Hydrogen-substituted ß-tricalcium phosphate synthesized in organic media.

ß-Tricalcium phosphate (ß-TCP) platelets synthesized in ethylene glycol offer interesting geometries for nano-structured composite bone substitutes but were never crystallographically analyzed. In this study, powder X-ray diffraction and Rietveld refinement revealed a discrepancy between the platelet structure and the known ß-TCP crystal model. In contrast, a model featuring partial H for Ca substitution and the inversion of P1O4 tetrahedra, adopted from the whitlockite structure, allowed for a refinement with minimal misfits and was corroborated by HPO42- absorptions in Fourier-transform IR spectra. The Ca/P ratio converged to 1.443 ±â€…0.003 (n = 36), independently of synthesis conditions. As a quantitative verification, the platelets were thermally decomposed into hydrogen-free ß-TCP and ß-calcium pyrophosphate which resulted in a global Ca/P ratio in close agreement with the initial ß-TCP Ca/P ratio (ΔCa/P = 0.003) and with the chemical composition measured by inductively coupled plasma (ΔCa/P = 0.003). These findings thus describe for the first time a hydrogen-substituted ß-TCP structure, i.e. a Mg-free whitlockite, represented by the formula Ca21 - x(HPO4)2x(PO4)14 - 2x, where x = 0.80 ±â€…0.04, and may have implications for resorption properties of bone regenerative materials.

Textured and hierarchically structured calcium phosphate ceramic blocks through hydrothermal treatment.

Synthetic calcium phosphate bone graft substitutes are widely recognized for their biocompatibility and resorption characteristics in the treatment of large bone defects. However, due to their inherent brittleness, applications in load-bearing situations always require reinforcement by additional metallic implants. Improved mechanical stability would eliminate the need for non-resorbable metallic implants. In this context a new approach to obtain calcium phosphate scaffolds with improved mechanical stability by texturing the material in specific crystal orientations was evaluated. Texture and reduction of crystal size was achieved by recrystallizing α-TCP blocks into calcium deficient hydroxyapatite (CDHA) under hydrothermal conditions. SEM and XRD analysis revealed the formation of fine CDHA needles (diameter ≈ 0.1-0.5 µm), aligned over several hundreds of micrometers. The obtained microstructures were remarkably similar to the microstructures of the prismatic layer of mollusk shells or enamel, also showing organization at 5 hierarchical structure levels. Brazilian disc tests were used to determine the diametral tensile strength, σdts, and the work-of-fracture, WOF, of the textured materials. Hydrothermal incubation significantly increased σdts and WOF of the ceramic blocks as compared to sintered blocks. These improvements were attributed to the fine and entangled crystal structure obtained after incubation, which reduces the size of strength-determining critical defects and also leads to tortuous crack propagation. Rupture surfaces revealed intergranular tortuous crack paths, which dissipate much more energy than transgranular cracks as observed in the sintered samples. Hence, the refined and textured microstructure achieved through the proposed processing route is an effective way to improve the strength and particularly the toughness of calcium phosphate-based ceramics.

Growth kinetics of hexagonal sub-micrometric ß-tricalcium phosphate particles in ethylene glycol.

Recently, uniform, non-agglomerated, hexagonal ß-tricalcium phosphate (ß-TCP) platelets (diameter≈400-1700nm, h≈100-200nm) were obtained at fairly moderate temperatures (90-170°C) by precipitation in ethylene glycol. Unfortunately, the platelet aspect ratios (diameter/thickness) obtained in the latter study were too small to optimize the strength of polymer-ß-TCP composites. Therefore, the aim of the present study was to investigate ß-TCP platelet crystallization kinetics, and based on this, to find ways to better control the ß-TCP aspect ratio. For that purpose, precipitations were performed at different temperatures (90-170°C) and precursor concentrations (4, 16 and 32mM). Solution aliquots were retrieved at regular intervals (10s-24h), and the size of the particles was measured on scanning electron microscopy images, hence allowing the determination of the particle growth rates. The ß-TCP platelets were observed to nucleate and grow very rapidly. For example, the first crystals were observed after 30s at 150°C, and crystallization was complete within 2min. The crystal growth curves could be well-fitted with both diffusion- and reaction-controlled equations, but the high activation energies (∼100kJmol(-1)) pointed towards a reaction-controlled mechanism. The results revealed that the best way to increase the diameter and aspect ratio of the platelets was to increase the precursor concentration. Aspect ratios as high as 14 were obtained, but the synthesis of such particles was always associated with the presence of large fractions of monetite impurities.

Control of the size, shape and composition of highly uniform, non-agglomerated, sub-micrometer ß-tricalcium phosphate and dicalcium phosphate platelets.

Calcium phosphates (CaPs) are widely used as bone graft substitutes but are inherently brittle, hence restricting their use to mechanically protected environments. Combining them with a tough polymer matrix could potentially lead to a composite with load-bearing properties. However, the highest mechanical properties can only be achieved if the CaP particles possess very precise features: they should be uniform in size and shape, non-agglomerated, elongated and thin. The aim of the present study therefore was to assess a novel method to produce such particles. This involved the precipitation of CaP particles in ethylene glycol at moderate temperatures (90-170 °C) and the variation of different reaction parameters (temperature, concentration, pH, etc) to study their influence on particle composition, size, shape and dispersion was studied. As a result, two main CaP phases were obtained as well-dispersed and highly uniform platelets in the form of: (i) ß-tricalcium phosphate (ß-TCP) hexagonal prisms and (ii) monetite (DCP) flat parallelepipeds. The size dispersion was the narrowest for ß-TCP (standard deviation/mean < 5%) whereas the aspect ratio was the highest for DCP (up to 25). In both cases, the thickness of the platelets was below 300 nm which should be ideal for the synthesis of strong CaP-based composites.

Evaluation of the ultrasonication process for injectability of hydraulic calcium phosphate pastes.

This study examined the use of ultrasonication to improve the injectability of an aqueous calcium phosphate paste. Ultrasonication was applied to the paste through the plunger of the delivery syringe. A factorial design of experiments with three investigated factors, liquid to powder ratio (LPR) (38%, 39% and 40%), the size of the delivery syringe (5 and 10 ml) and the amplitude of the 20 kHz power ultrasonication (0-30 µm), was used in this study. The volume fraction of the extruded paste was used to quantify injectability. Small injectability improvements were observed with an increase in LPR and decrease in syringe size, which is consistent with previously published results. The improvements due to ultrasonication were significant and remarkable. For example, when using the 5 ml syringe the injected volume fraction of the 38% LPR paste improved from 63.4 ± 2.3% without ultrasonication to 97.3 ± 2.4% with 30%. This result shows that ultrasonication is an effective solution to improve injectability.

Bone substitute: transforming beta-tricalcium phosphate porous scaffolds into monetite.

The goal of the present study was to assess the possibility to change the composition of a calcium phosphate scaffold from a high-temperature phase to a phase only stable at or close to room temperature without macrostructural changes. For that purpose, macroporous beta-TCP scaffolds were converted into alpha-TCP by high-temperature thermal treatment and then dipped into a phosphoric acid solution to obtain a more acidic calcium phosphate phase called monetite or dicalcium phosphate (DCP; CaHPO4). Two different solid-to-liquid ratios (SLR: 0.067 and 0.200g/mL) and three different temperatures (T: 37, 60 and 80 degrees C) were used. The reaction was followed by measuring the change of sample size and weight, by determining the compositional changes by X-ray diffraction (Rietveld analysis), and by looking at the micro- and macrostructural changes by scanning electron microscopy and micro-computed tomography. The results revealed that the transformation proceeded faster at a higher temperature and a higher SLR value but was achieved within a few days in all cases. Morphologically, the porosity decreased by 10%, the pore size distribution became wider and the mean macro pore size was reduced from 0.28 to 0.19mm. The fastest conversion and the highest compressive strength (9MPa) were measured using an incubation temperature of 80 degrees C and an SLR value of 0.2g/mL.