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Sintering and Mechanical Properties of Magnesium and Fluorine Co-Substituted Hydroxyapatites

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Sintering and Mechanical Properties of Magnesium and Fluorine Co-Substituted Hydroxyapatites Journal of Biomaterials and Nanobiotechnology, 2013, 4, 1-11 1 http://dx.doi.org/10.4236/jbnb.2013.41001 Published Online January 2013 (http://www.scirp.org/journal/jbnb) Sintering and Mechanical Properties of Magnesium and Fluorine Co-Substituted Hydroxyapatites Samia Nsar, Amel Hassine, Khaled Bouzouita* Laboratory of Industrial Chemistry, National School of Engineering, Sfax, Tunisia. Email: *[email protected] Received September 5th, 2012; revised October 17th, 2012; accepted November 10th, 2012 ABSTRACT Biological apatites contain several elements as traces. In this work, magnesium and fluorine co-substituted hydroxyapa- tites with the general formula Ca9Mg(PO4)6(OH)2-yFy, where y = 0, 0.5, 1, 1.5 and 2 were synthesized by the hydrother- mal method. After calcination at 500˚C, the samples were pressureless sintered between 950˚C and 1250˚C. The substi- tution of F− for OH− had a strong influence on the densification behavior and mechanical properties of the materials. Below 1200˚C, the density steeply decreased for y = 0.5 sample. XRD analysis revealed that compared to hydroxyl- fluorapatite containing no magnesium, the substituted hydroxyfluorapatites decomposed, and the nature of the decom- position products is tightly dependent on the fluorine content. The hardness, elastic modulus and fracture toughness of these materials were investigated by Vickers’s hardness testing. The highest values were 622 ± 4 GPa, 181 ± 1 GPa and 1.85 ± 0.06 MPa·m1/2, respectively. Keywords: Hydroxyapatite; Magnesium, Fluorine; Sintering; Mechanical Properties 1. Introduction tite containing magnesium and fluorine would be more suitable for dental and orthopedic applications. Hydroxyapatite (HA) is widely used in orthopedic and Hence, it is thought worthwhile to synthesize and char- reconstructive surgery thanks to its excellent bioactivity acterize Mg/F-co-substituted hydroxypatites. The present and biocompatibility with the human body [1]. However, study deals with the sintering of these materials and the the biological apatites contain several species as traces investigation of their mechanical properties, all the more such as F−, Cl−, CO2 , Na+, Sr2+, Mg2+, etc. Therefore, 3 as only few studies have dealt with this kind of materials the incorporation of one or several of these species into [21,22]. the hydroxyapatite structure should improve its bio- compatibility and bioactivity [2,3], and affects its physi- 2. Experimental Procedure cal and chemical properties such as crystallinity, thermal stability, solubility and osteoconductivity [4-6]. Among 2.1. Powder Preparation these latter species, Fluorine is known to delay the car- Analytical grades Ca(NO ) ·4H O, Mg(NO ) ·6H O, ies’ processes [7], improve the bonds between the bones 3 2 2 3 2 2 (NH ) HPO and NH F were used as starting materials. and the implant [8-10], and strengthen the bone structure 4 2 4 4 Appropriate amounts according to the stoichiometric [11]. Furthermore, this element decreases the solubility formulas of Ca (PO ) (OH)F and Ca Mg(PO ) (OH) F and enhances the thermal stability of the hydroxyapatite 10 4 6 9 4 6 2-y y with y = 0, 0.5, 1, 1.5 and 2, were weighed, respectively [12]; therefore, when fluorine is incorporated into bone and dissolved into 5 cm3 of deionised water under vig- mineral, its resorption is reduced. On the other hand, orous stirring. The pH of the mixed solution was adjusted Magnesium has a beneficial effect on the mineralization to 9 by adding a concentrated ammonia solution. After processes [13,14], osteoporosis [15] and might play a that, the mixed solution was transferred to a Teflon ves- role on the osteoblastic and osteoclastic activities [16,17]. sel (model 4749 Parr Instrument) and sealed tightly. The In addition, Mg is known to inhibit the crystallization of autoclave was oven-heated at 180˚C for 6 h, and then the hydroxyapatite, increase its dissolution and affect its cooled to room temperature naturally. The collected pre- thermal stability by lowering its decomposition tempera- cipitates were washed with deionised water and dried at ture [18-20]. Thus, ceramics designed from hydroxyapa- 70˚C overnight. After drying, the powders were calcined *Corresponding author. under argon flow at 500˚C for 1 h with a heating rate of Copyright © 2013 SciRes. JBNB 2 Sintering and Mechanical Properties of Magnesium and Fluorine Co-Substituted Hydroxyapatites 10˚C·min−1. the following equation: In the following sections, the compositions W d (2) Ca10(PO4)6(OH)F, Ca9Mg(PO4)6(OH)2, theo Aa2 csin120 Ca9Mg(PO4)6(OH)1.5F0.5, Ca9Mg(PO4)6(OH)F, where A is Avogadro’s number, and a and c are the lat- Ca9Mg(PO4)6(OH)0.5F1.5 and Ca9Mg(PO4)6F2 will be named tice parameters. as HFA, MHA, MHF0.5A, MHF1A, MHF1.5A and MFA, respectively. 2.4. Mechanical Characterization 2.2. Powder Characterization The mechanical properties were investigated on pellets of The (Ca + Mg)/P molar ratios in the as-prepared powders 13 mm in diameter sintered at different temperatures for were evaluated by a chemical analysis [23,24]. The fluo- 1 h. The sintered samples were polished to mirror finish ride content was measured using a fluoride selective prior to mechanical investigation using various grade electrode (Ingold, PF4-L). silicon carbide papers (grade 800 - 1200) and a 0.2 m The XRD patterns of the as-prepared and calcined diamond paste. powders were collected on a Philips X-pert diffractome- The hardness was checked with Vickers’ indentation ter operating with Cu-K radiation ( = 1.5406 Ǻ) for a technique using a Matsuzawa Seiki digital micro-hard- 2θ range from 20˚ to 55˚. The scan step was 0.02˚ and ness Tester (Japan). Five samples were used for each the integration time was 1 s per step. The crystalline hardness data point, and for each sample, ten indenta- phases were identified by comparing the experimental tions were performed at an applied load of 200 g for 15 s. XRD patterns to the standards compiled by the Joint Thus, the reported hardness Hv is the average of the fifty Committee on Powder Diffraction and Standards (JCPDS values calculated according to the equation [25]: cards). 31 1.8544P The P magic angle spinning nuclear magnetic reso- Hv 2 (3) nance (31P MAS NMR) spectra were performed on a d Brucker 300 WB spectrometer. The 31P observational where P is the indentation load and d is the length of the frequency was 121.49 MHz with a spin speed 8 kHz. The diagonal of the indentation. 31P shift is given in parts per million (ppm) referenced to The Elastic modulus (Young’s modulus) was esti- an aqueous solution of 85 wt% H3PO4. mated from an empirical relationship reported by Mar- The specific surface area (SSA) of the as-synthesized shall et al. [26] using Vickers’ microhardness: and calcined powders was measured with a Belsorp 28 045.H SP apparatus using the BET method, while nitrogen was E v (4) utilized as an adsorbed gas. ab ab' where Hv is Vickers’ indentation, a is the length of the 2.3. Sintering shorter diagonal, b is the length of the longer diagonal To carry out sintering experiments, the calcined powders determined using a Knoop’s indenter and b' is the crack were uniaxially pressed under 45 MPa into pellets in a 13 length. mm diameter steel die, then the pellets were sintered un- In Equation (4) der argon flow in a temperature ranging from 950˚C to a tg (5) 1250˚C with 50˚C in interval for various times. b The sintered samples were characterized based on re- with lative density, X-ray diffraction analysis and microstruc- tural analysis using a scanning electron microscope (PHI- π 172 30 (6) LIPS XL 30). 22 Both green and sintered densities (dex) of compacts The comparison of Vickers and Knoop’ hardness for were determined through dimension and weight, and the ceramics material reported by several authors [27,28] relative density was calculated using the formula: showed that the average value of the ratio HK/HV is d 1.105. ex (1) Under these conditions, the value of a according to the dtheo Knoop indentation is determined according to the fol- The theoretical density for each composition lowing equation: (Ca9Mg(PO4)6(OH)2-yFy) was calculated taking in ac- 14.23 count its molecular weight (W), the number of units per a tg l (7) unit cell (1) and the volume of the unit cell, according to 1.854 1.105 Copyright © 2013 SciRes. JBNB Sintering and Mechanical Properties of Magnesium and Fluorine Co-Substituted Hydroxyapatites 3 where l is the length of Vickers’ indenter diagonal. Table 1. Chemical analysis data of as-prepared powders. So, Equation (4) may be written as follows: Weight percent (wt%) 045.H E v (8) Composition Ca Mg P F (Ca+Mg)/P tg tg l2.63 b' Ca9Mg (PO4)6(OH)2 36.2 (1) 2.8 (3) 18.3 (1) - 1.680 Ca Mg(PO ) (OH) F 35.5 (9) 2.3 (4) 18.3 (5) 0.97 (1) 1.663 The fracture toughness (KIC) was determined using the 9 4 6 1.5 0.5 indentation technique, and following the relationship Ca9Mg(PO4)6(OH)F 36.2 (4) 2.3 (3) 18.5 (3) 1.86 (2) 1.671 given below [26]: Ca9Mg(PO4)6(OH) 0.5F1.5 36.2 (1) 2.3 (3) 18.4 (6) 2.85 (1) 1.677 23 12 Ca Mg(PO ) F 35.6 (9) 2.2 (6) 18.3 (1) 3.65 (1) 1.663 EPc 9 4 6 2 KIC 32/ 1 (9) Hac v Table 2. Lattice parameters of non- and Mg/F co-substituted hydroxyapatites.
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