Professional Documents
Culture Documents
To cite this article: I. Sopyan, N. A. Nawawi, Q. H. Shah, S. Ramesh, C. Y. Tan & M. Hamdi (2011): Sintering and Properties
of Dense Manganese-Doped Calcium Phosphate Bioceramics Prepared Using Sol-Gel Derived Nanopowders, Materials and
Manufacturing Processes, 26:7, 908-914
This article may be used for research, teaching and private study purposes. Any substantial or systematic
reproduction, re-distribution, re-selling, loan, sub-licensing, systematic supply or distribution in any form to
anyone is expressly forbidden.
The publisher does not give any warranty express or implied or make any representation that the contents
will be complete or accurate or up to date. The accuracy of any instructions, formulae and drug doses should
be independently verified with primary sources. The publisher shall not be liable for any loss, actions, claims,
proceedings, demand or costs or damages whatsoever or howsoever caused arising directly or indirectly in
connection with or arising out of the use of this material.
Materials and Manufacturing Processes, 26: 908–914, 2011
Copyright © Taylor & Francis Group, LLC
ISSN: 1042-6914 print/1532-2475 online
DOI: 10.1080/10426914.2011.557285
Dense manganese-doped biphasic calcium phosphate (Mn-BCP) ceramics were fabricated via uniaxial pressing using the sol-gel derived
powders. The compacted discs were sintered in ambient atmosphere with temperatures ranging from 800 C to 1400 C. Manganese (Mn) level was
varied in the range of 0.6, 1.9, 4.3, and 11.9 mol%, and its effect on physical and mechanical properties of the dense samples were investigated. All
dense samples have been proved to show HA and -TCP phases only. Mn doping has shifted the onset of the sintering temperature of the BCP,
leading to the improved densification of BCP ceramics. The relative density also increased with sintering temperature. Considerable grain growth
has been observed for Mn-doped BCP samples when compared to the undoped BCP. Furthermore, 11.9 mol% Mn-doped BCP dense samples
showed the maximum hardness of 6.66 GPa compared to 2.89 GPa for the undoped BCP. The incorporation of Mn was also found to be beneficial
in enhancing the fracture toughness of BCP throughout the temperature range employed. This study has shown that Mn doping was effective in
improving the sintering properties of BCP without affecting the phase stability.
increases in the presence of Mn, resulting in the promotion sintered dense samples was analyzed by X-ray diffraction
of cell adhesion. Moreover, manganese in the bone was also (XRD) (Shimadzu Diffractometer, XRD-6000), and the
found to cause a decrease in bone resorption [12]. scans were performed on the surface of the polished dense
Various research groups have attempted to dope calcium samples. The change in color intensity of the produced
phosphate materials with manganese [7–10, 13, 14] through dense samples was measured in the range of the visible
the solid-state reaction [8, 10] and precipitation method light using UV-Vis Spectrometer (Perkin Elmer, Lambda
[8]. In this work, manganese has been doped into BCP 35) with a diffuse reflectance accessory (AS-00552-210).
powder via the sol-gel technique. No work on sol-gel The bulk density of the sintered dense samples was
derived Mn-doped BCP powders reported by other groups. measured by water immersion technique [20–22] based on
Sol-gel synthesis allows the preparation of materials not the Archimedes principle using a standard densimeter (Alfa
easily accessible by other methods yet using mild and low Mirage, MD-300S). The immersion medium used in the
energy conditions. The obtained sol-gel powders were then measurement was distilled water. Subsequently, the relative
compacted and sintered to obtain dense BCP compacts density was calculated by taking the theoretical density of
with optimum mechanical properties. We have reported HA as 3.156 g/cm3 . For Vickers hardness determination, the
the synthesis of manganese doped BCP powder elsewhere indentations were made using a pyramidal diamond indenter
[15, 16]. This report presents the effect of Mn content (Mitutoyo, MHV H-2) with an applied load of 100 g. The
and sintering condition on phase behavior and mechanical load was applied smoothly, without impact, and held for
properties of the BCP dense samples. 10 seconds. In the present work, three indentations were
Downloaded by [International Islamic Uni Malaysia] at 23:34 27 June 2011
made for each sample, and the average value was taken.
Experimental The fracture toughness (KIc ) of the sintered dense samples
Preparation of Dense Undoped BCP and Mn-Doped was determined using Vickers indentation method and the
BCP Ceramics KIc value was calculated using the equation reported by
Undoped (Mn-free) BCP and Mn-doped BCP powders Niihara [23].
used to produce dense compacts were synthesized via
a sol-gel technique and have been reported elsewhere Results and discussion
[15, 16]. The sol-gel undoped BCP and Mn-doped Detailed characterization of undoped BCP and Mn-doped
BCP powders with four different molar concentrations BCP powders has been published elsewhere [15, 16]. The
ranging from 0.6 mol%, 1.9 mol%, 4.3 mol%, and 11.9 mol% transmission electron microscopy (TEM) measurement of
were synthesized. Manganese level in the BCP powder the undoped BCP powder calcined at 900 C shows spherical
samples was determined on a Perkin Elmer atomic crystals with crystallite size distribution between 10 nm and
absorption spectrometer (AAS), model AAnalyst 400. The 20 nm. The nanometric primary particles are globular in
undoped BCP and Mn-doped BCP powders were uniaxially shape and tightly agglomerated into micrometric aggregates.
compacted at 2.5 MPa pressure into disc shapes (20 mm Field emission scanning electron microscopy (FESEM)
diameter × 5 mm thickness) using hardened steel mould and revealed that doping of Mn into BCP particles caused fusion
die set. For each powder concentration, seven samples were of particles leading to larger individual particles.
fabricated. Cleanliness of the mould and die set was strictly Figure 1 shows UV-vis absorption bands of the dense
controlled to ensure that samples are not contaminated, samples of undoped and Mn-doped BCP sintered at 1300 C.
and it was also cleansed with WD-40 to prevent powder It was reported that intensity of the color increased with the
lamination. The green bodies were sintered in air using a increasing Mn content and calcination temperature [24]. In
heating furnace (Protherm, PLF 160/5) at seven different this study, the increase in Mn content has also increased the
temperatures ranging between 800–1400 C and held for 2 color intensity of dense BCP to darker shades, as verified by
hours. The ramp-rate was fixed at 2 C/min for both heating the increased light absorption for higher Mn content. This
and cooling process. Conventional pressureless sintering phenomenon was also probably influenced by the natural
was used in all processes. It has been well established that, appearance of Mn itself as blackish or brown solid. The
when the furnace ramp-rate exceeded 5 C/min, thermal and origin of the apatite blue color was due to the presence of
residual stresses would develop in the HA structure [17, 18]. Mn5+ or MnO3− 3−
4 ions at the PO4 sites in the apatite crystal
The reason behind this phenomenon is due to the low heat structure [24, 25]. Sintering at higher temperatures increases
conductivity and high shrinkage rate of HA which then led the intensity of oxidation in the oxidizing atmosphere and
to the formation of microcracks and macrocracks in the also provides enough energy for the oxidized manganese ion
samples [19]. (Mn2+ to Mn5+ to migrate within the crystal lattice [24, 25].
Nevertheless, the change in color in the present work was
Characterization of Dense Mn-BCP Ceramics found to have negligible effect on the phase stability for
Prior to characterization, the sintered dense samples were both Mn-doped BCP powder and dense samples. This is
ground and polished manually on one surface using Mecapol confirmed by the XRD phase analysis showing no presence
(Presi, P260). The samples were ground using silicon of other phases other than HA and -TCP up to the sintering
carbide (SiC) paper (600–1000 grit) in order to remove the temperature of 1200 C for the powder and 1400 C for dense
roughness and refine the surface for characterization. The samples [16].
samples were then polished using diamond paste (3 m– XRD analysis on the dense bodies of undoped and
1 m) slightly until an optically reflective surface was 0.6 mol% and 4.3 mol% Mn-doped BCP are shown in
obtained. The presence of the crystalline phase in the Fig. 2. All dense compacts showed peaks of HA phase
910 I. SOPYAN ET AL.
(2)
Figure 1.—UV-Vis spectra of pure and Mn-doped BCP dense samples
sintered at 1300 C (color figure available online).
According to these equations, both the dehydroxylation and
decomposition reactions include water vapor as a product.
that correspond to the standard International Centre for The rates at which these reactions proceed would depend
Diffraction Data (ICDD) card (no: 09-432 for HA) with no on the partial pressure of H2 O in the sintering atmosphere
secondary phases such as -TCP, TTCP, or CaO detected. [39]. Besides that, the high humidity content present in the
Within the sintering regime employed, the phase transition sintering atmosphere has the tendency to slow down the
of -TCP to HA was observed where the presence of - decomposition rate by preventing the dehydration of the OH
TCP peaks disappeared for Mn-doped BCP dense samples group from the HA matrix [16]. Thus, the secondary phases
sintered at higher temperatures. For undoped BCP dense could be suppressed by controlling the moisture content in
samples, -TCP was still detected at the temperature of the sintering atmosphere.
900 C but disappeared at higher temperatures. For 4.3 mol% In addition, it was observed from Fig. 2 that the HA
Mn-doped BCP, -TCP phase started to disappear at a crystallinity of the dense samples similar to the HA
higher temperature, 1200 C. The phase transition occurred crystallinity of the corresponding powder [Fig. 2(d)] used
as free Ca, which was expelled from -TCP by Mg for their fabrication. At 900 C, the crystallinity of undoped
substitution, which in turn reacts with -TCP phase to BCP dense samples was higher than the 4.3 mol% Mn dense
form HA phase [26]. As a consequence, the HA peaks sample due to higher crystallinity of its powder at that
were observed with the increasing sintering temperatures. temperature.
This result shows that at high sintering temperature
The decomposition of -TCP can be explained in details
> 1200 C, -TCP and Mn-doped -TCP becomes unstable
via the TG/DTA analysis performed on the as synthesized
and contributes to a decrease in solubility limit of Mn in
powder (Fig. 3). The presence of Mn caused a change
the -TCP. Other possible factors that contributed to the
disappearing of -TCP during the sintering process is the in the sintering behavior of dense BCP. The results from
presence of moisture [27] in the suspension and the fact the TG/DTA study suggest that the presence of Mn has
that also during the thermal treatments which was carried shifted the onset of the sintering temperature of the BCP,
out in air atmosphere [28]. Because of the characteristic of indicating that the presence of manganese improves the
TCP as unstable phase at elevated temperature, it may react densification of the -TCP phase in the BCP mixture [9].
with the moisture present in the furnace atmosphere to form This analysis revealed that the Mn is an effective sintering
stable HA. additive for -TCP, as it delayed the phase transformation
No peak of alpha-tricalcium phosphate (-TCP), of -TCP to other phases, which are HA or -TCP. This
tetracalcium phosphate (TTCP), and calcium oxide (CaO) characteristic allows Mn-doped -TCP to be sintered at
was detected in these dense samples throughout the sintering higher temperatures which can produce denser materials
regime to 1400 C, which points out that the phase transition with possibly better properties [9].
temperature from -TCP to -TCP probably happened Densification behavior of the sintered samples can be
above 1400 C. However, previous researches reported that affected by the difference in powder characteristics and
HA ceramics started to decompose into secondary phases morphologies. Moreover, in this study, the densifications are
when sintered beyond 1350 C [29–31] and some even studied in terms of Mn content and sintering temperatures.
reported that it started at about 1300 C [32–37]. Hence, it From the effect of sintering temperature on the relative
could be deduced that in this research work, sol-gel derived density, it was likely that the increase in relative density
HA phase stability was not disrupted by the fabrication was irrespective of Mn content. For undoped BCP
of dense samples parameters such as the initial pressing dense samples, the relative density also increased with
conditions, sintering cycle, and temperature employed. the increasing sintering temperature, as Fig. 4 shows.
MANGANESE-DOPED CALCIUM PHOSPHATE BIOCERAMICS 911
Downloaded by [International Islamic Uni Malaysia] at 23:34 27 June 2011
Figure 2.—XRD patterns of (a) dense pure BCP; (b) dense 0.6 mol% Mn-doped BCP; (c) dense 4.3 mol% Mn-doped BCP calcined at various temperatures; and
(d) BCP powders of different levels of Mn doping calcined at 900 C.
Moreover, it was observed that the density curve showed second stage of sintering would correspond to the onset of
small increment before the onset of densification. This densification and the removal of the majority of porosity
corresponds to the first stage of sintering in which necks [17], as indicated by the dramatic increase in the sintered
are formed between powder particles [40]. Furthermore, the dense samples density between 1000 C and 1300 C.
912 I. SOPYAN ET AL.
4. Weienböck, M.; Stein, E.; Undt, G.; Ewers, R.; Lauer, G.;
Turhani, D. Particle size of hydroxyapatite granules calcified from
red algae affects the osteogenic potential of human mesenchymal
stem cells in vitro. Cells Tissues Organs 2006, 182, 79–88.
5. Bohner, M.; Doebelin, N.; Baroud, G. Theoretical and
experimental approach to test the cohesion of calcium phosphate
pastes. European Cells and Materials 2006, 12, 26–35.
6. Ambard, A.J.; Mueninghoff, L. Calcium phosphate cement:
Review of mechanical and biological properties. Journal of
Prosthodontics 2006, 15, 321–328.
7. Ramesh, S.; Tan, C.Y.; Peralta, C.L.; Teng, W.D. The effect of
manganese oxide on the sinterability of hydroxyapatite. Science
and Technology of Advanced Materials 2007, 8, 257–263.
8. Mayer, I.; Cuisinier, F.J.G.; Popov, I.; Schleich, Y.; Gdalya, S.;
Burghaus, O.; Reinen, D. Phase relations between -tricalcium
phosphate and hydroxyapatite with manganese (II): Structural and
spectroscopic properties. European Journal of Chemistry 2006,
Downloaded by [International Islamic Uni Malaysia] at 23:34 27 June 2011
7, 1460–1465.
Figure 6.—Effect of sintering temperature and Mn doping on the fracture
9. Acchar, W.; Ramalho, E.G. Effect of MnO2 addition on sintering
toughness of BCP (color figure available online).
behavior of tricalcium phosphate: Preliminary results. Materials
Science Engineering C 2008, 28, 248–252.
Conclusion 10. Kazuhiko, K.; Hironobu, S.; Tamoyuki, Y. Local environment
analysis of Mn ions into -tricalcium phosphate. Journal of Japan
Manganese doped biphasic calcium phosphate dense Ceramic Society 2008, 116, 108–110.
bodies with manganese concentrations of 0.6, 1.9, 4.3, 11. Reilly, C. The Nutritional Trace Metals; Blackwell: Oxford, 2004.
and 11.9 mol% have been fabricated via uniaxial pressing 12. Mayer, I.; Diab, H.; Reinen, D.; Albrecht, C. Manganese
followed by 800–1400 C sintering using the sol-gel derived in apatites, chemical, ligand-field and electron paramagnetic
powders. Manganese doping has improved the thermal resonance spectroscopy studies. Journal of Materials Science
stability of dense BCP in all sintering temperatures as no
1993, 28, 2428–2432.
secondary phases other than HA and -TCP peaks detected.
13. Paluszkiewicz, C.; Ślósarczyk, A.; Pijocha, D.; Sitarz, M.;
The manganese doping also improved the mechanical
Bućko, M.; Zima, A.; Chróścicka, A.; Lewandowska-Szumiel,
properties dense BCP ceramics as investigated in terms of
M. Synthesis, structural properties and thermal stability of Mn-
density, hardness, and fracture toughness. The maximum
doped hydroxyapatite. Journal of Molecular Structure 2010, 976,
relative density of 99% relative density was achieved at
301–309.
1300 C by the 4.3 mol% Mn doped BCP compact. The
14. Mayer, I.; Cuisinier, F.J.; Gdalya, S.; Popov, I. TEM study of the
increased density of sintered BCP compacts with sintering
morphology of Mn2+ -doped calcium hydroxyapatite and beta-
temperature is attributed to the densification of -TCP phase
tricalcium phosphate. Journal of Inorganic Biochemistry 2008,
in the BCP structure. The hardness tended to increase with
102, 311–317.
sintering temperature and Mn content and the maximum
15. Natasha, A.N.; Sopyan, I.; Mel, M.; Ramesh, S. Influence of
hardness of 6.66 GPa was obtained by the 11.9 mol% Mn
manganese doping into HA powders on the properties of its dense
doped compact sintered at 1400 C. Similarly, higher level of
bodies. Medical Journal of Malaysia 2008, 63, 85–86.
Mn doped and sintering temperature has enhanced fracture
16. Sopyan, I.; Natasha, A.N. Preparation of nano-structured
toughness of BCP compacts, with the maximum value
manganese doped-biphasic calcium phosphate powders via sol-
was obtained at 11.9 mol% Mn doping showing a fracture
gel method. IONICS 2009, 15, 735–741.
toughness of 105 ± 001 MPam1/2 after 1400 C sintering. 17. Mostafa, N.Y. Characterization, thermal stability and sintering of
It can be concluded therefore that doping of Mn has hydroxyapatite powders prepared by different routes. Materials
greatly improved the mechanical properties of sintered BCP Chemistry and Physics 2005, 94, 333–341.
compacts. 18. Prokopiev, O.; Sevostianov, I. Dependence of the mechanical
properties of sintered hydroxyapatite on the sintering temperature.
References Materials Science and Engineering A 2006, 431, 218–227.
1. Sopyan, I.; Rahim, T.A. Recent progress of the development of 19. Pramanik, S.; Agarwal, A.K.; Rai, K.N.; Garg, A. Development
porous bioactive calcium phosphate for biomedical applications. of high strength hydroxyapatite by solid-state sintering process.
Recent Patents on Biomedical Engineering 2008, 1, 213–229. Ceramics International 2007, 33, 419–426.
2. Sopyan, I.; Mel, M.; Ramesh, S.; Khalid, K.A. Porous 20. Gibson, I.R.; Ke, S.; Best, S.M.; Bonfield, W. Effect of powder
hydroxyapatite for artificial bone applications. Science and characteristics on the sinterability of hydroxyapatite powders.
Technology of Advanced Materials 2007, 8, 116–123. Journal of Materials Science: Materials in Medicine 2001, 12,
3. Dey, A.; Mukhopadhyay, A.K.; Gangadharan, S.; Sinha, M.K.; 1163–1171.
Basu, D. Development of hydroxyapatite coating by microplasma 21. Ramesh, S.; Tan, C.Y.; Bhaduri, S.B.; Teng, W.D. Rapid
sprayin. Materials and Manufacturing Processes 2009, 24, densification of nanocrystalline hydroxyapatite for biomedical
1321–1330. applications. Ceramics International 2007, 33 (7), 1363–1367.
914 I. SOPYAN ET AL.
22. He, L.H.; Standard, O.C.; Huang, T.T.Y.; Latella, B.A.; Swain, additives at 1200 C. Journal of Materials Science: Materials in
M.V. Mechanical behaviour of porous hydroxyapatite. Acta Medicine 1995, 6, 297–301.
Biomaterialia 2008, 4, 577–586. 33. Van Landuy, P.; Li, F.; Keustermans, J.P.; Streydio, J.M.;
23. Niihara, K. Indentation microfracture of ceramics–Its application Delannay, F.; Munting, E. The influence of high sintering
and Problems. Journal of the Ceramic Society of Japan 1985, 20, temperatures on the mechanical properties of hydroxyapatite.
12–18. Journal of Materials Science: Materials in Medicine 1995, 6,
24. Kim, H.; Camata, R.P.; Vohra, Y.K.; Lacefield, W.R. Control 8–13.
of phase composition in hydroxyapatite/tetracalcium phosphate 34. Landi, E.; Tampieri, A.; Celotti, G.; Sprio, S. Densifictaion
biphasic thin coatings for biomedical applications. Journal behaviour and mechanisms of synthetic hydroxyapatites. Journal
of Materials Science: Materials in Medicine 2005, 16, of European Ceramic Society 2000, 20, 2377–2387.
961–966. 35. Rodriguez-Lorenzo, L.M.; Vallet-Regi, M.; Ferreira, J.M.F.
25. Li, Y.; Klein, C.P.A.T.; Zhang, X.; De Groot, K. Relationship Fabrication of hydroxyapatite bodies by uniaxial pressing from a
between the color change of hydroxyapatite and the trace element precipitated powder. Biomaterials 2001, 22, 583–588.
of manganese. Biomaterials 1993, 14, 969–972. 36. Yeong, K.C.B.; Wang, J.; Ng, S.C. Mechanochemical synthesis
26. Ryu, H.S.; Hong, K.S.; Lee, J.K.; Kim, D.J. Variations of nanocrystalline hydroxyapatite from CaO and CaHPO4 .
of structure and composition in magnesium incorporated Biomaterials 2001, 22, 2705–2712.
hydroxyapatite/-tricalcium phosphate. Journal of Materials 37. Kong, L.B.; Ma, J.; Boey, F. Nanosized hydroxyapatite powders
Research 2006, 21 (2), 428–436. derived from coprecipitation process. Journal of Materials
Downloaded by [International Islamic Uni Malaysia] at 23:34 27 June 2011
27. Itatani, K.; Takahashi, M.; Howell, F.S.; Aizawa, M. Effect Science 2002, 37, 1131–1134.
of metal-oxide addition on the sintering of -calcium 38. Wang, T.; Dorner-Reisl, A.; Muller, E. Thermogravimetric
orthophosphate. Journal of Materials Science: Materials in and thermokinetic investigation of the dehydroxylation of a
Medicine 2002, 13, 707–713. hydroxyapatite powder. Journal of European Ceramic Society
28. Gibson, I.R.; Bonfield, W. Preparation and characterization of 2004, 24, 693–698.
magnesium/carbonate co-substituted hydroxyapatites. Journal of 39. Wang, C.K.; Ju, C.P.; Chern-Lin, J.H. Effect of doped bioactive
Materials Science: Materials in Medicine 2002, 13, 685–93. glass on structure and properties of sintered hydroxyapatite.
29. Liao, C.; Lin, F.; Chen, K.; Sun, J. Thermal decomposition and Materials Chemistry and Physics 1998, 53, 138–149.
reconstitution of hydroxyapatite in air atmosphere. Biomaterials 40. Bhatt, H.A.; Kalita, S.J. Influence of oxide-based sintering
1999, 20, 1807–1813. additives on densification and mechanical behaviour of tricalcium
30. Muralitharan, G.; Ramesh, S. The effects of sintering temperature phosphate (TCP). Journal of Materials Science: Materials in
on the properties of hydroxyapatite. Ceramics International 2000, Medicine 2007, 18, 883–893.
26, 221–230. 41. Ramay, H.R.; Zhang, M. Preparation of porous HA scaffolds
31. Ramesh, S.; Tan, C.Y.; Bhaduri, S.B.; Teng, W.D.; Sopyan, by combination of the gel-casting and polymer sponge methods.
I. Densification behaviour of nanocrystalline hydroxyapatite Biomaterials 2003, 24, 3293–3302.
bioceramics. Journal of Materials Processing Technology 2008, 42. Xu, J.L.; Khor, K.A.; Kumar, R. Physicochemical differences
206, 221–230. after densifying radio requency plasma sprayed hydroxyapatite
32. Ruys, A.J.; Brandwood, A.; Milthorper, B.K.; Dickson, M.R.; powders using spark plasma and conventional sintering
Zeigler, K.A.; Sorrell, C.C. The effects of sintering atmosphere techniques. Materials Science and Engineering A 2007, 457,
on the chemical compatibility of hydroxyapatite and particulate 24–32.