Sintering effects on chemical and physical properties of bioactive ceramics

The objective of this study was to characterize the chemical and physical properties of bioactive ceramics prepared from an aqueous paste containing hydroxyapatite (HA) and beta tri-calcium phosphate (β-TCP). Prior to formulating the paste, HA and β-TCP were calcined at 800 °C and 975 °C (11 h), milled, and blended into 15%/85% HA/β-TCP volume-mixed paste. Fabricated cylindrical rods were subsequently sintered to 900 °C, 1100 °C or 1250 °C. The sintered specimens were characterized by helium pycnometry, X-ray diffraction (XRD), Fourier transform-infrared (FT-IR), and inductively coupled plasma (ICP) spectroscopy for evaluation of porosity, crystalline phase, functional-groups, and Ca:P ratio, respectively. Mechanical properties were assessed via 3-point bending and diametral compression. Qualitative microstructural evaluation using scanning electron microscopy (SEM) showed larger pores and a broader pore size distribution (PSD) for materials sintered at 900 °C and 1100 °C, whereas the 1250 °C samples showed more uniform PSD. Porosity quantification showed significantly higher porosity for materials sintered to 900 °C and 1250 °C (p< 0.05). XRD indicated substantial deviations from the 15%/85% HA/β-TCP formulation following sintering where lower amounts of HA were observed when sintering temperature was increased. Mechanical testing demonstrated significant differences between calcination temperatures and different sintering regimes (p < 0.05). Variation in chemical composition and mechanical properties of bioactive ceramics were direct consequences of calcination and sintering.Peer reviewedChemical Engineerin

Comparison of TCP and TCP/HA Hybrid Scaffolds for Osteoconductive Activity

Two types of porous ceramic scaffolds were prepared, consisting of β-tricalcium phosphate (TCP) or the mixed powder of TCP and hydroxyapatite (HA) at a 2:1 mass ratio. A variety of methods have been used to fabricate bone scaffolds, while the sintering approach was adopted in this work. An extremely high temperature was used on sintering that proposed to consolidate the ceramic particles. As revealed by SEM, a well opened pore structure was developed within the scaffolds. The θ-values were measured to be of 73.3° and 6.5° for the composite scaffold and TCP sample, respectively. According to XRD patterns, the existence of grains coalescence and partial bonding between HA and TCP powders was demonstrated. Scaffold mechanical property in the term of flexural strength was also determined. The result showed decreasing of the strength by HA supplement, suggesting the more brittle characteristic of HA in comparison with TCP. By soaking the composite scaffold in PBS for a period of 2 weeks, transformation from particles to flank-like crystalline was clearly observed. Such change was found to be favorable for cell attachment, migration, and growth. By implanting cell-seeded scaffolds into nude mice, an abundant osseous extracellular matrix was identified for the composite implants. In contrast, the matrix was minimally detected in TCP implanted samples. Thus, the composite scaffold was found superior for hard tissue regeneration

A mineralogical study in contrasts: highly mineralized whale rostrum and human enamel

The outermost enamel of the human tooth and the rostrum of the whale Mesoplodon densirostris are two highly mineralized tissues that contain over 95wt.% mineral, i.e., bioapatite. However, the same mineral type (carbonated hydroxylapatite) does not yield the same material properties, as revealed by Raman spectroscopy, scanning electron microscopy, electron microprobe analysis, and synchrotron X-ray diffraction analysis. Overall, the outermost enamel of a tooth has more homogeneous physical and chemical features than the rostrum. Chemical comparison of rostrum and enamel shows bioapatite in the rostrum to be enriched in Na, Mg, CO3, and S, whereas the outermost enamel shows only a slightly enriched Cl concentration. Morphologically, mineral rods (at tens of μm scale), crystallites and prisms (at μm and sub-μm scale), and platelets (at tens of nm scale) all demonstrate less organized texture in the rostrum than in enamel. Such contrasts between two mineralized tissues suggest distinct pathways of biomineralization, e.g., the nature of the equilibrium between mineral and body fluid. This study illustrates the remarkable flexibility of the apatite mineral structure to match its chemical and physical properties to specific biological needs within the same animal or between species.The work was partially funded by NIH grant 1R21AR055184-01A2 and SRF for ROCS, SEM

Mineral maturity and crystallinity index are distinct characteristics of bone mineral

The purpose of this study was to test the hypothesis that mineral maturity and crystallinity index are two different characteristics of bone mineral. To this end, Fourier transform infrared microspectroscopy (FTIRM) was used. To test our hypothesis, synthetic apatites and human bone samples were used for the validation of the two parameters using FTIRM. Iliac crest samples from seven human controls and two with skeletal fluorosis were analyzed at the bone structural unit (BSU) level by FTIRM on sections 2–4 lm thick. Mineral maturity and crystallinity index were highly correlated in synthetic apatites but poorly correlated in normal human bone. In skeletal fluorosis, crystallinity index was increased and maturity decreased, supporting the fact of separate measurement of these two parameters. Moreover, results obtained in fluorosis suggested that mineral characteristics can be modified independently of bone remodeling. In conclusion, mineral maturity and crystallinity index are two different parameters measured separately by FTIRM and offering new perspectives to assess bone mineral traits in osteoporosis

Hydroxyapatite crystallinity does not affect the repair of critical size bone defects

OBJECTIVE: The physicochemical properties of hydroxyapatite (HA) granules were observed to affect the biological behavior of graft materials. The aim of this work was to analyze the tissue response of two HA granules with different crystallinity and Ca/P ratio in vivo. MATERIAL AND METHODS: The HA granules were produced in the Biomaterials Laboratory (COPPE/UFRJ). The testing materials were HA granules presenting a Ca/P molar ratio of 1.60 and 28% crystallinity (HA-1), and a Ca/P molar ratio of 1.67 and 70% crystallinity (HA-2). Both HAs were implanted into a critical-size calvaria rat defects. RESULTS: To note, in the control group, the bone defects were filled with blood clot only. Descriptive and histomorphometric analyses after 1, 3, and 6 months postoperatively showed mild inflammatory infiltrate, mainly comprising macrophage-like and multinucleated giant cells, and an increase in the volume density of the fibrous tissues (p<0.05), which was in contrast to the similar volume density of the newly formed bone and biomaterials in relation to the control group. CONCLUSION: Thus, we concluded that HA-1 and HA-2 are biocompatible and non-degradable, and that crystallinity does not affect bone repair of critical size defects