S. M. Best

CHARACTERIZATION OF POROUS HYDROXYAPATITE

Hydroxyapatite has been considered for use in the repair of osseous defects for the last 20 years. Recent developments have led to interest in the potential of porous hydroxyapatite as a synthetic bone graft. However, despite considerable activity in this field, regarding assessment of the biological response to such materials, the basic materials characterization is often inadequate. This paper documents the characterization of the chemical composition, mechanical integrity, macro- and microstructure of a porous hydroxyapatite, Endobon ® (E. Merck GmbH), intended for the bone-graft market. Specimens possesed a range of apparent densities from 0.35 to 1.44 g cm-3. Chemical analysis demonstrated that the natural apatite precursor of Endobon® was not converted to pure hydroxyapatite, but retained many of the ionic substituents found in bone mineral, notably carbonate, sodium and magnesium ions. Investigation of the microstructure illustrated that the struts of the material were not fully dense, but had retained some traces of the network of osteocyte lacunae. Macrostructural analysis demonstrated the complex inter-relationship between the structural features of an open pore structure. Both pore size and connectivity were found to be inversely dependent on apparent density. Furthermore, measurement of pore aspect ratio and orientation demonstrated a relationship between apparent density and the degree of macrostructural anisotropy within the specimens, while, it was also noted that pore connectivity was sensitive to anisotropy. Compression testing demonstrated the effect of apparent density and macrostructural anisotropy on the mechanical properties. An increase in apparent density from 0.38 to 1.25 g cm-3 resulted in increases in ultimate compressive stress and compressive modulus of 1 to 11 MPa and 0.2 to 3.1 GPa, respectively. Furthermore, anisotropic high density (> 0.9 g cm-3) specimens were found to possess lower compressive moduli than isotropic specimens with equivalent apparent densities. These results underline the importance of full structural and mechanical characterization of porous ceramic implant materials. ©1999 Kluwer Academic Publishers

Calcium phosphate bone cements for clinical applications. Part I: solution chemistry.

Calcium phosphate cements have been the subject of many studies in the last decade because of their biocompatibility, their capacity to fill bone cavities and their hardening properties; properties which are desirable in a broad range of surgical applications. The setting and hardening of these materials are controlled by dissolution–precipitation chemical reactions at room or body temperature and involve crystalline phase transformations.

Carbonate substitution in precipitated hydroxyapatite: an investigation into the effects of reaction temperature and bicarbonate ion concentration.

Carbonate substitution in the apatite crystal lattice can occur in either the hydroxyl or the phosphate sites, designated as A or B type, respectively, and previous investigations generally have described precipitated carbonate hydroxyapatite as being B type on the basis of infra red and X-ray data. This paper documents the effects of two precipitation variables, namely temperature and bicarbonate ion concentration, on the morphology, phase composition, and calcium, phosphorus, and carbon contents of precipitated carbonate hydroxyapatite. Variations in both temperature and bicarbonate concentration could yield either acicular or spheroidal crystals. X-ray diffraction and infra red spectroscopy indicated the presence of carbonate in the A site for low carbonate contents (< 4 wt%), and at higher carbonate contents (> 4 wt%), the carbonate was located predominantly in the B site. On the basis of these observations and chemical analyses, a new AB carbonate substitution mechanism is proposed that better describes the experimental data than the B-type models used previously.

Characterization of the transformation from calcium-deficient apatite to beta-tricalcium phosphate.

The structural changes that occur during the transformation of a Ca-deficient apatite, prepared by a wet chemical method, to β-TCp were investigated. X-ray diffraction (XRD) analysis of as-prepared samples and samples calcined at temperatures between 500 and 1100 °C showed that the transformation occurs over the temperature range 710–740 °C, under non-equilibrium conditions. The change in crystallite size with increasing calcination/sintering temperature was studied by XRD using the Scherrer formula. Fourier transform infra-red (FTIR) analysis indicated considerable structural change in samples above and below this temperature range. Changes were observed in the hydroxyl, carbonate and phosphate bands as the calcination temperature was increased from 500 to 1100 °C. Even once a single β-TCP phase is obtained at 740 °C there remains a considerable amount of structural change at temperatures between 740 and 1100 °C. This effect was illustrated by an unusual change in the lattice parameters of the β-TCP structure and significant changes in the phosphate bands of FTIR spectra as the calcination temperature was increased. The results obtained in this study show that the combined experimental techniques of XRD and FTIR are excellent complimentary methods for characterizing structural changes that occur during phase transformations.

Calcium phosphate bone cements for clinical applications. Part II: Precipitate formation during setting reactions

Calcium phosphate bone cements (CPBC) have been of great interest in medicine and dentistry due to their excellent biocompatibility and bone-repair properties. In this article, a review is presented of the scientific literature concerning precipitate formation during setting reactions of CPBCs. Firstly, the available information has been classified according to the intended final product or calcium phosphate formed during setting reactions. Taking the final product into account, a second classification has been made according to the calcium phosphates present in the original powder mixture. This is the most natural classification procedure because it is based on thermodynamic reasons supported by solubility diagrams for the calcium phosphate salts. By understanding the thermodynamics of calcium phosphate salts in an aqueous solution at room or body temperature it is possible to optimize the manufacturing technology involved in the production of CPBCs. Knowledge of the limitations of this thermodynamic approach opens up new possibilities in the search for CPBCs with better in vitro and in vivo properties for clinical applications.

Synthesis and characterization of carbonate hydroxyapatite

Substituted apatite ceramics are of clinical interest as they offer the potential to improve the bioactive properties of implants. Carbonate hydroxyapatite (CHA) has been synthesized by an aqueous precipitation method and precipitates with two different levels of carbonate, processed as powders. Sintering experiments were performed to establish the influence of carbonate in significantly reducing the temperature required to prepare high-density ceramics when compared with stoichiometric hydroxyapatite (HA). High-temperature X-ray diffraction was used to characterize the phase stability of the apatites on sintering. Increasing carbonate content was shown to reduce the temperature at which decomposition occurred, to phases of CaO and β-TCP. Mechanical testing, performed using biaxial flexure, showed that the CHA specimens had strengths similar to stoichiometric HA.

Preparation and characterization of fluoride-substituted apatites.

Apatites were prepared with three different fluoride concentrations: 0.0 mM (pure hydroxyapatite) 2.5 mM and 5 mM. Reactions were performed in aqueous medium using a reaction between diammonium orthophosphate and calcium nitrate 4-hydrate and ammonium fluoride at temperatures of 3°, 25°, 60° and 90°C. The effects of reaction temperature and fluoride concentration on the crystal morphology, phase purity and crystallinity of the precipitates were observed, using transmission electron microscopy (TEM), X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy and ion chromatography. Transmission electron micrographs revealed that the crystallites precipitated at 3°C were spheroidal, but became increasingly acicular with increasing precipitation temperature. X-ray diffraction results indicated that all the materials produced were phase pure and that the crystallinity of apatites prepared at higher precipitation temperatures was higher than those prepared at lower precipitation temperatures. A significant difference in the a-axis dimension of fluoride-substituted apatites was observed, as compared to hydroxyapatite. FTIR spectroscopy revealed a hydroxyl band at 3568 cm-1, along with a broad peak of adsorbed water in the region of 3568 cm-1 to 2670 cm-1 in the hydroxyapatite and fluoride-substituted apatite powders. Hence by careful selection of the precipitation conditions and fluoride contents, the composition and morphology of fluoride-substituted apatite may be controlled and this has interesting implications for the development of these materials for biomedical implantation.

Quantification of bone ingrowth within bone-derived porous hydroxyapatite implants of varying density

Hydroxyapatite has been investigated for use in the osseous environment for over 20 years and the biocompatibility of the ceramic and its osseoconductive behavior is well established. Therefore, the use of porous hydroxyapatite for the repair of osseous defects seems promising with potential for complete penetration of osseous tissue and restoration of vascularity throughout the repair site. However, there have been few systematic studies of the effects of physical properties such as macropore size and pore connectivity on the rate and quality of bone integration within porous hydroxyapatite implants. This paper quantifies the early biological response to a well-characterized series of implants with uniform microstructure and phase composition, but differing macrostructures and demonstrates the dependence of the rate of osseointegration on the apparent density of porous hydroxyapatite as a function of pore connectivity. Furthermore, compression testing established that bony ingrowth has a strong reinforcing effect on porous hydroxyapatite implants, which is more pronounced in the lower density implants, as a result of a greater relative volume of bone ingrowth.

PRODUCTION AND CHARACTERIZATION OF NEW CALCIUM PHOSPHATE BONE CEMENTS IN THE CAHPO4-ALPHA -CA3(PO4)2 SYSTEM : PH, WORKABILITY AND SETTING TIMES

The initial setting properties of calcium phosphate cements in the CaHPOv4–α-Ca3(PO4)2 (DCP–α-TCP) system have been investigated. Interest was focused on the pH, workability, cohesion time and initial and final setting times. The addition of CaCO3 modified the structure of the cement reaction product such that it became more similar to the apatite phase in bone mineral. The addition of 10% w/w of CaCO3 reduced the viscosity of the cement pastes resulting in an increase in initial and final setting times and improved injectability.

Improvement of the mechanical properties of new calcium phosphate bone cements in the CaHPO4-α-Ca3(PO4)2 system: Compressive strength and microstructural development

The hardening properties of calcium phosphate cements in the CaHPO4-alpha-Ca3(PO4)2 (DCP-alpha-TCP) system have been investigated with interest focused on the compressive strength and microstructure development. Previous studies have shown that the addition of CaCO3(CC) leads to a modification of the calcium-deficient apatite structure of the reaction product, which results in a material more similar to the apatite in bone mineral. The addition of 10% w/w of CC to the initial DCP-alpha-TCP powder mixture resulted, with time, in a retardation of the development of compressive strength. However, the optimum compressive strength reached values up to 40% higher than CC-free samples. This retarding effect also has been monitored as a function of the calcium to phosphorus (Ca/P) ratio of the DCP and alpha-TCP mixture, showing the importance of the final cement properties of the relative quantities of the reactants in the mixture.