ARTICLE IN PRESS

Biomaterials 28 (2007) 618–624

www.elsevier.com/locate/biomaterials

Plasma-sprayed carbon nanotube reinforced hydroxyapatite coatings

and their interaction with human osteoblasts in vitro
Kantesh Balania, Rebecca Andersonb, Tapas Lahaa, Melanie Andaraa,
Jorge Terceroa, Eric Crumplerb, Arvind Agarwala,
a
Department of Mechanical and Materials Engineering, Florida International University, EC 3464, 10555 West Flagler Street, Miami, FL 33174, USA
b
Department of Biomedical Engineering, Florida International University, EC 2601, 10555 West Flagler Street, Miami, FL 33174, USA
Received 10 August 2006; accepted 8 September 2006
Available online 27 September 2006

Abstract

Carbon nanotubes (CNT) possess excellent mechanical properties to play the role as reinforcement for imparting strength and
toughness to brittle hydroxyapatite (HA) bioceramic coating. However, lack of processing technique to uniformly distribute multiwalled
CNTs in HA coating and limited studies and sparse knowledge evincing toxicity of CNTs has kept researchers in dispute for long. In the
current work, we have addressed these issues by (i) successfully distributing multiwalled CNT reinforcement in HA coating using plasma
spraying to improve the fracture toughness (by 56%) and enhance crystallinity (by 27%), and (ii) culturing human osteoblast hFOB 1.19
cells onto CNT reinforced HA coating to elicit its biocompatibility with living cells. Unrestricted growth of human osteoblast hFOB 1.19
cells has been observed near CNT regions claiming assistance by CNT surfaces to promote cell growth and proliferation.
r 2006 Elsevier Ltd. All rights reserved.

Keywords: Hydroxyapatite coating; Carbon nanotube (CNT); Plasma spraying; Titanium alloy; Crystallinity; Human osteoblast

1. Introduction required for the increased implant life. In addition,

Hydroxyapatite (HA), Ca10(PO4)6(OH)2, is an attractive
biomaterial owing to its close chemical resemblance (Ca/
P ¼ 1.67) with bone and teeth [1–3]. Osteoblasts proliferate
onto HA owing to its bioactivity and biocompatibility [3,4]
and therefore HA coatings have long been applied to
dental implants, bone repair scaffolds, skeletal implants,
and body/bioinsert material [5]. Microstructure, crystal-
linity, and phase composition of HA coating is critical in
deciding its cell response and mechanical performance.
Plasma sprayed HA coating often result in the generation
of secondary phases such as tricalcium phosphate (TCP),
tetracalcium phosphate (TTCP), calcium oxide (CaO), and
amorphous calcium phosphates (ACPs) [6]. Though HA is
very stable in the body environment, presence of secondary
phases causes dissolution leading to degradation of the
implant in vivo. Hence, higher crystallinity content is
Corresponding author. Tel.: +1 305 348 1701; fax: +1 305 348 1932.
E-mail address: agarwala@fiu.edu (A. Agarwal).
researchers have used carbon nanotubes (CNT), Ti-alloys,
yttria stabilized zirconia (YSZ), Ni3Al, and alumina
(Al2O3) reinforcements to HA coating [7–9] for improving
its fracture toughness and wear resistance [1,5,10–13].
Chen et al. investigated mechanical properties of laser
processed HA-multiwalled CNT coating showing strong
improvement in the fracture toughness and marginal
improvement in the elastic modulus [1,14]. However, laser
synthesized coating result in the formation of undesired
TiC phase [1]. The purpose of addition of CNT was to
enhance the mechanical performance of the coating with-
out deteriorating the biocompatible properties of HA
[15–17]. On the contrary, CNTs have also been debated
as toxic [18] under organic environment [1,19]. Though in a
recent study, osteosarcoma cell growth has been observed
on functionalized CNT [20], researchers have also depicted
micro patterning of CNTs to result directed growth of
osteoblasts [21], or surface modification with DNA- and
HA-nanostructured films for enhanced detection and
biosensitivity [22]. Haddon et al. has concluded that CNT

0142-9612/$ - see front matter r 2006 Elsevier Ltd. All rights reserved.
doi:10.1016/j.biomaterials.2006.09.013
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K. Balani et al. / Biomaterials 28 (2007) 618–624
surface also acts as crystallization site and scaffolding
substrate for the growth of needle like nano-apatite crystals
[19,20,23]. Hence, the debate on the use of CNT for
biomedical applications is still ongoing among researchers.
In the current work, we have synthesized HA–4 wt%
multiwalled CNT coating via plasma spraying onto Ti-6Al-
4V (orthopedic implant material) and performed human-
osteoblast biocompatibility studies.
Plasma spraying is an existing commercially viable
technique and has been used by researchers to economic-
ally coat HA for the real life implants [5,24]. Though new
materials processing and coating techniques are emerging
[3,12,14,25–28], their applicability is limited due to genera-
tion of non-biocompatible secondary phases [1], weight loss
and residue [26], degradation, non-homogeneity, amor-
phous and more carbonated HA coating [3] and very
limited functional scalability [29]. In the present work, our
research group has improvised the conventional plasma
spray technique in a novel manner for multiwalled CNT
addition and dispersion to HA coating, aiding bone growth
to act as scaffolding and nucleation for apatite crystals.
2. Materials and methods
2.1. Processing
Irregular HA powder (particle size 10–50 mm), Fig. 1a, was blended
with 4 wt% multiwalled CNTs (95%+ pure, OD ¼ 40–70 nm,
l ¼ 0.5–2 mm) in a jar mill for 18 hours to result in powder feedstock.
CNTs are well dispersed and spread over HA particles as seen in the SEM
image of the blended powder feedstock, Fig. 1b. From now on, multiwalled
CNTs are referred to as CNTs in the entire manuscript. Plasma spraying of
HA with and without CNTs was carried out using Praxair SG-100 gun
with optimized spray parameters presented in Table 1. Powders were
internally injected with Ar as the carrier gas to result coatings onto Ti-6Al-
4V bioimplant substrate (50 mm
50 mm
2 mm).
2.2. Microstructural and mechanical characterization
X-ray diffraction spectrum was obtained using Siemens D-500
operating at 40 kV and 20 mA with CuKa peak of 1.54 Å along with
unsuppressed CuKb peaks. Field Emission FESEM JEOL JSM 6330 F
was used for microstructural imaging and Shanghai Taiming Optical
Fig. 1. SEM image of (a) as-received HA powder with inset showing corresponding EDS, and (b) blended HA–CNT powder feedstock showing CNT
distribution over HA particles.
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Instruments HXD-100 TMC Lenovo Vickers microhardness tester was
used for estimating hardness and fracture toughness of the plasma sprayed
HA coatings. Indentation toughness of HA coatings was calculated for
load of 100 g for dwell time of 15 s using the following formula [30]
(assuming the Young’s modulus of HA to be 100 GPa):
K IC ¼ 0:016ðE=HÞ0:5 Pa1:5 , where E is the Young’s modulus, H is the
hardness, P is the applied load and a is the crack length from the center of
indent.
2.3. Cell culture
Human osteoblasts (ATCC, CRL-11372) were cultured in Dulbecco’s
Modified Eagle Media (DMEM) without phenol red (Gibco, 31053-028)
supplemented with 10% FBS (Hyclone, SH30071) and 1% penicillin/
streptomycin/glutamine (PGS) (Gibco, 15140-122). The fibroblasts were
seeded at a density of 300 cells/cm2 onto coated HA samples (with and
without CNT) and were grown under standard culture conditions (37 1C
and 5% CO2—95% air) for 3 days. Prior to seeding, the coated samples
were UV sterilized for 30 min on each side. The substrates were then
prepared for SEM analysis. The substrates were washed with PBS (Gibco,
14040-133) to remove any residual serum and were then incubated in a
25% formalin solution (1 part formalin/3 parts PBS) (Thermo—Shandon,
9990244) for 30 min. The samples were washed three times with fresh PBS.
The samples were incubated again in a 25% formalin/PBS solution for
30 min followed by washing three times with fresh PBS and placing in a
lyophilizer to dry for approximately 24 hours.
3. Results
HA coating with and without 4 wt% CNT has been
plasma sprayed onto real-life bioimplant Ti-6Al-4V mate-
rial. Similar plasma-spray processing conditions with
optimized parameters were used for fabrication of both
the coatings for comparison purpose. This representation
depicts the ease of HA–CNT coating fabrication for
applications with scalability to useful size. Plasma sprayed
Table 1
Optimized plasma spray parameters
Gun current 500–700 A
Power 20–25 kW
Primary gas Argon (0.20–0.25 N/m2)
Secondary gas Helium (0.50–0.55 N/m2)
Standoff distance 0.08–0.12 m
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620 K. Balani et al. / Biomaterials 28 (2007) 618–624

HA with CNT appears more grayish due to the presence
of CNTs.
3.1. Microstructural features of plasma sprayed HA and
HA–CNT coatings
Plasma sprayed coatings, Fig. 2a (HA without CNT)
and Fig. 2b (HA with CNT), depict typical lamellar
structure with sound interface showing no delamination
from the Ti-6Al-4V substrate. Coatings are uniformly thick
and appear microstructurally homogeneous at lower
magnifications. Thickness of the HA coating is observed
as 150 mm (Fig. 2a) whereas thickness of HA–CNT
coating is 110 mm (Fig. 2b). Both coatings are similar in
nature exhibiting transverse cracks and distributed micron-
size porosity. Image processing analysis evaluated density
of more than 92% for plasma sprayed coatings.
Microstructure of top surface of the plasma sprayed HA
coatings without CNTs (Fig. 3a) and with CNTs (Fig. 3b)
shows various contrasting microstructural features. In-
creased surface microcracks are typical in the plasma
sprayed HA coatings owing to brittle nature of HA
coatings undergoing thermal contraction upon cooling
[5]. Top surface of as-sprayed HA coating, Fig. 3a, elicits
layered structure. Various inter-splat cracks, flat appearing
melt surface, and partially fused particles are also observed
in the microstructure of plasma sprayed HA without
CNTs, Fig. 3a. On the other hand, plasma sprayed HA
with CNTs, Fig. 3b, demonstrates presence of melt-
resolidified fine and nodular HA particles. HA–CNT
coating surface appears rough owing to presence of
nodular surface particles. It must be mentioned that
surface roughness is critical in allowing the growth of cells
because surfaces influence the protein interaction leading to
subsequent cell adhesion [31]. Increased surface area
implies higher number of atoms and higher surface defects
at the delocalized surfaces open for cell adhesion. Melt
surface is more wavy when compared to that of plasma
sprayed HA without CNTs. In addition, the splats are
more spread out and flooded with uniformly embedded
spherical HA particles indicating higher surface undula-
tions in the HA–CNT coating. Retention and distribution
of CNTs after plasma spraying and the effect of CNTs
towards increasing crystallinity, enhancing fracture tough-
ness and assisting cell-growth is illustrated in later section.
3.2. Effect of CNTs on the crystallinity of as-sprayed
coatings
X-ray diffraction (XRD) spectrum of the plasma sprayed
coatings, Fig. 4, shows lower degree of crystallinity of
plasma sprayed HA coating without CNTs as observed by
peak broadening between the 2-theta values of 25–3531.
Absence of CaO, TiC, or other oxides (such as V2O5) peaks

Fig. 2. SEM cross-sectional image of plasma sprayed (a) hydroxyapatite, and (b) hydroxyapatite–4 wt% CNT coating.

Fig. 3. (a) As-sprayed HA coating, and (b) as sprayed HA–4 wt% CNT coating.
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K. Balani et al. / Biomaterials 28 (2007) 618–624
affirm the non-reactivity of substrate towards degrading
the HA coating during plasma spraying. HA coating
without CNTs depicted crystallinity of 53.7% whereas
HA–CNT coating has a crystallinity of 80.4% as calculated
from the differential HA peak degradation.
Generation of secondary phases such as calcium
phosphates, CaOs and ACPs [6] impair the mechanical
properties and deteriorate the biocompatibility of HA [32].
Reactivity of an implant material decides the resorption
and time of bonding with bone, which is believed to be
induced by the presence of TCP and HA via formation of
apatite layer [33]. Hence achieving higher degree of
crystallinity has always been one of the foremost concerns
in attaining lower dissolution of scaffold structures.
3.3. CNT distribution and subsequent fracture toughness
evaluation
Plasma sprayed HA coating without CNT is presented in
Fig. 5a for comparison purpose. Coated top surface,
Fig. 5b of plasma sprayed HA–CNT nanocomposite
coating display retention and uniform distribution of
CNTs, indicating that CNTs have survived the harsh
temperatures and high velocity impact observed during
plasma spraying. CNTs are uniformly distributed in the
coating without agglomeration. Retention and distribution
of CNTs is critical since CNTs provide enhanced strength
Fig. 4. X-ray diffraction spectrum of plasma sprayed coatings depicting
HA peaks.
Fig. 5. Top-surface of plasma sprayed (a) HA coating without CNT, and (b) HA–4 wt% CNT coating depicting CNT distribution.
621
and fracture toughness [33] reinforcing the poor mechan-
ical properties of HA [2]. Vicker’s indentation toughness
improvement of upto 56% is observed for HA–CNT
coating (0.6170.09 MPa m1/2 when compared to 0.397
0.09 MPa m1/2 for the plasma sprayed HA coating). T-test
statistical analysis confirmed significant difference between
the fracture toughness mean values of coatings associated
with greater than 95% confidence level.
3.4. Cell growth
Cell culture studies with human osteoblasts hFOB 1.19
cells were performed onto HA–4 wt% CNT plasma
sprayed coating. Differential cell growth (called osteocytes)
is unrestricted and seen embedded in the HA matrix,
Fig. 6a, in the presence of CNTs. Good spreading of the
hFOB 1.19 osteoblast cells, Fig. 6a, and unrestricted
growth along CNT-abutting surfaces, Fig. 6b, endorse
the non-toxicity of the CNTs in the body environment.
Fig. 6a shows nodular cells extending thread-like long
cytoplasmic prolongations [20] when cultured onto
HA–CNT biocomposite coating, Fig. 6b. Human osteo-
blast hFOB 1.19 progenitor cells have differentiated to
mature cells when coming in contact with neighbor cells.
This study on the in vitro behavior of non-functionalized
CNT reinforced HA coating with human osteoblasts
provides a detailed insight of enhancing the performance
of implant coatings.
4. Discussion
Transverse cracking observed in the coatings (Fig. 2)
results because of differential thermal quenching between
splats and deposited coating/substrate [2]. Thermal stresses
usually build up in the plasma sprayed coatings owing to
extreme cooling rates (in the order of 105–108 K/s)
observed during processing. Quenching stresses developed
during cooling therefore induces strain mismatches in the
successively depositing splats sometimes leading to crack-
ing in the coatings [2].
Extremely high cooling rates habitually lead to gene-
ration of non-equilibrium phases, as observed in the
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622 K. Balani et al. / Biomaterials 28 (2007) 618–624
Fig. 6. (a) Growth of human osteoblasts is observed embedded in HA matrix, and (b) cell-growth alongside of CNTs in vitro.
Fig. 7. (a) Cross-sectional image of plasma sprayed HA coating depicting needle phase, and (b) EDS of needle phase.
cross-sectional image of HA coating without CNT, Fig. 7a.
Spot analysis via energy dispersive spectroscopy (EDS),
Fig. 7b, showed needle-like regions to be rich in phosphate
corresponding to non-equilibrium secondary phase gen-
eration during plasma spraying. Presence of phosphate rich
needle phases imply transformation of HA to secondary
calcium phosphate phases ensuring reduced crystallinity. In
addition, amorphous phosphate regions also generate as a
result of non-thermodynamic cooling inherent to plasma
spraying lowering the initial crystallinity content. Unfo-
cussed spot size in the EDS analysis also depicted Ti peak
arising from the Ti substrate. Since the plasma spraying
parameters for the both coatings are same, addition of
CNTs is aiding the nucleation cites for the crystallization of
HA [19,23] preserving its inherent crystal structure.
CNTs are affecting the crystallinity of coating in a
peculiar way since crystallinity of 53.7% obtained for
plasma sprayed HA coating without CNTs, increased to
80.4% for the plasma sprayed HA–CNT coating. This in
turn, suggests that CNTs in some way assist the nucleation/
precipitation of HA. It is hypothesized that three orders of
higher thermal conductivity magnitude of CNTs
(3
103 W/m K compared to 0.7
103 W/m K for
HA) induce higher heating of CNTs when compared to
that of HA during plasma spraying. Owing to poor thermal
conductivity of HA, the cooling down allows isolation of
thermal energy near the CNT surfaces surrounded by HA
melt. Hence enhanced time is available at such regions for
HA nucleation when compared to that in the absence of
CNTs. Annealing thermal experience, therefore, initiates
recrystallization transformation, especially over CNT sur-
face, increasing HA content with increased time [33].
Powder feedstock treatment and controlled plasma
parameters have led to dispersion of undamaged CNTs in
the HA coating. Fractured surface of HA–4 wt% CNT
coating shows looped CNTs bridging the molten splats,
Fig. 8, endorsing the CNT fortification holding the splats
together. Fracture toughness improvement of 56% is
obtained for HA–4 wt% CNT nanocomposite coating.
Such remarkable improvement in the toughness of
HA–CNT coatings is attributed to CNT distribution and
anchoring of CNTs to form bridge structures. CNTs have
high bending stiffness and can take high bending deforma-
tions making it exceptional toughening addition [34].
Moreover, CNTs possess high tensile modulus (1 TPa)
behaving as rigid reinforcement with excellent elastic
recovery properties [35].
As confirmed by high magnification SEM image, Fig. 9,
mineralization of apatite is strongly observed over the
CNT surface. Barbed wire apatite mineralization has also
been observed by other researchers onto discrete CNT
surface [23]. Cell-culture studies demonstrated growth of
human osteoblast cell hFOB 1.19 alongside of CNTs.
It must be mentioned that enhanced apatite precipitation
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K. Balani et al. / Biomaterials 28 (2007) 618–624
Fig. 8. Fractured-surface of plasma sprayed HA–4 wt% CNT coating.
Fig. 9. Mineralization of apatite is seen over CNT surface.
along with higher crystallinity content is critical for
achieving stable scaffold structure for a successful body
implant performance [6]. Consequently, HA–CNT coating
allows growth and differentiation of nodular human
osteoblasts. Hence CNTs are presented as agents for
apatite re-precipitation, which will serve as reinforcing
scaffold because of tissue ingrowth. Novelty in adding
CNTs via plasma spraying demonstrated three-fold im-
provement by: (i) enhancing the fracture toughness of the
nanocomposite coating by 56%, (ii) aiding human osteo-
blast cell growth by its uniform dispersion, and (ii)
allowing precipitation and mineralization of apatite onto
CNT surface.
This interlinked interdisciplinary work presents a classic
example of synergy between materials science and engi-
neering, surface engineering, nanotechnology and biotech-
nology for practical applications.
623
5. Conclusions
Plasma sprayed HA–4 wt% CNT coating have demon-
strated uniform distribution of undamaged CNTs, im-
provement in fracture toughness by 56%, and increase in
crystallinity from 53.7% to 80.4%. Thus, plasma spraying
is a definitive tool for synthesizing HA–CNT coatings onto
Ti-6Al-4V implants and bringing benefits of nanotechnol-
ogy out of laboratory for real improvements in human
health life. CNTs have proved to nurture precipitation and
mineralization of HA over its surface. Unrestricted human
osteoblast hFOB 1.19 cell growth and proliferation during
cell culture studies demonstrate non-toxicity of HA–CNT
coating. Plasma sprayed HA–CNT nanocomposite bio-
coating opens the door for nanotechnology frontiers to tap
its properties and extend the limited life of body inserts and
implants.
Acknowledgements
The authors acknowledge Dr. Y. Liu, Advanced Materials
Engineering Research Institute (AMERI), Florida Inter-
national University (FIU), Miami, FL, USA for facilitating
SEM characterization. FIU Dissertation Year Fellowship
to Mr. Kantesh Balani and Mr. Tapas Laha is sincerely
acknowledged. The authors also thank FIU Foundation
for providing financial assistance to procure some of the
materials.
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