RESUMO
The main goal of the present study was to evaluate the effect of different setting accelerator agents on the developed microstructures of calcium phosphate cements (CPCs) by employing the impedance spectroscopy (IS) technique. Six compositions of CPCs were prepared from mixtures of commercial dicalcium phosphate anhydrous (DCPA) and synthesized tetracalcium phosphate (TTCP) as the solid phases. Two TTCP/DCPA molar ratios (1/1 and 1/2) and three liquid phases (aqueous solutions of Na(2)HPO(4), tartaric acid (TA) and oxalic acid (OA), 5% volume fraction) were employed. Initial (I) and final (F) setting times of the cement pastes were determined with Gillmore needles (ASTM standard C266-99). The hardened samples were characterized by X-ray powder diffraction (XRD), Fourier transformed infrared (FTIR) spectroscopy, scanning electron microscopy (SEM), and apparent density measurements. The IS technique was employed as a non-destructive tool to obtain information related to porosity, tortuosity and homogeneity of the cement microstructures. The formulation prepared from a TTCP/DCPA equimolar mixture and OA as the liquid phase presented the shortest I and F (12 and 20 min, respectively) in comparison to the other studied systems. XRD analyses revealed the formation of low-crystallinity hydroxyapatite (HA) (as the main phase) as well as the presence of little amounts of unreacted DCPA and TTCP after 24 h hardening in 100% relative humidity. This was related to the proposed mechanisms of dissolution of the reactants. The bands observed by FTIR allowed identifying the presence of calcium tartrate and calcium oxalate in the samples prepared from TA and OA, in addition to the characteristic bands of HA. High degree of entanglement of the formed crystals was observed by SEM in samples containing OA. SEM images were also correlated to the apparent densities of the hardened cements. Changes in porosity, tortuosity and microstructural homogeneity were determined in all samples, from IS results, when the TTCP/DCPA ratio was changed from 1/1 to 1/2. The cement formulated from an equimolar mixture of TTCP/DCPA and OA as the liquid phase presented setting times, degree of conversion to low-crystallinity HA and microstructural features suitable to be used as potential bone cement in clinical applications. The IS technique was shown to be a very sensitive and non-destructive tool to relate the paste composition to the developed microstructures. This approach could be very useful to develop calcium phosphate bone cements for specific clinical demands.
Assuntos
Cimentos Ósseos/química , Fosfatos de Cálcio/química , Cimentação/métodos , Impedância Elétrica , Microscopia Eletrônica de Varredura/métodos , Modelos Biológicos , Transição de Fase , Difração de Pó , Espectroscopia de Infravermelho com Transformada de Fourier/métodos , Fatores de Tempo , Difração de Raios XRESUMO
The aim of this work was to gain a better understanding about the synthesis of tetracalcium phosphate (TTCP, Ca(4)(PO(4))(2)O) through a solid-state reaction from mechanochemically activated CaCO(3)-(NH(4))(2)HPO(4) mixtures. The evolution of the reaction was followed by DTA, XRD, FTIR and SEM techniques. An enhanced reactivity of the mixtures was detected as the mechanochemical treatment times increased. This effect was related to both the loss of crystallinity of the reactants and the production of defects on their surfaces. 6 h of mechanochemical processing at 1190 rpm, followed by 3 h of thermal treatment at 1500 degrees C, were enough to obtain pure TTCP. The crystallinity and purity of the obtained TTCP were checked by XRD and FTIR. The morphologic characteristics were analyzed by SEM and BET analysis. The behavior of synthesized TTCP powder in combination with commercial dicalcium phosphate anhydrous (DCPA, CaHPO(4)), as the solid phase of bone cements, was tested. Both the combination of different particle sizes of TTCP and DCPA and the effect of different kinds of accelerator agents (disodium hydrogen phosphate, tartaric acid, citric acid and oxalic acid) on setting time and degree of conversion to hydroxyapatite (HA, Ca(10)(PO(4))(6)(OH)(2)) were evaluated. The combination of TTCP (0.32 m(2)/g) with DCPA (1.52 m(2)/g), in a 1/1 molar ratio, showed the shortest setting times and high conversions to HA when an oxalic acid solution (5% volume fraction) was used as the liquid phase of the formulation. Results obtained from this work demonstrated that synthesized TTCP shows promising behavior as a component of bone cements, exhibiting not only a smaller particle size than that usually reported but also a low degree of crystallinity, all of which increases the reactivity of the obtained TTCP. This study provided a very efficient method for synthesizing pure TTCP through a modified solid-state reaction from mechanochemically activated reactants, employing very short times of thermal treatment in comparison with the conventional processes.
Assuntos
Cimentos Ósseos/química , Fosfatos de Cálcio/química , Adesividade , Dureza , Teste de Materiais , Tamanho da Partícula , Estresse Mecânico , Propriedades de SuperfícieRESUMO
A commercial acrylic bone cement was modified by the incorporation of different weight fractions of polycrystalline hydroxyapatite (HA), and the modified formulation was investigated. The influence of the filler proportion on the flow characteristics and the mechanical behavior of the resultant composite was evaluated. The residual monomer present in the cured materials was measured by gas chromatography. The comparison of the residual monomer present in the cements with and without reinforcement demonstrated that the degree of polymerization was not affected by the addition of HA. Porosity morphology was analyzed by optical and scanning electron microscopy. Image examination revealed that the porosity and the pore size of the hardened cement increased with an increasing amount of particulate filler. Flexural, compressive, and fracture properties of the cement with varying amounts of HA reinforcement were measured. It was found that up to 15 wt% HA could be added for increases in flexural modulus and fracture toughness. HA acts as a rigid filler that enhances fracture resistance and flexural modulus. Our results show that the workability of the modified formulation limited the incorporation of the ceramic filler to a maximum value of 15 wt%.
Assuntos
Materiais Biocompatíveis/química , Cimentos Ósseos/química , Hidroxiapatitas/química , Polimetil Metacrilato/química , Microscopia Eletrônica de Varredura , PorosidadeRESUMO
Sintering of two hydroxyapatite (HA) samples with different Ca/P ratios was studied as a function of thermal pretreatments, sintering temperature and additives (0-0.6 ion % Li+ or 0-5 ion % Mg2+). The samples were sintered in air and characterized by density measurements, scanning electron microscopy, differential thermal analysis, X-ray diffraction and dilatometry. Upon sintering, samples with Ca/P ratio of 1.51 (HA C) transformed to beta-Ca3(PO4)2 and Ca10(PO4)6(OH)2, resulting in materials with low densities and containing agglomerated beta-Ca3(PO4)2 when sintered above 1200 degrees C. Samples with a Ca/P ratio of 1.77 (HA S), without beta-Ca3(PO4)2, showed better sinterability and homogeneous microstructures. Li+ additions favoured liquied-phase sintering and reduced the beta-Ca3(PO4)2 content in sintered materials. Mg2+ additions did not result in higher densities, but inhibited the hydroxyapatite grain growth rate. A significant percentage of the added Mg2+ was incorporated into the beta-Ca3(PO4)2 structure.