125 Magurele-IF, Bucharest, Romania
b
a r t i c l e
i n f o
Article history:
Received 20 March 2013
Accepted 28 May 2013
Available online 3 June 2013
Keywords:
CO2 laser pyrolysis
Silicon carbide nanoparticles
Silica nanoparticles
Titania nanoparticles
Nanoparticles synthesis
Nanomaterials applications
a b s t r a c t
Nanoparticles are the building blocks of many approaches for realizing nanostructured materials and
devices. The technique of CO2 laser pyrolysis of gas- or vapour-phase precursors for the synthesis of
nanoparticles has proven to be a very exible and versatile technique which permits to cope with several
challenges in different sectors of nanotechnology. Different kinds of pyrolytic nanopowders with average
size in the range 560 nm and a narrow size distribution, have been produced and tested for the fabrication
of structural materials and/or for functional applications in various elds. Here we report new results
on the synthesis of SiC, TiO2 and SiO2 nanoparticles for energetic applications and cultural heritage
preservation.
2013 Elsevier B.V. All rights reserved.
1. Introduction
Nanoparticles (NPs) are particles having at least one dimension that is less than 100 nm in size. In the 90s, scientic evidence
was found that materials on the nanoscale may possess properties (optical/electronic/magnetic) that are dramatically and even
entirely different from the bulk [1]. After this discovery, the development of nanoscience and nanotechnology has created a whole
new nanoworld. NPs can be regarded as one of the fundamental building blocks of nanotechnology since they are the starting
point of several bottom up approaches for fabricating nanomaterials used, or being evaluated for use, in many elds ranging from
catalysis to photonics and opto-electronics, from energy production to thermal management [2]. Moreover, biological systems are
considered as the ideal playground for NPs applications. In fact, due
to their very small size, NPs are able to gain access and even operate
within cells. Promising applications in bio-medicine span from drug
delivery to cancer therapy by hyperthermia and to bio-imaging [3].
Nowadays, NPs of a wide range of chemical compositions and
phases can be prepared by a variety of methods; however the production of large amounts of pure, non-agglomerated NPs, with
desired size and narrow size distribution, still results to be an
Corresponding author. Tel.: +39 069 400 5469; fax: +39 069 400 5312.
E-mail address: rosaria.damato@enea.it (R. DAmato).
0165-2370/$ see front matter 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.jaap.2013.05.026
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Fig. 1. Schematic of the set-up for laser synthesis of nanoparticles from gas-phase
reactants.
R. DAmato et al. / Journal of Analytical and Applied Pyrolysis 104 (2013) 461469
463
Fig. 2. Picture of the ENEA set-up for laser synthesis of nanoparticles from gas-phase
reactants.
3. Experimental
3.1. Experimental set-up
The set-up for the production of nanopowders by CO2 laser
pyrolysis is shown in Fig. 2. The CW CO2 laser beam ( = 10.6 m)
is focused by a spherical lens (focal length F.L. = 12 or 19 cm) at the
centre of the reaction chamber (volume V 6.8 103 m3 ) where it
orthogonally intersects the reactant gas ow. The maximum laser
power is 1.2 kW and the power density in the focal region can
be varied up to 275 kW/cm2 . Reactant gases enter the chamber
through the inner tube of a coaxial stainless steel nozzle. An inert
gas (He or Ar) ows through the outer tube with the purpose of
conning and cooling the particles. The pressure in the reaction
chamber is kept constant and measured by a pressure control unit.
Typical pressures are in the range 6.780 103 Pa.
In the laser pyrolysis process, the reactants are most often in the
gas-phase, however in some cases, liquid precursors are either the
only choice or the most advantageous from an economical point
of view. The use of liquid precursors is made possible by an evaporating system installed at the laser pyrolysis set-up: the liquid
precursor is extracted from the reservoir by bubbling the inert gas,
or one of the gas-phase reactants, and subsequently introduced
in the evaporator unit and maintained at proper temperature by
a heater; at the exit of the evaporator the vapour precursor and
gas mixture are carried out through a heated exible tube to the
reaction chamber.
At the exit of the reaction region, marked by a ame, a strong
quenching effect stops the particle growth at nanometric size. The
produced powder are driven by the gas ow through a chimney into
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Table 1
Experimental parameters, productivities and mean diameters (d) of SiC-NPs.
Powder
SiH4 (sccm)
Productivity (g/h)
d (nm)
SiC-15
SiC-16
SiC-17
SiC-20
SiC-21
SiC-22
SiC-23
SiC-24
SiC-26
12
12
12
19
19
19
19
19
19
3
3
4
3
4
4
4
4
6
500
300
500
500
300
500
500
500
500
630
630
630
630
630
630
400
900
630
50
15
50
55
30
55
50
50
50
25
30
30
35
45
40
35
50
50
2
2
3
13
18
13
3
18
22
Fig. 3. Left side: 3D view of the interaction region between the laser beam and the molecular gas ow in the focusing geometry with F.L. (focal length) = 19 cm. Right side:
ame luminosity map.
the map of ame temperatures can be used to gain insights into the
burning process itself and the subsequent evolution in space (and
time) of the nanoparticle growth.
In the following, the effect of two different types of laser focusing geometries on the nal characteristics of SiC nanopowders will
be analyzed and discussed. The most common optical conguration
consists in matching the CO2 laser beam waist in the focal region
with the reactant ow cross-section in the interaction volume. To
get this condition, in our set-up the CO2 laser beam was focused by
a spherical lens (F.L. = 19 cm) down to a spot of about 5 mm in diameter on the reactant ow, a few mm below the exit of the gas inlet
nozzle having an internal diameter of 4 mm (see Fig. 3 left side). The
laser power was varied in the range 400900 W (cfr SiC 222324
in Table 1), all the other process parameters being kept constant:
the pressure in the reaction chamber was set at 8.0 104 Pa, the
acetylene ow was set at 250 sccm and the Ar ow, which ensures
the connement of the reaction, was set at 5 slm. Typical productivities ranged between 3050 g/h and reaction yields were near to
100%.
The temperature distribution in the reaction zone is visualized
by the ame luminosity map in the picture shown in Fig. 3 right
side. The observed ame asymmetry is due to the Ar ow at the
optical window to avoid powder deposition and accumulation on
the inner surface. It is evident that in this focusing conguration the
temperature distribution is rather uniform in the reaction volume
(3.2 102 mm3 ), which is laterally limited by the conning Ar gas
ow. However, the temperature appears lower at the edge of the
ame where the reactant molecules are diluted (and cooled) by the
Ar ow. The maximum temperature in the ame depends on the
laser power density that is varied from 2.0 to 4.6 kW/cm2 . The high
productivities (and reaction yields) observed in the whole range of
laser power densities ensure that all the reactant molecules are dissociated. SEM analysis of the produced SiC particles shows a broad
size distribution (Fig. 4) that can be explained by the temperature
gradient at the edge of the ame. At the ame boundaries, in fact,
the reactants are more strongly diluted with Ar and smaller particles are formed as a consequence of the lower radical concentration
and lower reaction temperature T [2830]. On the other hand, the
results reported in Table 1 conrm that the peak of the size distribution depends on the laser power when all the other process
parameters are kept constant (cfr SiC 222324).
In order to narrow the particle size distribution, a different
focusing geometry was designed to change the temperature prole
of the ame and minimize the particle formation at the ame edge.
To this purpose, tight focusing of the laser beam on the reactant
ow was realized by use of a shorter focal length, spherical lens
(F.L. = 12 cm) (see Fig. 5a). After SiH4 ignition in the laser focus,
the ame propagates in the reaction volume and the temperature
R. DAmato et al. / Journal of Analytical and Applied Pyrolysis 104 (2013) 461469
465
Fig. 5. Left side: 3D view of the interaction region between the laser beam and the molecular gas ow in the focusing geometry with F.L. (focal length) = 12 cm. Right side:
ame image and luminosity map.
Fig. 7. Typical IR spectrum and X-ray diffraction pattern (inset) of laser synthesized
SiC nanopowders.
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Table 2
Effect of synthesis parameters: experimental parameters, carbon contamination, mean diameters (d, as obtained by SEM analysis) and Zave (as obtained by DLS) of SiO2 -NPs.
Powder
Tev ( C)
C2 H4 (sccm)
TEOS-1
TEOS-2
TEOS-3
TEOS-4
TEOS-8
TEOS-9
TEOS-7
TEOS-14
TEOS-12
TEOS-10
TEOS-15
TEOS-11
TEOS-16
TEOS-17
140
140
140
140
160
160
160
170
170
170
170
170
180
180
400
0
400
600
400
400
400
0
200
400
600
400
600
400
Laser (W)
800
1200
1200
1200
800
1000
1200
700
700
700
700
900
700
800
%C (w/w)
10
10
20
18
8
10
13
15
9
6
6
9
5
9
d (nm)
Zave (DLS)
12
15
20
18
28
25
22
18
15
35
25
35
28
10
221
248
241
235
150
158
190
204
180
157
186
183
195
204
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467
Table 3
Experimental parameters for the synthesis of pure and N-doped TiO2 -NPs.
Powder
Sensitizer
TTIP (g/h)
sensitizer (sccm)
Pressure (Pa)
TiO2 -1
N-TiO2 -2
N-TiO2 -3
N-TiO2 -4
C2 H4
NH3
NH3
NH3
50
40
40
50
400
600
600
600
5.3 104
8.7 104
4.7 104
5.7 104
Fig. 10. Raman spectra of TiO2 samples and attribution of peaks to anatase () and
rutile () phase on the basis of their intensity and position, showing the prominence
of anatase phase.
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to distilled water, when impact on Al, Cu and stainless steel targets. Moreover, evaluation tests of the heat transfer performance
of water-based nanouids containing either TiO2 or SiC pyrolytic
nanoparticles (in different concentrations) were carried out in the
same dual test rig [39]. Using the Reynolds number as a reference
parameter, it has been found that the heat transfer coefcient for
the nanouids is higher than for the basic uid. This result has
been attributed to the higher viscosity of the nanouids, which,
for the same Reynolds number, corresponds to a higher velocity,
thus allowing for a better heat transfer performance [39]. However, due to the higher velocity for the same Reynolds number,
pressure drops associated with nanouids are higher than those
typical of the basic uid. It follows that higher pumping power values are required. These conclusions have to be taken into account
when considering the perspectives for exploitation of nanouids in
practical applications.
5.2. Development of TiO2 -based porous semiconductor electrodes
TiO2 nanopowders are considered for applications in many hot
areas as photocatalysis, functional surface coating and working
electrodes for dye-sensitized solar cells (DSSC) just to name a few.
While traditional synthesis methods like ame pyrolysis or solgel
approaches are the most investigated, laser-assisted pyrolysis can
provide advantageous material characteristics related to the morphology of aggregates, and to the possibility of efcient doping.
Presently, we are exploring nitrogen-doped titania for applications in photocatalysis and DSSC electrodes. In the rst case,
the visible absorption band produced by doping is expected to
extend the photocatalytic activity of the material beyond the UV
range proper of intrinsic titania [40], with obvious energy efciency gain. For DSSC applications, the N-doped working electrodes
are reported to improve the electron collection efciency [41]. Our
preliminary results show that the conversion efciency of a nonoptimised DSSC device using N-doped titania compare well with
those of a standard device. Work is in progress to study the transport properties of doped and undoped electrodes, in order to assess
their respective electronic performances also in different applications requiring porous semiconductor electrodes as hydrogen
generation, sensors, and others.
5.3. Development of nanocomposites for cultural heritage
preservation
In the last few years, nanoparticles and nanostructured materials have been applied to restoration and conservation of artworks.
The modulation of physical and chemical properties of a protective
coating can be obtained by a proper blending of the coating material with suitably chosen nanoparticles. In particular, nanosilica and
nanotitania were selected for their physical properties, such as the
improved water repellence.
For that reason, SiO2 and TiO2 nanoparticles with mean size
of about 15 nm, as produced by CO2 laser pyrolysis, were added
as nanometric llers to two commercial products, largely used
for protective coatings, i.e. an acrylic resin and a silicon-based
polymer. The purity of the nanopowders and their low aggregation are considered important items to obtain homogeneous
nanocomposites that do not alter the colour of the artworks. In
fact the synthesis of nanocomposites to get a nal homogenous
dispersion is a tricky step, depending on the chosen preparation
method, solvent and particle concentrations. Different solutions of
the polymers with dispersed silica and titania nanoparticles were
prepared and applied on the surface of two different litotypes,
very common in outdoor cultural heritage: white marble (statuary
and veined Carrara) and travertine [42]. Articial ageing processes,
both in climatic chamber and in solar box, were carried out to
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[8] R. Alexandrescu, E. Borsella, S. Botti, M.C. Cesile, S. Martelli, R. Giorgi, S. Turtu,
G. Zappa, Synthesis of TiC and SiC/TiC nanocrystalline powders by gas-phase
laser-induced reaction, Journal of Materials Science 32 (1997) 56295635.
[9] R. Vassen, D. Stoever, Processing and properties of nanophase silicon carbide,
Journal of the American Ceramic Society 82 (1999) 25852593.
[10] D. Sciti, J. Vicens, A. Bellosi, Microstructure and properties of alumina-SiC
nanocomposites prepared from ultrane powders, Journal of Materials Science
37 (2002) 37473758.
[11] M. Lekka, N. Kouloumbi, M. Gajo, P.L. Bonora, Corrosion and wear resistant electrodeposited composite coatings, Electrochimica Acta 50 (2005) 45514556.
[12] R. DAmato, M. Falconieri, F. Fabbri, V. Bello, E. Borsella, Preparation of luminescent Si nanoparticles by tailoring the size, crystallinity and surface composition,
Journal of Nanoparticle Research 12 (2010) 18451858.
[13] F. Huisken, G. Ledoux, O. Guillois, C. Reynaud, Light emitting silicon nanocrystals from laser pyrolysis, Advanced Materials 14 (2002) 18611864.
[14] X. Li, Y. He, S.S. Talukdar, M.T. Swihart, Process for preparing macroscopic
quantities of brightly photoluminescent silicon nanoparticles with emission
spanning the visible spectrum, Langmuir 19 (2003) 84908496.
[15] S. Veintemillas-Verdaguer, M.P. Morales, C.J. Serna, Continuous production of
gamma-Fe2 O3 ultrane powders by laser pyrolysis, Materials Letters 35 (1998)
227321.
[16] I. Morjan, R. Alexandrescu, I. Soare, F. Dumitrache, I. Sandu, I. Voicu, A. Crunteanu, E. Vasile, V. Ciupina, S. Martelli, Nanoscale powders of different iron
oxide phases prepared by continuous laser irradiation of iron pentacarbonylcontaining gas precursors, Materials Science and Engineering C 23 (2003)
211216.
[17] A. Donato, E. Borsella, S. Botti, S. Martelli, C.A. Nannetti, M.R. Mancini, I. Morjan,
Thermal shock tests of -SiC pellets prepared from laser synthesized nanoscale
SiC powders, Journal of Nuclear Materials 233237 (1996) 814817.
[18] E. Trave, V. Bello, F. Enrichi, G. Mattei, E. Borsella, M. Carpanese, M. Falconieri,
C. Abate, N. Herlin-Boime, K. Jursiokova, F. Costa, L. Costa, L. Gini, Towards
controllable optical properties of silicon based nanoparticles for applications
in opto-electronics, Optical Materials 27 (2005) 10141019.
[19] J. Boucle, A. Kassiba, M. Makowska-Janusik, N. Herlin-Boime, C. Reynaud, A.
Desert, J. Emery, A. Bulou, J. Sanetra, A.A. Pud, S. Kodjikian, Linear electro-optical
behavior of hybrid nanocomposites based on silicon carbide nanocrystals and
polymer matrices, Physical Review B 74 (2006) 205417205427.
[20] E. Borsella, R. DAmato, M. Falconieri, E. Trave, A. Panariti, I. Rivolta, An outlook on the potential of Si nanocrystals as luminescent probes for bioimaging,
Journal of Materials Research 28 (2013) 193204.
[21] E. Borsella, M. Falconieri, N. Herlin, V. Loschenov, G. Miserocchi, Y. Nie, I. Rivolta,
A. Ryabova, D. Wang, Biomedical sensor applications of silicon nanoparticles,
in: L. Pavesi, R. Turan (Eds.), Silicon Nanocrystals: Fundamentals, Synthesis and
Applications, Wiley-VCH Verlag/GmbH & co. KgaA, Weinheim, Germany, 2010,
pp. 507536.
[22] F. Erogbogbo, K.-T. Yong, I. Roy, G. Xu, P.N. Prasad, M.T. Swihart, Biocompatible luminescent silicon quantum dots for imaging of cancer cells, ACS Nano 2
(2008) 873878.
[23] F. Erogbogbo, C.-W. Chang, K.-T. Yong, W.-C. Law, I. Roy, M.T. Swihart, P.N.
Prasad, Bioconjugation of luminescent silicon quantum dots for selective
uptake by cancer cells, Bioconjugate Chemistry 22 (2011) 10811088.
[24] S. Veintemillas-Verdaguer, Y. Leconte, R. Costo, B. Bouchet-Fabre, M.P. Morales,
P. Bonville, S. Prez-Rial, I. Rodriguez, N. Herlin-Boime, Continuous production of inorganic magnetic nanocomposites for biomedical applications by laser
pyrolysis, Journal of Magnetism and Magnetic Materials 311 (2007) 120124.
[25] F. Erogbogbo, C.-W. Chang, J.L. May, L. Liu, R. Kumar, W.-C. Law, H. Ding, K.T.
Yong, I. Roy, M. Sheshadri, M.T. Swihart, P.N. Prasad, Bioconjugation of luminescent silicon quantum dots to gadolinium ions for bioimaging applications,
Nanoscale 4 (2012) 54835489.
469