Novel Materials and Biosystems - UA/i3N-FSCOSD

Calcium phosphate-based biomaterials: electrical polarization

P.R. Prezasa,
B.M.G. Meloa, M.C. Lançab, L.F.V. Pintoc, J. Venturac, M.A. Valentea, M.P.F. Graçaa
ai3N-FSCOSD (“Novel Materials and Biosystems”) and Physics Department, University of Aveiro, Portugal

bi3M-CENIMAT/Department of Materials Science, Faculty of Science and Technology, New University of Lisbon, Portugal

cAltakitin S.A., Rua José Gomes Ferreira, 1-Arm, D2660-360 São Julião do Tojal, Portugal

Abstract Results
Bone grafting and interventions related with orthopedic disorders are a large business,
generating more than $2.5 billion per year. As an example, it is expected that the market of
dental implants grows at a rate of 7.2% until 2021, generating then about $12.32 billions.

Bioactive materials for orthopedic-related applications are gaining attention and “climbing”
in the market, due to the important drawbacks related with use of autografts (bones
obtained from another anatomic site in the same patient) and allografts (bones obtained
from another person).

Among these promising biomaterials it is included the calcium phosphate-based

biomaterials group, namely hydroxyapatite [Hap, Ca10(PO4)6(OH)2] and b-tricalcium
phosphate [b-TCP, b-Ca3(PO4)2].

The bioactivity of Hap and b-TCP is referred as their ability to promote the growth and
directly bond with new host biologic bone. These materials are also osteoconductive, having
the ability to act as a template and guide the formation of new bone along their surface.

Methods to enhance the bioactivity of these materials are being researched. In the mid-
nineties it was discovered by Yamashita et al. that the electrical polarization of these
bioceramics enables the storage of a substantial charge density that considerably enhances
the bioactivity – new host bone growth rate is increased.

Experimental Details
Commercial powder

Fit the spectra to allow a better visualization of the depolarization processes and to
Samples ID Composition (wt%)
Encontro Ciência 2017

enable an accurate calculation of relevant parameters, such as the stored charge density
Hap 100% Ca10(PO4)6(OH)2 (Qp) and the activation energy for depolarization (Ea)
b-TCP 100% b-Ca3(PO4)2
HTCP 75% Ca10(PO4)6(OH)2 + 25% Ca3(PO4)2

p1
Fig 1/ Scheme of the electrical polarization
p3
experimental procedure. After reaching
p2
the polarization temperature Tp the dc p3
p2 p1
electric field was applied during 30
minutes (tp) and, before the
depolarization current measurements, the
electrodes were short-circuited (SC step)
during about 5 minutes. The heating rate 500 ºC - HTCP 500 ºC - Hap 500 ºC - b-TCP
is 6 ºC/min. 2 kV/cm 3 kV/cm 4 kV/cm 5 kV/cm 5 kV/cm 5 kV/cm
Energy Peak Temperature

Tp1 (ºC) 498 497 527 598 579 530

Tp2 (ºC) 533 545 555 746 --------------- 601

Tp3 (ºC) 642 642 677 783 882 690

Ea p1 (eV) 0,49 0,57 0,61 0,75 0,75 0,91

Conclusions
x10-3 (C/cm2)
Stored Charge Density Activation

Ea p2 (eV) 2,27 3,21 4,49 14,77 --------------- 3,45

• b-TCP samples revealed a stored charge density in the magnitude of 10-2 C/cm2, two
orders of magnitude higher than hydroxyapatite (Hap) thermoelectrically polarized Ea p3 (eV) 1,17 1,51 1,7 1,83 1,81 1,47
under the same conditions.
Qp x10-3(C/cm2) 1,35 2,69 2,37 2,76 0,18 14,48
• Contrarily to what is believed in the literature, b-TCP has an excellent charge storage
ability, surpassing largely Hap. p1 contribution (%) 66,8 61,3 72,0 79,6 3,6 23,9

• The idea prevailing in the literature that b-TCP is not electrically polarizable has p2 contribution (%) 12,7 13,7 9,3 1,2 --------------- 16,9
established itself due the fact that in the few reports regarding this subject, the
polarization process parameters, Ep and Tp, were not high enough to fully activate p3 contribution (%) 20,5 25,0 18,7 19,2 96,4 59,2
the b-TCP polarization processes.
We found that, contrarily to what was reported in the literature, the b-TCP phase has
• A future work on b-TCP is the assessment of the effects of the electrical a higher ability to store electrical charge compated with the more “popular”
polarization on its bioactivity, both in vitro and in vivo, since this material may hydroxyapatite (about two orders of magnitude!). Further information is avaiable in
have a considerably higher potential of application than it was thought to have. our recent publication:

- P.R. Prezas, B.M.G. Melo, L.C. Costa, M.A. Valente, M.C. Lança, J.M.G. Ventura, L.F.V.
Pinto, M.P.F. Graça, TSDC and impedance spectroscopy measurements on hydroxyapatite,
β-tricalcium phosphate and hydroxyapatite/β-tricalcium phosphate biphasic bioceramics,
Applied Surface Science (2017)