Grain Growth in Sintered Natural Hydroxyapatite

Hydroxyapatite $(HA: Ca_{10}(PO_4)_6(OH)_2)$ can be synthesized using several methods or manufactured from natural materials such as coral or bone after removal of the organic matter by heating (denoted as NHA). The "in vitro" and "in vivo" studies showed that the natural apatite was well tolerated and has better osteoconductive properties than synthetic HA. In addition, the exploitation of natural source represents an economical way of synthesizing NHA by means of sintering, rather than by sol-gel techniques. For these reasons, the NHA was manufactured from cortical bovine bones in all our studies. Moreover, there has been much effort to improve the mechanical properties of HA by introducing foreign oxides or finding out other alternative processes such as grain growth control. Indeed, encouraging lower AGS instead of exaggerated grain growth may be jugged useful for many applications. Since the works carried out on the correlation between AGS and physico-chemical properties of NHA were very limited, the present study was mainly focused on its grain growth. A carful combination between the main parameters controlling NHA production such as milling techniques, compacting pressure, sintering temperature and holding time may lead to an interesting NHA based bio-ceramics. In this way, a simple and energetically vibratory multidirectional milling system using bimodal distribution of highly resistant ceramics has been used for obtaining sub-micron sized NHA powders. For example, the AGS was ranged between 0.75 and 1.40 μm (using intercept method) when NHA samples were sintered at 1250°C for 15 and 480 min, respectively

Effect of stabilized ZrO2, Al2O3 and TiO2 on sintering of hydroxyapatite

International audienceIn this work, the hydroxyapatite was prepared from cortical bone after calcination at 700°C during 1 hour. In order to improve mechanical properties of HA, 5 wt% of the ZrO2 (stabilized with 12.0 wt% CeO2), Al2O3 and TiO2 were added to HA powder as a reinforcing phase. All the powders were sintered at 1300°C for 2 hours. The XRD was utilized to identify the phases composition. It was found that the initial calcined powder is hydroxyapatite with the following chemical composition Ca5(PO4)3OH. In addition, the phenolphthalein test has put into evidence the existence of free CaO. For powders containing ZrO2, the XRD spectra has showed a little percent of formed b-tricalcium phosphate (b-TCP); the HA was decomposed to (b-TCP) and CaO which forms with ZrO2 the calcium zirconate (CaZrO3). Nevertheless, in powders containing TiO2, the XRD spectra showed that a partial decomposition of HA to b-TCP was occurred with formation of calcium titanium oxide (CaTiO3). However, for powders containing Al2O3, a nearly full decomposition of HA to b-TCP was occurred, the free Al2O3 was present. Finally, it has been found that HA composites containing a large amount of b-tricalcium phosphate are resorbale than HA composites containing a small amount of b-TCP and they were not well densified. The microhardness values of HA- ZrO2 composites were greater than those of HA- Al2O3 and HATiO2 composites

Grain Growth in Sintered Natural Hydroxyapatite

Hydroxyapatite (HA: Ca10(PO4)6(OH)2) can be synthesized using several methods or manufactured from natural materials such as coral or bone after removal of the organic matter by heating (denoted as NHA). The in vitro and in vivo studies showed that the natural apatite was well tolerated and has better osteoconductive properties than synthetic HA. In addition, the exploitation of natural source represents an economical way of synthesizing NHA by means of sintering, rather than by sol-gel techniques. For these reasons, the NHA was manufactured from cortical bovine bones in all our studies. Moreover, there has been much effort to improve the mechanical properties of HA by introducing foreign oxides or finding out other alternative processes such as grain growth control. Indeed, encouraging lower AGS instead of exaggerated grain growth may be jugged useful for many applications. Since the works carried out on the correlation between AGS and physico-chemical properties of NHA were very limited, the present study was mainly focused on its grain growth. A carful combination between the main parameters controlling NHA production such as milling techniques, compacting pressure, sintering temperature and holding time may lead to an interesting NHA based bio-ceramics. In this way, a simple and energetically vibratory multidirectional milling system using bimodal distribution of highly resistant ceramics has been used for obtaining sub-micron sized NHA powders. For example, the AGS was ranged between 0.75 and 1.40 µm (using intercept method) when NHA samples were sintered at 1250 C for 15 and 480 min, respectively

Nanostructure and morphology of poly(vinylidene fluoride)/polymethyl (methacrylate)/clay nanocomposites: correlation to micromechanical properties

11 pags., 7 figs., 2 tabs.Nanocomposites based on poly(vinylidene fluoride) (PVDF)/poly(methyl methacrylate) (PMMA) with untreated clay were prepared in one step by reactive melt extrusion. Chemical reactions took place between the polymer matrices, the inorganic clay particles, and three reactive agents, leading to the PVDF/PMMA/clay nanocomposites. The microstructure characterizations were carried out by differential scanning calorimetry and wide-angle X-ray scattering (WAXS). The mechanical behavior was investigated by tensile experiments, impact tests, and microhardness measurements. The morphological characterization was carried out by optical and atomic force microscopy (AFM). The decrease of the melting and crystallization temperatures of the PVDF with the increasing PMMA content is attributed to the interactions between the oxygen of the PMMA carbonyl group and the PVDF’s hydrogen atom. WAXS analysis shows that there is neither an intercalation step nor total exfoliation in any composition. As the PMMA content increases, WAXS diagrams show either the PVDF α-crystallographic form, both, α- and β-forms, or only the β-form. For PMMA contents higher than 40 wt%, the materials became amorphous. The microhardness of the samples decrease for a PMMA content up to 20 wt%. The study by optical microscopy and AFM illustrates the significant effect in the presence of clay on the film’s surface morphology.FJBC gratefully acknowledges the MINECO, Spain (Grant MAT 2013–47898-C2-1-R) for the generous support of this work.Peer Reviewe

Sintering of anorthite based ceramics prepared from kaolin DD2 and calcite

Abstract In this work, the preparation of anorthite based ceramics using a modified milling system and 80 wt% kaolin (DD2 type) and 20 wt% calcium oxide extracted from CaCO3 is shown. The choice of these raw materials was dictated by their natural abundance. Previous studies have shown that a simple and vibratory multidirectional milling system using a bimodal distribution of highly resistant ceramics can be successfully used for obtaining fine powders. The prepared samples were sintered at different temperatures ranging between 800 and 1100 °C. It has been found that the relative density of samples sintered at 900 °C for 1 h with a heating rate of 5 °C/min was about 96% of the theoretical density of anorthite (2.75 g/cm3). Finally, the prepared samples were also characterized by scanning electron microscopy, X-ray diffraction and Raman spectroscopy

Mechanical properties of anorthite based ceramics prepared from kaolin DD2 and calcite

Abstract Good quality ceramics costs a lot that has limited their use in developing countries. This work was devoted to prepare low-cost and good quality anorthite based ceramics. The proposed composition was 80 wt% kaolin (DD2 type) and 20 wt% calcium oxide (CaO). The choice of these raw materials was dictated by their natural abundance coupled with a modified milling system, as another interesting advantage. Previous studies have shown that a simple vibratory multidirectional milling system using bimodal distribution of highly resistant ceramic milling elements has been successfully applied for obtaining fine powders. The influence of the relatively lower sintering temperature, ranging from 800 to 1100 °C, on the porosity and the average pore size (APS) have been investigated. The APS and the porosity values of samples sintered at 950 °C were about 1 μm and 4%, respectively. The best Vickers microhardness and 3-point bending strength values for these sintered samples, using this proposed milling system, were 7.1 GPa and 203 MPa, respectively. Finally, the crystalline phase evolution during heat treatment was investigated by X-ray diffraction, Fourier transform infrared spectroscopy and scanning electron microscopy techniques

Nanostructural characterization of poly (vinylidene fluoride)-clay nanocomposites prepared by a one-step reactive extrusion process

10 pags.; 8 figs.; 5 tabs.Poly (vinylidene fluoride) (PVDF)-untreated clay nanocomposites were successfully prepared using an innovative one-step reactive melt extrusion process. Through specific temperature and shear conditions, the chemical reactions took place between the polymer matrix, the inorganic clay particles, and three main reactive agents: an organic peroxide, sulfur, and a specific activator led finally to the PVDF-clay nanocomposites. The materials were formulated with various amounts of clay in order to identify the best conditions, enabling to obtain the optimal particle exfoliation in the polymer matrix at the nanometric scale. The microstructure and nanostructure modifications were characterized by Fourier transform infrared (FTIR) spectroscopy, differential scanning calorimetry (DSC), and wide- and small-angle X-ray scattering (WAXS and SAXS). The relationship between nanostructure and mechanical behavior was investigated by tensile experiments, impact tests, and microhardness measurements. The FTIR results suggest that there is a chemical interaction between the clay and the polymer. Furthermore, the WAXS study shows that no intercalation step takes place in any composition. In addition to this, the sample with 2.5 wt.% clay could present a total exfoliation of the clay particles. The PVDF matrix is found to be exclusively of the α-form in all compositions. The final microhardness slightly increases with both nanoclay content and degree of crystallinity.F.J.B.C. gratefully acknowledges the MINECO, Spain (Grant FIS2010-18069), for the generous support of this investigation. F.J.B.C. also wishes to acknowledge the Alexander von Humboldt Foundation for the generous support during this work. S.B. and M.E.C. thank the Agencia Española de Cooperación Internacional para el Desarrollo (AECID) (Grant C/032183/10) for financial support and also the cooperation project between the Spanish CSIC and the University of Sétif, Algeria (Grant I-COOP0123).Peer Reviewe

Interobserver variability study for daily cone beam computed tomography registration of prostate volumetric modulated arc therapy

Purpose. - This work evaluated the interobserver variability in cone beam computed tomography (CBCT) registration for prostate cancers treated with intensity-modulated radiotherapy. Material and methods. - Twelve technologists realized 286 CBCT/CT registrations (bone registration followed by prostate to prostate registration). The registration results were compared to those obtained by two radiation oncologists (reference). Each technologist reported the shifts calculated by the software in all three axes. A statistical analysis allowed us to calculate the minimum threshold under which 95% of the observers found similar values. A variance analysis followed by the post hoc test were used to find differences in interobserver registration variability and determine whether any individual users performed registrations which differed significantly from those of the other users. Results. - The registration differences compared to the reference in the three directions in terms of 95th percentile are: 2.1 mm left-right, 3.5 mm target-gun, 7.3 mm anterior-posterior. In the posterior direction, 4% of the observers have found differences superior to 8 mm, margin used in routine without the use of a daily CBCT. The variance test revealed a P-value <0.05 only for target-gun and for all observers there was no significant difference compared to the reference. Conclusion. - This study confirmed the interest of a 3D tissue registration for prostate treatments. The registration study showed a good interobserver reproducibility. This showed the importance of a daily CBCT/CT registration in prostate treatment with the possibility of a planning target volume margin reduction in the three directions. An evaluation of a partial delegation of registration to technologists should be done by the radiation oncologists. (C) 2015 Societe francaise de radiotherapie oncologique (SFRO). Published by Elsevier Masson SAS. All rights reserved