See discussions, stats, and author profiles for this publication at: https://www.researchgate.

net/publication/262818269

Dielectric properties of Fe doped hydroxyapatite prepared by sol–gel method

Article  in  Ceramics International · August 2014

DOI: 10.1016/j.ceramint.2014.02.009

CITATIONS READS

94 778

5 authors, including:

Omer Kaygili Sergey V. Dorozhkin

Firat University N/A
81 PUBLICATIONS   947 CITATIONS    232 PUBLICATIONS   11,439 CITATIONS   

SEE PROFILE SEE PROFILE

Tankut Ates Ahmed Al-Ghamdi

Malatya Turgut Özal University, Turkey King Abdulaziz University
41 PUBLICATIONS   594 CITATIONS    483 PUBLICATIONS   13,284 CITATIONS   

SEE PROFILE SEE PROFILE

Some of the authors of this publication are also working on these related projects:

A new shape memory alloy film/p-Si solar light four quadrant detector for solar tracking applications View project

Synthesis, Optical and Photoluminescence Properties of Cu-Doped Zno Nano-Fibers Thin Films: Nonlinear Optics View project

All content following this page was uploaded by Sergey V. Dorozhkin on 05 March 2021.

The user has requested enhancement of the downloaded file.

 Available online at www.sciencedirect.com

CERAMICS
INTERNATIONAL
Ceramics International 40 (2014) 9395–9402
www.elsevier.com/locate/ceramint

Dielectric properties of Fe doped hydroxyapatite prepared

by sol–gel method
Omer Kaygilia,n, Sergey V. Dorozhkinb, Tankut Atesa,
Ahmed A. Al-Ghamdic, Fahrettin Yakuphanoglua,c
a
Department of Physics, Faculty of Science, Firat University, 23119 Elazig, Turkey
b
Kudrinskaja square 1-155, 123242 Moscow, Russia
c
Department of Physics, Faculty of Science, King Abdulaziz University, Jeddah, Saudi Arabia
Received 27 January 2014; received in revised form 1 February 2014; accepted 3 February 2014
Available online 10 February 2014

Abstract

Iron-doped hydroxyapatite (HAp) samples with variable amounts of Fe were synthesized and their properties were investigated. Namely, the
structure and composition of the prepared samples were analyzed using X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy,
scanning electron microscopy (SEM) and energy dispersive X-ray (EDX) techniques. In addition, the dielectric and alternating current
conductivity properties were investigated at room temperature. The samples were found to consist of a high crystalline HAp with a minor
admixture of β-tricalcium phosphate (β-TCP). With increasing amount of Fe, the crystallite sizes of the samples were found to gradually decrease
from 32.54 nm to 27.91 nm with simultaneous changes in the crystallinity degree, lattice parameters, unit cell volume and the phase composition.
The fine-grained microstructure was observed and EDX analysis confirmed Fe-substitution in the apatitic structure because the Ca/P molar ratios
were gradually decreased from 1.68 to 1.35 by addition of Fe. The alternating current conductivity confirmed that Fe doped HAp samples
exhibited the insulator behavior. The relative permittivity of the HAp was increased with the addition of Fe. The samples exhibited a non-Debye
relaxation mechanism.
& 2014 Elsevier Ltd and Techna Group S.r.l. All rights reserved.

Keywords: Dielectric permittivity; Dielectric relaxation; Fe-doping; Hydroxyapatite

1. Introduction Namely, Panseri et al. [8] demonstrated that the FeHAp

Hydroxyapatite (HAp, chemical formula Ca10(PO4)6(OH)2)
has been investigated for biomedical applications due to its
excellent bioactivity, biocompatibility and osteoconductivity
[1–3]. HAp has the close match with the mineral component
of bones [4]. Iron (Fe) is an essential trace element in bones
and teeth. Since Fe3 þ ions can substitute Ca2 þ ions of HAp,
they affect the crystallinity and solubility of HAp [5–10].
In addition, small amounts of iron were found to have the
positive impact on the biomedical properties of HAp [8–10].
n
Corresponding author. Tel.: þ90 424 2370000, þ90 424 2373623;
fax: þ90 424 2330062.
E-mail address: okaygili@firat.edu.tr (O. Kaygili).
nanoparticles had the positive effects on the osteoblast viability
and they could be used for diagnostic imaging or drug
delivery. Li et al. [9] showed that the addition of Fe3 þ ions
in HAp enhanced the osteoblast adhesion and FeHAp samples
had no toxic effect on the osteoblast cells. Iafisco et al. [10]
reported that the FeHAp had eminent biocompatibility and cell
proliferation properties.
As known, bone is a dielectric material [11] and the
electromagnetic fields, which are one of the non-invasive
methods, have been used for fracture healing or bone growth
applications for many years [12,13]. The dielectric properties
of the HAp have been investigated a lot [14,15]. These
properties are important for HAp applications in the fabrication
of biological sensors and acceleration of healing in bone

http://dx.doi.org/10.1016/j.ceramint.2014.02.009
0272-8842 & 2014 Elsevier Ltd and Techna Group S.r.l. All rights reserved.
9396 O. Kaygili et al. / Ceramics International 40 (2014) 9395–9402

fractures with electromagnetic fields [12,13]. Therefore, the
investigation of the dielectric and electrical properties of a
material, which can be used for bone repairing, gains a great
importance. This study describes the synthesis and character-
ization processes of the HAp samples with various percents of
Fe (0, 0.7, 1.4 and 2.1 at%). The effects of the Fe-content on
the crystal, chemical and dielectric properties of the HAp were
investigated in more detail.
2. Materials and method
2.1. Synthesis and characterization of Fe doped HAp samples
Calcium nitrate tetrahydrate (Ca(NO3)2  4H2O, Merck),
diammonium hydrogen phosphate ((NH4)2HPO4, Merck), iron
(III) nitrate nonahydrate (Fe(NO3)3  9H2O, Sigma-Aldrich)
and polyvinyl alcohol (PVA, Merck, MW 72,000) were used
as the starting reagents. Four HAp samples with different
Fe contents of 0, 0.7, 1.4 and 2.1 at% were synthesized and
referred to HAp, 0.7FeHAp, 1.4FeHAp and 2.1FeHAp,
respectively. Their (Caþ Fe)/P molar ratios were maintained
at the value of 1.67. Ca(NO3)2  4H2O and Fe(NO3)3  9H2O
were dissolved together in de-ionized (DI) water in a beaker.
Then, (NH4)2HPO4 was also dissolved in DI water and added
drop by drop to the Ca(NO3)2  4H2O and Fe(NO3)3  9H2O
mixture, and 5 ml of 0.14 mM PVA solution prepared with DI
water was added to this solution. The final solution was mixed
Indexed peaks : Hydroxyapatite
♦ : β −TCP
2.1FeHAp
at the ambient temperature for 1.5 h, the gel formation was
observed, and then this gel was dried in an oven at 120 1C
for 24 h. The dried samples were calcined at 800 1C for 1 h
and the powder samples were investigated after cooling.
The crystal structure and phase composition of the samples
were determined by means of X-ray diffraction (XRD, Bruker
D8 Advance) within a 2θ range from 201 to 551 at every 0.021
for the scan speed of 21 min  1 using Cu Kα radiation with
wavelength of λ=0.15406 nm generated at 40 kV and 40 mA.
The identification of the crystalline phases was carried out by
comparing with the Joint Committee on Powder Diffraction
Standards (JCPDS) cards. To identify the vibration modes of
the functional groups such as hydroxyl and phosphate, Fourier
transform infrared (FTIR) spectra of the as-synthesized sam-
ples were recorded by a PerkinElmer Spectrum One spectro-
photometer in the range of 450–4000 cm  1 using the KBr disc
method with a spectral resolution of 4 cm  1. The investigation
of the microstructure and elemental compositions of the as-
synthesized samples was carried out by a scanning electron
microscope (SEM, ZEISS EVO 50) equipped with an energy
dispersive X-ray (EDX, Oxford Instruments Inca Energy 350)
spectrometer operated at an accelerating voltage of 10 kV. The
dielectric and alternating current conductivity properties were
investigated using a HIOKI 3532-50 LCR HiTESTER at room
temperature.
3. Results and discussion
3.1. Phase, crystal structure, chemical and microstructure
analyses of the samples

Using the XRD patterns shown in Fig. 1, the detailed crystal

Intensity (a.u.)

1.4FeHAp structure analysis was done. The estimated values of the crystal-
lite size (D), crystallinity degree (XC), lattice parameters of a and
0.7FeHAp c, c/a ratio and volume of the unit cell (V) are presented together
with the standard values for HAp (JCPDS card no: 09-432) in
Table 1. For all the samples, the major phase was HAp, the minor
HAp phase was β-tricalcium phosphate (β-TCP) and no peaks of any
third phase were found. Therefore, a biphasic composite of HAp
♦ ♦ ♦ (88–94%) and β-TCP (6–12%) was prepared in all cases. The
HAp/β-TCP ratio was found to depend on the amount of iron: the
20 25 30 35 40 45 50 55
higher the amount of Fe, the lower the HAp/β-TCP ratio (Fig. 1).
2θ (Degree)
This could be related to a partial transformation of HAp into a
Fig. 1. XRD patterns of the as-synthesized samples. Fe-containing β-TCP.

Table 1
The detailed crystal structure analysis results of the as-synthesized samples.

Sample D (nm) XC% Phase (%) a (nm) c (nm) c/a V (nm3)

HAp β-TCP

Standard HAp – – 100.00 – 0.9418 0.6884 0.7309 0.5288

HAp 32.54 87.63 93.53 6.47 0.9418 0.6880 0.7305 0.5285
0.7FeHAp 31.43 79.10 88.09 11.91 0.9412 0.6880 0.7310 0.5278
1.4FeHAp 29.09 84.34 91.53 8.47 0.9439 0.6896 0.7306 0.5321
2.1FeHAp 27.91 80.82 90.29 9.71 0.9440 0.6901 0.7310 0.5326
 O. Kaygili et al. / Ceramics International 40 (2014) 9395–9402
The lattice parameters (a and c) and volume of the unit
cell were computed from the relations belonging to a hexa-
gonal structure. The crystallite size (D) was determined using
well-known Scherrer equation [16]. As seen in Table 1, the
crystallite size decreases by the addition of Fe. This is an
expected result since the ionic radius of Fe3 þ (0.064 nm) ions
is smaller than that of Ca2 þ (0.099 nm) ions [17,18].
The crystallite size of the HAp (32.54 nm) is in perfect
harmony with the value (33 nm) reported by Sarath Chandra
et al. [19]. The calculated values of a, c, c/a and V are in
perfect agreement with the standard values. While the lattice
parameters (a and c) and volume of the unit cell (V) were
changed with the addition of Fe, the c/a ratio remained almost
constant. The lattice parameters and volume of the unit cell
increased with increasing Fe content.
The crystallinity degree (XC%) was calculated from the
relation derived by Landi et al. [20]. The numerical values of
XC% were affected by Fe content, and comparing to the pure
HAp, the calculated XC% values of the Fe-containing samples
were smaller. In addition, the crystallinity degree was directly
affected by the phase composition since the XC% value
increased with higher amount of HAp phase and decreased
with higher amount of β-TCP (Table 1).
The FTIR spectra (Fig. 2) exhibited the vibrational modes
of the hydroxyl and phosphate groups. The vibrational modes
of the hydroxyl group were observed at 3577 cm  1 and
2.1FeHAp
1.4FeHAp
Transmitance (a.u.)
0.7FeHAp
HAp
4000 3600 3200 2800 2400 2000 1600 1200 800
Wavenumber (cm−1)
Fig. 2. FTIR spectra of the as-synthesized samples.
9397
633 cm  1. The intensity of the band observed at 3577 cm  1
was very high for HAp, which confirmed the high crystallinity
degree calculated from the XRD pattern. The bands observed
at 1044, 601 and 565 cm  1 were due to the vibrational modes
of the phosphate groups [21]. A wide band in the range of
3200–3500 cm  1 and a sharp band centered at 3648 cm  1
were assigned to water, which was absorbed in the samples
and/or in the KBr pellet [22].
SEM micrographs and the results of EDX analysis are
shown in Fig. 3. The particle size of the samples was less than
1 μm. As expected, the detected amount of Fe increased with
increasing amount of added Fe. While at the sample prepara-
tion stage the (Ca þ Fe)/P molar ratios were kept close to the
stoichiometric value of 1.67, in the final samples, the Ca/P
molar ratios gradually decreased from 1.68 to 1.35 with
increasing amount of Fe. The decrease in the Ca/P molar ratio
confirmed the partial replacement of Ca with Fe. This result is
in good agreement with Tampieri et al. [23]. Thus, both
(Ca þ Fe)/P and Ca/P molar ratios could be controlled by the
Fe content.
3.2. Dielectric properties of Fe doped HAp samples
The relative permittivity (ε0 ), often called the dielectric
constant, was determined from measured capacitance of the
samples [24]. Fig. 4 shows the change of the ε0 values with
increasing frequency. The ε0 values of the samples at different
frequencies are presented in Table 2. The ε0 value of the HAp
at 1 kHz was very close to the reported values for HAp
samples synthesized by different experimental processes [25].
It is seen that the relative permittivity (ε0 ) increased by the
addition of Fe for all frequency values, which was in good
agreement with the previous results [26]. As it is well known,
the induced electric dipoles cause the formation of polariza-
tion. Therefore, the change in the relative permittivity values
could be explained by polarization mechanism, and ionic
polarization was responsible for this change [27]. As seen in
Fig. 4, the relative permittivity of 0.7FeHAp was lower than
that of pure HAp at some frequencies (around 4.25 MHz). This
can be due to the higher phase percentage (11.91%) of β-TCP
in the 0.7FeHAp sample. The higher β-TCP phase causes
the change in the polarization of HAp sample and in turn,
the 0.7FeHAp sample exhibits the lower dielectric constant
around 4.25 MHz. Furthermore, the crystalline phase amount
of 0.7FeHAp sample is lower than that of pure HAp. This
suggests that the 0.7FeHAp sample has some amorphous
regions and these regions create the non-homogeneous dielec-
tric polarization in the 0.7FeHAp sample. That is why, at some
frequency ranges, the relative permittivity of 0.7FeHAp is
lower than that of pure HAp.
Using the measured values of the dielectric permittivity
and loss tangent (tan δ), the dielectric loss ε00 was calculated.
The plots of ε00 vs. frequency of the samples are shown in
Fig. 5. With increase in frequency, the ε00 values remained
400
almost the same until 4 MHz and changed at higher frequencies.
The changes in both ε0 and ε00 values with increasing frequency
were similar to the reported values for femur [28]. The alternating
9398 O. Kaygili et al. / Ceramics International 40 (2014) 9395–9402

Fig. 3. SEM micrographs and EDX analysis reports of the pure-HAp and Fe doped HAp samples.
 O. Kaygili et al. / Ceramics International 40 (2014) 9395–9402 9399

current conductivity (sac) value was determined using the
impedance values of the sample [29]. The plots of the calculated
sac values as a function of increasing frequency are depicted in
Fig. 6. The sac values increased with increasing frequency. The
measured values of the relative permittivity, dielectric loss and
alternating current conductivity belonging to the HAp were in
perfect harmony with Dubey et al. [30]. These three parameters
were affected by increasing frequency and amount of Fe [31].
Jonscher relation [32] determines the conductivity mechanism
of the samples
sac ¼ sdc þ Bωs
the incorporation of Fe into the HAp structure. The Fe content
increased the dielectric polarization and, in turn, the diameter
and position were changed. The Cole–Cole equation was used
to make quantitative analysis of the dielectric spectra [35]
εo  ε1
εn  ε1 ¼ ð2Þ
1 þ ðiωτo Þ1  α
where εn is the complex dielectric constant ðεn ¼ ε0  iε00 Þ, ε1
and εo are the “infinite frequency or optical” and “static”
dielectric constants, respectively, τo is the relaxation time and α
is an exponent, which takes the values between 0 and 1. As seen
ð1Þ

where sdc is the direct current conductivity, B is a constant, 7

ω is the angular frequency and s is an exponent. The increase of HAp
6
the alternating current conductivity with increasing frequency 0.7FeHAp
until 4 MHz obeyed the universal power law behavior. The 5 1.4FeHAp
measured resistance values of all the samples are in the range of 2.1FeHAp
4
1011–1012 Ω, and they exhibited the insulator behavior. The s
values determined from the slope of log sac vs. log ω plot were

ε′′
3
found to be 0.980, 0.970, 0.982 and 0.975 for HAp, 0.7FeHAp, 2
1.4FeHAp, and 2.1FeHAp, respectively. s values were equal to
unity because all the samples lacked measurable direct current 1
conductivity. This result specifies that the hopping motion 0
involved a translational motion with a sudden hopping [33,34].
In order to analyze the dielectric relaxation mechanism of -1
3.0M 3.5M 4.0M 4.5M 5.0M
the samples, we plotted the curves of ε00 vs. ε0 , as shown in
Frequency (Hz)
Fig. 7. Fig. 7 indicates the circles and the position, while
diameter of the circles changes with Fe content. This confirms Fig. 5. The plots of the dielectric loss vs. frequency.

18 6x10-3
17 HAp
5x10-3 0.7FeHAp
16 HAp 1.4FeHAp
0.7FeHAp 4x10-3 2.1FeHAp
15
1.4FeHAp
(S m−1)

14 2.1FeHAp
ε′

3x10-3
13
ac

12

11 2x10-3
10

9
3.0M 3.5M 4.0M 4.5M 5.0M 3M 3.5M 4M 4.5M 5M
Frequency (Hz) Frequency (Hz)

Fig. 4. The relative permittivity values as a function of frequency. Fig. 6. The alternating current conductivity as a function of frequency.

Table 2
The relative permittivity values of the samples at different frequencies.

Sample ε0 1 kHz ε0 50 kHz ε0 100 kHz ε0 1 MHz ε0 3 MHz

HAp 11.09 10.60 10.42 11.15 10.66

0.7FeHAp 11.11 10.84 10.57 11.25 10.77
1.4FeHAp 11.78 11.31 11.72 11.99 11.58
2.1FeHAp 12.34 11.98 12.13 12.64 12.13
9400 O. Kaygili et al. / Ceramics International 40 (2014) 9395–9402

7 in Table 3, the values of ε1 , εo , εo  ε1 (dielectric strength),

α and τo parameters determined from the Cole–Cole plots of
6
the samples shown in Fig. 7 were affected by the Fe content.
5 The obtained τo values of the Fe-substituted HAp samples were
slightly higher than those of the pure HAp. As mentioned in the
4
XRD analysis, the phase composition of the samples is affected
ε′′

3 by the amount of Fe. The dielectric properties of the samples are

also changed with the addition of Fe. Hence, the phase
HAp
2 composition of the samples influences the dielectric properties
0.7FeHAp
1.4FeHAp such as the relative permittivity and dielectric loss [36]. The
1
2.1FeHAp relation between the crystal structure and dielectric properties is
0 easily seen from Fig. 8. With increasing atomic percent of Fe in
9 10 11 12 13 14 15 16 17 18 HAp, the relative permittivity is increased, whereas the crystal-
ε′ lite size is decreased. This indicates that there is an inverse
Fig. 7. The Cole–Cole plots of the samples. proportion between relative permittivity and crystallite size.

Table 3
The quantitative analysis of the dielectric spectra of the samples.

Sample ε1 εo εo ε1 α τo (ns)

HAp 9.31 16.11 6.80 0.125 32.10

0.7FeHAp 9.49 15.66 6.17 0.135 33.24
1.4FeHAp 10.30 17.07 6.77 0.062 33.17
2.1FeHAp 10.66 17.91 7.25 0.088 33.11

12.4
33

32
12.0
31
D (nm)
ε'

11.6 30

29
11.2
28

10.8 27
0.0 0.5 1.0 1.5 2.0 2.5 0.0 0.5 1.0 1.5 2.0 2.5
Atomic percent of Fe Atomic percent of Fe

12.4 12.4

12.0 12.0
ε'

11.6 11.6
ε'

11.2 11.2

10.8 10.8
86 88 90 92 94 96 27 28 29 30 31 32 33
Percent of HAp phase D (nm)

Fig. 8. The plots of ε0 vs. atomic percent of Fe, D vs. atomic percent of Fe, ε0 vs. percent of HAp phase and ε0 vs. D.
 O. Kaygili et al. / Ceramics International 40 (2014) 9395–9402
The percent of HAp phase affects the relative permittivity and in
turn, the relative permittivity is decreased with increase in the
crystallite size.
4. Conclusions
High crystalline Fe-doped HAp samples with admixture of
β-TCP as the secondary phase were prepared. The addition of
Fe was found to affect the crystal structure of HAp. Fe3 þ ions,
which are smaller than those of Ca2 þ ions, caused a gradual
decrease in the crystallite size from 32.54 nm to 27.91 nm and
had an obvious effect on the values of the crystallinity degree,
lattice parameters and unit cell volume, as well as the phase
composition. The bands belonging to the characteristic vibra-
tion modes of hydroxyl and phosphate groups of the HAp
structure were observed by FTIR spectra. SEM photographs
verified the fine-grained microstructure having the small
particle size distribution and EDX analysis confirmed
Fe-incorporation in the apatitic structure since the Ca/P molar
ratios were gradually decreased from 1.68 to 1.35 by addition
of Fe. Since the measured resistance values of the as-
synthesized samples were within 1011–1012 Ω, all samples
exhibited the insulator behavior. The dielectric properties of
the HAp sample were changed by Fe content, and the relative
permittivity was increased with the addition of Fe. The
alternating current conductivity increased with increasing
frequency and obeyed the universal power law behavior. The
dielectric properties and crystal structure are closely related to
each other.
Acknowledgments
The authors gratefully acknowledge and thank the Deanship
of Scientific Research, King Abdulaziz University (KAU),
Jeddah, Saudi Arabia, for the research group “Advances in
composites, Synthesis and applications”. This work is as a
result of international collaboration of the group with Prof. F.
Yakuphanoglu.
References
[1] S.V. Dorozhkin, in: Calcium Orthophosphates: Applications in Nature,
Biology, and Medicine, Pan Stanford, Singapore, 2012, p. 854.
[2] W. Suchanek, M. Yoshimura, Processing and properties of hydroxyapatite-
based biomaterials for use as hard tissue replacement implants, J. Mater.
Res. 13 (1998) 94–117.
[3] S.M. Zakaria, S.H.S. Zein, M.R. Othman, F. Yang, J.A. Jansen,
Nanophase hydroxyapatite as a biomaterial in advanced hard tissue
engineering: a review, Tissue Eng. B: Rev. 19 (2013) 431–441.
[4] C. Rey, C. Combes, C. Drouet, M.J. Glimcher, Bone mineral: update
on chemical composition and structure, Osteoporos. Int. 20 (2009)
1013–1021.
[5] W. Pon-On, N. Charoenphandhu, J. Teerapornpuntakit, J. Thongbunchoo,
N. Krishnamra, I.M. Tang, Physicochemical and biochemical properties
of iron-loaded silicon substituted hydroxyapatite (FeSiHAp), Mater.
Chem. Phys. 141 (2013) 850–860.
[6] Q. Chang, D.L. Chen, H.Q. Ru, X.Y. Yue, L. Yu, C.P. Zhang,
Toughening mechanisms in iron-containing hydroxyapatite/titanium
composites, Biomaterials 31 (2010) 1493–1501.
9401
[7] W. Pon-On, S. Meejoo, I.M. Tang, Substitution of manganese and iron
into hydroxyapatite: core/shell nanoparticles, Mater. Res. Bull. 43 (2008)
2137–2144.
[8] S. Panseri, C. Cunha, T. D’Alessandro, M. Sandri, G. Giavaresi,
M. Marcacci, C.T. Hung, A. Tampieri, Intrinsically superparamagnetic
Fe-hydroxyapatite nanoparticles positively influence osteoblast-like cell
behaviour, J. Nanobiotechnol. 10 (2012) 32.
[9] Y. Li, J. Widodo, S. Lim, C.P. Ooi, Synthesis and cytocompatibility of
manganese (II) and iron (III) substituted hydroxyapatite nanoparticles,
J. Mater. Sci. 47 (2012) 754–763.
[10] M. Iafisco, M. Sandri, S. Panseri, J.M. Delgado-López, J. Gómez-Morales,
A. Tampieri, Magnetic bioactive and biodegradable hollow Fe-doped
hydroxyapatite coated poly(L-lactic) acid micro-nanospheres, Chem. Mater.
25 (2013) 2610–2617.
[11] P.M. Meaney, T. Zhou, D. Goodwin, A. Golnabi, E.A. Attardo,
K.D. Paulsen, Bone dielectric property variation as a function of
mineralization at microwave frequencies, Int. J. Biomed. Imaging 2012
(2012) 649612.
[12] S.A.W. Pickering, B.E. Scammell, Electromagnetic fields for bone
healing, Int. J. Low. Extrem. Wounds 1 (2002) 152–160.
[13] S.P. Bowen, J.D. Mancini, V. Fessatidis, M. Grabiner, Why do electro-
magnetic pulses enhance bone growth?, Ann Biomed. Eng. 36 (2008)
195–203.
[14] N. Horiuchi, J. Endo, K. Nozaki, M. Nakamura, A. Nagai, K. Katayama,
K. Yamashita, Dielectric evaluation of fluorine substituted hydroxyapa-
tite, J. Ceram. Soc. Jpn. 121 (2013) 770–774.
[15] K.P. Tank, B.V. Jogiya, D.K. Kanchan, M.J. Joshi, Dielectric properties
of pure and strontium doped nano-hydroxyapatite, Solid State Phenom.
209 (2014) 151–155.
[16] B.D. Cullity, Elements of X-ray Diffraction, Addison-Wesley Publishing
Company, Massachusetts, 1978.
[17] R.U. Mene, M.P. Mahabole, K.C. Mohite, R.S. Khairnar, Improved gas
sensing and dielectric properties of Fe doped hydroxyapatite thick films:
effect of molar concentrations, Mater. Res. Bull. 50 (2014) 227–234.
[18] P. Kanchana, N. Lavanya, C. Sekar, Development of amperometric
L-tyrosine sensor based Fe-doped hydroxyapatite nanoparticles, Mater.
Sci. Eng. C 35 (2014) 85–91.
[19] V. Sarath Chandra, K. Elayaraja, R.V. Suganthi, M.I. Ahymah Joshy,
I. Sulania, P.K. Kulriya, K. Asokan, D. Kanjilal, S. Narayana Kalkura,
Effect of irradiation of Si5 þ ion on Fe doped hydroxyapatite, Adv. Mater.
Lett. 4 (2013) 438–443.
[20] E. Landi, A. Tampieri, G. Celotti, S. Sprio, Densification behaviour and
mechanisms of synthetic hydroxyapatites, J. Eur. Ceram. Soc. 20 (2000)
2377–2387.
[21] E.R. Kramer, A.M. Morey, M. Staruch, S.L. Suib, M. Jain, J.I. Budnick,
M. Wei, Synthesis and characterization of iron-substituted hydroxy-
apatite via a simple ion-exchange procedure, J. Mater. Sci. 48 (2013)
665–673.
[22] H. Wang, K. Sun, A. Li, W. Wang, P. Chui, Size-controlled synthesis and
characterization of fluorapatite nanocrystals in the presence of gelatin,
Powder Technol. 209 (2011) 9–14.
[23] A. Tampieri, T. D’Alessandro, M. Sandri, S. Sprio, E. Landi,
L. Bertinetti, S. Panseri, G. Pepponi, J. Goettlicher, M. Bañobre–López,
J. Rivas, Intrinsic magnetism and hyperthermia in bioactive Fe-doped
hydroxyapatite, Acta Biomater. 8 (2012) 843–851.
[24] O. Kaygili, S. Keser, T. Ates, F. Yakuphanoglu, Synthesis and characteriza-
tion of lithium calcium phosphate ceramics, Ceram. Int. 39 (2013)
7779–7785.
[25] C.C. Silva, M.A. Valente, M.P.F. Graça, A.S.B. Sombra, The modulus
formalism used in the dielectric analysis of hydroxyapatite and calcium
phosphate with titanium formed by dry ball milling, J. Non-Cryst. Solids
351 (2005) 2945–2950.
[26] O. Kaygili, S. Keser, T. Ates, A.A. Al-Ghamdi, F. Yakuphanoglu,
Controlling of dielectrical and optical properties of hydroxyapatite based
bioceramics by Cd content, Powder Technol. 245 (2013) 1–6.
[27] K.K. Bamzai, S. Suri, V. Singh, Synthesis, characterization, thermal and
dielectric properties of pure and cadmium doped calcium hydrogen
phosphate, Mater. Chem. Phys. 135 (2012) 158–167.
9402 O. Kaygili et al. / Ceramics International 40 (2014) 9395–9402
[28] I.V. Ciuchi, C.S. Olariu, L. Mitoseriu, Determination of bone mineral
volume fraction using impedance analysis and Bruggeman model, Mater.
Sci. Eng. B 178 (2013) 1296–1302.
[29] C.K. Suman, J. Yun, S. Kim, S.D. Lee, C. Lee, AC impedance
spectroscopic studies of transport properties in metal oxide doped
α-NPD, Curr. Appl. Phys. 9 (2009) 978–984.
[30] A.K. Dubey, P.K. Mallik, S. Kundu, B. Basu, Dielectric and electrical
conductivity properties of multi-stage spark plasma sintered HA–CaTiO3
composites and comparison with conventionally sintered materials,
J. Eur. Ceram. Soc. 33 (2013) 3445–3453.
[31] O. Kaygili, C. Tatar, F. Yakuphanoglu, Structural and dielectrical
properties of Mg3–Ca3(PO4)2 bioceramics obtained from hydroxyapatite
by sol–gel method, Ceram. Int. 38 (2012) 5713–5722.
View publication stats
[32] A.K. Jonscher, The ‘universal’ dielectric response, Nature 267 (1977)
673–679.
[33] J.C. Dyre, T.B. Schrøder, Universality of ac conduction in disordered
solids, Rev. Mod. Phys. 72 (2000) 873–892.
[34] K. Funke, Jump relaxation in solid electrolytes, Prog. Solid State Chem.
22 (1993) 111–195.
[35] K.S. Cole, R.H. Cole, Dispersion and absorption in dielectrics
I. Alternating current characteristics, J. Chem. Phys. 9 (1941) 341–352.
[36] R. Gregorio Jr., E.M. Ueno, Effect of crystalline phase, orientation and
temperature on the dielectric properties of poly (vinylidene fluoride)
(PVDF), J. Mater. Sci. 34 (1999) 4489–4500.