Biphasic Calcium Phosphate Bioceramics Research Articles

Fabrication and characterization of novel nano hydroxyapatite/β‐tricalcium phosphate scaffolds in three different composition ratios

The biphasic calcium phosphate (BCP) concept was introduced to overcome disadvantages of single phase biomaterials. Different composition ratios of BCP bioceramics have been studied, yet controversies regarding the effects of ratio on biomaterial behavior still exist. In this study, BCP scaffolds were prepared from nano hydroxyapatite (HA) and β-tricalcium phosphate (β-TCP) that were synthesized via a solid state reaction. Three different composition ratios of pure BCP and collagen-based BCP scaffolds (%HA/%β-TCP; 30/70, 40/60, and 50/50) were produced using a polymeric sponge method. Physical and mechanical properties of all materials and scaffolds were investigated. SEM showed overall distribution of both macropores (80-200 μm) and micropores (0.5-2 μm) with high interconnected porosities. Total porosity of pure BCP (90% ± 3%) was found to be higher than collagen-based BCP (85% ± 2%). It was observed that following sintering process, dimensional shrinkage of large scaffolds (39% ± 4%) was lower than small ones (42% ± 5%) and scaffolds with high HA ratios (50%) experienced higher dimensional changes than those with higher β-TCP (70%) ratios (45% ± 3% and 36% ± 1%, respectively). Compressive strength of both groups was less than 0.1 MPa and collagen coating had almost no influence on mechanical behavior. Further studies may improve the physical properties of these scaffolds and investigate their exact biological behaviors.

Comparison of Biphasic Calcium Phosphate Bioceramics Fabricated Using Different Techniques

In this work three different preparation techniques of biphasic calcium phosphate (BCP) bioceramics (consisting of both hydroxyapatite (HAp) and β-tricalcium phosphate (TCP)) are compared: sintering of synthetic calcium-deficient apatites (CDAs) (intimate mixture of HAp and TCP - SBCP), sintering of mechanical mixture of synthetic HAp and apatitic tricalcium phosphate (Ap-TCP) - MBCP and sintering of mechanical mixture of synthetic HAp and calcium metaphosphate glass (CMG) - GBCP. Two different HAp/TCP phase ratios were investigated: 20/80 and 60/40. Phase composition, microstructure, sintering properties and microporosity of obtained BCP bioceramics were investigated. The open porosity of prepared BCP bioceramics is strongly influenced by phase composition and preparation technique. BCP bioceramics SBCP and MBCP have homogeneous microstructure, whereas GBCP has inhomogeneous inclusions of dense TCP. High content of hydroxyapatite (HAp) phase in MBCP and SBCP correlates with high microporosity.

Dense fine-grained biphasic calcium phosphate (BCP) bioceramics designed by two-step sintering

In this study, dense, fine-grained biphasic calcium phosphate bioceramics were designed via the two-step sintering method. The starting powder was nanosized calcium-deficient hydroxyapatite, whose phase composition, average particle size and morphology were characterized by XRD, FTIR, Raman spectroscopy, laser diffraction and FE-SEM. The phase transformations of the initial powder during heating up to 1200 °C were examined using TG/DSC. At first, conventional sintering was performed and the recorded shrinkage/densification data were used to find out the appropriate experimental conditions for two-step sintering. The obtained results show that two-step sintering yields BCP ceramics, consisting of hydroxyapatite and β-TCP, with full dense, homogeneous structure with average grain size of 375 nm. Furthermore, BCP ceramics obtained by the two-step sintering method exhibit improved mechanical properties, compared to conventionally sintered BCP.

Influence of Strontium on the Synthesis and Surface Properties of Biphasic Calcium Phosphate (BCP) Bioceramics

Biphasic calcium phosphate (BCP) ceramics are suitable for synthetic bone applications. The strontium substituted calcium phosphate ceramics have potential for use in orthopedic surgeries. Aim of the present work is to introduce strontium into BCP (composed of hydroxyapatite and tricalcium phosphate) ceramics and to study their bioactivity and mechanical properties. BCP ceramics have been synthesized at room temperature under the physiological pH of 7.4 by gel method in the presence of strontium (5, 10 M %). The appropriate choice of anhydrous CaCl₂ as precursor solution has promoted the formation of BCP instead of pure HA for CaCl₂.2H₂O. Powder X-ray diffraction analysis confirmed the formation of BCP with different HA and ß -TCP ratios depending upon the Sr content. The presence of Sr has reduced the nucleation and growth rate of BCP when compared to pure system. The SEM micrographs showed that the microstructural morphology of BCP changes from fibrous to platelet. Nanoindentation studies indicate a significant decrease in the hardness and elastic modulus values of BCP ceramics due to Sr doping. In vitro bioactivity study has revealed the formation of apatite layer on the Sr doped BCP samples and the doping enhanced its bioactivity.

Synthesis and characterization of hydroxyapatite/β-tricalcium phosphate nanocomposites using microwave irradiation

Microwave assisted synthesis method is a relatively new approach employed to decrease synthesis time and form a more homogenous structure in biphasic calcium phosphate bioceramics. In this study, nanocrystalline HA/β-TCP composites were prepared by microwave assisted synthesis method and, for comparison reason, by conventional wet chemical methods. The chemical and phase composition, morphology and particle size of powders were characterized by FTIR, XRD and SEM, respectively. The use of microwave irradiation resulted in improved crystallinity. The amount of hydroxyapatite phase in BCP ranged from 5% to 17%. The assessment of bioactivity was done by soaking of powder compacts in simulated body fluid (SBF). The decreasing pH of the solution in the presence of β-TCP indicated its biodegradable behavior. Rod-like hydroxyapatite particles were newly formed during the treatment in SBF for microwave assisted substrate synthesis. In contrast, globular particles precipitate under same conditions if BCP substrates were synthesized using conventional wet chemical methods.

Thorough analysis of silicon substitution in biphasic calcium phosphate bioceramics: A multi-technique study

Four samples of composition Ca(10)(PO(4))(6-x)(SiO(4))(x)(OH)(2-x), with x=0.0, 0.1, 0.2 and 0.5, were prepared and characterized using powder X-ray and neutron powder diffraction, and (1)H, (31)P and (29)Si nuclear magnetic resonance (NMR) spectroscopy. The composition of the Si-substituted HAp phases was determined by joint Rietveld refinements from powder X-ray and powder neutron diffraction data. Taking into account electroneutrality, a chemical formula for the Si-substituted HAp phases with indication of the incorporated silicate amount is proposed. Solid-state (29)Si NMR confirms the presence of only Q(0) species, in good agreement with the presence of substituted HAp and beta-TCP phases only. Thanks to NMR spectroscopy, two types of protons in the Si-substituted HAp phase were identified, the new site corresponding to species engaged in hydrogen bonding with silicate anions. This allowed further refinement of the formulae for these phases with very good quantitative agreement for populations derived from the refinement and integration of NMR data.

Influence of microporosity and macroporosity on the mechanical properties of biphasic calcium phosphate bioceramics: Modelling and experiment

Macroporous biphasic calcium phosphate (BCP) bioceramics, for bone substitution applications, have been synthesized, cold isostatically pressed and pressureless sintered, using naphthalene particles as a porogen to produce macropores. The resulting materials are mixtures of β-tricalcium phosphate and hydroxyapatite with various microporosities and macroporosities. Mechanical properties (Young's modulus, compressive strength and fracture toughness) were measured on specimens over the widest attainable ranges of porosities, and compared to previously proposed analytical models and hypotheses. These models describe the evolution of the mechanical properties as functions of macroporosity and microporosity separately, the strength model considering macropores as critical flaws in the ceramic. Results show that the presence of macropores strongly influences the critical flaw size, but the latter appears to increase with macroporosity. This phenomenon can be explained by the presence of clusters of macropores, acting as critical flaws, becoming larger as macroporosity increases.

Influence of surface porosity and pH on bacterial adherence to hydroxyapatite and biphasic calcium phosphate bioceramics

Hydroxyapatite (HA) and biphasic calcium phosphate (BCP) ceramic materials are widely employed as bone substitutes due to their porous and osteoconductive structure. Their porosity and the lowering of surrounding pH as a result of surgical trauma may, however, predispose these materials to bacterial infections. For this reason, the influence of porosity and pH on the adherence of common Gram-positive bacteria to the surfaces of these materials requires investigation. Mercury intrusion porosimetry measurements revealed that the pore size distribution of both bioceramics had, on a logarithmic scale, a sinusoidal frequency distribution ranging from 50 to 300 nm, with a mean pore diameter of 200 nm. Moreover, total porosity was 20 % for HA and 50 % for BCP. Adherence of Staphylococcus aureus and Staphylococcus epidermidis was studied at a physiological pH of 7.4 and at a pH simulating bone infection of 6.8. Moreover, the effect of pH on the zeta potential of HA, BCP and of both staphylococci was evaluated. Results showed that when pH decreased from 7.4 to 6.8, the adherence of both staphylococci to HA and BCP surfaces decreased significantly, although at the same time the negative zeta-potential values of the ceramic surfaces and both bacteria diminished. At both pH values, the number of S. aureus adhered to the HA surface appeared to be lower than that for BCP. A decrease in pH to 6.8 reduced the adherence of both bacterial species (mean 57 %). This study provides evidence that HA and BCP ceramics do not have pores sufficiently large to allow the internalization of staphylococci. Their anti-adherent properties seemed to improve when pH value decreased, suggesting that HA and BCP bioceramics are not compromised upon orthopaedic use.

Effect of Sintering Process of HA/TCP Bioceramics on Microstructure, Dissolution, Cell Proliferation and Bone Ingrowth

The purpose of this study was to determine the effect of sintering conditions on microporosity of and cell proliferation and bone ingrowth on biphasic calcium phosphate (BCP) bioceramics. Discs were prepared from a calcium-deficient apatite preparation that upon sintering at 1050oC and above, results in a BCP with 60% hydroxyapatite (HA)/ 40% beta-tricalcium phosphate (β-TCP) ratio. The discs were divided into groups which were sintered under different conditions of heating rate (programmed vs. non-programmed) and temperature (1050°C vs. 1200°C). The discs were characterized in terms of composition (HA/β-TCP ratio), surface morphology, surface area, surface microporosity, per cent microporosity, and dissolution properties. The in vitro effect of sintering conditions on cell proliferation was determined using an established mouse fibroblast cell line (L929). Results demonstrated the following: (a) the HA/β-TCP ratio remained 60/40 regardless of sintering conditions; (b) the % microporosity, surface microporosity, surface area of the BCP and cell proliferation on the BCP significantly decreased with increasing sintering temperature, and (c) the extent of dissolution decreased with decreasing per cent microporosity. The in vivo study indicated no tissue adverse reaction and direct bone contact with the implant surface, confirming the biocompatibility of the BCP bioceramics. Resorption of the BCP and bone ingrowth was directly related to the sintering temperature: the higher the temperature, the lower the resorption and the bone ingrowth. Results of this study indicate that per cent microporosity of the BCP bioceramics affects its dissolution properties and cell response. The study demonstrates that optimum per cent microporosity elicits optimum cell response and should be considered to provide osteogenic/osteoinductive property to bioceramics.

Validation of an Analytical Model Describing Mechanical Properties of Porous BCP Ceramics

Macroporous biphasic calcium phosphate bioceramics, for use as bone substitutes, have been fabricated by cold isostatic pressing and conventional sintering, using naphthalene particles as a porogen to produce macropores. The resulting ceramics, composite materials made of hydroxyapatite and β-tricalcium phosphate containing various macroporosities and microporosities, have been submitted to compression and three-point bending tests. The mechanical tests performed on the sintered ceramics tend to validate the modelling approach and its hypothesis, i.e. the material can be considered as a microporous matrix containing isolated macropores, and the critical flaw is a macropore.

In Vivo Demonstration of 2 Types of Microporosity on the Kinetic of Bone Ingrowth and Biphasic Calcium Phosphate Bioceramics Resorption

Microporosity and granules size are important parameters for the development of suspension, composites and injectable bone substitutes. In this experimental study performed in a rat bone model of critical size defects, were have determined the kinetics of bioceramic resorption and bone ingrowth. Two kinds of granules (1mm in diameter) of Biphasic Calcium Phosphate BCP (60/40 HA/TCP ratio) with 20% and 40% microporosity of less of 5 microns in size, were used. Higher bone ingrowth was observed for low porosity (LP) at 3 weeks versus high porosity (HP); the contrary was measured after 6 weeks. About the kinetics of BCP resorption, significant difference between the 2 porosities was noticed, the higher for high microporosity. High porosity on time, promotes more bone ingrowth at the expense of the bioceramic than lower microporosity.

Preparation of Biphasic Calcium Phosphate Porous Ceramics Prepared from Fine Powders with Different Particle Size and its Dissolution Behavior in Simulated Body Fluid

Biphasic calcium phosphate (BCP) ceramics, a mixture of hydroxyapatite (HAp) and betatricalcium phosphate (β-TCP), of varying HAp/β-TCP ratios was prepared. One kinds of HAp and one kind of β-TCP powders were used to produce porous BCP bioceramics with HAp/β-TCP weight rations of 20/80, 40/60, and 80/20. A slip was obtained by adding a mixed powders of HAp and β-TCP to a solution 1.5% of deflocculant and 0.5 wt% of foaming agent. The optimum value for the minimum viscosity in these present slips with respect to its solid loading and the optimum amount of the deflocculant were investigated. The specimen obtained by casting a polyurethane foam with 1.5 wt% of deflocculant into a slip, and drying it under vacuum, was heated at 1150°C for 3 hours. The resultant porous BCP sintered body had large spherical pores of 300 /m with interconnecting rectangular voids. Many small pores in the size range of 2-3 /m or below were observed in the specimen obtained by heating at 1150°C for 3 hours. The dissolution test was done as follows. The obtained porous ceramics samples about 0.5g individually soaked into 30 mL of simulated body fluid (SBF) solution at 36.5°C. The calcium and phosphorous content of the SBF solution was analyzed by ICP. The porous body was dried, and characterized using SEM, XRD, and FT-IR.

Microwave Plasma Sintering and In Vitro Study of Porous HA/β-TCP Biphasic Bioceramics

Porous HA/β-TCP biphasic calcium phosphate (BCP) bioceramics were prepared by microwave plasma in order to solve the problems on sintering of Ca-P bioceramics by a conventional furnace. The plasma-sintered samples exhibit a higher densification rate, smaller grain size and higher compressive strength compared to those of conventional sintered samples. The [Ca2+] concentration and the dissolution rate are also higher than those of conventional sintered samples in physiological saline. After immersed in simulated body fluid (SBF) and simulated inflammation body fluid, the amount of bone-like apatite formed on plasma-sintered samples is more than that formed on conventional sintered samples. The results indicate that plasma sintered porous BCP bioceramics have better mechanical properties and may also have better biological properties. On the other hand, the surface of samples that underwent a simulated inflammation procedure is smoother and the amount of bone-like apatite formed on them is less than that formed on the samples immersed in normal SBF all the time, which may indicate that the light acid in an inflammation response would affect the bone reconstruction when Ca-P bioceramics implanted in living body.

Mechanical Properties of Macroporous Biphasic Calcium Phosphate Bioceramics Fabricated Using a Porogen

Macroporous biphasic calcium phosphate bioceramics, for use as bone substitutes, have been fabricated by cold isostatically pressing and conventional sintering, using naphtalen or saccharose particles to produce macropores. The resulting ceramics, composite materials made of hydroxyapatite and b-tricalcium phosphate containing ~ 45% macropores and ~ 25% micropores, have been submitted to compression and three-point bending tests, toughness tests by single-edge-notched-bending, and spherical indentation tests. A new model is established to describe mechanical properties as a function of the amount and morphology of porosity, and propositions are made to optimise the fabrication procedure. Finally, those highly porous ceramics, although very brittle, exhibit a damage-tolerant contact behaviour, due to the compaction of the porous body under the indenter.

Modeling Relations between Processing, Microstructure and Mechanical Properties of Porous Bioceramics

Biphasic calcium phosphate (BCP) bioceramics, for use as resorbable bone substitutes, containing both isolated macropores and interconnected micropores, have been fabricated by sintering, using naphtalen particles as a porogen to produce macropores. The resulting ceramics contain ~ 45% macropores and various amounts of microporosity. Mechanical properties (compression and bending strength, toughness and hardness) have been measured and modeled by combining two approaches, at two different scales: the one describes the mechanical properties of a partly sintered stacking of grains, supposed to account for the interconnected microporosity, the other one holds in the case of closed and isolated macropores within a continuous matrix. The material is then represented as a quasi-continuous matrix containing macropores, the matrix being itself microporous. The model also considers that fracture always initiates on a macropore, which allows to set a correspondence between fracture toughness and fracture stress equations. The mechanical tests performed on the sintered ceramics tend to validate the modeling approach.

Modelling the mechanical properties of microporous and macroporous biphasic calcium phosphate bioceramics

Macroporous biphasic calcium phosphate bioceramics, for use as bone substitutes, have been fabricated by cold isostatic pressing and conventional sintering, using naphtalen particles as a porogen to produce macropores. The resulting ceramics, composite materials made of hydroxyapatite and β-tricalcium phosphate (TCP) containing ∼45% macropores and with various microporosities, have been submitted to compression and three-point bending tests, toughness tests by single-edge-notched-bending (SENB), and spherical indentation tests. By combining two approaches at two different scales, one for closed porosity and one for open porosity, a model is established to describe mechanical properties as a function of the amount and morphology of porosity. The model assumes a quasi-continuous matrix containing macropores, the matrix being itself microporous, and considers that fracture always initiates on a macropore. The preliminary mechanical tests performed on the sintered ceramics tend to validate the modelling approach.

Preparation and Properties of Zinc Containing Biphasic Calcium Phosphate Bioceramics

Preparation and Properties of Zinc Containing Biphasic Calcium Phosphate Bioceramics

Effect of zirconia on the formation of calcium phosphate bioceramics under microwave irradiation

Bi-phasic calcium phosphate (BCP) bioceramics containing hydroxyapatite (HA) and tri-calcium phosphate (TCP) phases have recently attracted attention as an ideal bone graft substitute due to their controlled resorption in the body fluid upon implantation. In this study, the HA and BCP phases were prepared by in situ method, using natural goniopora under microwave irradiation. Fourier-transform infrared (FT-IR) and powder X-ray diffraction (XRD) methods were employed to investigate proof of HA and BCP formations. XRD results show that the major characteristic peaks of HA appear in the regions of approximately 26°, 28°, 29°, 30–35°, 39°, 46°, 49° and 50° (2 θ). FT-IR results indicate that there are no occurrences of impurities during HA and BCP formations. Reinforcement of zirconia in the in situ formation of HA leads to a more resorbable phase of β-TCP since the influence of zirconia induces faster decomposition of HA, as indicated by differential thermal (DT) analysis. The in vitro physiological stability of prepared materials was performed in phosphate-buffered saline (PBS) of pH 7.4 at 37 °C in a thermostatic water bath, and the results indicate that the resorbable nature of BCP lies in between the resorption levels of HA and TCP. Solubility of the BCP can be controlled by the addition of zirconia corresponding to clinical applications.

Biphasic Calcium Phosphate (BCP) Bioceramics: Preparation and Properties

Biphasic Calcium Phosphate (BCP) Bioceramics: Preparation and Properties

Biphasic calcium phosphate bioceramics: preparation, properties and applications.

Biphasic calcium phosphate (BCP) bioceramics belong to a group of bone substitute biomaterials that consist of an intimate mixture of hydroxyapatite (HA), Ca(10)(PO(4))(6)(OH)(2), and beta-tricalcium phosphate (beta-TCP), Ca(3)(PO(4))(2), of varying HA/beta-TCP ratios. BCP is obtained when a synthetic or biologic calcium-deficient apatite is sintered at temperatures at and above 700 degrees C. Calcium deficiency depends on the method of preparation (precipitation, hydrolysis or mechanical mixture) including reaction pH and temperature. The HA/beta-TCP ratio is determined by the calcium deficiency of the unsintered apatite (the higher the deficiency, the lower the ratio) and the sintering temperature. Properties of BCP bioceramics relating to their medical applications include: macroporosity, microporosity, compressive strength, bioreactivity (associated with formation of carbonate hydroxyapatite on ceramic surfaces in vitro and in vivo), dissolution, and osteoconductivity. Due to the preferential dissolution of the beta-TCP component, the bioreactivity is inversely proportional to the HA/beta-TCP ratio. Hence, the bioreactivity of BCP bioceramics can be controlled by manipulating the composition (HA/beta-TCP ratio) and/or the crystallinity of the BCP. Currently, BCP bioceramics is recommended for use as an alternative or additive to autogeneous bone for orthopedic and dental applications. It is available in the form of particulates, blocks, customized designs for specific applications and as an injectible biomaterial in a polymer carrier. BCP ceramic can be used also as grit-blasting abrasive for grit-blasting to modify implant substrate surfaces. Exploratory studies demonstrate the potential uses of BCP ceramic as scaffold for tissue engineering, drug delivery system and carrier of growth factors.