Direct Determination of Sugar Cane Quality Parameters by X-ray Spectrometry and Multivariate Analysis

Current methods for quality control of sugar cane are performed in extracted juice using several methodologies, often requiring appreciable time and chemicals (eventually toxic), making the methods not green and expensive. The present study proposes the use of X-ray spectrometry together with chemometric methods as an innovative and alternative technique for determining sugar cane quality parameters, specifically sucrose concentration, POL, and fiber content. Measurements in stem, leaf, and juice were performed, and those applied directly in stem provided the best results. Prediction models for sugar cane stem determinations with a single 60 s irradiation using portable X-ray fluorescence equipment allows estimating the % sucrose, % fiber, and POL simultaneously. Average relative deviations in the prediction step of around 8% are acceptable if considering that field measurements were done. These results may indicate the best period to cut a particular crop as well as for evaluating the quality of sugar cane for the sugar and alcohol industries.

The T-2 phase in the Nb-Si-B system studied by ab initio calculations and synchrotron X-ray diffraction

The solid solution based on Nb5Si3 (Cr5B3 structure type, D8(l), tl32, 14/mcm, No140, a=6.5767 angstrom, c=11.8967 angstrom) in the Nb-Si-B system was studied from the structural and thermodynamic point of view both experimentally and by ab initio calculations. Rietveld refinement of powder X-ray synchrotron data allowed to determine the boron to silicon substitution mechanism and the structural parameters. Ab initio calculations of different ordered compounds and selected disordered alloys allowed to obtain in addition to the enthalpy of formation of the solution, substitution mechanism and structural parameters which are in excellent agreement with the experimental data. The stability of the phase is discussed. (C) 2012 Elsevier Inc. All rights reserved.

Quantification of Short and Medium Range Order in Mixed Network Former Glasses of the System GeO2-NaPO3: A Combined NMR and X-ray Photoelectron Spectroscopy Study

Glasses in the system xGeO(2)-(1-x)NaPO3 (0 <= x <= 0.50) were prepared by conventional melting quenching and characterized by thermal analysis, Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), and P-31 nuclear magnetic resonance (MAS NMR) techniques. The deconvolution of the latter spectra was aided by homonuclear J-resolved and refocused INADEQUATE techniques. The combined analyses of P-31 MAS NMR and O-1s XPS lineshapes, taking charge and mass balance considerations into account, yield the detailed quantitative speciations of the phosphorus, germanium, and oxygen atoms and their respective connectivities. An internally consistent description is possible without invoking the formation of higher-coordinated germanium species in these glasses, in agreement with experimental evidence in the literature. The structure can be regarded, to a first approximation, as a network consisting of P-(2) and P-(3) tetrahedra linked via four-coordinate germanium. As implied by the appearance of P-(3) units, there is a moderate extent of network modifier sharing between phosphate and germanate network formers, as expressed by the formal melt reaction P-(2) + Ge-(4) -> P-(3) + Ge-(3). The equilibrium constant of this reaction is estimated as K = 0.52 +/- 0.11, indicating a preferential attraction of network modifier by the phosphorus component. These conclusions are qualitatively supported by Raman spectroscopy as well as P-31{Na-23} and P-31{Na-23} rotational echo double resonance (REDOR) NMR results. The combined interpretation of O-1s XPS and P-31 MAS NMR spectra shows further that there are clear deviations from a random connectivity scenario: heteroatomic P-O-Ge linkages are favored over homoatomic P-O-P and Ge-O-Ge linkages.

X-ray absorption spectroscopy study on La0.6Sr0.4CoO3 and La0.6Sr0.4Co1¡yFeyO3 nanotubes and nanorods for IT-SOFC cathodes.

In the last years, extensive research has been devoted to develop novel materials and structures with high electrochemical performance for intermediate-temperatures solid-oxide fuel cells (IT-SOFCs) electrodes. In recent works, we have investigated the structural and electrochemical properties of La0:6Sr0:4CoO3 (LSCO) and La0:6Sr0:4Co1¡yFeyO3 (LSCFO) nanostructured cathodes, finding that they exhibit excellent electrocatalytic properties for the oxygen reduction reaction [1,2]. These materials were prepared by a pore-wetting technique using polycarbonate porous membranes as templates. Two average pore sizes were used: 200 nm and 800 nm. Our scanning electronic microscopy (SEM) study showed that the lower pore size yielded nanorods, while nanotubes were obtained with the bigger pore size. All the samples were calcined at 1000oC in order to produce materials with the desired perovskite-type crystal structure. In this work, we analyze the oxidation states of Co and Fe and the local atomic order of LSCO and LSCFO nanotubes and nanowires for various compositions. For this pur- pose we performed XANES and EXAFS studies on both Co and Fe K edges. These measurements were carried out at the D08B-XAFS2 beamline of the Brazilian Synchrotron Light Laboratory (LNLS). XANES spectroscopy showed that Co and Fe only change slightly their oxidation state upon Fe addition. Surprisingly, XANES results indicated that the content of oxygen vacancies is low, even though it is well-known that these materials are mixed ionic-electronic conductors. EXAFS results were consistent with those expected according to the rhombohedral crystal structure determined in previous X-ray powder dffraction investigations. [1] M.G. Bellino et al, J. Am. Chem. Soc. 129 (2007) 3066 [2] J.G. Sacanell et al., J. Power Sources 195 (2010) 1786

Effects of the particle sizes and concentrations on the X-ray absorption by CuO compounds

This work presents a study on the effects of the particle size, material concentration and radiation energy on the X-ray absorption. CuO nanoparticles and microparticles were incorporated separately into a polymeric resin in concentrations of 5%, 10% and 30% relative to the resin mass. X-ray absorption by these materials was analyzed with a CdTe detector. The X-ray absorption is higher for the nanostructured material compared to the microstructured one for low energy X-ray beams for all CuO concentrations. (c) 2011 Elsevier Ltd. All rights reserved.

Preparation and Structural Characterization of Vulcanized Natural Rubber Nanocomposites Containing Nickel-Zinc Ferrite Nanopowders

Single-phase polycrystalline mixed nickel-zinc ferrites belonging to Ni0.5Zn0.5Fe2O4 were prepared on a nanometric scale (mean crystallite size equal to 14.7 nm) by chemical synthesis named the modified poliol method. Ferrite nanopowder was then incorporated into a natural rubber matrix producing nanocomposites. The samples were investigated by means of infrared spectroscopy, X-ray diffraction, scanning electron microscopy and magnetic measurements. The obtained results suggest that the base concentration of nickel-zinc ferrite nanoparticles inside the polymer matrix volume greatly influences the magnetic properties of nanoconnposites. A small quantity of nanoparticles, less than 10 phr, in the nanocomposite is sufficient to produce a small alteration in the semi-crystallinity of nanocomposites observed by X-ray diffraction analysis and it produces a flexible magnetic composite material with a saturation magnetization, a coercivity field and an initial magnetic permeability equal to 3.08 emu/g, 99.22 Oe and 9.42 X 10(-5) respectively.

Surface Segregation in Chromium-Doped Nanocrystalline Tin Dioxide Pigments

Surface properties play an important role in understanding and controlling nanocrystalline materials. The accumulation of dopants on the surface, caused by surface segregation, can therefore significantly affect nanomaterials properties at low doping levels, offering a way to intentionally control nanoparticles features. In this work, we studied the distribution of chromium ions in SnO2 nanoparticles prepared by a liquid precursor route at moderate temperatures (500 degrees C). The powders were characterized by infrared spectroscopy, X-ray diffraction, (scanning) transmission electron microscopy, Electron Energy Loss Spectroscopy, and Mossbauer spectroscopy. We showed that this synthesis method induces a limited solid solution of chromium into SnO2 and a segregation of chromium to the surface. The s-electron density and symmetry of Sn located on the surface were significantly affected by the doping, while Sn located in the bulk remained unchanged. Chromium ions located on the surface and in the bulk showed distinct oxidation states, giving rise to the intense violet color of the nanoparticles suitable for pigment application.

Fluorcalciomicrolite, (Ca,Na,□)2Ta2O6F, a new microlite-group mineral from Volta Grande pegmatite, Nazareno, Minas Gerais, Brazil

Fluorcalciomicrolite, (Ca,Na,□)2Ta2O6F, is a new microlite-group, pyrochlore supergroup mineral approved by the CNMNC (IMA 2012-036). It occurs as an accessory mineral in the Volta Grande pegmatite, Nazareno, Minas Gerais, Brazil. Associated minerals include: microcline, albite, quartz, muscovite, spodumene, "lepidolite", cassiterite, tantalite-(Mn), monazite-(Ce), fluorite, "apatite", beryl, "garnet", epidote, magnetite, gahnite, zircon, "tourmaline", bityite, hydrokenomicrolite, and other microlite-group minerals under study. Fluorcalciomicrolite occurs as euhedral, untwinned, octahedral crystals 0.1-1.5 mm in size, occasionally modified by rhombododecahedral faces. The crystals are colourless and translucent; the streak is white, and the lustre is adamantine to resinous. It does not fluoresce under ultraviolet light. Mohs' hardness is 4½- 5, tenacity is brittle. Cleavage is not observed; fracture is conchoidal. The calculated density is 6.160 g/cm3. The mineral is isotropic, ncalc. = 1.992. The Raman spectrum is dominated by bands of B-X octahedral bond stretching and X-B-X bending modes.The chemical composition (n = 6) is (by wavelength dispersive spectroscopy, H2O calculated to obtain charge balance, wt.%): Na2O 4.68, CaO 11.24, MnO 0.01, SrO 0.04, BaO 0.02, SnO2 0.63, UO2 0.02, Nb2O5 3.47, Ta2O5 76.02, F 2.80, H2O 0.48, O=F -1.18, total 98.23. The empirical formula, based on 2 cations at the B site, is (Ca1.07Na0.81□0.12)∑2.00(Ta1.84Nb0.14Sn0.02)∑2.00 [O5.93(OH)0.07]6.00[F0.79(OH)0.21]. The strongest eight X-ray powder-diffraction lines [d in Å(I)(hkl)] are: 5.997(59)(111), 3.138(83)(311), 3.005(100)(222), 2.602(29)(400), 2.004(23)(511), 1.841(23)(440), 1.589(25)(533), and 1.504(24)(444). The crystal structure refinement (R1 = 0.0132) gave the following data: cubic, Fd3m, a = 10.4191(6) Å, V = 1131.07(11) Å3, Z = 8.

Size-dependent phase transitions in nanostructured zirconia-scandia solid solutions

The dependences of phase stability and solid state phase transitions on the crystallite size in ZrO2-10, 12 and 14 mol% Sc2O3 nanopowders are investigated by X-ray powder diffraction using a synchrotron source (S-XPD). The average crystallite sizes lie within the range of 35 to 100 nm, approximately. At room temperature these solid solutions were previously characterised as mixtures of a cubic phase and one or two rhombohedral phases, beta and gamma, with their fractions depending on composition and average crystallite sizes. In this study, it is shown that at high temperatures these solid solutions become cubic single-phased. The size-dependent temperatures of the transitions from the rhombohedral phases to the cubic phase at high temperature are determined through the analyses of a number of S-XPD patterns. These transitions were studied on cooling and on heating, exhibiting hysteresis effects whose relevant features are size and composition dependent.

Spin-glass-like behavior of uncompensated surface spins in NiO nanoparticulated powder

Nickel oxide nonoparticles successfully synthesized by a polymer percursor method are studied in this work. The analysis of X-ray powder diffraction data provides a mean crystallite size of 22 +/- 2 nm which is in a good agreement with the mean size estimated from transmission electron microscopy images. Whereas the magnetization (M) vs. magnetic field (H) curve obtained at 5 K is consistent with a ferromagnetic component which coexists with an antiferromagnetic component, the presence of two peaks in the zero-field-cooled trace suggests the occurrence of two blocking process. The broad maximum at high temperature was associated with the thermal relaxation of uncompensated spins at the particle core and the low temperature peak was assigned to the freeze of surface spins clusters. Static and dynamic magnetic results suggest that the correlations of surface spins clusters show a spin-glass-like below T-g = 7.3 +/- 0.1 K with critical exponents zv = 9.7 +/- 0.5 and beta = 0.7 +/- 0.1, which are consistent with typical reported for spin-glass systems. (C) 2012 Elsevier B.V. All rights reserved.

Spray Congealing of Pharmaceuticals: Study on Production of Solid Dispersions Using Box-Behnken Design

This work aimed at evaluating the spray congealing method for the production of microparticles of carbamazepine combined with a polyoxylglyceride carrier. In addition, the influence of the spray congealing conditions on the improvement of drug solubility was investigated using a three-factor, three-level Box-Behnken design. The factors studied were the cooling air flow rate, atomizing pressure, and molten dispersion feed rate. Dependent variables were the yield, solubility, encapsulation efficiency, particle size, water activity, and flow properties. Statistical analysis showed that only the yield was affected by the factors studied. The characteristics of the microparticles were evaluated using X-ray powder diffraction, scanning electron microscopy, differential scanning calorimetry, and hot-stage microscopy. The results showed a spherical morphology and changes in the crystalline state of the drug. The microparticles were obtained with good yields and encapsulation efficiencies, which ranged from 50 to 80% and 99.5 to 112%, respectively. The average size of the microparticles ranged from 17.7 to 39.4 mu m, the water activities were always below 0.5, and flowability was good to moderate. Both the solubility and dissolution rate of carbamazepine from the spray congealed microparticles were remarkably improved. The carbamazepine solubility showed a threefold increase and dissolution profile showed a twofold increase after 60 min compared to the raw drug. The Box-Behnken fractional factorial design proved to be a powerful tool to identify the best conditions for the manufacture of solid dispersion microparticles by spray congealing.

Witzkeite: A new rare nitrate-sulphate mineral from a guano deposit at Punta de Lobos, Chile

Witzkeite, ideally Na4K4Ca(NO3)(2)(SO4)(4)center dot 2H(2)O, is a new mineral found in the oxidation zone of the guano mining field at Punta de Lobos, Tarapaca region, Chile. It occurs as colorless, tabular crystals up to 140 mu m in length, associated with dittmanite and nitratine. Witzkeite is colorless and transparent, with a white streak and a vitreous luster. It is brittle, with Molts hardness 2 and distinct cleavage on {001}. Measured density is 2.40(2) g/cm(3), calculated density is 2.403 g/cm(3). Witzkeite is biaxial (-) with refractive indexes alpha = 1.470(5), beta = 1.495(5), gamma = 1.510(5), measured 2V = 50-70 degrees. The empirical composition is (electron microprobe, mean of five analyses, H2O, CO2, and N2O5 by gas chromatography; wt%): Na2O 12.83, K2O 22.64, CaO 7.57, FeO 0.44, SO3 39.96, N2O5 12.7, H2O 4.5, total 100.64; CO2 was not detected. The chemical formula, calculated based on 24 O, is: Na3.40K3.95Ca1.11Fe0.05(NO3)(1.93)(SO4)(4.10)(H4.10O1.81). Witzkeite is monoclinic, space group C2/c, with unit-cell parameters: a = 24.902(2), b = 5.3323(4), c = 17.246(1) angstrom, beta = 94.281(7)degrees, V = 2283.6(3) angstrom(3) (Z = 4). The crystal structure was solved using single-crystal X-ray diffraction data and refined to R-1(F) = 0.043. Witzkeite belongs to a new structure type and is noteworthy for the very rare simultaneous presence of sulfate and nitrate groups. The eight strongest X-ray powder-diffraction lines [d in angstrom (I in %) (h k l)] are: 12.38 (100) (2 0 0), 4.13 (19) (6 0 0), 3.10 (24) (8 0 0), 2.99 (7) ((8) over bar 02), 2.85 (6) (8 02), 2.69 (9) ((7) over bar 1 3), 2.48 (12) (10 0 0), and 2.07 (54) (12 0 0). The IR spectrum of witzkeite was collected in the range 390-4000 cm(-1). The spectrum shows the typical bands of SO42- ions (1192, 1154, 1116, 1101, 1084, 993, 634, and 617 cm(-1)) and of NO3- ions (1385, 1354, 830, 716, and 2775 cm(-1)). Moreover, a complex pattern of bands related to H2O is visible (bands at 3565, 3419, 3260, 2405, 2110, 1638, and 499 cm(-1)). The IR spectrum is discussed in detail.

Carlosbarbosaite, ideally (UO2)(2)Nb2O6(OH)(2)center dot 2H(2)O, a new hydrated uranyl niobate mineral with tunnels from Jaguaracu, Minas Gerais, Brazil: description and crystal structure

Carlosbarbosaite, ideally (UO2)(2)Nb2O6(OH)(2)center dot 2H(2)O, is a new mineral which occurs as a late cavity filling in albite in the Jaguaracu pegmatite, Jaguaracu municipality, Minas Gerais, Brazil. The name honours Carlos do Prado Barbosa (1917-2003). Carlosbarbosaite forms long flattened lath-like crystals with a very simple orthorhombic morphology. The crystals are elongated along [001] and flattened on (100); they are up to 120 mu m long and 2-5 mu m thick. The colour is cream to pale yellow, the streak yellowish white and the lustre vitreous. The mineral is transparent (as individual crystals) to translucent (massive). It is not fluorescent under either long-wave or short-wave ultraviolet radiation. Carlosbarbosaite is biaxial(+) with alpha = 1.760(5), beta = 1.775(5), gamma = 1.795(5), 2V(meas) = 70(1)degrees, 2V(calc) = 83 degrees. The orientation is X parallel to a, Y parallel to b, Z parallel to c. Pleochroism is weak, in yellowish green shades, which are most intense in the Z direction. Two samples were analysed. For sample I, the composition is: UO3 54.52, CaO 2.07, Ce2O3 0.33, Nd2O3 0.49, Nb2O5 14.11, Ta2O5 15.25, TiO2 2.20, SiO2 2.14, Fe2O3 1.08, Al2O3 0.73, H2O (calc.) 11.49, total 104.41 wt.%; the empirical formula is (square 0.68Ca0.28Nd0.02Ce0.02)(Sigma=1.00)[U-1.44 square O-0.56(2.88)(H2O)(1.12)](Nb0.80Ta0.52Si0.27Ti0.21Al0.11Fe0.10)(Sigma=2.01) O-4.72(OH)(3.20)(H2O)(2.08). For sample 2, the composition is: UO3 41.83, CaO 2.10, Ce2O3 0.31, Nd2O3 1.12, Nb2O5 14.64, Ta2O5 16.34, TiO2 0.95, SiO2 3.55, Fe2O3 0.89, Al2O3 0.71, H2O (calc.) 14.99, total 97.43 wt.%; the empirical formula is (square 0.67Ca0.27Nd0.05Ce0.01)(Sigma=1.00)[U-1.04 square O-0.96(2.08)(H2O)(1.92)] (Nb0.79Ta0.53Si0.42Ti0.08Al0.10Fe0.08)(Sigma=2.00)O-4.00(OH)(3.96)(H2O)(2.04). The ideal endmember formula is (UO2)(2)Nb2O6(OH)(2)center dot 2H(2)O. Calculated densities are 4.713 g cm(-3) (sample 1) and 4.172 g cm(-3) (sample 2). Infrared spectra show that both (OH) and H2O are present. The strongest eight X-ray powder-diffraction lines [listed as d in angstrom(I)(hkl)] are: 8.405(8)(110), 7.081(10)(200), 4.201(9)(220), 3.333(6)(202), 3.053(8)(022), 2.931(7)(420), 2.803(6)(222) and 2.589(5)(040,402). The crystal structure was solved using single-crystal X-ray diffraction (R = 0.037) which gave the following data: orthorhombic, Cmem, a = 14.150(6), b = 10.395(4), c = 7.529(3) angstrom, V = 1107(1) angstrom(3), Z = 4. The crystal structure contains a single U site with an appreciable deficiency in electron scattering, which is populated by U atoms and vacancies. The U site is surrounded by seven 0 atoms in a pentagonal bipyramidal arrangemet. The Nb site is coordinated by four 0 atoms and two OH groups in an octahedral arrangement. The half-occupied tunnel Ca site is coordinated by four 0 atoms and four H2O groups. Octahedrally coordinated Nb polyhedra share edges and comers to form Nb2O6(OH)(2) double chains, and edge-sharing pentagonal bipyramidal U polyhedra form UO5 chains. The Nb2O6(OH)(2) and UO5 chains share edges to form an open U-Nb-phi framework with tunnels along [001] that contain Ca(H2O)(4) clusters. Carlosbarbosaite is closely related to a family of synthetic U-Nb-O framework tunnel structures, it differs in that is has an (OH)-bearing framework and Ca(H2O)(4) tunnel occupant. The structure of carlosbarbosaite resembles that of holfertite.

Engineering Active Pharmaceutical Ingredients by Spray Drying: Effects on Physical Properties and In Vitro Dissolution

Active pharmaceutical ingredients have very strict quality requirements; minor changes in the physical and chemical properties of pharmaceuticals can adversely affect the dissolution rate and therefore the bioavailability of a given drug. Accordingly, the aim of the present study was to investigate the effect of spray drying on the physical and in vitro dissolution properties of four different active pharmaceutical ingredients, namely carbamazepine, indomethacin, piroxicam, and nifedipine. Each drug was dispersed in a solution of ethanol and water (70:30) and subjected to single-step spray drying using similar operational conditions. A complete characterization of the spray-dried drugs was performed via differential scanning calorimetry (DSC), scanning electron microscopy (SEM), X-ray powder diffraction (XRPD), particle size distribution analysis, solubility analysis, and an in vitro dissolution study. The results from the thermal analysis and X-ray diffraction showed that, except for carbamazepine, no chemical modifications occurred as a result of spray drying. Moreover, the particle size distribution of all the spray-dried drugs significantly decreased. In addition, SEM images showed that most of the particles had an irregular shape. There was no significant improvement in the solubility of the spray-dried drugs compared with the unprocessed compounds; however, in general, the dissolution rates of the spray-dried drugs showed a remarkable improvement over their non-spray-dried counterparts. Therefore, the results from this study demonstrate that a single spray-drying step may lead to changes in the physical properties and dissolution characteristics of drugs and thus improve their therapeutic action.

Microstructure and metal-insulator transition in single crystalline KMo4O6

High quality KMo4O6 single crystals with tetragonal structure (space group P4/mbm) have been prepared by fused salt electrolysis. The crystals were studied by scanning electron microscopy (SEM), X-ray diffractometry, electrical resistivity, and magnetization measurements. X-ray powder diffraction patterns and SEM have given some information on the growth of single crystals. Electrical resistivity as a function of temperature shows that the KMo4O6 compound is a bad metal with resistivity change of approximately 30% in the temperature range from 2 to 300K. A metal-insulator transition (MIT), observed at approximately 110K, has been also confirmed for this material. Magnetization as a function of temperature agrees with previous report, however a magnetic ordering has been observed in M(H) curves in the whole temperature range.