Atmospheric synthesis of superhydrophobic TiO

2
nanoparticle
deposits in a single step using Liquid Flame Spray
Mikko Aromaa
a,n
, Anssi Arffman
a
, Heikki Suhonen
a
, Janne Haapanen
a
, Jorma Keskinen
a
,
Mari Honkanen
b
, Juha-Pekka Nikkanen
b
, Erkki Lev anen
b
, Maria E. Messing
c
, Knut Deppert
c
,
Hannu Teisala
d
, Mikko Tuominen
d
, Jurkka Kuusipalo
d
, Milena Stepien
e
, Jarkko J. Saarinen
e
,
Martti Toivakka
e
, Jyrki M. M akel a
a
a
Department of Physics, Tampere University of Technology, PO Box 692, FI-33101 Tampere, Finland
b
Department of Materials Science, Tampere University of Technology, PO Box 589, FI-33101 Tampere, Finland
c
Solid State Physics and the Nanometer Structure Consortium, Lund University, PO Box 118, SE-22100 Lund, Sweden
d
Department of Energy and Process Engineering, Tampere University of Technology, PO Box 541, FI-33101 Tampere, Finland
e
Laboratory of Paper Coating and Converting, Center for Functional Materials, Abo Akademi University, Porthansgatan 3, FI-20500 Turku, Finland
a r t i c l e i n f o
Article history:
Received 20 December 2011
Received in revised form
12 April 2012
Accepted 19 April 2012
Available online 15 May 2012
Keywords:
Liquid Flame Spray
Titanium dioxide
Nanoparticle deposition
Functional coating
a b s t r a c t
Titanium dioxide nanoparticles are synthesised in aerosol phase using the Liquid Flame
Spray method. The particles are deposited in-situ on paperboard, glass and metal
surfaces. According to literature, titanium dioxide is supposed to be hydrophilic.
However, hydrophobic behaviour is observed on paperboard substrates but not on
metal or glass substrates. Here, the water contact angle behaviour of the deposits is
studied along with XRD, XPS, BET and HR-TEM. The deposits are compared with silicon
dioxide deposits having, as expected, hydrophilic properties synthesised with the same
method. It seems probable that the deposition process combusts some substrate
material from the paperboard substrate, which later on condenses on top of the deposit
to form a carbonaceous layer causing the hydrophobic behaviour of the TiO
2
deposit.
The similar layer does not form when depositing the nanoparticles on a metal or glass
surfaces. The observations are more than purely aerosol phenomena. However, they are
quite essential in nanoparticle deposition from the aerosol phase onto a substrate
which is commonly utilised.
& 2012 Elsevier Ltd. All rights reserved.
1. Introduction
Nanoparticles are synthesised using several different methods (Kodas & Hampden-Smith, 1999), by liquid, solid and
gaseous routes. Gaseous aerosol routes are highly promising for a number of reasons. Compared to liquid chemistry and
milling of bulk materials, aerosol techniques are simple and offer high production rates (Strobel & Pratsinis, 2007). There
are various different aerosol reactors including hot wall (Backman et al., 2004), laser (Cannon et al., 1982a & b & Morita
et al., 1999), plasma (Pfender, 1999) and ame reactors (Pratsinis, 1998). Flame synthesis has been used for a long time in
material science (Ulrich, 1971) and offers multicomponent and composite nanoparticle synthesis in a single step (Jud et al.,
2006).
Contents lists available at SciVerse ScienceDirect
journal homepage: www.elsevier.com/locate/jaerosci
Journal of Aerosol Science
0021-8502/$ - see front matter & 2012 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.jaerosci.2012.04.009
n
Corresponding author: Tel.: 358 40 8490370.
E-mail address: mikko.aromaa@tut. (M. Aromaa).
Journal of Aerosol Science 52 (2012) 5768
Liquid Flame Spray has been widely used in various applications e.g., glass colouring and synthesis of anti-microbial
deposit layers (Gross et al., 1999; Keskinen et al., 2006). Recently, we have shown that titania nanoparticles can be
deposited directly from the ame onto a paperboard substrate. This process is done in roll-to-roll fashion and in a pilot
scale with line speeds up to 150 m/min. The nanoparticle deposits have highly hydrophobic properties (M akel a et al.,
2011; Stepien et al., 2011; Teisala et al., 2010). However, there has been speculation about the mechanism of obtaining
hydrophobicity, as titanium dioxide is, by nature, hydrophilic (Takeda et al., 1999). Several other groups have also
synthesised superhydrophobic titanium dioxide structures such as nanorods, nanotubes, composites etc. (Borras et al.,
2008; Feng et al., 2005) as well as combinations of different structures (Lai et al., 2009). Also other hydrophilic materials
have been turned hydrophobic due to the creation of nanosized features using techniques such as deep reactive ion
etching of e.g., Si surfaces (Song & Zou, 2007). The cause of the superhydrofobicity is claimed to be due to the so called
lotus structure (Barthlott & Neinhuis, 1997). This means basically, that there are micron sized features together with
nanosized characteristics on top of lotus structured surfaces, which cause the superhydrophobicity. Similar phenomenon
to lotus effect is a petal effect in which the superhydrophobic surface has also a high adhesive force (Feng et al., 2008).
Another method for tuning a hydrophilic material into hydrophobic is to modify the surface with a layer of organic
molecules (Balaur et al., 2005). The aim of this paper is to further investigate the particles in order to reveal the causes of
hydrophobicity on the LFS nanoparticle deposits on paperboard surfaces which is left open in previous papers (M akel a
et al., 2011; Stepien et al., 2011; Teisala et al., 2010).
Recently, core-shell particles have attracted great attention. Core materials can be encapsulated and functionalised by
different shell materials. One of the shell materials of interest is carbon because of its great potential with properties
achieved with attaching functional groups on the surface (Athanassiou et al., 2006). A carbon shell can be easily produced
in aerosol reactors. Carbon is also stable and it can be functionalised with additive molecules (Grass et al., 2007). The
formation of carbon shells has been performed in ame reactors by adding acetylene after formation of the core particles.
Thus, the incomplete combustion of acetylene forms carbon structures on top of the particles. If the acetylene feed is
sufcient, the particles are encapsulated with a graphene shell. The graphene shell can afterwards be functionalised with
liquid chemistry. Also, some precursor materials and solvents for ame spray synthesis assist the formation of the carbon
shell. Ernst et al. (2008) noticed that usage of xylene as a solvent for platinum precursor in platinum particle synthesis
embeds the platinum particles in a carbon shell resulting in inactive platinum catalyst particles.
Papers and boards are highly versatile materials with various benecial properties, e.g., biodegradability, renewability,
mechanical exibility and affordability. The complete utilisation of the versatility of paper and board requires the ability to
control the surface properties. Numerous technologies, especially plasma techniques, have been used to fabricate state of
the art coatings on paper and board surfaces. Superhydrophobic surfaces have been created by uorinating the paper using
grafting and post-functionalisation (Nystr om et al., 2006) or by silane coating the paper through solution immersion
processes (Li et al., 2008). Plasma-assisted deposition of thin uorocarbon (Mukhopadhyay et al., 2002; Pyk onen et al.,
2010; Vaswani et al., 2005), organosilicon (Pyk onen et al., 2010) and hydrocarbon coatings (Pyk onen et al., 2010) have also
resulted in hydrophobic paper surfaces. Balu et al. (2009) created a superhydrophobic paper surface by combining plasma
etching with plasma enhanced chemical vapour deposition (PECVD) of uorocarbon lm. Generally, manufacturing and
converting processes of paper and board are usually continuous, high volume operations where the line speeds can vary
from hundreds up to two thousand metres per minute. This sets high demands also for the surface modication and
deposition techniques used in the further processing of paper and board substrates. Therefore, the utilisation of batch- and
wet chemical-type processes is limited in paper and board industry.
2. Experimental
2.1. Synthesis of the nanoparticles
Flame spray methods introduce precursor material into a ame and produce nanoparticles by evaporation and
subsequent nucleation of the precursor material followed by condensation growth. Precursor materials may also undergo
some chemical reactions prior to nucleation. Liquid Flame Spray (LFS) is one type of apparatus for aerosol synthesis of
nanoparticles. It has been described in several papers (Aromaa et al., 2007; M akel a et al., 2004). In this study, the substrate
travels through the ame causing the nanoparticles to deposit onto the substrate forming the nanoparticle layer. The term
deposit is used throughout the text as a reference to the nanoparticles deposited on the surface of the substrate. The term
coating is reserved here for a later use.
The main principle in LFS is that the liquid precursor is fed into a turbulent oxygenhydrogen ame. The hydrogen ow
atomises the precursor ow into micron-sized droplets (Keskinen et al., 2008) which are subsequently evaporated in the
ame. The liquid ow rate and combustion gas ow rates are controllable. In this study, we use titanium(IV) isopropoxide
(TTIP, 97% Alfa Aesar) in isopropanol solution as precursor material for titanium dioxide particles. In the ame,
evaporated TTIP molecules decompose thermally according to the following overall reaction (Courtecuisse et al., 1996):
TTIP-TiO
2
4C
3
H
6
2H
2
O
This reaction takes place even at temperatures as low as 250 1C (Chen et al., 1993). Propene is an additional product for
thermal decomposition of TTIP. When burning the ame with stoichiometric gas ows of oxygen and hydrogen, the
M. Aromaa et al. / Journal of Aerosol Science 52 (2012) 5768 58
surrounding oxygen is also available for isopropanol and propene to combust into carbon dioxide and water. Propene
might also react with hydrogen to form propane and combust after the reduction. However, if the gas ows for the ame
are oxygen lean, there is insufcient amount of oxygen for isopropanol, propene and propane to combust and partial
oxidation forms other carbon species such as CO or elemental C (e.g., Hart et al., 2003).
In this study, silicon dioxide deposits are only synthesised as a reference to titanium dioxide in order to study the
differences between the deposits as the synthesis is done in a same way and the particle deposits are supposed to have
similar physical characteristics. In earlier studies SiO
2
deposits have shown hydrophilic properties (Stepien et al., 2011).
Tetraethyl ortosilicate (TEOS, 98% Alfa Aesar) in isopropanol solution is used as precursor for synthesis of silicon dioxide.
The reactions for synthesis of SiO
2
from TEOS are similar to reactions for TTIP with the exception that the by-product is
C
2
H
4
instead of C
3
H
6
. However, Cho et al. (2009) have studied the formation of SiO
2
from TEOS in ame reactors and found
out that in ame spray reactors precursor volatility is playing a role in particle formation via gas phase instead of
intradroplet reaction and SiO
2
formation through liquid-to-solid conversion. Thermal decomposition of TEOS usually
occurs at temperatures above 600 1C (Xia et al., 2000).
2.2. Devices for depositing material on the substrate
LFS nanoparticle deposits have been synthesised in a paper converting machine in a roll-to-roll process (M akel a et al.,
2011; Stepien et al., 2011; Teisala et al., 2010) located at the Tampere University of Technology, Finland. The line speed and
burner distance can be controlled in the machine environment together with other parameters of the process such as
precursor concentration and burner gas ow rates. A simplied illustration of the deposition process is presented in Fig. 1.
The burner is installed into a fume hood facing downwards in the middle of the substrate which is rolling underneath the
hood. The fume hood is closed from three sides and open in the front. The dimensions of the hood in mm are
800400800 (height widthlength). The hood lies 20 mm above the substrate and the gap is closed from the three
sides with a piece of ame-proofed cloth. From the ceiling of the hood, exhaust fumes are ventilated away using a tube
with a diameter of 100 mm. The system is also simulated as such.
A laboratory scale conveyor line was built to mimic the on-line deposition process in the paper converting machine.
With the conveyor line A4-sized (21.029.7 cm) samples of paper and paperboard together with other materials can be
used as substrates for nanoparticle deposits in order to do quick tests with several parameters. The conveyor line makes it
easier to prepare samples because the length of one sample in the paper converting machine is in the order of hundreds of
metres. The conveyor line is illustrated in Fig. 2. It contains a stainless steel sample carriage travelling along a track. The
track is oval shaped with a straight part in the deposition area. The carriage is pushed by arm from an electric motor which
controls the speed of the carriage. A sample holder is attached on the carriage. The height of the holder can be altered in
order to alter the distance between the burner and the sample. Also the speed of the sample running under the deposition
process can be adjusted portably from 0 to 150 m/min. It has been showed previously that the orientation of the burner
does not play a role in nanoparticle formation (Arabi-Katbi et al., 2002) and thus the ame can also direct the particles
upwards in the laboratory scale conveyor.
2.3. Sample preparation
All the samples were synthesised using the same parameters. Precursor concentration 50 mg(Atomic metal)/ml;
precursor feed rate 32 ml/min; gas ow rates 15/50 (O
2
/H
2
) slpm; line speed 50 m/min; burner distance 150 mm. These
parameter sets have been used previously on paperboard and other materials (Teisala et al., 2010). Teisala et al. (2010)
reported that the TiO
2
nanoparticle deposit on paperboard synthesised with the oxygen lean process parameters have
hydrophobic nature with a water contact angle up to 1601. However, as mentioned in the introduction part, titanium
dioxide, as well as other ceramic materials, is supposed to be hydrophilic by nature (Takeda et al., 1999). The hydrophilicity
is induced by hydroxyl groups that attach onto the titania surface. Stoichiometric gas ows of 20/40 (O
2
/H
2
) slpm have been
used otherwise previously with LFS studies (Keskinen et al., 2006). Thus, some of the samples are also synthesised here with
Fig. 1. The deposition unit in the paper converting machine with the fume hood which is modelled. The fume hood is closed from three sides and open in
the front. Exhaust fumes are ventilated from the top of the hood.
M. Aromaa et al. / Journal of Aerosol Science 52 (2012) 5768 59
stoichiometric ow ratio as they act as a reference parameter set as the oxygen lean process might have some special feature
in forming the superhydrophobic deposits.
Samples of paperboard (pigment coated Natura paperboard 210 g/m
2
, Stora Enso, Skoghall, Sweden) were used as
substrates for nanoparticle deposition with both a converting machine and a specially built laboratory scale track. Also
samples for scanning electron microscopy (SEM) and transmission electron microscopy (TEM) were prepared with both
devices. Several SEM and TEM samples were prepared in order to verify the similarity of the deposits so that the deposits
can be reproduced with the laboratory scale conveyor line with the same parameters in both. TEM samples were prepared
so that the TEM grid (Agar, Holey Carbon, 300 mesh, Cu) was attached onto the paperboard sample by attaching a mask of
the same material with an opening on top of which the TEM grid peeked out. The mask was large enough to avoid edge
effects. The studied TEM and SEM samples were similar with similar process parameters on the paper converting machine
and with the conveyor line so the results presented here are not differentiated by the method of the deposit synthesis.
In the conveyor line, also glass and metal sheets (steel, aluminium and copper) were prepared together with TEM
samples. The sheet replaced the paperboard in order to investigate whether the paperboard as a substrate affects the
deposition process. The TEM sampling was performed in the same way with metal sheets as it was performed with the
paperboard.
Powder samples of the LFS synthesised nanoparticles were collected using a custom-made plate-type electrostatic
precipitator (ESP). The charging and collecting plates are combined. There are two steel plates with a distance of 8 cm and
the voltage between the plates is 20 kV. On the negative plate, there are corona needles to charge the particles before the
collection section. The collection plate is grounded.
2.4. Analysis
Paperboard and metal sheet samples were studied using a water contact angle (WCA) measurement device (KSV CAM200).
SEM samples were cut from the paperboard and studied with Field Emission SEM (Zeiss ULTRAplus). Paperboard sheets were
also analysed using X-ray photoelectron spectroscopy (XPS; PHI Quantum 2000). TEM grids were studied with JEOL JEM-2010
and high resolution TEM JEOL, JEM-3000-F, equipped with an energy dispersive spectrometry, EDS, for elemental analysis. The
crystallinity of the powder samples was analysed with X-ray diffraction (XRD, Kristalloex D-500, Siemens) and the specic
surface area of the powders with the BrunauerEmmettTeller (BET) method (Coulter Omnisorp 100cx).
2.5. Modelling tool
The LFS deposition process was simulated employing CFD package of Ansys Fluent 12.1. The ow eld was solved in a
coupled manner with the chemical species transport and combustion reactions in a 3D-model. RANS-based (Reynolds-
averaged NavierStokes) modelling approach was used. That is, equations describing the time averaged ow eld were
solved and the effects of turbulence on reaction rates and transfer phenomena are modelled solving two additional partial
Fig. 2. An illustration of the laboratory scale machine mimicking the deposition process performed in the paper converting machine. A view of the track
from (a) above and (b) side. The carriage is moving along the track and passing by the deposition point.
M. Aromaa et al. / Journal of Aerosol Science 52 (2012) 5768 60
differential equations that describe the state of turbulence. In addition, the radiation heat transfer was simulated using the
discrete ordinates model.
Combustion of hydrogen and isopropanol with oxygen from the spraying nozzle and surrounding air were the modelled
reactions. For the isopropanol a single step overall reaction scheme was used and the combustion of hydrogen was
assumed to be purely mixing limited. Stainless steel walls were assumed to be in constant temperature but the moving
paperboard was simulated in more detail. The paperboard was assumed to have a nite thickness and to radiate and
convect the heat to the surroundings. This way, the surface temperature of the paperboard was possible to be solved.
Motion of the paperboard has also an effect on the ame tip shape and this motion is also included in the model. A more
thorough description of the simulations and the results can be found from Arffman et al. (2012). A schematic gure of the
simulated case geometry is shown in Fig. 1.
Together with the CFD simulation, the equivalence ratio of the ame is calculated. Referring Turns (1996), Ernst et al.
(2008) dene the equivalence ratio as a measure for stoichiometricity of the process. In the equivalence ratio, the ratio of
molar amounts between fuel and oxidant is compared in the real situation against the stoichiometric one. The equivalence
ratio is dened as:
F
n
fuel
=n
oxidant

real
n
fuel
=n
oxidant

stoichiometric
where n is the molar concentration. The ratio means that if Fo1, the system is oxidant rich and if F41, the system is fuel
rich, i.e., oxygen lean. The ratio easily denes whether there is enough oxygen for all the compounds to oxidise.
3. Results and discussion
In previous studies, we have synthesised titanium dioxide nanoparticle deposits on various substrates using the
stoichiometric gas ow rates (Keskinen et al., 2006; M akel a et al., 2004). In a previous paper (M akel a et al., 2011) we
introduced an application with non-stoichiometric gas ow rates of O
2
H
2
along with a simple model calculation.
A thorough CFD model on the nanoparticle deposition system from the ame on a moving substrate is presently developed
for that system, and will be reported later in a full paper (Arffman et al., 2012). Here, we report a limited set of the data on
the temperature and concentration proles to assist the consideration on nanoparticle and deposit morphology. Especially
comparison between stoichiometric and oxygen lean parameters will be relevant. We have previously synthesised
hydrophobic surfaces with the oxygen lean gas ows (M akel a et al., 2011; Stepien et al., 2011; Teisala et al., 2010), but the
reason for hydrophobicity has not been clear. The aim for the results is to show the reason for different wetting behaviour
of the titanium dioxide and silicon dioxide deposits. The titanium dioxide and silicon dioxide deposits on paperboard have
water contact angle values of 151711 and 21711 respectively, the WCA for the reference paperboard is 60711.
3.1. Simulation model
The CFD-simulation of the process was used to clarify the differences between the two processes presented in the
experimental section. Based on simple estimations on material balances, the processes do not seem to be much different.
Both of the parameter sets used in this study are highly oxygen lean. Equivalence ratio describes how sub- or
superstoichiometric the process is. When feeding precursor solution of 50 mg(Ti)/ml (TTIP and isopropanol) with 32 ml/min
into the ame of 15 slpm of oxygen and 50 slpm of hydrogen, the ratio between the amount of oxygen in a process that
would be stoichiometric and the amount of oxygen in the real process is 4.6: 1 being stoichiometric and over 1 being
oxygen lean environment. Of course, as the deposition is performed in open atmosphere, the ambient oxygen decreases
the calculated equivalence ratio to some extent, but not the amount needed. The calculation allows a possibility of
insufcient combustion of isopropanol and propene.
In the case of stoichiometric gas ows (20 slpm O
2
and 40 slpm H
2
) the equivalence ratio still remains high with a value
of 3.3. The vast amount of precursor solution increases the amount of reducing components in the ame and keeps the
ratio high. Therefore, no major conclusions can be drawn from the synthesis conditions for the nanoparticles to be
different in both cases.
Fig. 3 shows the simulated temperature contours from the cross-section of the deposition process and from the surface
of the paperboard with different hydrogenoxygen ratios. Fig. 3(a) shows that temperatures in the stoichiometric case are
much higher than in the oxygen lean case (b). All images show the temperature of the gas in the process. The upper image
is a view from the side (white square being the burner) and the image below is the temperature of the gas right above the
substrate. The maximum temperature of the ame is approximately 2300 1C with the stoichiometric gas ows and around
1700 1C with the oxygen lean gas ows. This means that turbulent mixing cannot provide enough oxygen from the
surroundings for the complete combustion of both isopropanol and hydrogen in the hydrogen rich ame. The conditions
are oxygen lean and as combustion of hydrogen consumes oxygen, there is not enough left for the solvent (isopropanol)
and by-products of decomposition of TTIP (propene) to oxidise. The incomplete combustion is also modelled. The reference
system with stoichiometric conditions does not have such strong incomplete oxidation of the precursor material according
to the model leaving the possibility of unreacted precursor material to cause the hydrophobic effect. However, TTIP
M. Aromaa et al. / Journal of Aerosol Science 52 (2012) 5768 61
decomposes thermally at very low temperatures. Here, the temperature of the ame does not limit the formation of
titanium dioxide.
3.2. Crystallinity and chemical composition of the synthesised TiO
2
nanoparticles
Powder collection of the nanoparticles was carried out in aerosol phase in order to study the difference of the powder
material that is being deposited on the substrate between the studied parameters. XRD analysis was performed for both of
the powders. The analysis spectra are shown in Fig. 4. The powder is mainly composed of anatase with some peaks of rutile
present in the spectra. This is in line with previous studies dealing with formation of rutile as residual particles which
appear in small amounts (Keskinen et al., 2007). With both parameter sets the graphs look alike and the peaks are similar.
Thus the nanoparticles are in both cases mainly anatase and the differences in gas ows and ame temperature do not
Fig. 3. Simulated temperature contours from the ame cross-section and from the paperboard surface. (a) Stoichiometric gas ows (20/40) slpm (O
2
/H
2
)
(b) Oxygen lean gas ows (15/50) slpm (O
2
/H
2
).
Fig. 4. XRD spectra for TiO
2
powder produced with (a) oxygen lean combustion gas ows of 15/50 slpm (O
2
/H
2
) and (b) stoichiometric gas ows of
20/40 slpm (O
2
/H
2
). The peaks for anatase (A) and rutile (R) are labelled in the gure.
M. Aromaa et al. / Journal of Aerosol Science 52 (2012) 5768 62
have an effect on the particle crystallinity. BET analysis was also performed for the samples in order to measure the
specic surface area (SSA). The SSA of powder samples collected with ESP is 48.92 m
2
/g for the oxygen lean 15/50 slpm
(O
2
/H
2
) gas ow sample and 56.86 m
2
/g for the stoichiometric gas ow 20/40 slpm (O
2
/H
2
) sample. The surface area values
are quite close to each other and the small difference can be explained by the difference in primary particle formation and
aggregation processes because of the signicant temperature difference in the ame shown by the model.
XPS spectrum is shown here only for the TiO
2
deposits on paperboard with the gas ows of 15 slpm O
2
and 50 slpm H
2
as XRD results indicate that the gas ow ratio of the burner does not have an impact on the particle crystallinity. The XPS
spectrum is shown in Fig. 5. XPS is essential in order to nd out whether there is unburned precursor material left in some
form. The oxidation state of the deposited titanium oxide can be concluded from the XPS spectrum. The spectrum shows
the peaks for oxygen and titanium and thus no other oxidation states than TiO
2
are virtually detectable in the deposit. This
clearly demonstrates that there is no possibility of a titanium suboxide or other titanium species on the deposit. The XPS
spectrum also shows a peak for calcium which comes from the substrate. There is a large peak for carbon visible which can
be from the substrate or it can be a result of incomplete combustion of the precursor solution, which is justied with the
calculation of equivalence ratio in the simulation chapter. The calculation leaves a possibility of insufcient combustion of
isopropanol and propene which may result in carbon formation. Also one possible source for carbon peak is slight
combustion of the substrate which forms carbon soot.
3.3. Deposit morphology
SEM images, already published in Stepien et al. (2011), of the deposited TiO
2
and SiO
2
particles show no differences
between the materials. Images show lotus-like structures as there are micron sized features and nanosized characteristics
as well. Stepien et al. (2011) refer to a petal effect which is similar to lotus effect, but there is additionally high adhesion
between the water droplet and the surface. However, TiO
2
deposit has a water contact angle of 156.271.11 and SiO
2
deposit has a water contact angle of 12.271.21 with the reference being 76.870.71. Also, the surface roughness values
presented by Stepien et al. (2011) are quite alike with the RMS roughness being 70.3 nm (reference paperboard), 94.3 nm
(TiO
2
deposit on paperboard) and 86.0 nm (SiO
2
deposit on paperboard).
TEM sampling was performed for both deposited TiO
2
and SiO
2
particles in order to examine if the particle
morphologies of the deposits have any differences in smaller scale. TEM images acquired at different magnications for
both titania and silica are presented in Fig. 6. The TEM images reveal an unexpected difference between the deposits.
Fig. 6(a) is showing the magnication set for TiO
2
and Fig. 6(b) a set for SiO
2
. A surprising observation can be made from
Fig. 6(a), where a coating or a shell of quite a light material (less contrast in the TEM images) is visible in the TiO
2
sample
on top of the deposited particles. Similar coating is not seen in any of the previous studies of TiO
2
synthesised with LFS
(e.g., Aromaa et al., 2007 and Keskinen et al., 2006). Summing up the XPS results with the TEM images leads to a conclusion
that the coating shell on the particle deposits consists of carbon. Carbon is highly hydrophobic, which supports the water
contact angle test results. On the other hand, TiO
2
and SiO
2
particles look quite alike in SEM. The particle size for both
materials is similar and thus the hydrophobic effect might not be alone due to lotus-shaped surface but also from the
coating on top of the particles.
Another unexpected result is seen in Fig. 6(b), with SiO
2
particles. Visually, the shape of the particles is not round as it
would be for air-borne particles. With incomplete sintering in aerosol phase, the particles would still have round shapes,
but here the shape is rougher. Instead, the shape of the particles would rather indicate that the nanoparticle deposit is
formed directly from deposited liquid precursor droplets which have reacted and formed SiO
2
. Similar deposition of liquid
Fig. 5. XPS sample of the hydrophobic paperboard on which titania nanoparticles have been deposited.
M. Aromaa et al. / Journal of Aerosol Science 52 (2012) 5768 63
in ame reactor has been previously observed by Tricoli et al. (2010). Camenzind et al. (2008) published similar formation
of silicon dioxide from unreacted precursor in diffusion ames. Another alternative for the deposit formation would be
chemical vapour deposition, if the gaseous compounds do not have time to nucleate and the formation of solid deposits
takes place on the surface. Both of the presented alternatives may happen at the same time because some of the precursor
material is for sure evaporated from the initial droplets but possibly not all. XPS analysis of the deposit conrms the
material being SiO
2
. Cho et al. (2009) studied the particle formation of SiO
2
from TEOS in a similar aerosol ame spray
generator and found out that the temperature of the ame is limiting the particle formation. They found out that if the
ame temperature is low, the particles form before the evaporation of the precursor. As the model for the ame shows,
here, the temperature of the ame is as low as in the study of Cho et al., where particles formed through liquid-to-solid
route and the residence time in the hot region is small. Thus, it is quite possible that there is deposition of tiny liquid
precursor droplets onto the substrate and nanoparticle deposit is formed from liquid-to-solid conversion via hydrolysis of
the precursor or thermal decomposition of the precursor. The lack of similar shell as there is with the TiO
2
particles could
be explained with the temperature difference. The liquid layer formed from precursor droplets is absorbing the heat of the
ame and the thermal conductivity is not big enough to heat up the substrate in order to combust it sufciently.
3.4. Possibilities for the formation of the coating shell
As a reference, a set of TiO
2
deposits was prepared on inorganic substrates with various thermal conductivities: glass
(both matt and glossy), copper, aluminium and stainless steel sheets. The deposits were synthesised on the plates using
the same conveyor line that was used for the paperboard samples. The water contact angle tests were performed on
selected reference substrates and the contact angles were (WCA for the fresh reference surface in brackets after the WCA
value for TiO
2
nanoparticle deposit sample): aluminium 49781 (89711); glass, matt 01 (24731); glass, glossy 17711
(26721). The WCA of TiO
2
deposited on the matt glass sample is marked as 01 as the water droplet spread over the width
Fig. 6. A set of TEM images with different magnications for (a) TiO
2
nanoparticles and (b) SiO
2
nanoparticles. The scale bars for the images: on left
100 nm and on right 20 nm.
M. Aromaa et al. / Journal of Aerosol Science 52 (2012) 5768 64
of the camera screen immediately after the droplet touched the surface. All the samples obtain hydrophilic behaviour and
all the samples have a lower WCA as the reference and even the rough structure in matt glass does not offer a platform for
lotus-like effect. TEM images of the set show no evidence of the shell on top of the particles with either of the deposition
parameters. Some of the images of particles from TEM analysis on copper surface without the shell are shown in Fig. 7. The
water contact angle of the nanoparticle layer deposited on the reference materials is relatively low, which is in agreement
with the ndings of ceramic materials being hydrophilic (Takeda et al., 1999) if there is no lotus or petal effect. XPS
analysis left a possibility of insufcient combustion of isopropanol and propene from precursor solution. These results
together rule out the possibility of formation of the carbon from precursor material and are strongly suggesting that the
formation of the carbonaceous shell is due to the combustion of hydrocarbons in the substrate material.
TEM sample grids collected on paperboard were also analysed in HR-TEM. Analysis was performed on the edge of the
hole in holey carbon grid. Analysis shows that the shell does not have signicant order between the atoms. An example of
HR-TEM image is shown in Fig. 8(a). Therefore, the shell is not clearly graphene or graphite but more amorphous.
Elemental mapping was also performed for the HR-TEM samples. Elemental map shows that the particles mainly
consist of titanium and oxygen. There is also carbon and copper present which are the peaks originating from the TEM grid.
Furthermore, one can see sharp edges on the peak of titanium when scanning across the particle. There is virtually no
signal in the region outside the particle, where the shell is present. Therefore, the elemental mapping rules out unreacted
precursor and titanium carbide as part of the shell, in the limit of detection. The nding supports the results from XPS. The
EDS line scan of the particle is shown in Fig. 8(b).
The oxygen lean ame with ow rates of 15 and 50 slpm of O
2
and H
2
, respectively, is reducing the ame temperature
from the maximum. Therefore, slight combustion of the substrate may occur and the material is able to burn and form
carbon as a product of incomplete combustion in oxygen lean atmosphere. Also the substrate material plays a role. Is
seems that the substrate needs to contain organic material and a carbon source must be available and in such a form that it
can evaporate and form the shell on the titania deposit as a result of the combustion. The temperature of the paperboard is
around 100300 1C (Teisala et al., 2010) 0.5 m after the deposition process. Thus, the temperature is suitable for
evaporation and even combustion of hydrocarbons that are in the substrate material. Oxygen lean process promotes
carbon formation over carbon monoxide and carbon dioxide formation. The source of carbon is lacking from the metal
sheets and no deposition parameters are found to form hydrophobic deposits on the metal sheets. SiO
2
deposits on the
other hand have a hydrophilic nature. The deposits form via different processes. However, the fact that SiO
2
deposits are
hydrophilic together with the coating shell on TiO
2
particle deposits do not rule out the possibility of hydrocarbon
contaminants as analysed by Takeda et al. (1999) or the petal effect being the key factor in superhydrophobic behaviour of
TiO
2
deposits as there is more to the micro- and nanosized patterning than only the RMS roughness value.
4. Conclusions
In literature, carbon coating of particles has been created in specially designed aerosol reactors in order to functionalise
the surface of nanoparticles. In this study, we have synthesised TiO
2
nanoparticle aerosol and deposited it onto a
paperboard substrate. The nature of the substrate promotes formation of carbonaceous coating on top of the deposited
particles, when using specic parameters for nanoparticle deposit synthesis. The temperature of the process needs to be
controlled so that carbon containing materials are evaporated from the substrate, combusted and re-condensed onto the
particles. The resulting nanoparticle deposit has a uniform carbonaceous shell. TEM images conrm the shell consisting of
carbon and explain the origin of the carbon peak in the XPS results. The deposit may also have adsorbed hydrocarbon
Fig. 7. HR-TEM image of the TEM grid attached on copper sheet. There are no signs of carbon lm on top of the particles as there is when the TEM grid is
attached on the paperboard. Gas ow rate 15/50 slpm (O
2
/H
2
).
M. Aromaa et al. / Journal of Aerosol Science 52 (2012) 5768 65
contaminants on the surface. Altogether, the deposit gives hydrophobic properties for the substrate (or transforms the
hydrophilic particles into hydrophobic). The particles do not have other changes in crystalline form depending on the
process parameters. Produced titania nanoparticles can be deposited from aerosol on a surface to obtain white, stable,
hydrophobic deposit on paper or paperboard. Silica deposits, on the other hand, produce a white and also stable
hydrophilic deposit on paper and paperboard. The particles are produced in large scale and the deposition can be done in a
roll-to-roll process in a pilot scale.
Fig. 8. (a) HR-TEM image on the edge of the hole in the holey carbon TEM grid containing a particle. The image shows a high magnication of the shell.
No clear atomic layers are visible in the shell. (b) Line scan elemental analysis of one particle and the surrounding shell (different from (a)).
The sharp edges of the material peaks show that there are no titanium atoms in the shell. Also no other materials are detected. The peak of carbon cannot
be analysed with the method because of the carbon lm of the grid. The plotted signals in the image (from upper left to lower right): titanium, oxygen
and carbon.
M. Aromaa et al. / Journal of Aerosol Science 52 (2012) 5768 66
Acknowledgements
This work was performed under the Nanorata 2 project funded by The Finnish Funding Agency for Technology and
Innovation, Tekes.
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