Angel L. Ortiz

Influence of preparation conditions in the textural and chemical properties of activated carbons from a novel biomass precursor: The coffee endocarp

In this work a novel biomass precursor for the production of activated carbons (AC) was studied. The lignocellulosic material used as precursor is the coffee bean endocarp, which constitutes an industrial residue from the Portuguese coffee industry. Activation by carbon dioxide and potassium hydroxide produces activated carbons with small external areas and pore volumes up to 0.22 and 0.43cm3g(-1), respectively, for CO2 and KOH activation. All the ACs produced are very basic in nature with point of zero charge higher than 8. SEM/EDX studies indicate the presence of K, O, Ca and Si. By FTIR it was possible to identify the formation on the ACs surface of several functional groups, namely phenol, alcohol, quinone, lactone, pyrone and ether as well as SiH groups. The tailoring of the porous and chemical structure of the activated carbons produced is possible by selecting the appropriate production conditions.

Analytical formulation of the variance method of line-broadening analysis for Voigtian X-ray diffraction peaks

An alternative formulation of the variance method for the line-broadening analysis of polycrystalline materials is presented. It maintains the theoretical basis of the earlier formulations of the variance method, but differs in the manner of calculating the variance coefficients of the line profiles. In the proposed formulation, these are evaluated analytically in terms of the shape parameters of Voigt functions fitted to the X-ray diffraction data. Explicit expressions are thus derived for calculating the (surface-weighted) crystal sizes and (root-mean-square) lattice microstrains from the integral breadths of the Gauss and Lorentz components of the Voigt functions that model the experimental and instrumental line profiles.

A Family of Hydrogels Based on Ureido-Linked Aminopolyol-Derived Amphiphiles and Bolaamphiphiles: Synthesis, Gelation under Thermal and Sonochemical Stimuli, and Mesomorphic Characterization

This article describes the systematic preparation of a novel family of carbohydrate amphiphiles and bolaamphiphiles in which hydrophilic and hydrophobic units are connected via a ureido or bis(ureido) moiety. The sugar core is derived from aminopolyols such as D-glucamine (1), N-methyl-D-glucamine (2), or the sugar-like species tris(hydroxymethyl)aminomethane (3). The O-unprotected derivatives behave as self-organizing nonionic surfactants with good water gelation ability, which can be induced under thermal or ultrasound-driven stimuli. In addition, some derivatives of 1 and 2, and rarely 3 also formed lyotropic liquid crystals with lamellar or hexagonal structures that exhibit low-temperature transitions.

X-ray powder diffraction analysis of a silicon carbide-based ceramic

Abstract Accurate X-ray powder diffraction (XRD) analysis of SiC-based ceramics is a difficult task due to the significant overlap of the Bragg reflections from the different SiC polytypes. For this reason, results obtained by traditional XRD methods are, in general, unsatisfactory. Here, we have applied the Rietveld and two line-broadening (variance and integral breadth) methods to analyze a liquid phase-sintered SiC sample. The Rietveld method was used to carry out the quantitative phase-composition analysis and to resolve (as a first step) the overlapped SiC Bragg reflections. Starting from the Rietveld results, the different SiC peaks were then unambiguously obtained by a Levenberg–Marquardt non-linear least-squares fit. Subsequently, the variance and integral breadth methods were used to perform the microstructural analysis. It is shown not only that the procedure is especially useful, but also that both line-broadening methods lead to similar crystallite sizes. The co-existence of β (3C) and α (4H and 6H) SiC polytypes and the nanometric diffraction domain sizes for the SiC polytypes were also found. Finally, these results are discussed in the light of the β to α partial transformation that took place during the sintering.

Structure determination of di-μ-hydroxo-bis[(2-(2-pyridyl)phenyl-κ2N,C1)palladium(II)] by X-ray powder diffractometry

The title compound was synthesized in the form of a powder, and was studied by elemental analysis, IR spectroscopy, thermogravimetry and mass spectroscopy. Its crystal structure was then determined by X-ray powder diffractometry, using X-ray diffraction data collected in the reflection Bragg-Brentano geometry. The methodology followed in the present study to resolve the crystal structure consisted of peak indexing, then the use of the Monte-Carlo/parallel tempering search algorithm, and finally Rietveld refinement coupled with difference-Fourier synthesis. We found that the crystals are composed of monoclinic unit cells, with 1.5 molecules in the asymmetric unit and therefore six molecules per unit cell. In addition, we concluded that the complexes adopt a planar conformation, forming trimers created by groups of parallel molecules.

Fundamental parameters approach in the Rietveld method: a study of the stability of results versus the accuracy of the instrumental profile

The Rietveld refinement method is a valuable tool for structural and microstructural analysis of a variety of crystalline materials. In spite of many important developments in the last decade, most current Rietveld programs suAer from a number of drawbacks. In order to overcome these disadvantages, the ‘‘fundamental parameter approach’’ (FPA) has been used recently. The FPA uses a convolution-based method to build up X-ray line profiles. Instrumental and sample aberrations are calculated from first principles, and convoluted with the emission profile to form the final line profile. Although this methodology eliminates the need for a standard, in practice some instrumental parameters must be refined, resulting in certain empiricism in this procedure. Therefore, the comparison with a strain-free and ‘infinite crystallite size’ standard becomes necessary. In this work we have performed a study of the stability of quantitative analysis and microstructural results versus simulated inaccurate instrumental profiles. All the FPA calculations were performed on X-ray diAraction data from a technologically attractive and scientifically challenging system: liquidphase-sintered SiC (LPS SiC). # 2000 Elsevier Science Ltd. All rights reserved.

The prolific polytypism of silicon carbide

A worked example of polytypism is presented, aimed at assisting undergraduates in the learning and instructors in the teaching of this topic. In particular, this crystallography concept, not necessarily obvious for beginners, is illustrated pedagogically using to that end the model case of the prolific polytypism of silicon carbide (SiC). On the basis of concepts that are easily assimilated by students (i.e. simple topological constraints) this article first presents a unified description of the polytypism phenomenon in SiC that allows one to understand without difficulty the existence of its numerous polytypic variants and how they develop. Then the various notations used to designate these different polytypes are described, and finally the crystal structures of the most common are discussed. This worked example is thus expected to contribute to motivating undergraduates in the study of a crystallography topic that often is not treated in sufficient depth in class.

Risk in Dosing Regimens for 25-OH Vitamin D Supplementation in Chronic Haemodialysis Patients

Introduction: 25-OH vitamin D (25-OHvitD) insufficiency or deficiency should be treated in haemodialysis (HD) patients, although the 25-OHvitD target, drug or dosing regimens are unclear. Aims: To describe factors associated with 25-OHvitD levels in HD patients and to assess the effect of three dosing regimens to supplement 25-OHvitD (calcifediol) on serum calcium (Ca), phosphate (P), parathyroid hormone (PTH), 25-OHvitD and 1,25-OHvitD. Methods: Two hundred and seventeen patients from three HD units were studied. Demographic and biochemical data were collected at baseline. Two different 25-OHvitD assays were used. One hundred and sixty-seven patients were treated with various calcifediol dosing regimens. The same biochemical determinations were repeated after 3 months of treatment. Results: At baseline, 12.9% of patients had 25-OHvitD <10 ng/ml. In multivariate linear regression, the season (lower in winter) and the assay method were determinants of 25-OHvitD concentration. Following calcifediol supplementation, 25-OHvitD, calcium and phosphate increased, while PTH diminished with statistical significance. After treatment, there were positive correlations between 25-OHvitD and Ca (r = 0.28, p < 0.0001) or 1,25-OHvitD (r = 0.75, p < 0.0001) that were not observed in the baseline dataset. High concentrations of post-treatment 25-OHvitD were associated with higher 1,25-OHvitD levels. Calcemia increased more in those treated with concomitant active vitamin D or those having suppressed baseline PTH, while PTH decreased more in those having above-target PTH levels. Conclusions: Standardisation of methods to determine 25-OHvitD blood levels is needed. In HD patients, calcifediol increased 25-OHvitD, calcemia and phosphatemia and lowered PTH. Caution should be exercised with the higher calcifediol dosing regimens, especially in patients with suppressed PTH or on vitamin D receptor activators.

Spark Plasma Sintering and Microstructural Characterization of Additive-Free Polycrystalline β-SiC

Additive-free -SiC powders were sintered by means of Spark Plasma Sintering System. Experiments were performed in the temperature range from 1650°C to 2200°C, 3 to 10 min holding time and pressure from 50 until 150 MPa. In order to favour sinterization, the starting powder was mechanically activated: defect concentration was increased by centrifugal ball milling. Applied temperature, holding time and/or pressure were varied to analyze their effect on the densification and grain growth kinetics. The full sinterization of the material was obtained for temperatures as high as 1900°C and over. The relative density of the obtained material was high, up to 97.0  0.6 % the theoretical density for 2200°C sintering temperature. An intense grain growth took place while sintering. The final microstructure exhibited a grain size distribution range from 1.0 to 2.5 m, depending on the sintering conditions. Such grain growth strongly depends on the sintering time, not so much on the sintering temperature.

A line-broadening analysis model for the microstructural characterization of nanocrystalline materials from asymmetric x-ray diffraction peaks.

Nanograin sizes and crystal lattice microstrains in nanocrystalline materials are typically evaluated from the broadening of their x-ray diffraction (XRD) peaks under the assumption of symmetrical diffraction profiles. Since this assumption is not entirely satisfactory, we formulate a line-broadening analysis model of a single peak that considers explicitly the XRD peak asymmetry. The model is a generalization of the variance method in which the shape of the XRD peaks is idealized through asymmetrical split pseudo-Voigt functions. The model is validated on two nanocrystalline powders.