Synthesis of CaSiO3 whiskers in alkaline salt flux for biomaterials reinforcement

Materials reinforcement by ceramic whiskers has been employed for a long time in a variety of industrial applications. Nevertheless, the materials by which these whiskers are commonly made of (carbide and silicon nitride) do not allow their use in biomaterials field due to their high toxicity. Then, it is of interest to synthesize ceramic whiskers which could reinforce biocompatible ceramic and polymeric biomaterials without harming the patients' health. In this manner, the aim of this work is to propose and analyze the limiting process variables of a new synthetic route to produce whiskers of CaSiO3 (wollastonite): a biocompatible, bioactive and readsorbable biomaterial. It was employed the molten salt synthesis at 900 ºC to grow wollastonite crystals which were characterized by X-ray diffraction and scanning electron microscopy. The proposed method was efficient in growing whiskers; however, the dwell time was not sufficient to guarantee a 100% reaction yield, leading to the formation of cristobalite.Há tempos empregam-se whiskers cerâmicos como reforço de materiais nas mais diversas aplicações, porém os materiais com os quais estes são comumente fabricados (carbeto e nitreto de silício) não permitem a sua utilização no campo dos biomateriais devido sua elevada toxicidade. Assim, torna-se interessante sintetizar whiskers biocompatíveis capazes de reforçar biomateriais cerâmicos e poliméricos sem prejudicar a saúde dos pacientes. Dessa forma, este trabalho tem como objetivo desenvolver e determinar os parâmetros limitantes de uma nova rota de síntese por fusão de sais de whiskers de CaSiO3, uma biocerâmica biocompatível, bioativa e reabsorvível. Este método é simples, barato e permite a produção em larga escala. Utilizou-se um fluxo de NaCl/KCl a 900 ºC para sintetizar whiskers de wollastonita, que foram caracterizados por difração de raios X e microscopia eletrônica de varredura. O método proposto mostrou-se eficiente, entretanto os tempos de patamar empregados não foram suficientes para garantir 100% de rendimento da reação de formação de CaSiO3, ocorrendo a formação de cristobalita.UNIFESP Instituto de Ciência e TecnologiaUNIFESP, Instituto de Ciência e TecnologiaSciEL

Optimizing the Water-Oil Emulsification Process for Developing CPC Microspheres

Spherical calcium phosphate cement carriers were synthesized by water/oil emulsion. A 23 factorial design was employed in order to optimize the size and form of the microspheres. Stirring speed, liquid-to-powder ratio and cement paste-to-oil ratio were varied in two different levels and the response variable was the microsphere's sphericity. The results showed that cement's setting reaction was responsible for stabilizing the microspheres within the oil phase resulting in a low crystalline hydroxyapatite. The sizes varied from 6.29 to 64.23 mu m. From the factors studied, the stirring velocity and the interaction between the L/P ratio with the P/O ratio are the ones that are more effective in controlling microspheres' sphericity. The results suggest that the methodology studied may provide microspheres with appropriate properties to deliver cells and/or drugs without inducing inflammatory reactions.Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)UNIFESP, Inst Sci & Technol, Bioceram Lab, Sao Jose Dos Campos, SP, BrazilBioceramics Laboratory, Science and Technology Institute - Universidade Federal de São Paulo (UNIFESP), São José dos Campos, SP, BrazilFAPESP: 2012/21198-0FAPESP: 2013/26248-9FAPESP: 2011/09240-9FAPESP: 2013/19642-2Web of Scienc

Si-tricalcium phosphate cement: preparation, characterization and bioactivity in SBF

There are evidences considering the effectiveness of Si on enhancing biological properties of calcium phosphates; however, there are not many works relating to the Si-alpha-TCP bone cement. The influence of silicon doping on the properties of Α-TCP cement was analyzed. Si-TCP was obtained by a solid state reaction employing CaCO3, CaHPO4 and CaSiO3 and powder was analyzed by XRD, FTIR, XRF and BET specific area. Cement samples were analyzed for their surface of fracture morphology, mechanical resistance and SBF bioactivity. Cement mechanical resistance was not satisfactory for biomedical application; nonetheless, sample's surface was coated by an apatite layer after immersion in SBF. Notwithstanding, to ensure that silicon is the element responsible for increasing the material's bioactivity it is necessary to evaluate the in vivo performance of the bone cement obtained in this work.Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)Universidade Federal de São Paulo (UNIFESP) Instituto de Ciência e TecnologiaUniversidade Estadual de Campinas Instituto Nacional de Ciência e Tecnologia em BiofabricaçãoConsejo Superior de Investigaciones Científicas Instituto de Cerámica y VidrioUniversidade Estadual de Campinas Faculdade de Engenharia Mecânica Faculdade de Engenharia MecânicaUNIFESP, Instituto de Ciência e TecnologiaSciEL

Analysis of the influence of two different milling processes on the properties of beta-TCP precursor powder and cement

There are several characteristics that put calcium phosphate cements in evidence, like its bioactivity and in vivo resorption. The influence of two milling processes on the morphological properties of the [beta]-tricalcium phosphate powder, [beta]-TCP, and in the mechanical properties of the cement were analyzed. The powder was obtained by solid state reaction of CaCO3 and CaHPO4 at 1050 ºC. It showed high phase purity and absence of toxic elements. The powder was processed in ball mill (A) and high-energy vibratory mill (B), with posterior analysis by SEM and particle size distribution. The powders showed different average and distribution of grain size. Finally, the cement prepared with powder submitted to process (B) showed values of axial tensile strength significantly greater than that prepared with powder submitted to process (A). The milling process (B) is much more efficient than the process (A).São várias as características que tem colocado os cimentos de fosfato de cálcio em evidência na área dos biomateriais, como sua bioatividade e reabsorção in vivo. Neste trabalho, analisou-se a influência de dois processos de moagem nas propriedades morfológicas do pó de [beta]-fosfato tricálcico, [beta]-TCP, e na resistência mecânica do cimento. O pó foi obtido via reação no estado sólido de CaCO3 e CaHPO4 a 1050 ºC, apresentando pureza de fase e ausência de elementos tóxicos. O pó foi moído em: (A) moinho de bolas e (B) moinho vibratório de alta energia; sendo analisado por MEV e distribuição granulométrica. Os pós apresentaram propriedades diferentes com relação à distribuição e tamanho médio de grão. Finalmente, o cimento preparado com o pó submetido ao processo (B) apresentou valores de resistência mecânica significativamente maiores que o preparado com o pó submetido ao processo (A). Conclui-se que o processo de moagem (B) é muito mais eficiente que o processo (A).Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)UNICAMP FEM DEMAUNIFESP Instituto de Ciência e TecnologiaUNIFESP, Instituto de Ciência e TecnologiaSciEL

Influence of Si substitution on the reactivity of a-tricalcium phosphate

Silicon substituted calcium phosphates have been widely studied over the last ten years due to their enhanced osteogenic properties. Notwithstanding, the role of silicon on a-TCP reactivity is not clear yet. Therefore, the aim of this work was to evaluate the reactivity and the properties of Si-a-TCP in comparison to a-TCP. Precursor powders have similar properties regarding purity, particle size distribution and specific surface area, which allowed a better comparison of the Si effects on their reactivity and cements properties. Both Si-a-TCP and a-TCP hydrolyzed to a calcium-deficient hydroxyapatite when mixed with water but their conversion rates were different. Si-a-TCP exhibited a slower setting rate than a-TCP, i.e. kSSA for Si-TCP (0.021 g·m- 2·h- 1) was almost four times lower than for a-TCP (0.072 g·m- 2·h- 1). On the other hand, the compressive strength of the CPC resulting from fully reacted Si-a-TCP was significantly higher (12.80 ± 0.38 MPa) than that of a-TCP (11.44 ± 0.54 MPa), due to the smaller size of the entangled precipitated apatite crystals.Preprin

Si-TCP synthesized from Mg-free reagents employed as calcium phosphate cement

The influence of silicon doping on calcium phosphate cement were explored in this work. α-TCP and Si-α-TCP were prepared by solid state reaction employing Mg-free CaHPO4, CaCO3 and CaSiO3 as precursors. It was possible to obtain TCP powders with low contents of β phase as contaminant. Cement liquid phase was an aqueous solution containing 2.5 wt. (%) of Na2HPO4 and 1.5 wt. (%) of citric acid. The liquid-to-powder ratio was 0.6 mL.g-1. Chemical, physical and mechanical properties of the cement samples were determined by means of XRD, FTIR, XRF, compressive strength and SEM. The calcium phosphate cements obtained achieved satisfactory properties; however, Si-α-TCP presented a decrease on the rate of setting reaction.568572Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP

In situ synchrotron X-ray powder diffraction study of the early hydration of α-tricalcium phosphate/tricalcium silicate composite bone cement

Bioactivity, osteogenicity and mechanical properties of α-tricalcium phosphate (α-TCP) based phosphates cements can be improved by adding tricalcium silicate (C3S); however, the addition of C3S delays the precipitation and growth of calcium deficient hydroxyapatite (CDHA). Thus, the aim of this work was the study of in situ setting reaction of α-TCP/C3S composite bone cement under high energy X-ray generated by a synchrotron source within the first 72h. The results showed that the addition of C3S induces the precipitation of nanosized CDHA at early times depending on the added content. Calculated crystallite sizes showed that the higher the content of C3S, the smaller the crystal size at the beginning of the precipitation. These results are different from those obtained by conventional XRD method, suggesting that the proposed technique is a powerful tool in determining the composition and extent of reaction of CPCs surfaces in real time

Si-tricalcium phosphate cement: preparation, characterization and bioactivity in SBF

There are evidences considering the effectiveness of Si on enhancing biological properties of calcium phosphates; however, there are not many works relating to the Si-alpha-TCP bone cement. The influence of silicon doping on the properties of Α-TCP cement was analyzed. Si-TCP was obtained by a solid state reaction employing CaCO3, CaHPO4 and CaSiO3 and powder was analyzed by XRD, FTIR, XRF and BET specific area. Cement samples were analyzed for their surface of fracture morphology, mechanical resistance and SBF bioactivity. Cement mechanical resistance was not satisfactory for biomedical application; nonetheless, sample's surface was coated by an apatite layer after immersion in SBF. Notwithstanding, to ensure that silicon is the element responsible for increasing the material's bioactivity it is necessary to evaluate the in vivo performance of the bone cement obtained in this work.493498Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP