Cerâmicas bioativas: estado da arte

Bioactive glasses undergo corrosion with leaching of alkaline ions when exposed to body fluids. This results in the spontaneous formation of a layer of hydroxyapatite (HA), the mineral component of natural bone, which in turn can induce bone growth in vivo. This paper describes the different types of bioactive glasses, the characterization methods currently used, and the main factors that influence their bioactivity. Nucleation and crystallization, the main mechanisms involved in the formation of hydroxyapatite, Ca10(PO4)6(OH)2, are discussed as a function of the chemical composition and the reactivity of the surface of the material. Finally, promising applications are considered.

Comportamento de cristalização de lipídios estruturados obtidos a partir de gordura de palmiste e óleo de peixe

The aim of this study is to evaluate the crystal structure of binary mixtures of palm kernel fat and fish oil, before and after chemical and enzymatic interesterification. The crystal structure was analyzed by polarized light microscopy. The addition of fish oil didn't change the palm kernel fat crystallization characteristics, spherullites of types A and B being observed. However, due to chemical and enzymatic interesterification, smaller crystals were obtained. There was no difference between chemical and enzymatic interesterification, probably as a function of acyl migration in discontinuous processes catalyzed by lipases.

Estudio de la cristalización de vídrios procedentes de rocas magmáticas de Catalunya

En este trabajo se ha estudiado por difracción de rayos X y MEB -I- EDX la nucleación de cinco muestras de vidrios, obtenidos a partir de rocas basálticas de Cataluña. Las diferentes fases obtenidas al nuclear los vidrios sometiéndolos a distintas temperaturas, entre 680° y 770°C, y tiempos entre media y ocho horas, fueron magnetita, clinopiroxeno y plagioclasa. La evolución de estas fases con la variación de las condiciones de tratamiento fue estudiada mediante la realización de gráficas I/t para cada temperatura, donde se aprecia la variación de la intensidad de difracción de las principales reflexiones producidas por estos minerales con el tiempo de tratamiento térmico. En ellas se observa que la nucleación empieza a partir de los 700° C y, después de un cierto tiempo que varía según la temperatura de tratamiento, llamado tiempo de inducción, en el cual el aumento de la nucleación con el tiempo es débil, se incrementa más rápidamente la proporción de las diferentes fases minerales con la duración del tratamiento hasta llegar a una estabilización que se produce a partir de las seis horas. La observación de estas muestras al microscopio electrónico de barrido permitió ver que aparece una microestructura homogéneamente distribuida en las muestras tratadas a partir de los 700°C en la que se distinguen dos fases ricas en Fe y Ti inmersas en una matriz. La fase clara es rica en Mg y pobre en Na y la otra, oscura, al revés. Los microanálisis químicos de dichas fases han sido realizados mediante EDX.

La calorimetría diferencial de barrido y su aplicación a la Ciencia de Materiales

Se pone de manifiesto la idoneidad de la técnica de calorimetría diferencial de barrido para la caracterización de materiales. Se presentan ejemplos específicos de aplicación de dicha técnica en el estudio de los fenómenos ligados a la transición vitrea y cinética de cristalización de vidrios calcogenuros y metálicos así como en el estudio de la reordenación de fases desordenadas metastables.

Critical behavior of a water monolayer under hydrophobic confinement

The properties of water can have a strong dependence on the confinement. Here, we consider a water monolayer nanoconfined between hydrophobic parallel walls under conditions that prevent its crystallization. We investigate, by simulations of a many-body coarse-grained water model, how the properties of the liquid are affected by the confinement. We show, by studying the response functions and the correlation length and by performing finite-size scaling of the appropriate order parameter, that at low temperature the monolayer undergoes a liquid-liquid phase transition ending in a critical point in the universality class of the two-dimensional (2D) Ising model. Surprisingly, by reducing the linear size L of the walls, keeping the walls separation h constant, we find a 2D-3D crossover for the universality class of the liquid-liquid critical point for L/h=~50, i.e. for a monolayer thickness that is small compared to its extension. This result is drastically different from what is reported for simple liquids, where the crossover occurs for , and is consistent with experimental results and atomistic simulations. We shed light on these findings showing that they are a consequence of the strong cooperativity and the low coordination number of the hydrogen bond network that characterizes water.

Quantification of the bond-angle dispersion by Raman spectroscopy and the strain energy of amorphous silicon

A thorough critical analysis of the theoretical relationships between the bond-angle dispersion in a-Si, Δθ, and the width of the transverse optical Raman peak, Γ, is presented. It is shown that the discrepancies between them are drastically reduced when unified definitions for Δθ and Γ are used. This reduced dispersion in the predicted values of Δθ together with the broad agreement with the scarce direct determinations of Δθ is then used to analyze the strain energy in partially relaxed pure a-Si. It is concluded that defect annihilation does not contribute appreciably to the reduction of the a-Si energy during structural relaxation. In contrast, it can account for half of the crystallization energy, which can be as low as 7 kJ/mol in defect-free a-Si

Estudo da influência dos íons K+, Mg2+, SO4(2-) e CO3(2-) na cristalização biomimética de fosfato de cálcio amorfo (ACP) e conversão a fosfato octacálcico (OCP)

The crystallization of hydroxyapatite (HA) in aqueous solution can be described by the mechanism ACP -> OCP -> HA. In this work, it was studied the influence of K+, Mg2+, SO4(2-) and CO3(2-) ions in the formation of ACP and in its conversion to OCP, using biomimetic coatings on metallic substrates of commercially pure titanium (Ti c.p.). The results showed that Mg2+ and CO3(2-) ions favored both the formation of ACP and its conversion to OCP. Differently, K+ and SO4(2-) ions did not influence the formation of ACP and, consequently, interfered in the conversion to OCP.

Decomposição térmica de espumas de poliuretano para fabricação de vitrocerâmica celular de Li2O-ZrO2-SiO2-Al2O3 (LZSA)

Characterization of the thermal decomposition of polyurethane (PUR) foams was performed by Fourier-transformed infrared (FT-IR) spectroscopy and thermogravimetric analysis (TGA). Three main weight loss paths were observed by TGA, the residue being lower than 3 wt.% for 3 different PUR foams analyzed. FT-IR spectra indicated CO2, CO, NH3 and isocyanides as main decomposition products. PUR foams of different cell sizes were immersed in a slurry of the parent glass ceramic of composition Li2O-ZrO2-SiO2-Al 2O3 (LZSA) and submitted to heat treatment. The LZSA cellular glass ceramics obtained after sintering and crystallization resembled the original morphology of the PUR foams.

Comportamento de cristalização de lipídios estruturados por interesterificação química de banha e óleo de soja

The aim of this study was to evaluate the crystallization behavior of binary mixtures of lard and soybean oil in different ratios and their respective structured lipids obtained by chemical interesterification. Crystallization kinetics and polarized light microscopy were used to analyze the mixtures before and after interesterification. The addition of soybean oil changed the lard crystallization, by the effect of the dilution. Crystal diameter increased, while the number of crystals decreased, as a function of temperature. Interesterification resulted in the formation of fewer crystals, with larger diameter in comparison with the original mixtures.

Advanced chemometric methods: Applicability on industrial data

Recent years have produced great advances in the instrumentation technology. The amount of available data has been increasing due to the simplicity, speed and accuracy of current spectroscopic instruments. Most of these data are, however, meaningless without a proper analysis. This has been one of the reasons for the overgrowing success of multivariate handling of such data. Industrial data is commonly not designed data; in other words, there is no exact experimental design, but rather the data have been collected as a routine procedure during an industrial process. This makes certain demands on the multivariate modeling, as the selection of samples and variables can have an enormous effect. Common approaches in the modeling of industrial data are PCA (principal component analysis) and PLS (projection to latent structures or partial least squares) but there are also other methods that should be considered. The more advanced methods include multi block modeling and nonlinear modeling. In this thesis it is shown that the results of data analysis vary according to the modeling approach used, thus making the selection of the modeling approach dependent on the purpose of the model. If the model is intended to provide accurate predictions, the approach should be different than in the case where the purpose of modeling is mostly to obtain information about the variables and the process. For industrial applicability it is essential that the methods are robust and sufficiently simple to apply. In this way the methods and the results can be compared and an approach selected that is suitable for the intended purpose. Differences in data analysis methods are compared with data from different fields of industry in this thesis. In the first two papers, the multi block method is considered for data originating from the oil and fertilizer industries. The results are compared to those from PLS and priority PLS. The third paper considers applicability of multivariate models to process control for a reactive crystallization process. In the fourth paper, nonlinear modeling is examined with a data set from the oil industry. The response has a nonlinear relation to the descriptor matrix, and the results are compared between linear modeling, polynomial PLS and nonlinear modeling using nonlinear score vectors.

Determinação quantitativa de TNT e HNS por TG e FT-IR

2,4,6-trinitrotoluene (TNT) is an energetic material that shows scarce crystalline properties that can be improved by addition of 2,2',4,4',6,6'-hexanitrostilbene (HNS) in the crystallization process. HNS is a very important high explosive used in a variety of military, aerospace and industrial formulations owing to its suitable properties. It is an insensitive and thermal stable explosive that can be produced from 2,4,6-trinitrotoluene (TNT). The purpose of this work is the quantitative determination of HNS and TNT in explosives by thermogravimetric analysis (TG) and Fourier transform infrared spectroscopy (FT-IR).

Estudo por espectroscopia micro-Raman dos mecanismos de separação de fase em vidros fosfatos de metais de transição

Glass-ceramics are prepared by controlled separation of crystal phases in glasses, leading to uniform and dense grain structures. On the other hand, chemical leaching of soluble crystal phases yields porous glass-ceramics with important applications. Here, glass/ceramic interfaces of niobo-, vanado- and titano-phosphate glasses were studied by micro-Raman spectroscopy, whose spatial resolution revealed the multiphase structures. Phase-separation mechanisms were also determined by this technique, revealing that interface composition remained unchanged as the crystallization front advanced for niobo- and vanadophosphate glasses (interface-controlled crystallization). For titanophosphate glasses, phase composition changed continuously with time up to the equilibrium composition, indicating a spinodal-type phase separation.

Evolução biomolecular homoquiral: a origem e a amplificação da quiralidade nas moléculas da vida

The fact that biologically relevant molecules exist only as one of the two enantiomers is a fascinating example of complete symmetry breaking of chirality and has long intrigued our curiosity. The origin of this selective chirality has remained a fundamental enigma with regard to the origin of life since the time of Pasteur, 160 years ago. The symmetry breaking processes, which include autocatalytic crystallization, asymmetric autocatalysis, spontaneous crystallization, adsorption and polymerization of amino acids on mineral surfaces, provide new insights into the origin of biomolecular homochirality.

Efeitos da história térmica nas propriedades do polímero pet: um experimento para ensino de análise térmica

Polyethilenetherephtalate (PET) is commonly used in manufacturing of beverage bottles representing a didactic appeal in thermal analysis education due to its presence in the student's day life. Additionally such polymer presents well defined thermal analytical curves and a well known thermal behavior. TGA curve is used to present the thermal stability. The thermal history effects in the thermal properties of a PET sample from a soft drink bottle are used to demonstrate the effect of different heating/cooling conditions on glass transition, melting, crystallization and crystalline degree using DSC curves.

Influência dos precursores de prata no crescimento de nanopartículas metálicas em vidros óxidos de metais pesados

In this work we report a systematic study on the influence of the chemical nature of silver precursors on the formation of glass-ceramics from oxide glasses. Thermal, structural and optical properties were analyzed as a function of the glass composition. Controlled crystallization was achieved by thermal treatment of the samples above glass transition. The influence of time of treatment on both nanoparticle growth and optical properties of the samples was studied by transmission electron microscopy and UV-Vis spectroscopy, respectively. Results showed that only glasses containing AgCl and AgNO3 led to glass-ceramics growth after thermal treatment.