Materials Chemistry and Physics 111 (2008) 42–49

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Materials Chemistry and Physics

journal homepage: www.elsevier.com/locate/matchemphys

Electrodeposition of composite materials containing functionalized

carbon nanotubes
T. Casagrande, G. Lawson, H. Li, J. Wei, A. Adronov, I. Zhitomirsky ∗
Department of Materials Science and Engineering, McMaster University, 1280 Main Street West, Hamilton, Ontario, Canada L8S 4L7

a r t i c l e i n f o a b s t r a c t

Article history: New methods have been developed for the synthesis and electrodeposition of functionalized single-
Received 29 June 2007 walled carbon nanotubes (f-SWNTs). Polystyrene sulfonate functionalized nanotubes (PSS-f-SWNTs) and
Received in revised form 9 March 2008 poly(ethylene imine) functionalized nanotubes (PEI-f-SWNTs) were co-deposited with cationic chitosan
Accepted 20 March 2008
macromolecules. It was shown that chitosan promotes cathodic deposition of anionic PSS-f-SWNTs. The
strategies for charging and electrodeposition of PEI-f-SWNTs include partial protonation of PEI in acidic
Keywords:
chitosan solutions or formation of cationic Ag+ –PEI complexes. The thickness of chitosan–PSS-f-SWNTs
Fullerenes
and chitosan–PEI-f-SWNTs composite films was varied in the range of up to 0.5–5 ␮m. The amount of
Electrochemical techniques
Polymers
f-SWNTs in the deposits was varied by controlling the SWNT concentration in the solutions. It was
Thin films shown that the use of chitosan enabled co-deposition of other materials, such as hydroxyapatite (HA).
The proposed method enabled the fabrication of composite films.
© 2008 Elsevier B.V. All rights reserved.

1. Introduction
Carbon nanotubes (CNTs) exhibit a unique combination of elec-
trical, mechanical, thermal, optical and structural properties that
make them potentially important components of optoelectronic,
high-strength and biomedical materials. Recently, many interest-
ing investigations have focused on the biological properties of CNTs
[1–6]. For instance, it has been shown that carbon nanotubes can
penetrate cell membranes, support the growth of neuronal tissue
and promote biomineralization [4]. Cell adhesion experiments have
revealed that CNTs are promising materials for the fabrication of
advanced neural and orthopedic implants [5], and may also serve as
functional coatings on implants in blood-contacting environments
[6]. Significant interest has been generated in the applications
of CNT in drug delivery, diagnostic tools, biosensors and probes,
implantable materials and optoelectronic devices [7–11].
The realization of these carbon nanotube applications has been
hindered by the insolubility of CNTs in all aqueous and organic sol-
vents. In particular, numerous biological applications of CNTs will
require aqueous solubility. Fortunately, the solubility in water can
be improved by chemical modification of CNTs [12–14]. Moreover,
the functionalization of CNTs has enabled the introduction of novel
properties, such as temperature and pH responsiveness [15–18],
biomolecule complexation [19–22] and improved biocompatibility
∗ Corresponding author. Fax: +1 905 528 9295.
E-mail address: zhitom@mcmaster.ca (I. Zhitomirsky).
[23–26]. In addition, it has been found that carboxylic acid groups
introduced on the nanotube surface can not only improve aque-
ous solubility, but can also promote biomineralization [12] and
allow surface modification of biomedical devices [27]. Furthermore,
significant interest has been generated in the immobilization of
biomolecules on CNTs [28–30] for applications in biosensors, and
functionalized CNTs are under investigation for the development
of new drug delivery systems [7].
The fabrication of composite materials containing functional-
ized CNTs is an area of particular interest. These composites may
consist of biopolymers, bioceramics, bioglasses and other materials
[31–35]. Chitosan is one of the most studied natural biopoly-
mers for the fabrication of biosensors, coatings and scaffolds for
biomedical applications [36]. The utility of chitosan stems from
the advanced properties of this material, such as antimicrobial
activity, corrosion resistance and biocompatibility. Hydroxyapatite
(HA) Ca10 (PO4 )6 (OH)2 is another important material for biomedical
implants, as its chemical composition is similar to that of bone tis-
sue. Synthetic HA is a biocompatible prosthetic material, bonding
strongly to bone and promoting the formation of bone tissue on its
surface. However, its poor mechanical properties compared with
natural bone make it unsuitable for major load-bearing applica-
tions. Recent studies indicate that the mechanical properties of HA
can be improved by the development of CNT reinforced composites
[37].
For many applications of functionalized CNTs the formation
of composite films is an important requirement. For example,
charged groups have been introduced to enable layer-by-layer

0254-0584/$ – see front matter © 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.matchemphys.2008.03.010
 T. Casagrande et al. / Materials Chemistry and Physics 111 (2008) 42–49
(LBL) deposition of CNTs onto surfaces to provide well-defined,
homogeneous coatings of controlled thickness [7,30]. In addi-
tion, ligand-functionalized polymers have been introduced on the
nanotube surface to enable multivalent binding to biomolecules
[28,30]. Our previous work has involved the development of var-
ious strategies for the functionalization of single-walled carbon
nanotubes (SWNTs) with well-defined polymers [38–43], including
ones exhibiting pH-responsive functional groups such as amines
and sulfonic acids. In addition, an important recent finding was
the feasibility of electrodeposition of composite HA–chitosan films
[44–46]. These films could be obtained as monolayers, multilayers
or materials of graded composition. These combined results pave
the way for the fabrication of thin film nanocomposites, containing
functionalized CNT.
Here, we report the fabrication of nanocomposite films contain-
ing functionalized SWNT and HA nanoparticles in a chitosan matrix.
Electrochemical strategies for the cathodic electrodeposition of
SWNTs modified with cationic and anionic polymers have been
developed, allowing the formation of homogeneous films where
the nanotube loading within the HA/chitosan matrix can be con-
trolled. We compare the deposition of cationically and anionically
functionalized nanotubes and show that the different mechanisms
involved in deposition of these structures lead to different degrees
of nanotube aggregation in the product films. This work paves the
way for further investigation of multicomponent films containing
intimately mixed nanostructures produced by a simple, one-step
electrodeposition method.
2. Experimental procedures
2.1. Materials
The pristine SWNTs used in this study were purchased from Carbon Nanotech-
nologies Inc. These SWNTs were produced by the HiPco process and were used
without further purification. tert-Butyl 4-aminobenzoate was prepared according
to literature procedures [47] and characterized using 1 H NMR. Filtrations were car-
ried out using VWR filtration apparatus equipped with a stainless steel support
screen and Sartorius PTFE membranes (4.7 cm diameter, 200 nm pore size). All addi-
tional reagents and solvents were obtained from commercial suppliers and used as
received.
2.2. Preparation of t-butyl benzoate functionalized SWNTs [48]
In a typical experiment, SWNTs (200 mg, 16.67 mmol of carbon) and tert-butyl 4-
aminobenzoate (12.87 g, 66.60 mmol, 4 equiv. mol−1 of carbon) were added to a flask
equipped with a reflux condenser and a magnetic stir bar. The flask was evacuated
and backfilled with nitrogen three times and then left under nitrogen. Subsequently,
isoamyl nitrite (11.18 ml, 83.89 mmol, 5 equiv. mol−1 of carbon) was added slowly via
syringe. The mixture was then placed in an oil bath and stirred vigorously at 60 ◦ C
for 5 h. The resulting paste was diluted with dimethylformamide (DMF, 250 mL) and
filtered through a Teflon membrane. The collected solid was washed with DMF until
the filtrate became colorless. Dispersing the solid in DMF by sonication followed by
another filtration step through a Teflon membrane afforded purified functionalized
SWNTs. The resulting mat of functionalized SWNTs was washed with diethyl ether
(500 ml), and the product was dried in a vacuum oven (55 ◦ C) for 72 h. The product
was analyzed using Raman spectroscopy.
2.3. Preparation of benzoic acid-functionalized SWNTs
In a typical experiment, t-butyl benzoate functionalized SWNTs (100 mg) were
stirred in a 10% solution of triflouroacetic acid (TFA) in anhydrous dichloromethane
(DCM, 80 ml) for 12 h under nitrogen, after that excess TFA and DCM was removed
under a constant flow of nitrogen. The resulting nanotubes were filtered through a
Teflon membrane. The collected solid was washed with dichloromethane (500 ml),
diethyl ether (250 ml) and dried in vacuo.
2.4. Preparation of poly(ethylene imine) functionalized SWNTs
In a typical experiment, benzoic acid f-SWNTs (8.9 mg, 0.74 mmol of carbon)
were dispersed in 20 ml anhydrous DMF and stirred at 0 ◦ C under a constant flow of
nitrogen. Thionyl chloride (1.5 ml, 20.56 mmol) was added slowly and reaction tem-
perature was raised to room temperature and allowed to stir for 4 h. Acyl chloride
functionalized tubes were obtained by filtration through a Teflon membrane and
43
washed (anhydrous DCM, 250 ml) to remove excess thionyl chloride. Nanotubes
were then dispersed in 50 ml anhydrous DCM and added slowly to a solution of
PEI (MW = 10,000 g mol−1 , 9.0 g) in 100 ml anhydrous DCM at 0 ◦ C. The reaction was
allowed to stir overnight at room temperature under nitrogen, after which the tem-
perature was slowly raised to 60 ◦ C over a period of 4 h. The resulting nanotubes were
obtained by filtration through a Teflon membrane and washed with DMF (750 ml),
water (500 ml) and diethyl ether (250 ml). On average, approximately 65 wt% soluble
polymer functionalized SWNTs were obtained using this procedure.
2.5. Synthesis of hydroxyapatite
Stoichiometric HA nanoparticles for electrodeposition were prepared by a wet
chemical technique described in previous works [44–46]. Precipitation was per-
formed at 70 ◦ C by the slow addition of a 0.6 M ammonium phosphate solution into a
1.0 M calcium nitrate solution. The pH of the solutions was adjusted to 11 by NH4 OH.
Stirring was performed during 8 h at 70 ◦ C and then 24 h at room temperature. The
precipitate was washed with water and finally with ethanol. It has been previously
reported [44] that the average length of the needle-shape HA crystals, prepared by
this method, is about 200 nm and the average aspect ratio is 8.
2.6. Electrodeposition
Chitosan (Mw = 200,000) with a degree of deacetylation of about 85% was
dissolved in 1% acetic acid and used for the preparation of solutions for elec-
trodeposition. Functionalized SWNTs were dispersed in the 0–0.5 g l−1 chitosan
solutions containing 0–5 mM of AgNO3 . Before the deposition, the suspensions
were ultrasonicated for 30 min to achieve a homogeneous dispersion of the SWNTs.
The electrochemical cell for the deposition included a cathodic substrate cen-
tered between two parallel platinum counter electrodes. The distance between the
cathode and counter electrode was 15 mm. Electrodeposition was performed at a
constant voltage of 10–30 V. Cathodic deposits were obtained on stainless steel, Ti
and Pt foils (50 mm × 50 mm × 0.1 mm).
2.7. Characterization
The X-ray diffraction (XRD) studies were carried out with a diffractometer (Nico-
let I2) using monochromatized Cu K␣ radiation at a scanning speed of 1◦ min−1 . The
microstructures of the deposited coatings were studied using a JEOL JSM-7000F
scanning electron microscope (SEM) equipped with energy dispersive spectroscopy
(EDS). Thermogravimetric analysis (TGA) was performed using a thermoanalyzer
(Netzsch STA-409) operated in argon at a heating rate of 5 ◦ C min−1 . Laser Raman
spectroscopy was performed on solid samples (powders) placed in glass capillary
tubes, using a Bruker RFS 100 instrument equipped with a YAG laser (1064 nm irra-
diation) and a Ge high-sensitivity detector. 1 H NMR measurements were made in
deuterated chloroform (CDCl3 ) using a Bruker 500 MHz instrument.
3. Results and discussion
3.1. Functionalization of SWNTs with poly(stryrene sulfonate)
(PSS)
Functionalization of pristine SWNTs with poly(stryrene sul-
fonate) was accomplished by previously published procedures
[18]. Briefly, atom transfer radical polymerization (ATRP) was uti-
lized to prepare a polystyrene (PS) sample (MW = 7000 g mol−1 ,
PDI = 1.10) where the terminal bromide functionality was subse-
quently converted to an azide group via substitution using NaN3 .
Alkyne functionalized SWNTs (2) were prepared by diazotization
of aminophenyl propargyl ether (1), followed by its coupling to the
surface of pristine SWNTs (Fig. 1) [41]. The azide-bearing polymer
(3) was coupled to alkyne-functionalized SWNTs (2) via copper(I)
catalyzed [3 + 2] Huisgen “click” cycloaddition to achieve a degree
of functionalization of approximately one polymer chain per 1000
nanotube carbons, as previously reported (Fig. 1) [41]. The resulting
PS–SWNTs were sulfonated using acetyl sulfate in dry chloroform
solution to produce the desired PSS–SWNTs, in which the degree
of sulfonation was approximately 30 mol% [18].
3.2. Functionalization of single-walled carbon nanotubes with
poly(ethylene imine)
SWNTs grafted with PEI were prepared by first introducing
acid-chloride functionalities on the nanotube surface, followed by
44 T. Casagrande et al. / Materials Chemistry and Physics 111 (2008) 42–49

Fig. 1. Functionalization of SWNTs with PSS.

amidation with the free amine groups of PEI. To achieve this, tert-
butyl 4-aminobenzoate was introduced on the nanotube surface
via the solvent-free diazotization and coupling reaction mentioned
above (Fig. 2) [41,48]. The degree of functionalization obtained
using this procedure was determined by thermogravimetric anal-
ysis, which indicated a mass loss of 23%. Based on the molecular
weight of the t-butyl benzoate groups and the mass of nanotubes
used in the experiment, the degree of functionalization was calcu-
lated to be approximately one functional group for every 30-carbon
atoms (Fig. 3). Subsequently, the t-butyl protecting groups were
removed by stirring in trifluoroacetic acid overnight to liberate
acid-functionalized SWNTs (6), which were then converted to ben-
zoyl chloride-functionalized SWNTs (7) via exposure to thionyl
chloride at room temperature for 4 h (Fig. 2). The product was then
immediately dispersed in anhydrous DCM by sonication, followed
by slow addition to a chilled (0 ◦ C) solution of PEI in anhydrous DCM.
To prevent crosslinking of nanotubes, which can occur if a single
PEI chain undergoes amidation with multiple nanotubes (result-
ing in insoluble material), a large excess of PEI was used. Efficient
stirring also proved to be crucial in preventing the crosslinking of
nanotubes, allowing isolation of the PEI-SWNTs (8) in 65 wt% yield,
upon completion and work-up of this reaction.
Thermogravimetric analysis was again used to quantify the
degree of functionalization of PEI-functionalized SWNTs (Fig. 3).
Upon heating the product to 800 ◦ C under an inert atmosphere,
a mass loss of 25% was attributed to decomposition of polymer
(beyond the mass decrease from the benzoic acid linker). Given
that the molecular weight of the polymer was approximately
10,000 g mol−1 , this corresponds to a functionalization of approxi-
mately one polymer chain for every 1600 nanotube carbon atoms.

Fig. 2. Functionalization of SWNTs with PEI.

 T. Casagrande et al. / Materials Chemistry and Physics 111 (2008) 42–49
Fig. 3. TGA data, acquired under argon. The temperature profile involved a hold at
100 ◦ C for 1 h followed by a ramp of 5 ◦ C min−1 to 800 ◦ C. (A) Pristine SWNTs, (B)
benzoic acid-functionalized SWNTs, (C) PEI-functionalized SWNTs and (D) PEI.
Even with this relatively low degree of polymer functionaliza-
tion, it was found that PEI-decorated nanotubes exhibited high
solubility in aqueous solution, indicating that attachment of PEI
was successful. For comparison, pristine SWNTs are completely
insoluble in water, while benzoic acid-functionalized nanotubes
displayed some solubility in aqueous solution (83 mg l−1 ). Con-
versely, PEI-functionalized nanotubes displayed a much higher
aqueous solubility (180 mg l−1 on average), forming a clear dark-
brown solution that contains no visible particulate and is stable
over a period of several weeks.
In addition to TGA, Raman spectroscopy was conducted to deter-
mine the structural integrity of modified SWNT samples and also
to obtain information regarding the degree of nanotube functional-
ization (Fig. 4). The intensity of the disorder band (ωd ≈ 1290 cm−1 )
relative to that of the tangential mode (ωt ≈ 1590 cm−1 ) is indicative
of the presence of sp3 hybridized carbon atoms within the nanotube
framework. Following reaction of pristine nanotubes with t-butyl
amino benzoate the disorder band underwent a significant increase
in intensity, confirming that functionalization had occurred suc-
cessfully. After the attachment of PEI, the intensity of the disorder
band did not increase further, indicating that the reaction with PEI
did not introduce any further defects on the nanotube structure.
Fig. 4. Raman spectra of (A) pristine SWNTs; (B) benzoic acid-functionalized
SWNTs; (C) PEI-functionalized SWNTs.
45
3.3. Electrodeposition of chitosan–PSS-f-SWNT composites
PSS-f-SWNTs were used for the fabrication of composite
chitosan–PSS-f-SWNTs films by cathodic electrodeposition. Chi-
tosan is a natural cationic polysaccharide that can be produced
by alkaline N-deacetylation of chitin. Important properties of this
material, such as biocompatibility, chemical resistance, mechanical
strength, antimicrobial properties and thermal stability, have been
utilized in biotechnology [36]. Moreover, the excellent film forming
properties of chitosan have been utilized for the fabrication of chi-
tosan films. The mechanism of electrodeposition of chitosan films
has been described in the literature [36].
The water soluble and positively charged chitosan can be pre-
pared by protonation in acidic solutions:
CHIT–NH2 + H3 O+ → CHIT–NH3 + + H2 O (1)
In aqueous solutions, the cathodic reduction of water results in
increasing pH at the cathode surface:
2H2 O + 2e− → H2 + 2OH− (2)
The neutralization of the positively charged chitosan macro-
molecules results in the deposition of insoluble chitosan:
CHIT–NH3 + + OH− → CHIT–NH2 + H2 O (3)
In our investigation, PSS-f-SWNTs were dispersed in aqueous
0.5 g l−1 chitosan solutions and deposited cathodically on stain-
less steel, Ti and Pt substrates. The concentration of SWNT in the
solutions was in the range of up to 0.1 g l−1 . Further increase in
SWNT concentration resulted in SWNT precipitation. It is suggested
that positively charged chitosan and negatively charged PSS form
water soluble non-stoichiometric complexes, which carry a positive
charge. Therefore PSS-f-SWNTs can be deposited cathodically from
chitosan solutions (Fig. 5A). However, it is important to note that the
interaction of carbon nanotubes and chitosan can be electrostatic,
non-electrostatic [49,50] or a combination of both.
Fig. 6 shows SEM images of the PSS-f-SWNTs–chitosan compos-
ite films on stainless steel substrates deposited at a cell voltage of
20 V and deposition time of 2 min. The SEM images (Fig. 6A and
B) indicate that the increase in PSS-f-SWNTs concentration in the
solutions resulted in an increasing amount of PSS-f-SWNTs in the
deposits. The PSS-f-SWNTs form bundles in a chitosan matrix. SEM
observations indicate that film thickness was varied in the range of
up to 0.5–5 ␮m by variation of the deposition voltage in the range
of 20–30 V and deposition time in the range of 1–10 min.
3.4. Electrodeposition of chitosan–PEI-f-SWNTs composites
Composite chitosan–PEI-f-SWNTs films were obtained from
0.5 g l−1 chitosan solutions, containing 0.05–0.2 g l−1 SWNTs. The
thickness of chitosan–PEI-f-SWNTs composite films was varied in
the range of 0.5–5 ␮m by variation in deposition voltage and depo-
sition time in the range of 10–30 V and 1–10 min, respectively. Fig. 7
shows an SEM image of a composite film obtained at a deposition
voltage of 20 V. PEI-f-SWNTs are distributed in a chitosan matrix
(Fig. 7) and show much lower aggregation compared to the PSS-f-
SWNTs (Fig. 6), which form bundles. It is important to note that PEI
is a cationic polyelectrolyte exhibiting a positive charge over a wide
pH range below 11 [50,51]. However, the pH of a 1 wt% aqueous PEI
solution was found to be about 11 [51,52] (PEI is a polybase), and
lowering the pH of this solution was achieved through protonation
of the amine groups using strong acids. Without addition of acids,
PEI films cannot be deposited cathodically [53].
It is suggested that PEI can be partially protonated in acidic chi-
tosan solutions to form positively charged PEI-f-SWNTs. Compared
46 T. Casagrande et al. / Materials Chemistry and Physics 111 (2008) 42–49

Fig. 5. Electrodeposition of (A) PSS-f-SWNTs–chitosan and (B) PEI-f-SWNTs–chitosan nanocomposites.

to negatively charged PSS-f-SWNTs, the positively charged PEI-f-
SWNTs can be better dispersed in chitosan solutions, due to the
electrostatic repulsion of cationic chitosan and PEI-f-SWNTs. It is
suggested that PEI-f-SWNTs can be deposited independently of chi-
tosan (Fig. 5B), unlike the chitosan–nanotube complexes formed
with PSS-f-SWNTs. The better dispersion and independent deposi-
tion of PEI-f-SWNTs resulted in lower aggregation of PEI-f-SWNTs
(Fig. 7) compared to PSS-f-SWNTs (Fig. 6).
In this work, we have also found it possible to deposit PEI-f-
SWNTs using PEI–metal ion complexes. It is known that metal ions
such as Ag+ , Mn2+ , Cu+ , Ni2+ , Co2+ and Zn2+ have remarkable binding
affinity towards PEI [54]. Several excellent recent reviews highlight
the materials science and applications of polymer–metal ion com-
plexes [54–56]. A soluble polymer–metal ion complex behaves as
a polyelectrolyte in aqueous solutions and can be used for cathodic
electrodeposition. This novel approach has been utilized for the
fabrication of superparamagnetic films, electrochemical superca-
pacitors and coatings for corrosion protection of metals [53]. The
results pave the way for the deposition of PEI-f-SWNTs using
PEI–metal ion complexes.
As an extension of the previous investigations, we studied the
feasibility of electrodeposition of SWNTs using solutions of PEI-f-
SWNTs containing Ag+ ions. No deposition was achieved from pure
PEI-f-SWNTs solutions. However, the addition of AgNO3 to the PEI-
f-SWNTs solutions resulted in the formation of cathodic deposits.
The SEM images shown in Fig. 8 indicate that PEI-f-SWNTs can be

Fig. 6. SEM images of PSS-f-SWNTs–chitosan nanocomposites prepared from 0.5 g l−1 chitosan solutions containing (A) 0.02 g l−1 and (B) 0.08 g l−1 SWNTs.
 T. Casagrande et al. / Materials Chemistry and Physics 111 (2008) 42–49 47

Fig. 7. SEM image of PEI-f-SWNTs–chitosan nanocomposite prepared from 0.5 g l−1

Fig. 9. X-ray diffraction pattern of a deposit prepared from a PEI-f-SWNTs solution,
chitosan solutions containing 0.05 g l−1 SWNTs.
containing 0.2 g l−1 SWNTs and 5 mM AgNO3 at a current density of 2 mA cm−2 (()
silver, JCPDS file 04-0783 and (䊉) substrate).

deposited together with Ag species. The deposits shown in Fig. 8,

consist of PEI-f-SWNTs and Ag nanoparticles bonded to Ag nan-
otubes. The X-ray diffraction pattern shown in Fig. 9 indicates the
deposition of Ag metal (JCPDS file 04-0783).
It is suggested that PEI-f-SWNTs acquire a positive charge as
a result of complex formation with Ag+ . In this case, the electric
field provides the electrophoretic motion of charged Ag+ –PEI-f-
SWNTs towards the electrode surface. The complexed Ag+ ions can
be reduced at the cathode surface to form Ag metal. It is important
to note that free Ag+ ions, which are not complexed by PEI, also exist
in solutions and contribute to the formation of Ag nanoparticles. It
is suggested that Ag+ ions bonded to PEI-f-SWNTs and reduced at
the cathode surface provide nucleation sites for further growth of
Ag nanoparticles by reduction of free Ag+ ions. Indeed, the SEM
studies of a thin deposit (Fig. 8A) and EDS analysis showed the for-
mation of separate Ag crystals attached to carbon nanotubes. It is
important to note that a wide variety of PEI–metal ion complexes
can be obtained by loading the polymer with different metals.
Therefore, the proposed approach represents a new and unex-
plored way for the fabrication of nanocomposites containing carbon Fig. 10. X-ray diffraction pattern of HA prepared by a chemical precipitation method
nanotubes. The antimicrobial properties of Ag and Ag–metal ion (() HA, JCPDS file 09-0432).

Fig. 8. SEM images of composite deposits prepared from PEI-f-SWNTs solutions, containing 0.2 g l−1 SWNTs and 5 mM AgNO3 at a current density of 2 mA cm−2 and deposition
times of (A) 3 min and (B) 5 min.
48 T. Casagrande et al. / Materials Chemistry and Physics 111 (2008) 42–49

Fig. 11. SEM images (A and B) of PSS-f-SWNTs–chitosan–HA nanocomposites prepared by cathodic electrodeposition from 0.5 g l−1 chitosan solutions, containing 0.01 g l−1
SWNTs and (A) 1 g l−1 , (B) 5 g l−1 HA (arrows show nanotubes).

Fig. 12. SEM images (A and B) of PEI-f-SWNTs–chitosan nanocomposite films prepared from 0.5 g l−1 chitosan solutions, containing 1 g l−1 HA (arrows show nanotubes).

complexes [57,58] are important for the development of biomed-
ical implants. Further experiments showed that Ag+ –PEI-f-SWNTs
can be co-deposited together with chitosan to form composite
films.
Turning again to the proposed mechanism of the deposition
of composite films (Fig. 5B), it should be noted that independent
deposition of PEI-f-SWNTs can be achieved using protonated PEI
or PEI–metal ion complexes. The advanced film forming and func-
tional properties of chitosan can be utilized for the fabrication of
composite films. Moreover, the use of chitosan enables the incor-
poration of other functional materials in the composite films.
3.5. Electrodeposition of HA–PSS-f-SWNTs–chitosan and
HA–PEI-f-SWNTs–chitosan composite films
Composite HA–PSS-f-SWNTs–chitosan and HA–PEI-f-
SWNTs–chitosan films were obtained by electrodeposition.
Fig. 10 shows an X-ray diffraction pattern of HA crystals prepared
by a chemical precipitation method. The observed diffraction
peaks are in good agreement with the JCPDS file 09-0432.
The prepared HA nanocrystals were used for the fabrication
of composite coatings. Fig. 11 shows the SEM images of HA–
PSS-f-SWNTs–chitosan coatings, which contain HA nanoparticles
and bundles of PSS-f-SWNTs in a chitosan matrix. In contrast,
the deposition of HA together with PEI-f-SWNTs and chitosan
resulted in the composite films containing individual PEI-f-SWNTs,
as shown in Fig. 12. This is in agreement with the results shown
in Figs. 6 and 7, which indicate the formation of bundles of
PSS-f-SWNTs and individual PEI-f-SWNTs in a chitosan matrix.
These results show that functionalized carbon nanotubes can
be deposited together with chitosan HA, and Ag nanoparticles to
form composite coatings. Moreover, the use of carbon nanotubes
containing functional groups can impart new properties. There-
fore, the results of this work will enable the fabrication of novel
nanocomposite coatings. The suitability of the obtained coatings
for biomedical applications has yet to be determined.
4. Conclusions
New methods have been developed for the synthesis and elec-
trodeposition of PSS-f-SWNTs and PEI-f-SWNTs. It was shown
that chitosan promotes cathodic deposition of anionic PSS-f-
 T. Casagrande et al. / Materials Chemistry and Physics 111 (2008) 42–49 49

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