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Evaluation of calcium titanate as apatite growth promoter

J. Coreño, O. Coreño
Centro de Investigaciones en Materiales y Metalurgia, Universidad Autónoma del Estado de Hidalgo, Carretera
Panchuca – Tulancingo KM 4.5, Ciudad Universitaria, C. P. 42184, Pachuca de Soto, Estado de Hidalgo, Mexico

Received 9 July 2004; revised 8 April 2005; accepted 22 April 2005


Published online 8 August 2005 in Wiley InterScience (www.interscience.wiley.com). DOI: 10.1002/jbm.a.30447

Abstract: Calcium titanate (CaTiO3, perovskite) has been up to pH 7.4. Results suggest that phosphate ions are not
used to determine its apatite nucleation ability and propose adsorbed only on Ca sites but also on TiO2 groups sites of
a possible nucleation initial step. Measurements of calcium the surface, formed after calcium leaching from the surface.
leaching from the calcium titanate surface and phosphate When both ions are simultaneously added in a modified
adsorption experiments were carried out separately by us- simulated body fluid containing calcium titanate, at 37°C,
ing commercial calcium titanate suspensions at room tem- apatite growth occurs on its surface after 1 week of immer-
perature. Adsorption behaviour determined by ␨ potential sion. © 2005 Wiley Periodicals, Inc. J Biomed Mater Res 75A:
measurements shows that phosphate is strongly adsorbed 478 – 484, 2005
on the calcium titanate surface. It was found that the higher
the pH, the higher the Ca present on the calcium titanate Key words: apatite nucleation; calcium titanate; simulated
surface, but phosphate adsorption followed this trend only body fluid; point of zero charge; isoelectric point

INTRODUCTION calcium phosphate apatite crystals occurs on the sur-


face of the piece.
Titanium1 and its alloys have been successfully used In the case of the aqueous alkaline treatment it has
as biomaterials under load-bearing situations such as been found that during the first step a titania gel is
orthopaedic or dental applications. In order to im- formed on the surface. The ability of this surface to
prove their bone-bonding ability, various surface growth apatite when it is immersed in the SBF is
modification methods have been proposed to intro- higher than the surfaces that are not treated.7 It has
duce bioactive ceramic coatings onto their surfaces. been thermodynamically demonstrated that Ti pre-
Among these processes, the hydroxyapatite plasma- treated in a NaOH solution can lead to the formation
spraying technique has been extensively studied.1 of calcium titanate layer.9 Subsequent studies have
This technique is clinically used but can not be applied found that an intermediate stage on the apatite nucle-
onto complex shapes, besides control of crystallinity ation on Ti and Ti alloy surfaces is the formation of a
and structure of the hydroxyapatite layer deposited is calcium titanate layer from the titania– gel surface
difficult and adherence of the coating layer to metallic once they have been immersed in the SBF solution10,11
substrate is low.2,3 after NaOH treatment.
To overcome these disadvantages other coating On the other hand, different modifications of tita-
methods, such as hydrothermal,4 sol-gel,5 or the so- nium surfaces have been found to form a calcium
called biomimetic methods, have been proposed. Gen- titanate layer on them before immersing in SBF solu-
erally, these techniques involve a chemical surface tions. Those modified surfaces enhanced formation of
modification step, for example, ion implantation,6 calcium phosphate or apatite in vitro.6,12,13 In spite of
aqueous alkaline treatments,7 or the self-assembly these findings, it is interesting to note that formation
technique,8 followed by the immersion of the piece of calcium phosphate was not convincingly demon-
thus treated in a biomimetic, acellular simulated body strated onto sol-gel calcium titanate coatings after a 12
fluid (SBF) containing calcium and phosphate ions. In weeks immersion period in SBF.14
this biomimetic solution nucleation and growth of Sol-gel prepared titania and silica15–17 have been
extensively used as substrates to explain the formation
Correspondence to: J. Coreno; e-mail: jcoreno@uaeh.reduaeh.mx
of apatite in the surface of Ti alloys and bioglasses,
respectively, because it is known that hydrated titania
© 2005 Wiley Periodicals, Inc. and silica groups promotes apatite growth. In this
CALCIUM TITANATE AS APATITE GROWTH PROMOTER 479

article, calcium titanate (perovskite) is used to evalu- CaCl2 or Na2HPO4. Finally, pH was adjusted with diluted
ate its ability to grow apatite on its surface and to HNO3 or NaOH solutions and each suspension was com-
propose a possible nucleation mechanism. Results are pleted to 50 mL with deionized water. A potentiometer
discussed in terms of surface chemical and physical (Orion 720 A) equipped with a combined electrode and
automatic temperature compensation (ATC) probe was used
properties of this material. The present results could
to monitor the pH. The potentiometer was calibrated before
help to understand the role of calcium titanate formed each test with buffer solutions 4, 7, and 10. Before perform-
on Ti surfaces on apatite growth. ing the ␨ potential measurements, we conditioned the sus-
pensions for 15 min.
The point of zero charge was determined adding succes-
sively small amounts of the calcium titanate to an aqueous
EXPERIMENTAL solution at a particular pH. The increase or decrease in pH
was measured after 1 h. If no further pH change was noted,
the system was considered to be at its p.z.c.
Calcium release and phosphate adsorption

Calcium titanium oxide, CaTiO3, powder (Alfa Aesar


99⫹%, 325 mesh) was used for all the experiments. The Apatite growth in a modified SBF
X-ray diffraction pattern of this compound corresponds to
CaTiO3 perovskite (Joint Committee on Powder Diffraction
Calcium titanate (1 g) was immersed in 20 mL of a solu-
Standard, JCPDS-42-0423). Phosphate adsorption kinetics
tion containing 0.14M NaCl and 1 mM Na2HPO4 in deion-
experiments were performed by adding 2 g of the solid to 20
ized water. The suspension was stirred for 24 h at room
mL of a 1mM Na2HPO4 solution using deionized water. The
temperature. The solid was centrifuged and suspended at
resulting suspension was stirred at room temperature. Peri-
pH 7.4 in 10 mL of a solution containing 0.14M NaCl and 1
odically, samples were taken from the stirred suspension
mM Na2HPO4. These suspensions did not contain Ca be-
maintaining the initial weight-to-volume ratio. Samples
cause this ion was leached from the calcium titanate. After a
were filtered or centrifuged to measure phosphate concen-
mild stirring 24 h period at 37°C, the solid was centrifuged
tration in the liquid. Experiments to measure phosphate
and suspended three times in 10 mL of a solution containing
adsorption and calcium leaching were performed separately
0.14M NaCl, 2.5 mM CaCl2, and 1 mM Na2HPO4 in deion-
by adding 0.4 g of the powder to 15 mL of pH-buffered NaCl
ized water at pH 7.4. The suspensions were stirred for 24 h
solutions. The different solutions were prepared by using
under mild stirring. pH was adjusted with tris (hydroxy-
deionized water, buffered at the desired pH using tris (hy-
methyl aminomethane) and 0.1M HCl.
droxymethyl aminomethane) or potassium biphtalate and
Calcium titanate was not immersed initially in a SBF
0.1M HCl or NaOH, respectively. Phosphate adsorption was
containing both calcium and phosphate ions because cal-
performed in a 0.14M NaCl solution in order to prevent any
cium released from the solid could have produced calcium
possible calcium phosphate homogeneous precipitation. The
phosphate spontaneous nucleation and growth. Successive
ionic strength of the solution due to NaCl diminishes the
immersion in SBF solutions were done to restore the ions
activity ionic coefficients of calcium and phosphate ions thus
consumed during the apatite growth and avoid microorgan-
raising the solubility of the amorphous calcium phosphate
isms proliferation.
that could precipitate. An initial 1 mM Na2HPO4 concentra-
tion was used. Phosphate concentration was measured by
conventional molybdenum blue method. Calcium concen-
tration was measured by titration with ethylenediaminotet- Characterization techniques
raacetic acid disodium salt (EDTA), using eriochrome T
black indicator.
Transmission electron microscopy (TEM) was carried out
in a LEO EM 910 Zeiss microscope at 100 kV. ␨ potential
measurements were carried out with a Malvern Instruments
Zetasizer 3000HSA. Infrared spectrum was obtained using a
Zeta (␨) potential measurements and determination PerkinElmer Spectrum GX FT-Raman spectrometer. Sam-
of the immersion point of zero charge (p.z.c.) ples were prepared as KBr pellets.

A stock suspension of calcium titanate was prepared by


adding 1 g of this powder to 100 mL of deionized water. The
suspension was stirred for 30 min. After 20 min without RESULTS
stirring the resulting suspension was separated from the
solid. One hundred milliliters of deionized water were
added again to the solid and the previous procedure was
Phosphate adsorption and calcium release were
repeated. The suspensions were put together and aged for 1 measured separately as a function of time and pH. As
week prior to the ␨ potential measurements. Measurements can be seen in Figure 1, phosphate is quickly ad-
were carried out with 5 mL of the shaked stock suspension, sorbed, reaching equilibrium approximately 3 h after
followed by addition of water and the necessary quantity of mild stirring at room temperature. Calcium is released
the respective salt to obtain the desired concentration of from the calcium titanate surface during the very first
480 COREÑO AND COREÑO

Figure 3. ␨ potential as a function of pH for CaTiO3 sus-


Figure 1. Phosphate adsorbed (1 g/10 mL) and Ca released
pensions immersed in: deionized water (a), 1 mM PO4 so-
(0.3 g/10 mL) of aqueous calcium titanate suspensions at
lution (b), and 1 mM PO4 ⫹ 10 mM NaCl solution (c).
room temperature.

observed in Figure 3. As can be seen, calcium titanate


minutes of stirring. Concentration of this ion does not
has a negative surface at pH 7.4, according to the
change after a 24-h stirring period.
electrokinetic technique used in this work [Fig. 3(a)],
Ions specifically adsorbed on a surface are strongly
because the isoelectric point (i.e.p.), ␨ ⫽ 0, is close to
attracted on it forming a layer, called the Stern layer,
pH 3. Figure 3(b) shows that the presence of phos-
which moves with the surface. Interaction of these
phate ions increases the negative surface potential and
ions with the surface can be determined by means of ␨
lowers the i.e.p. These results indicate that phosphate
potential experiments. Adsorption of phosphate ions
ions are chemically adsorbed on the calcium titanate
on calcium titanate was studied by using this tech-
surface.18 A similar trend is observed in the presence
nique. ␨ potential corresponds to the potential at the
of phosphate ions and NaCl [Fig. 3(c)].
slippage plane that is commonly assumed to be lo-
A number of experiments were done in order to
cated at the outer limit of the Stern layer, and it can be
estimate the dependence of Ca release and phosphate
directly related to the magnitude and sign of the sur-
adsorption as a function of pH. It was observed that
face charge. Figure 2 shows the variation of potential
Ca is released from the calcium titanate surface in the
as a function of concentration of this anion at pH 2,
pH range studied. In Table I it can be seen that the
where the calcium titanate surface is positively
higher the pH of an aqueous calcium titanate suspen-
charged. As can be seen, phosphate ions can reverse
sion, the higher the calcium that remains on the sur-
the sign of the ␨ potential at concentrations higher
face. On the other hand, it was observed that in the
than 1 ⫻ 10⫺2 M. This means that the adsorption of
second immersion of calcium titanate at pH 2 only a
phosphate ions on the surface of calcium titanate is
little proportion of Ca ions is leached compared to the
influenced by forces other than the electrical potential
amount released in the first immersion. Thus, it can be
(specific adsorption). Results corresponding to mea-
approximately considered that all of the Ca has been
surements of calcium titanate suspended in deionized
leached out from the surface after two immersions at
water and in the presence of Na2HPO4 and NaCl are
pH 2. Therefore, calcium at the surface is roughly
estimated subtracting the amount of Ca leached at
each pH from that leached at pH 2 after two immer-
sions. Regarding the phosphate adsorption, it in-
creases at the same time that pH does up to pH 7.4.
Above this pH its adsorption diminishes. Also, it was
noted that phosphate can be adsorbed at pH 7.2 using
a calcium titanate that is suspended twice at pH 2,
where it is presumed that Ca at this surface is negli-
gible. Ti dissolution was not detected for any of the
experiments.
Table II shows pH variation for different amounts of
solid added to deionized water along with the pH
tendency when CaTiO3 is added to deionized water or
to solutions at different initial pH (not buffered). For
Figure 2. ␨ potential as a function of phosphate concentra- all of the experiments the observed final pH is around
tion at pH 2. 8.3. This value is considered as a rough estimation of
CALCIUM TITANATE AS APATITE GROWTH PROMOTER 481

TABLE I
Calcium at Surface and Phosphate Adsorption after 3 h of Immersion for a Calcium Titanate Suspension
(0.4 g/15 mL 0.14M NaCl solution, initial [PO4] ⴝ 1 mM)
Ca Leached Final [Ca] Ca at Surface Phosphate Consumed Final [PO4] Initial pH after
Experiment ⫻ 105 (mol/g) (mM) ⫻ 105 (mol/g) ⫻ 106 (mol/g) (mM) pH 3h

pH 2 12 3.2 1 — 1.93 2.11


pH 4 11 2.9 2 1.75 0.95 3.86 4.25
pH 7.4 7.2 1.9 5.8 8.15 0.78 7.0 7.5
pH 8 5.4 1.4 7.6 6.0 0.84 8.1 8.3
pH 9 1.8 0.5 11.2 7.0 0.81 9.3 9.14
pH 7.2** 13* 0 3.9 7.0 7.2
*Ca released after two immersions at pH 2.
**Experiment using 0.6g/15 mL. CaTiO3 resuspendended twice at pH 2.0 (30 mL).

the immersion point of zero charge. On the other and the apatite formed has to develop. As can be seen
hand, it was observed that calcium titanate behaves as in Figure 3, phosphate ions are chemically adsorbed
an amphoteric oxide because the final pH increases if on the calcium titanate surface because they are able to
the initial pH is less than 8.3, while the final pH shift the i.e.p. and remain adsorbed even when the
decreases if the initial pH is grater than 8.3, both in surface has a negative charge.18 Thus, the chemical
buffered (Table I) and nonbuffered (Table II) experi- bonds formed could help apatite present a good ad-
ments. hesion to the CaTiO3 surface.
In Figure 4, a TEM image of crystals formed calcium It has been proposed that the calcium titanate forms
titanate particles are observed after four 24-h immer- on the surface of a NaOH-treated Ti alloy when ex-
sion periods in the modified SBF. The diffraction pat- posed to SBF10,11 as a consequence of the electrostactic
terns corresponding to the (300), (222), and (421) interaction between the positive Ca ions in the solu-
planes of crystalline apatite are shown. Figure 5 shows tion and the negative titania gel developed on the
the FTIR spectrum of the solid immersed four times in alloy surface after the alkaline treatment. This calcium
SBF. Two noticeable bands attributed to the Ti-O vi- titanate layer is suggested to promote apatite nucle-
bration are observed at 455 and 580 cm⫺1. Due to the ation because it gains a positive charge where phos-
small proportion of crystals formed, only the most phate anions can be attached, thus forming nuclei for
intense band at 1036 cm⫺1 ascribed to a phosphate apatite growth.9 –11 On the other hand, it has been
vibration19 was detected. Finally, the crystals formed found that Ca-implanted titanium shows improved
are assumed to be apatite because it is the calcium calcium phosphate precipitation and bone conductiv-
phosphate phase thermodynamically favored at the ity when compared to titanium. This surface consists
pH and temperature conditions of our experiments. of calcium titanate and it is proposed to be more
positively charged than titanium in bioliquid, thus
facilitating the adsorption of phosphate ions. Besides,
calcium ions dissolve from the surface and help to
DISCUSSION
supersaturate the bioliquid near the surface causing
calcium phosphate precipitation.6 Ca dissolution has
A very important desirable characteristic that bio- also been proposed in other surfaces where calcium
active materials for osteointegration must show is that titanate was formed before immersing in SBF solu-
a very strong bonding between the substrate surface tions.12,13
␨ potential experiments (Fig. 3) show that calcium
TABLE II titanate surface is negative at pH 7.4. However, this
pH Variation for CaTiO3 Suspensions over Time for a negative charge could be apparent. The i.e.p. of Ba-
Suspension with Successive Additions of the Solid (exp. TiO3 has been matter of debate for some years. Re-
1) and for the Same Amount of the Solid at Different
cently Paik and Hackley have reported i.e.p. values
Initial pH (exps. 2, 3, and 4)
ranging from 10.8, for a BaTiO3 suspension containing
Time (h) 0 1.0 2.0a 7.0b 22.0 5% of solids, to 3.6 for a 0.005% suspension.20 In the
pH (exp. 1) 6.9 8.5 8.3 8.2 8.2
present work we used a 5% solids concentration in the
Time (h) 0 3.5 7.0 20.0 28
pH (exp. 2) 3.9 8.0 8.1 8.0 8.3 first immersion step of the apatite growth experi-
pH (exp. 3) 9.8 8.3 8.2 7.9 8.2 ments, while in the ␨ potential experiments a much
pH (exp. 4) 6.9 8.5 8.1 8.0 8.3 lower solid concentration was used. Paik and Hackley
Exp. 1: Initial CaTiO3 concentration: 0.05 g/20 mL. a, b proposed that low particle concentration, produced a
addition of 0.05 g of CaTiO3 at 2 and 7 hours, respectively. low i.e.p., close to that of TiO2, due to the formation of
Exp. 2, 3, and 4: Experiments using 0.5 g CaTiO3/20 mL. a surface rich in acidic TiO2 sites. This layer forms as
482 COREÑO AND COREÑO

Figure 4. TEM photograph of apatite crystals grown on CaTiO3 particles after four 24-h periods of immersion in a modified
SBF.

a consequence of Ba leaching. On the other hand, it oxide, TiO2, and as a partially soluble inorganic salt,
has been reported that CaTiO3 in contact with water CaO, such as it has been proposed for BaTiO3.23 At pH
develops an amorphous Ti-O layer depleted in Ca 7.4 the TiO2 sites formed would show a net negative
depending on temperature, pH, and Ca concentra- charge because TiO2 has an i.e.p. around pH 5.24
tion.21 The approximate point of zero charge determined in
In Table I it can be observed that calcium is leached this work (pH ⫽ 8.3) according to the rapid method of
from calcium titanate at room temperature as a func- Bérubé and De Bruyn25 is close to the one reported for
tion of pH. As a result, a surface layer containing an perovskite (8.1).6 The i.e.p. is the pH at which the
amount of Ca lower than the original is formed, ac- charge on the solid arising from all sources is zero.
cording to the next equations: P.z.c. equals the i.e.p. if no specific adsorption of
⫺ counter ions occurs on the oxide. The specific adsorp-
CaTiO 3(s) ⫹ H 2O 3 Ca (aq)
2⫹
⫹ TiO 2(s) ⫹ 2HO (aq) (1)
tion of cations raises the i.e.p., while adsorption of
This reaction would explain the increase in pH ob- anions lowers it.26 According to Table I, approxi-
served in Table I. mately 55% of Ca is released from CaTiO3 at pH 7.4. If
Calcium titanate is a mixed oxide.22 It is possible that the remainder Ca ions were specifically adsorbed, the
in an aqueous suspension it behaves as an insoluble i.e.p. would be higher than 8.3.

Figure 5. FTIR spectrum from the calcium titanate immersed four times in a modified SBF.
CALCIUM TITANATE AS APATITE GROWTH PROMOTER 483

At this point it is interesting to analyze the possibilities Low phosphate adsorption below pH 4 can be due
that the CaTiO3 surface might be either positive or neg- to the low Ca concentration at the surface. At pH 2
ative. It has been observed that a negatively charged there is approximately 7.7% of the original Ca at the
surface at pH 7.4 is a common factor for materials to surface, while at pH 4 this value is 15%. However,
induce apatite nucleation.15,27,28 If there are more nega- calcium titanate treated twice at pH 2 and later resus-
tive sites at the calcium titanate surface than positive pended at pH 7.2 shows higher phosphate consump-
ones, a net negative surface would develop. This would tion than the observed for the experiments at pH 2 and
be in accordance with the above-mentioned observa- 4. In that surface it is considered that all of the surface
tions. On the contrary, if calcium titanate had a posi- calcium has been released (Table I). These observa-
tively charged surface at pH 7.4, as has been proposed tions could be explained taking into account that, be-
for the amorphous calcium titanate formed on Ti surfac- sides the amount of calcium at the surface, phosphate
es,10,11,28 it would mean that positive surfaces could be adsorption may also be due to the phosphate species
able to nucleate apatite. This fact is important to notice present at low pH. It is possible that H2PO4⫺ adsorp-
because it has been suggested that alumina, which has tion is lower than adsorption of HPO4⫽, which is the
an i.e.p. around pH 9.0, is not a good substrate for apatite predominant anion between pH 7.3 and pH 9. The
nucleation on its surface because it is positively charged adsorption of this anion is proposed as part of the
at pH 7.4.13,26,27 However, this might not be the direct compositional structure to explain the calcium phos-
reason to explain that observations, but the surface to- phate uptake on TiO2.32 At pH values higher than 7.4
pography, as has been proposed in the case of some adsorption diminishes although Ca present on the
titania and silica surfaces.29 –31 surface is higher than at pH 7.4. This fact could be due
As can be seen in Table I, the higher the calcium to an increase of the electrostatic repulsion between
present at the surface, the higher the phosphate ad- the surface and the present phosphate species.
sorption up to pH 7.4. It would be expected that the According to the previous discussion, a possible
sites for binding of phosphate anions are the calcium mechanism for apatite nucleation on crystalline calcium
atoms on the surface, as has been proposed for TiO2.32 titanate could be as follows: Calcium titanate slightly
It seems that only some Ca sites are available for dissolves in water releasing some of the Ca ions of the
phosphate adsorption because the maximum amount surface, thus forming a surface richer in TiO2 than the
of phosphate adsorbed (pH 7.4) is approximately six original, which could then transform into TiOH groups.
times lesser than the amount of Ca ions that remains at Then, some of the calcium ions could be re-adsorbed at
the surface at this pH. At this point, it is interesting to the surface. Phosphate could be adsorbed both on some
note that it has been reported that Ca is incorporated of the remaining or re-adsorbed Ca on the surface along
on the surface of an amorphous calcium titanate with the TiOH groups. On the other hand, as can be seen
within 0.5 h after its immersion in SBF, while phos- in Eq. (1), calcium titanate dissolution raises OH⫺ and
phate does within 72 h.11 In this work phosphate Ca2⫹ concentrations, thus helping to supersaturate the
uptake occurred immediately in the presence of cal- solution near the vicinity of the solid for calcium phos-
cium titanate. It means that maybe some kind of sur- phate precipitation. A similar mechanism could happen
face characteristic should be present in order to trigger in surfaces where calcium titanate has been formed pre-
phosphate adsorption such as a minimum surface cal- vious its immersion in SBF.
cium or TiOH groups concentration, certain surface In accordance with the presented results it seems that the
charge value, or some type of structural arrangement. calcium titanate used in this work is a good substrate for
On the other hand, it is possible that TiO2 sites apatite nucleation and growth. However, apatite growth
present in the calcium titanate surface after Ca leach- on sol-gel calcium titanate coatings has not been fully dem-
ing can also act as binding sites for phosphate anions. onstrated previously.14 Manso and colleagues reported that
From Figure 3 it can be seen that phosphate anions can this surface developed Ca and P nucleation according to
be adsorbed on the calcium titanate surface at low pH SEM and EDX evidences, but the formation of calcium
values where apparently no Ca is present on the sur- phosphate phases could not be detected by using FTIR and
face. A similar observation was made for the CaTiO3 XRD after a 12 weeks immersion period in SBF. On the
that has been suspended twice at pH 2 and later contrary, in the present study apatite crystals were detected
resuspended at pH 7.2. In Table I it can be seen that after a 2-week immersion period in a modified SBF. Differ-
this surface adsorbs almost half of the phosphate that ences in apatite growth ability in this case could be due to
is adsorbed when the original CaTiO3 is suspended at different surface structural arrangements of the nucleation
pH 7.4. Phosphate adsorption on TiO2 sites has previ- sites, but also to the surface topography, as has been pro-
ously been reported for titania.17,33 In the case of the posed to explain differences on apatite nucleation ability for
amorphous calcium titanate formed when immersed other substrates.26,27
in SBF, it is possible that phosphate ions can be ad- As in the case of calcium titanate, for silica and
sorbed on TiO sites once appropriate conditions, as titania it has also been reported that some times these
the above mentioned, are created. substrates do not nucleate apatite on its surface. This
484 COREÑO AND COREÑO

would imply that the design of an appropriate bioac- 12. Hamada T, Kon M, Hanawa T, Yokoyama K, Miyamoto Y,
tive ceramic surface should consider not only the Asaoka K. Hydrotermal modification of titanium surface in
calcium solutions. Biomaterials 2002;23:2265–2272.
chemical aspects of the surface but also the structural 13. Hanawa T, Kon M, Ukai H, Murakami K, Miyamoto Y, Asaoka
or topographical characteristics. K. Surface modification of titanium in calcium-ion-containing
solutions J Biomed Mater Res 1997;34:273–278.
14. Manso M, Langlet M, Martı́nez-Duarte JM. Testing sol-gel
CaTiO3 coatings for biocompatible applications. Mater Sci Eng
2003;23:447– 450.
CONCLUSIONS 15. Li P, Ohtsuki C, Kokubo T, Nakanishi K, Soga N, de Groot K.
The role of hydrated silica, titania and alumina in inducing
apatite implants. J Biomed Mater Res 1994;28:7–15.
Calcium titanate, perovskite, seems a good sub-
16. Coreno J, Martı́nez A, Bolarin A, Sanchez F. Apatite nucleation
strate for apatite growth. Results indicate that the on silica surface: a ␨ potential approach. J Biomed Mater Res
surface releases some Ca ions, thus forming a surface 2001;57:119 –125.
richer in TiO2 than the original, which would in turn 17. Coreno J, Martı́nez A, Coreno O, Bolarin A, Sanchez F. Calcium
transform into TiOH groups. Later, phosphate ions are and phosphate adsorption as initial steps of apatite nucleation
on sol-gel-prepared titania surface. J Biomed Mater Res 2003;
adsorbed and may be bound both to surface Ca and
64A:131–137.
TiOH sites. It seems that only certain surface sites are 18. Hunter RJ. Zeta potential in colloid science. Principles and
available for phosphate adsorption. When immersed applications London: Academic Press; 1988. p 234.
in aqueous suspension calcium titanate slightly dis- 19. Liu Q, Ding J, Mante FK, Wunder SL, Baran GR. The role of
solves, pH raises and Ca is leached, thus promoting surface functional groups in calcium phosphate nucleation on
titanium foil: a self assembled monolayer technique. Biomate-
apatite nucleation on its surface.
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20. Paik U, Hackley VA. Influence of solids concentration on the
isoelectric point of aqueous barium titanate. J Am Ceram Soc
2000;83:2381–2384.
21. Turner PS, Jones CF, Myrha S, Neall FB, Pharm DK, Smart R St
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