synthesis of surfactant assisted hydroxyapatite …joics.org/gallery/joics - 4163.pdfsurfactant...
Post on 26-Feb-2021
13 Views
Preview:
TRANSCRIPT
SYNTHESIS OF SURFACTANT
ASSISTED HYDROXYAPATITE POWDER
USING ULTRASONIC METHOD
Dr. Neeraj Sagar
M.Sc.(Chemistry),B.Ed.,Ph.D.
L. N. Mithila University, Darbhanga.
ABSTRACT
Hydroxyapatite [HAP], is chemically represented asCa10(PO4)6(OH)2
and its excellent bioceramic material for the regeneration of hard tissue
because of its high bioactivity, biocompatibility, non-toxicity and also
osteoconductive properties. Hydroxyapatite is chemically and
crystallographicaly similar to the natural bone. Especially this material is
currently used in dental and orthopaedic applications. In this research work,
the influence of non-ionic surfactant assisted hydroxyapatite powder was
prepared by ultrasonic method. The particle size, morphology, and phase
purity of the powder samples were characterised using analytical methods
such as FTIR, XRD andSEM. This work report, thesynthesisof hydroxyapatite
powder using ultrasonic method offered an effective and economical route to
succeedsmaller particle size with high quality nano-sized hydroxyapatite and
also high level of crystallinity after calcination. The as synthesised powder is
to be tested further for its biocompatibility.
KeyWords: Hydroxyapatite, Biomaterials, Tween, PVA, Ultrasonic method.
GRAPHICAL ABSTRACT FOR HYDROXYAPATITE
Journal of Information and Computational Science
Volume 10 Issue 3 - 2020
ISSN: 1548-7741
www.joics.org1624
Introduction
Hydroxyapatite (HAP) is one of the main inorganic component [1] and
is mostly used in several biomedical applications due to its excellent
biocompatibility, osteoconductivity,bioactivity and also non-toxicity[2-4]and
its economical and naturally friendly[5]. Besides this, hydroxyapatite is also
used in other applications such as catalysts and in column
chromatography,gas sensors, [6, 7] etc. HAP prepared from natural sources can
producebone tissue with strong chemical bonds. This type of HAP has been
known as agreatbone substitute material. HAP are involved in the calcium
phosphate material having the chemical formula Ca10(PO4)6(OH)2, is a
prominent biomaterial for dental and orthopaedic applications[8,9] and its
similar in chemical composition to the mineral phase of bone and teeth
tissues[10, 11].
Many technique approaches have been developedtopreparation of
ceramic hydroxyapatite nanoparticles, including sol-gel[12], precipitation[13, 14], microwave irradiation[15, 16], hydrothermal[17,18,], ultrasonic irradiation[19, 20] and so on. Till now, these chemical techniques suffer from inherent
problems such as the uniform size distribution, morphology, agglomeration
readily and aggregation due to stringent processes, rigid experimental
condition and uncontrolled long term aging. Among these, ultrasonic method
presented special features in controlling the particle properties such as
particle agglomeration and reducing the particle size, morphology and
homogeneity [21].
Recently, ultrasonic system has become a novel technique to achieve
nano-particle [22]
. Ultrasonic method provides many advantages such as,
nano-sized particles, shape control, simple and inexpensive, effectively
decrease the particle aggregation to achieve in the formation of nano sized
structures [23]. Therefore it can be well expected that, ultra-
sonication route is promising and effective technique for formation of nano-
hydroxyapatite particles. Since ultra-sonication mainly depends on
parameters such as power, time, frequency, and temperature etc.
Poly vinyl alcohol (PVA) and Tween are a non-ionic surfactant, to
prevent agglomeration and controlling the morphology. PVA gel used in
variousapplicationsbecause of its excellent physical and chemical properties,
biocompatibility as well as elastic modules,high mechanical propertiesand
high water contents. In addition to this, the formations of hydroxyapatite
powder have been attempted in the presence of surfactant and
Journal of Information and Computational Science
Volume 10 Issue 3 - 2020
ISSN: 1548-7741
www.joics.org1625
organic molecules in aqueous solution, since the product of hydroxyapatite in
organs such as teeth and bone is controlled using surfactant and organic
molecules. [24, 25]
In the present study, the preparation of nano-hydroxyapatite by
ultrasonic method using two type of non-ionic surfactant (tween & PVA).
PVA assisted-hydroxyapatite powderwas well crystallinity with control the
particle size and uniform flower morphology was achieved through this
ultrasonic method and these powders could be successfully employed for
biomedical applications.
2. EXPERIMENTAL METHOD
2.1. Chemicals and Reagents
Ca2(NO3)2· 4H2O, Na2HPO4, poly vinyl alcohol (PVA), tween-20
Ammonia, and ethanol which were purchased from merk. All the chemicals
were ofanalytical grade and DI water was used throughout the experimental
process.
2.2 Synthesis of Hydroxyapatite powder
Hydroxyapatite (HAP) nanoparticles were prepared according to the
following procedure: 0.5M of calcium nitrate and 0.5g of poly vinyl alcohol
(PVA) dissolving in 50 ml of (DI) water. 0.3M of Na2HPO4dissolving in
50ml (DI) water. In order to obtain hydroxyapatite slurry, phosphate solution
was added drop wise into calcium solution, conditions of continuously
stirring for 1hour. During the addition the pH was kept at 10 by using
ammonia solution. The resulting suspension was stirred until a clear
suspension was achieved without any visible solids. After the complete
addition, the suspension was irradiated with an ultrasound for about 40
minutes at 60℃, a transparent dispersion was obtained. In order to eliminate
any impurities the resulting suspension was kept 24 hours aging. The
resulting precipitate was collected using centrifugation and washed several
time for water with ethanol, followed by dryingat 100 oC for 4 h in an oven to
obtain a fine HAP powder. The resulting powder was calcinated and
sintering, finally to achieve pure hydroxyapatite. The synthesis was repeated
with 0.5g of tween-20 and without the addition of tween and PVA.
Journal of Information and Computational Science
Volume 10 Issue 3 - 2020
ISSN: 1548-7741
www.joics.org1626
[A]
606
567 1087
1032
3589
[B]
469 632 966
1652 3431
[C]
3. RESULTS AND DISCUSSION
3.1 FT-IR spectra
The FTIR spectra for hydroxyapatite and surfactant assisted
hydroxyapatite sample are presented in Fig.1. The sharp peak at 3589 cm-1 is
assigned to symmetric stretching vibration of the lattice OH− ions, while the
broad band at 3431 cm-1attributed to adsorbed water, and a medium peak at
632 cm−1, is due to be OH- group of HAP. The PO43- group appeared at 966
cm-1which can be assigned to symmetric stretching mode of phosphate group,
ν1, and the band at 469 cm-1 is due to symmetric bending mode of phosphate
group υ2. The absorption band at 1087 cm-1, 1032 cm-1 corresponds to of υ3
mode [(P-O) asymmetric stretching] of phosphate group. The peak at 567 cm-
1 and 606 cm-1 is attributed to asymmetric bending mode of phosphate group
υ4.Additionally, the peak at 1400 cm-1 is attributed to the presence of the
CO32- group in Fig (a, b), [26]. All characteristic peaks for hydroxyapatite are
present in FTIR spectrum and no impurities appeared in Fig 1 (c) [27, 28].
Hence the FT–IR result designates that the quality of our sample is good.
4000 3500 3000 2500 2000 1500 1000 500
Wavenumber (cm-1)
Fig. 1 – FTIR spectra of the HAP powder prepared by the
ultrasonic technique at different surfactants: (a) HAP, (b)
Tween and (c) PVA
Tra
nsm
itta
nce
(%
)
Journal of Information and Computational Science
Volume 10 Issue 3 - 2020
ISSN: 1548-7741
www.joics.org1627
Table 1 FTIR spectral assignment of the functional groups
HYDROXYAPATITE
Sample OH Phosphate
(Sharp)
&
Broad
(Medium) 1 2 3 4
HAP 3580,
3450
643 958 467 1078 &
1023
606
HAP-
Tween
3580,
3440
624 961 476 1097&
1032
604
HAP-
PVA
3589,
3431
632 966 469 1087&
1032
606
3.2. X-Ray Diffractions (XRD)
The XRD diffraction patterns of the synthesized hydroxyapatite
powder with and without the surfactant are presented in Fig.2. In these XRD
patterns, the major peaks were observed at 2θ values at 25.90, 29.10,
31.66, 32.72, 34.18, 39.59, 45.39, 49.32 and
53.48corresponding to the (002), (210), (211), (300), (202), (310), (222), (213), and
(004)
confirmsthe formation of hydroxyapatite. Similar peaks were also detected in
the XRD patterns of tween–HAP. The XRD spectra of surfactant assisted
hydroxyapatite showed higher crystallinity when compare to without
surfactant. It is clear thatall demonstrable peaks in all samples were identified
to pure hydroxyapatite with hexagonal phase and no impurities peaks
according to standard JCPDS card no -09-0432. The particle size of
surfactant assisted hydroxyapatite powder is found to be lower when
compared to hydroxyapatite, which is calculated by scherrer’s equation[29].
As a typical result from the XRD, the addition of non- ionic surfactant as a
plays a major role in the crystallization and growth of HAP nano- particles
and it is effective formation of biological hard tissue withstrong chemical
bond.
D = K/λ βcosθ
Journal of Information and Computational Science
Volume 10 Issue 3 - 2020
ISSN: 1548-7741
www.joics.org1628
10 20 30 40 50 60 70 80
2 degree
Fig. 2 – XRD pattern of HAP powder prepared by the ultrasonic technique at
different surfactants: (a) HAP, (b) Tween and (c) PVA
3.3 Scanning electron microscopic studies
The morphology of hydroxyapatite powder synthesize by ultrasonic
method with different surfactants (PVA and tween-20). In Fig. 3(a), the
hydroxyapatite powder formed were non- uniform particle in size, the
particles are joined to each other and produced aggregated particles and
irregular morphology present in micro metre range. Fig. 3(b, c) show the
presence of surfactant assisted hydroxyapatite powder, having a uniform size,
well- controlled and regular array of nano-particles. Furthermore, converted
from plate shape (b) to flower like morphology were clearly observable in the
case of Fig.3 (c). It was observed that the morphology of a flower and plate
like HAP powder was affected remarkably by the concentration of PVA and
tween in the ultrasonic method. It has been well-known that, organic
materials may have interacted with inorganic substances of calcium and
phosphate in the ultrasonic method to obtained a uniformly arrangement
structure. The flower structures were then retained after the removal of PVA
and tween by calcination at a high temperature. Finally, the SEM images
showed that the PVA (0.5g) was optimal for the preparation of flower
morphology of hydroxyapatite powder and prevent agglomeration.
[A]
[B]
[C]
* * **
- TCP# 09-0169
- HAP# 09-0432
Inte
nsi
ty (
a.u
)
Journal of Information and Computational Science
Volume 10 Issue 3 - 2020
ISSN: 1548-7741
www.joics.org1629
[C]
Fig. 3 – The surface morphology of the HAP powder prepared by
the ultrasonic technique at different surfactants: (a) HAP,
(b) Tween and (c) PVA
[A]
[B]
Journal of Information and Computational Science
Volume 10 Issue 3 - 2020
ISSN: 1548-7741
www.joics.org1630
Conclusions
In this study, hydroxyapatite nanoparticles have been successfully
prepared by ultrasonic irradiation method using poly vinyl alcohol (PVA) and
tween-20 as a non-ionic surfactant. The result indicated that, in FT-IR
spectrum showed that no impurities peaks was observed and in XRD, the
synthesis of surfactant assisted hydroxyapatite powder has a hexagonal
structure with higher crystallinity and smaller particle size. The SEM image
revealed that uniform morphology, control the size and regular array of nano-
particles was achieved using PVA. It can be concluded that, ultrasonic
method with PVA as a growth regulator can result in fine nanometre sized
HAP. The obtained HAP powder could serve as a favourable candidate in
biomedical applications and hence this technique could be a novel approach
to synthesis of HAP nanoparticles.
ACKNOWLEDGEMENTS
One of the authors (Dr. V. Collins ArunPrakash) thanks the Abdul
Kalam Research centre (AKRC), Sacred Heart College (Autonomous)
Tirupattur, for the financial assistance through received under “Don Bosco
grant” scheme.
REFERENCES
1. P. Rouhani, N. Taghavinia, S. Rouhani,. (2010)Rapid growth of
hydroxyapatite nanoparticles using ultrasonic irradiation,Ultrason.
Sonochem17, 853.
2. C.Fu, X.Zhang, K.Savino, P.Gabrys, P.Gao, W.Chaimayo and B.
L.Miller (2016)Antimicrobial silver-hydroxyapatite composite
coatings through two-stage electrochemical synthesis," Surface and
Coatings Technology. 301,13-19.
3. A.T.Cucuruz, E.Andronescu, A.Ficai, A.Ilie and F.Iordache(2016)
Synthesis and characterization of new composite materials based on
poly (methacrylic acid) and hydroxyapatite with applications in
dentistry International journal of pharmaceutics,510, 516-23.
4. S.V.Dorozhkin(2015) Calcium orthophosphate deposits: preparation,
properties and biomedical applications Materials Science and
Engineering. 55,272-326.
5. S.C.Wu, H.C.Hsu, S. K.Hsu, F.W.Lin and W.F.Ho(2015)Preparation
and characterization of porous calcium-phosphate microspheres
Ceramics International. 417596-7604.
6. J. Torrent-Burgues,T.Boix, J.Fraile, (2001) Precipitation of
stoichiometric hydroxyapatite by a continuous method. Cryst. Res.
Technol. 36, 1075-1082.
Journal of Information and Computational Science
Volume 10 Issue 3 - 2020
ISSN: 1548-7741
www.joics.org1631
7. J.Arensds, J.Chistoffersen,M.R.Chistoffersen, (1987)A calcium
hydroxyapatite precipitated from an aqueous solution: An
international multi method analysis. J. Cryst. Growth. 84, 515.
8. L.L. Hench, (1991)Bioceramics: From concept to clinic. J. Am. Ceram. Soc. 74,
1487.
9. E. Landi, G. Celotti, G. Logroscino, A. Tampieri, (2003)Carbonated
hydroxyapatite as bone substitute, J. Eur. Ceram. Soc. 23 2931.
10. Z. Zhao, M. Espanol, J. Guillem-Marti, D. Kempf, A. Diez-Escudero,
M.P. Ginebra, (2016)Ion-doping as a strategy to modulate
hydroxyapatite nanoparticle internalization.Nanoscale 8, 1595.
11. L.-Y. Cao, C.-B. Zhang, J.-F. Huang, (2005) Synthesis of
hydroxyapatite nanoparticles in ultrasonic precipitation,Ceram. Int.
31, 1041.
12. G. Bezzi, G. Celotti, E. Landi, T. M. G. La Torretta, I. Sopyan, and A.
Tampieri,(2003) A novel sol–gel technique for hydroxyapatite
preparation. Mater. Chem. Phy. 78, 816.
13. M. R. Saeri, et al., (2003) The wet precipitation process of
hydroxyapatite. Mater. Lett., Vol. 57, 4064-4069.
14. A. Afshar, et al., (2003)Some important factors in the wet-
precipitation process of hydroxyapatite. Materials and Design. 24,
197-202.
15. B. Vaidhyanathan and K. J. Rao, (1996)Rapid microwave assisted
synthesis of hydroxyapatite. Bull. Mater. Sci. 19, 1163.
16. Lo´pez-Macipe, A., Go´mez-Morales, J., Rodrı´guez-Clemente, R.:
(1998)Nanosized hydroxyapatite precipitation from homogeneous
calcium/citrate/phosphate solutions using microwave and
conventional heating. Adv. Mater.10, 49–53.
17. Y. Wang, et al., (2006)Hydrothermal synthesis of hydroxyapatite
nano-powders using cationic surfactant as a template. Mater. Lett.,
60, 1484-1487.
18. H.S. Liu, T.S. Chin, L.S. Lai, S.Y. Chiu, K.H. Chuang, C.S. Chang,
and M.T. Lui, (1997)Hydroxyapatite synthesized by a simplified
hydrothermal method. Ceram. Int. 23, 19.
19. G.E.J. Poinern, et al., (2011)Thermal and ultrasonic influence in the
formation of nanometre scale hydroxyapatite bio-ceramic.
International Journal of Nanomedicine, 6, 2083-2095.
20. W. Kim and F. Saito, (2001) Sonochemical synthesis of
hydroxyapatite from H3PO4 solution with Ca(OH)2.
UltrasonicsSonochem. 8, 85.
21. F. Franco, L.A.P. Maqueda, J. L. P. Rodriguez, (2004)The effect of
ultrasound on the particle size and structural disorder of a well-
ordered kaolinite, J. Colloid Interface Sci. 274 107-117.
22. D.P. Dutta, B.P. Mandal, R. Naik, G. Lawes, A.K. Tyagi,
Journal of Information and Computational Science
Volume 10 Issue 3 - 2020
ISSN: 1548-7741
www.joics.org1632
(2013)Magnetic, Ferroelectric, and Magnetocapacitive Properties of
Sonochemically Synthesized Sc- Doped BiFeO3 NanoparticlesJ. Phys.
Chem. C 117, 2382.
23. N. Mandzy, E. Grulke, T. Druffel, (2005)Breakage of TiO2
agglomerates in electrostatically stabilized aqueous dispersions,
Powder Technol. 160 121 – 126.
24. C.E. Fowler, M.Li, S.Mann, H.C. Margolis,(2005) Influence of
surfactant assembly on the formation of calcium phosphate materials-
A model for dental enamel formation. J. Mater. Chem. 15, 3317–
3325.
25. C.He, F.Zhang, L.Cao, W.Feng, K.Qiu, (2012)Rapid mineralization of
porous gelatine scaffolds by electrode position for bone tissue
engineering. J. Mater. Chem. 22, 2111-2119.
26. M. Sadat-Shojai, M.T. Khorasani, A. Jamshidi,(2012)Hydrothermal
processing of hydroxyapatite nanoparticles—A Taguchi experimental
design approach J. Cryst. Growth 361, 73.
27. L. FernandesCo´ta, K.P.M. Licona, J.D.N. Lunz, A.A. Ribeiro, L.M.
Alonso, M.V. De Oliveira, L.C. Pereira, Mater. Sci. Forum 869, 896
(2016)
28. A.B.H. Yoruc¸, Y. Ipek, (2012)Acta Phys. Pol., A 121, 230.
29. A. Siddharthan, S.K. Seshadri, and T.S. Sampathkumar,
(2004)Microwave accelerated synthesis of nanosized calcium
deficient hydroxyapatite. J. Mater. Sci. Mater. Med. 15, 1279.
Journal of Information and Computational Science
Volume 10 Issue 3 - 2020
ISSN: 1548-7741
www.joics.org1633
top related