Surface & Coatings Technology 204 (2009) 399–403

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Surface & Coatings Technology

j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / s u r f c o a t

Apatite coatings onto titanium surfaces submitted to laser ablation with different
energy densities
R.A. Bini a, M.L. Santos a, E.A. Filho a, R.F.C. Marques b, A.C. Guastaldi a,⁎
a
Unesp — Universidade Estadual Paulista, Instituto de Química, Biomaterials Group, Caixa Postal 355, 14800-900, Araraquara, SP, Brazil
b
Unesp — Universidade Estadual Paulista, Instituto de Química, Magnetic Materials and Colloids Group, Caixa Postal 355, 14800-900, Araraquara, SP, Brazil

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

Article history: Apatite coatings were deposited on titanium surfaces modified by Nd:YVO4 laser at different energy densities
Received 9 February 2009 in environment atmosphere. Apatite was synthesized by sol–gel method using calcium nitrate and
Accepted in revised form 9 July 2009 phosphoric acid as precursors. The titanium modified surfaces were dip-coated into precursor solution and
Available online 5 August 2009
pre-fired at 700 °C in air for 3 h. Analyses by XRD, FTIR and SEM showed the formation of a mixture of
phases: hydroxyapatite (HA) and tricalcium phosphate (β-TCP) onto the surfaces submitted to laser ablation.
PACS Codes:
[B] 61.05.cp
Surface Rietveld analysis showed that a larger amount of non-stoichiometric oxides produced by laser
[C] 52.38.Mf ablation resulted in greater formation of HA on the coating. However, more of the β-TCP phase than HA was
[C] 81.20.Fw observed on surfaces with low amounts of oxides.
[D] 68.35.bd © 2009 Published by Elsevier B.V.
[X] 61.66.Fn

Keywords:
[B] X-ray diffraction
[C] Laser
[C] Sol–gel coatings
[D] Titanium
[X] Hydroxyapatite

1. Introduction
Musculoskeletal disorders and bone deficiencies have been estab-
lished as one of the most important diseases affecting the human health;
they cost billions of dollars to society yearly. As these conditions are
prevalent in elderly populations, and as it is expected that the number of
people over 50 years old will double between 1990 and 2020 [1], many
studies have been conducted to develop appropriate devices to improve
their life quality.
Titanium (commercially pure) and its alloys present good interaction
with biological tissues. This interaction is known as osseointegration
and the surface properties play an essential role in osteoblast adhesion
[2]. Thus, implant surface modifications have been investigated and
classified in two main groups: (i) bioinert to bioinert and (ii) bioinert to
bioactive. Both groups have shown satisfactory clinical results; however,
bioactive surfaces have demonstrated better interaction at the tissue/
implant interface [3–6].
Different surface treatments in implantable titanium devices are
currently on the market in order to improve the osseointegration phe-
nomenon. Among the group (i) surface modifications, the laser technique
⁎ Corresponding author. Tel.: +55 16 3301 6655; fax: +55 16 3301 6637.
E-mail address: guastald@iq.unesp.br (A.C. Guastaldi).
has gained prominence due to the fact that the concentrated light beam
only needs a physical medium to spread [7]. By controlling the laser
parameters, an increase in roughness and in oxidation of the surface can
be produced. Cellular answers in short term (migration and anchorage)
and long term (differentiation and expression of the matrix) are affected
by topographical characteristics and by chemical surface composition [8].
Regarding their morphology and phases, preliminary studies have
indicated similar results with the common techniques, such as mechan-
ical processes (machining and abrasive sandblasting), chemical processes
(acid etching and oxidation), and thermal processes (plasma spray);
however a smaller degree of contamination is produced by laser [7–10].
Among the bioactive ceramics, hydroxyapatite [Ca10(PO4)6(OH)2,
(HA)] has been widely used as coating in metallic implants due to the
good strength and ductility of the metal, and its excellent biocompat-
ibility and bioactivity [11,12]. Some methods have been applied to
deposit HA coatings, such as dip coating–sintering [13,14], electro-
phoretic deposition [15], immersion coating [16,17], solution deposition
[18], thermal spraying techniques such as plasma spraying [19,20], ion-
beam sputter coating [21], and dynamic mixing [22]. Another calcium
phosphate ceramic commonly used for bone replacement is tricalcium
phosphate [Ca3(PO4)2, (TCP)]. This apatite can occur in the allotropic
phases α, α′ and β. In low temperatures the β-TCP phase is mainly
formed, and in high temperatures the phase α-TCP (1120–1180 °C)
and α′-TCP (1430–1470 °C) are formed starting from the β-TCP phase.

0257-8972/$ – see front matter © 2009 Published by Elsevier B.V.

doi:10.1016/j.surfcoat.2009.07.013
400 R.A. Bini et al. / Surface & Coatings Technology 204 (2009) 399–403

Table 1 Among the coating methods, the sol–gel process is considered

Laser parameter configurations. the most flexible and commercially practicable technique for the
Parameters Samples preparation of high quality bioceramic thin films on metal substrates
TL1 TL2 with long-term stability. When compared to other methods, the sol–
Power (%) 100 100 gel technique offers a molecular-level mixing of the calcium and
Scanning velocity (mm/s) 100 500 phosphorus precursors, which is capable of improving HA chemical
Repetition rate (kHz) 35 35 homogeneity to a significant extent [26–28].
Pulse energy a (mJ) 0.24 0.24 In this work calcium phosphate was deposited by a sol–gel process
Spot diameter (mm) 0.03 0.03
Fluency (J/cm2) 280 56
onto c.p. Ti surfaces previously irradiated by a Nd:YVO4 continuous
a
laser beam. The relationship between different Ti suboxides formed on
Data from equipment curves.
surface and the final amount of apatite in the coating were described.

Recently, researches have claimed that biphasic calcium phosphate
(BCP) ceramics consisting of a mixture of β-TCP and HA at various ratios
have demonstrated more efficiency in repairing bone defects than in
pure HA or in pure β-TCP. As previously shown, these two phases have
similar chemical composition, but they differ in their in vivo absorption
capacity [23]. The HA is considered the most stable phase and a non-
biodegradable bone replacement material, while β-TCP is biodegradable
and significantly more soluble in body fluid than HA. Their physico-
chemical properties, such as the cristallinity, determine surface reac-
tivity in vivo, which is important for chemical and cell-mediated
degradation of the material, and also for osteogenic differentiation
of endogenous cells, so-called osteoinduction [23–25].
2. Experimental procedures
Titanium samples (grade 2, 10 × 10 × 2 mm) were submitted to
multi-pulse Nd:YVO 4 laser beams from a DML-100 Digilaser
(λ = 1064 nm).The laser system was focused through a 160 mm focal
length lens. The number of passes and distance between scanning lines
were kept constant. The peak power, average power, pulse width and
pulse energy varied as a function of repetition rate, according to values
obtained from the equipment manufacturer's guide. The accumulated
energy per unit area (fluency) can be calculated as the product of the
pulse energy (Ep) and repetition rate ( f ) divided by the product of the
spot diameter (D) and scanning velocity (V) [29]. Table 1 shows both
fluency values investigated, as well as laser parameters that were

Fig. 1. Titanium surface after laser ablation — SEM micrographs of the surface are: (a) TL1 and (c) TL2; XRD spectra after Rietveld refinements are: (b) TL1 and (d) TL2.
 R.A. Bini et al. / Surface & Coatings Technology 204 (2009) 399–403 401

Table 2 velocities are displayed in Fig. 1. It was observed that by varying the
Rietveld analysis results for samples TL1, TL2, TLA1, and TLA2. scanning speed different morphologies will be obtained. It can be seen
After laser ablation After apatite coating that lower scanning speed resulted a higher rough surface, due to
Phases TL1 (%) TL2 (%) Phases TLA1 (%) TLA2 (%) greater laser exposure time on the surface, producing a larger molten
α-Ti 24.2 63.5 HA 77.56 63.19 metal zone. In the TL1 and TL2 XRD patterns, it was observed that
Ti3O 52.4 1.0 β-TCP 6.09 20.68 the peaks were slightly displaced from their standard position due to
Ti6O 4.6 18.8 Ti6O 6.79 8.04 the high residual stress developed during the fast heating and cooling
TiO 5.4 0.5 TiO2 9.56 8.09 process resulting from laser ablation. Although uncertainty in the
β-Ti 13.4 16.2
discrepancy factors of Rietveld refinements were in some cases high, it
can be stated that the phase percentages obtained provided a good
approach.
varied, which TL meanings titanium sample after modification by laser. In addition to the α-Ti peaks (100), (002), (101), (102), (110),
The irradiations were carried out under room temperature and (103), (112), the presence of the phases Ti3O, Ti6O, TiO and β-Ti were
pressure. Before and after irradiation, the samples were cleaned by also verified in XRD patterns. Table 2 shows the phase percentages
sonication in acetone, washed in methanol and distilled water, and obtained by Rietveld refinement. An increase of the Ti oxidation state
then dried in an oven at 60 °C. was caused by fluency increment, with a decrease of the α-Ti phase.
Analytical grade calcium nitrate and phosphoric acid were dissolved By analyzing the Ti–O phase diagram, it can be verified that when the
in methanol to form 1.4746 mol L− 1 Ca(NO3)2.4H2O and 1.0533 mol L− 1 titanium is heated to 400–600 °C, under room temperature and pressure,
H3PO4 solutions, respectively. The solutions were mixed and then compounds of TiOx system will be formed, and the phases Ti3O, Ti6O, Ti2O
vigorously stirred to form a stable sol for dip coating. Before coating, the and Ti3O2, corresponding to smaller titanium oxidation states, will be
dry samples were placed in 5.0 mol L− 1 NaOH solution for 24 h at 60 °C. produced [32]. These phases are classified as non-stoichiometric oxides
After that period, the samples were dried for 3 h at 60 °C in the oven. deficient in oxygen, i.e., they possess oxygen vacancies in their crys-
The cleaned substrates were dip-coated onto the starting solution at talographic structure. Those vacancies are defects, which are deviations
52 mm/min for 60 s in air. The as-deposited coating was pre-fired at from the stoichiometric composition [33]. Their presence may be ex-
300 °C for 60 s in air. The process was repeated five times to prepare a plained by the oxygen diffusion through the melted treated surface to the
10 μm thick coating. Then, the final heat treatment was performed in air bulk material [29,34–37]. This non-equilibrium phenomenon is caused
at 700 °C for 3 h. The samples after coatings were designated as TLA by fast heating and cooling processes to which the surfaces were sub-
(titanium/laser/apatite). mitted [37,38]. The Ti3O and Ti6O formations can be explained by their
The samples were characterized by X-ray diffraction (XRD) (Rigaku structural similarities. The Ti3O or Ti6O phases belong to the same crys-
Co. D/Max/1200/PC). XRD patterns were recorded using CuKα radiation, a talline system (hexagonal cell and P-31c space group), differentiating
20–60° 2θ range, and continuous scanning at 0.01 2θ s− 1. Coating analyses only by their cell parameters that are very similar (Ti3O: a = 5.1418 Å
were obtained by Rietveld refinements using the General Structure and c =9.5354 Å; Ti6O: a = 5.13000 Å and c = 9.48000 Å). The c lattice
Analysis Software package (GSAS) computer program [30], which the parameters observed in Ti3O or Ti6O structures are larger than α-Ti initial
starting model used in refinements was based on the single crystal deter- lattice (α-Ti: a = 2.9505 Å and c = 4.6826 Å) [39]. The β-Ti phase was
mination [31]. Fourier transform infrared (FTIR) spectroscopy (Co. Perkin found in both samples (TL1 and TL2). According to Ti–O phase diagram,
Elmer spectrum 6xFTIR system) was used to analyze the stretching and the β-Ti phase occurs in high temperatures and low oxygen concentra-
deformation modes. Morphological observations were done using a tion. Thus, the presence of this phase on the surfaces is due to the low
scanning electron microscope (SEM) (JEOL Co. JSM/T-330). oxygen teor in the laser central zone [9].

3. Results and discussion 3.2. Coating via the sol–gel process

3.1. Titanium surface irradiated by Nd:YVO4 laser Fig. 2 presents XRD patterns and Rietveld refinements for TLA1 and
TLA2. The presence of Bragg peaks corresponding to the HA phase
The SEM micrographs, XRD patterns and the phinal graphics of [(100), (002), (210), (211), (112), (300), (202) and (310)] and the
Rietveld refinements of the surfaces obtained with different scanning β-TCP phase [(02.10), (119), (208), (217), (220), (21.10) and (312)]

Fig. 2. XRD spectra after Rietveld refinements for (a) TLA1 and (b) TLA2.
402 R.A. Bini et al. / Surface & Coatings Technology 204 (2009) 399–403

Table 3
Pattern and experimental unit cells for the HA and CHA phases.

Unit cell HA[34] CHA[34] HA HA

(Å) (ICSD # 87-0670) (ICSD # 19-0272) TLA1 TLA2
a and b 9.417 9.309 9.427 9.423
c 6.879 6.927 6.885 6.886
Volume (Å3) 528.39 519.85 530.055 529.543

reached during NaOH treatment to form a sodium titanate hydrogel

Fig. 3. Phase percentages in all samples; in which the sum of all non-stoichiometric
oxides is represented by oxides only.
layer on surface. This gel layer is dehydrated and stabilized as sodium
titanate partially crystallized after heat treatment above 60 °C for 3 h.
The goal of this pre-treatment is to produce an TiO2 layer, inducing a
more active and favorable layer to coating [41,42]. Therefore, the TiO2
might have been formed during thermal treatment of samples.
Fig. 4 shows FTIR measurements for the coating samples. The PO43−
stretching mode was observed from 910 to 1220 cm− 1 and the bands
associated to deformation mode from 540 to 600 cm− 1. These fre-
quencies can be attributed to the major absorption modes associated
with the presence of phosphates [43]. The OH− stretching modes were
observed in the 3570 and 630 cm− 1 regions. The appearance of three

were observed [39]. Table 2 shows the coating phase percentages

obtained by Rietveld refinement, in which the influence of laser
ablation on final coating can be verified. Fig. 3 displays the infor-
mation from Rietveld analysis; the relation between oxides formed
and the final amount of apatites in the coating, can be observed. The
largest amount of HA was found in TLA1 (77.56%) against 63.19% in
TLA2. The TL1 sample was submitted to a five-fold fluency value,
therefore producing a larger amount of oxides (62.4%) and greater
roughness, which influenced the larger formation of HA. However,
the smaller energy density (TL2) has influenced the formation of
the β-TCP phase. Despite being biocompatible, this phase is also
more biodegradable than the HA phase [23]. According to results
obtained by the Rietveld analysis, the formation of β-TCP and stoi-
chiometric HA on the coatings may be attributed to non-stoichio-
metric HA decomposition via dehydration (Eq. (1)) [40], after
thermal treatment at 700 °C.

Δ
Ca10 − x ðHPO4 Þx ðPO4 Þ6 − x ðOHÞ2 − x :nH2 O →ð1 − xÞCa10 ðPO4 Þ6 ðOHÞ2 ð1Þ

+ 3xCa3 ðPO4 Þ2 + H2 Oð gÞ

According to XRD analyses, Ti6O and TiO2 phases were also iden-
tified on coatings. The presence of those substrates oxides can be
justified by the greatest depth of the X-ray during diffractions analysis.
Ti6O phase is related to the surface modification via laser. TiO2 can be

Fig. 4. FTIR spectra of apatite coatings (a) TLA1 and (b) TLA2. Fig. 5. SEM micrographs of coatings; (a) TLA1, (b) and (c) TLA2.
 R.A. Bini et al. / Surface & Coatings Technology 204 (2009) 399–403
distinct bands in the regions at 630, 1000–1200and 3500 cm− 1 has been
observed as a HA signature [43,44].
In the FTIR measurements, a CfO stretching mode was observed in
the range of 1460–1412 cm− 1; indicating possible formation of
carbonated apatite (CHA). The molecular structure of CHA is similar to
HA and it consists of an hexagonal unit cell and a P63/m space group;
however, they can be differentiated by cell parameters. According to
Legeros [45], when substitution of CO32− ions takes place in PO43− or
OH− sites, contractions in parameters a and b and expansion in
parameter c will occur, with a resulting decrease of unit cell volume.
Table 3 shows coating refinement results, in which no contractions
or expansions in cell parameters are observed. These results agree
with Knowles et al. [46], who investigated the HA crystallographic
parameters by Rietveld analysis. Therefore, since all the reagents used
in the synthesis were analytical grade and the coatings were obtained
in air and at atmospheric pressure, the CfO stretching mode in FTIR
measurements come from atmospheric CO2.
The SEM micrographs of coatings heat-treated at 700 °C showed
that coating was very heterogeneous in both samples, in which two
distinct areas that corresponding to the HA and β-TCP phases can be
observed (Fig. 5a). In TLA1 samples (Fig. 5b) the predominant for-
mation of micro-spheres, characteristic of the HA phase [27,47], can be
seen. In TLA2 (Fig. 5c) the formation of typical plates of the β-TCP
phase were observed [40].
4. Conclusions
The surfaces of both coatings are suitable to be used in biomedical
applications due to the presence of biphasic calcium phosphate
ceramics. It was verified that the fluency of 280 J cm− 2 produced a
greater percentage of non-stoichiometric oxides onto titanium sur-
face, leading to the formation of a greater amount of HA on the final
coating. However, smaller energy density (56 J cm− 2) produced a
greater amount of the β-TCP phase. Therefore, the control of the laser
parameters can produce different active surfaces by ablation process,
resulting in different BCP proportions. Further investigations are
required to carry out in vitro and in vivo studies of coatings.
Acknowledgments
The authors would like to thank CAPES and FAPESP for the financial
support.
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