synthesis of surfactant assisted hydroxyapatite …joics.org/gallery/joics - 4163.pdfsurfactant...

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



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.



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

(%

)



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 nanoparticles

and it is effective formation of biological hard tissue withstrong chemical

bond.

D = K/λ βcosθ



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

)



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]



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.



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,



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.



ISSN: 1548-7741

www.joics.org1633

synthesis of surfactant assisted hydroxyapatite …joics.org/gallery/joics - 4163.pdfsurfactant...

Documents