Papers by Author: R. García Carrodeguas

Abstract: The effect of using Na2HPO4 solution as mixing liquid in the physicochemical and mechanical properties of calcium aluminate cement (CAC), with a view to a possible reinforcement additive of conventional α-TCP-based CPC was studied. The results showed that the degree of the hydration reaction of CaAl2O4 (CA) increased when Na2HPO4 solution was used as mixing liquid. The porosity of cement was also lower (37.9 ± 1.3 %) than for H2O (33.2 ± 3.6 %). The values of compressive strength for cements prepared with both mixing liquids were lower than 3 MPa due to the excessive L/P ratio employed and large porosity. After immersion in SBF, only the Al(OH)3 hydrate is observed and no other crystalline hydrated calcium aluminate nor calcium phosphate was formed in any of the cements. Both cements released Ca ions to, and removed P ions from SBF, being this effect more remarkable when Na2HPO4 was used. As for other CAC, no Al was released to the SBF and no potential toxicity due to this ion should be expected.

Abstract: On this study the influence of silicon dopping on the properties of the final calcium phosphate cement were analysed and compared to the ones of the conventional Si and Mg-free α-TCP cement. In spite of silicon doping, Si-α-TCP calcination temperature (1400°C) was higher than the one used for conventional α-TCP (1300°C) as a result of Mg contamination on the commercial precursor used on the Si-α-TCP synthesis. Because of the high temperature used, Si-α-TCP sample was difficult to mill. Even after 1 week milling, the particle size achieved was 12µm while Si-free α-TCP reached 7.7µm. Consequently, the reactivity of both powders was different. In conclusion, the properties of Si-α-TCP cement were not satisfactory for clinical application. In order to do it so, it is essential to enhance the powder reactivity by reducing Mg contamination, lowering the sintering temperature and reducing the particle size to, then, achieve the desired reactivity and compressive strength.

Abstract: This document describes and discusses the non-isothermal devitrification process of the wollastonite-tricalcium phosphate (W-TCP) eutectic glass. This eutectic glass has been studied in situ, from room temperature up to 1375 °C, by Neutron Diffractometry (ND) in vacuum. The data obtained were complemented and compared with those performed on ambient atmosphere by Differential Thermal Analysis (DTA) and with those of samples fired in air, at selected temperatures, and then cooled down and subsequently studied by laboratory X-ray Powder Diffraction (LXRD) and Field Emission Scanning Electron Microscopy (FE-SEM) fitted with Energy X-Ray Dispersive Spectroscopy (EDS). Selected samples have been investigated by quantitative full-phase analysis (including the amorphous content) using the Rietveld method. The experimental evidence indicates that the devitrification of W-TCP eutectic glass, begins at ~870°C, with the crystallization of a Ca-deficient apatite phase (Ca9.92(P5.85O23.54)(OH)2.03 (H2O)2.194) followed by wollastonite-2M (-CaSiO3) crystallization at 1006°C. At 1375°C the bio glassceramic is comprised of quasi-rounded colonies formed by a homogeneous mixture of pseudowollastonite (-CaSiO3) and -tricalcium phosphate (-Ca3(PO4)2). This microstructure corresponds to irregular eutectic structures and is similar to that of Bioeutectic® W-TCP material obtained previously, via controlled slow solidification of the eutectic composition, by some of the present authors. It has also been found that from the eutectic composition of the wollastonite – tricalcium phosphate binary system is possible to obtain a wide range of bio glass-ceramics through appropriate design of thermal treatments.

Abstract: In this study a ceramic composite with nominal composition 40 wt% Ca3(PO4)2 – 60 wt% CaMg(SiO3)2 was obtained by solid state sintering of compacts of both synthetic fine powders. The ceramic composite showed a fine grained and homogeneous microstructure consisting of CaMg(SiO3)2 and b-Ca3(PO4)2 grains. The results of X-ray diffraction and scanning electron microscopy demonstrated that, during soaking in SBF, the grains of β-Ca3(PO4)2 dissolved preferably than those of CaMg(SiO3)2, leaving a porous surface layer rich in CaMg(SiO3)2. Subsequently, partial dissolution of the remaining CaMg(SiO3)2 occurred and the porous surface of the b-Ca3(PO4)2-CaMg(SiO3)2 ceramic became coated by a bone-like apatite layer after 7 days in SBF.

Abstract: The biological response following subcutaneous and bone implantation of β-wollastonite(β-W)-doped α-tricalcium phosphate bioceramics in rats was evaluated. Tested materials were: tricalcium phosphate (TCP), consisting of a mixture of α- and β-polymorphs; TCP doped with 5 wt. % of β-W (TCP5W), composed of α-TCP as only crystalline phase; and TCP doped with 15 wt. % of β-W (TCP15), containing crystalline α-TCP and β-W. Cylinders of 2x1 mm were implanted in tibiae and backs of adult male Rattus norvegicus, Holtzman rats. After 7, 30 and 120 days, animals were sacrificed and the tissue blocks containing the implants were excised, fixed and processed for histological examination. TCP, TCP5W and TCP15W implants were biocompatible but neither bioactive nor biodegradable in rat subcutaneous tissue. They were not osteoinductive in connective tissue either. However, in rat bone tissue β-W-doped α-TCP implants (TCP5W and TCP15W) were bioactive, biodegradable and osteoconductive. The rates of biodegradation and new bone formation observed for TCP5W and TCP15W implants in rat bone tissue were greater than for non-doped TCP.

Abstract: The biological behavior of a new bioactive material composed of calcium-deficient hydroxyapatite, octacalcium phosphate, and β-tricalcium phosphate was investigated by in vitro indirect and direct cytotoxicity, cell adhesion and proliferation tests, and by in vivo subcutaneous and bone implantation in rats. The results of the in vitro studies showed that the material is biocompatible and no cytotoxic. Slightly poorer initial cell adhesion and lower cell proliferation than in control was observed, which were attributed to the reactivity and roughness of the material surface. In vivo results showed that the material is biodegradable and bioactive in bone tissue, but only biocompatible and partially biodegradable in soft tissue.

Abstract: Wollastonite bioceramics prepared from synthetic and natural precursors were implanted in rats in bone and subcutaneous tissues. The implant sites were excised after 7, 30 and 120 days, fixed, dehydrated, embedded in paraffin wax for serial cutting and examined under transmitted light microscope. It was found a very similar behavior for both wollastonite bioceramics. They were biocompatible, bioactive and biodegradable when implanted in rat bone. The synthetic ceramic was more reabsorbable than the one from natural powder. When implanted in subcutaneous rat tissue, both materials elicited a mild initial inflammatory reaction that practically disappeared after 120 days. Both materials were encapsulated with a very thin fibrous capsule and slightly reabsorbed at their surfaces. None of the materials induced ectopic osteogenesis. According to the results, the studied materials seem to be able for manufacturing reabsorbable bone implants.

Abstract: In this work a new kind of CaSiO3-doped α-Ca3(PO4)2 ceramic materials, with compositions lying outside the field of the Ca3(PO4)2 solid solution in the system Ca3(PO4)2- CaSiO3, were obtained and some of their properties, relevant for bone repairing, were studied in vitro. Crystalline α-Ca3(PO4)2 solid solution and minor amounts of non-equilibrium residual glass were the only phases in the materials containing 2 and 5 wt% of CaSiO3. α-Ca3(PO4)2, crystalline eutectic-like phase and residual glass were observed for sample containing 15 and 20 wt% of CaSiO3. The mechanical strength improved for all the doped ceramics with regard to un-doped Ca3(PO4)2. The release of ionic Ca and Si in simulated physiological conditions increased with the content of CaSiO3 and favored α-Ca3(PO4)2 surface transformation. The soluble components extracted from the CaSiO3-doped α-Ca3(PO4)2 bioceramics were not cytotoxic to human fibroblastlike cells. Initial cell adhesion onto the surface of the materials seemed to be partially hindered by surface reactivity and remodeling, however those cells adhered to the experimental bioceramics were viable and proliferated normally.

Abstract: On this paper, methods to obtain Mg-free reagents for synthesizing pure phase Sistabilized α-TCP were established. The Mg contents of synthesized reagents were considerably lower than those in commercially available reactants. Pure Si-doped (2.5 at.-% of P by Si substitution) α-TCP was obtained by solid state reaction from synthetic reagents at temperature as low as 1200°C. When commercial reagents were employed for the solid state synthesis, a mixture of α- and β-TCP was obtained even when the solid state reaction was conducted at 1300 °C.