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Ferroelectric materials exhibit switchable spontaneous polarization below Curie's temperature, driven by octahedral distortions and rotations, as well as ionic displacements. The ability to manipulate polarization coupled with persistent remanence, drives diverse applications, including piezoelectric devices. In the last two decades, nanoscale exploration has unveiled unique material properties influenced by morphology, including the capability to manipulate polarization, patterns, and domains. This paper focuses on the characterization of nanometric sodium niobate (SN) synthesized from metallic niobium through alkali hydrothermal treatment, utilizing electron microscopy techniques, including high-resolution differential phase contrast (DPC) in scanning transmission electron microscopy (STEM). The material exhibits a nanoribbon structure forming a tree root-like network. The study identifies crystallographic phase, atomic columns displacement directions, and surface features, such as exposed planes and the absence of particular atomic columns. The high sensitivity of integrated DPC images proves crucial in overcoming observational challenges in other STEM modes. These observations are essential for potential applications in electronic, photocatalytic, and chemical reaction contexts.
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Global concrete production, reaching 14×1013m3/year, raises environmental concerns due to the resource-intensive nature of ordinary Portland cement (OPC) manufacturing. Simultaneously, 32.7×109 kg/year of expanded polystyrene (EPS) waste poses ecological threats. This research explores the mechanical behavior of lightweight concrete (LWAC) using recycled EPS manufactured with a hybrid cement mixture (OPC and alkali-activated cement). These types of cement have been shown to improve the compressive strength of concrete, while recycled EPS significantly decreases concrete density. However, the impact of these two materials on the LWAC mechanical behavior is unclear. LWAC comprises 35% lightweight aggregates (LWA)-a combination of EPS and expanded clays (EC) - and 65% normal-weight aggregates. As a cementitious matrix, this LWAC employs 30% OPC and 70% alkaline-activated cement (AAC) based on fly ash (FA) and lime. Compressive strength tests after 28 curing days show a remarkable 48.8% improvement, surpassing the ACI 213R-03 standard requirement, which would allow this sustainable hybrid lightweight aggregate concrete to be used as structural lightweight concrete. Also obtained was a 21.5% reduction in density; this implies potential cost savings through downsizing structural elements and enhancing thermal and acoustic insulation. X-ray diffraction (XRD) and Fourier transform infrared (FTIR) spectroscopy reveal the presence of C-S-H, C-(A)-S-H, and N-A-S-H gels. However, anhydrous products in the hybrid LWAC suggest a slower reaction rate. Further investigation into activator solution dosage and curing temperature is recommended for improved mechanical performance on the 28th day of curing. This research highlights the potential for sustainable construction incorporating waste and underscores the importance of refining activation parameters for optimal performance.
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The association of scanning transmission electron microscopy (STEM) and detection of a diffraction pattern at each probe position (so-called 4D-STEM) represents one of the most promising approaches to analyze structural properties of materials with nanometric resolution and low irradiation levels. This is widely used for texture analysis of materials using automated crystal orientation mapping (ACOM). Herein, we perform orientation mapping in InP nanowires exploiting precession electron diffraction (PED) patterns acquired by an axial CMOS camera. Crystal orientation is determined at each probe position by the quantitative analysis of diffracted intensities minimizing a residue comparing experiments and simulations in analogy to x-ray structural refinement. Our simulations are based on the two-beam dynamical diffraction approximation and yield a high angular precision (â¼0.03°), much lower than the traditional ACOM based on pattern matching algorithms (â¼1°). We anticipate that simultaneous exploration of both spot positions and high precision crystal misorientation will allow the exploration of the whole potentiality provided by PED-based 4D-STEM for the characterization of deformation fields in nanomaterials.
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TbxPr1-xAl2are ferrimagnetic materials exhibiting magnetocaloric effect that have gained considerable attention due to their potential use as an alternative in refrigeration, magnetic sensors and in information storage technology. Here using the mean field approach numerical simulations were conducted forx= 0.1, 0.2, 0.3, 0.4, 0.5, and 0.75, to analyze selected physical properties, such as x-ray and neutron powder diffraction, magnetization and heat capacity. The simulations successfully reproduced the experimental data providing a comprehensive characterization and improved understanding of this family of compound.
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This work presents the structural and electrical characterization of K2NiF4-type layered perovskites of LaSrAl1-xMgxO4-δ composition to be used as oxide-ion electrolytes for a solid-oxide fuel cell (SOFC). These perovskites were prepared by mechano-chemical synthesis (ball milling), an alternative to traditional synthesis methods such as citrate-nitrates and solid-state reaction. With these methods, two things are avoided: first, the use of nitrate salts, which are more environmentally harmful than oxide precursors, and second, it saves the series of long thermal treatments associated with solid-state reactions. After grinding the precursors, nanometric particles were obtained with a combination of crystalline regions and amorphous regions; this effect was determined by XRD and TEM, showing that Mg has a positive effect on the phase formation by only mechanical synthesis. R2C4: After sintering, it was found by XRD that the sample x = 0.1 only presents the diffraction peaks corresponding to the desired phase, which shows a phase purity greater than 97%, even higher than that of the standard undoped sample. For x = 0.2 and 0.3, there was a segregation of impurities, possibly by the local migration of La and Sr heavy cations; this was determined by SEM and EDS. The electrical characterization of the sintered pellets was carried out by electrochemical impedance spectroscopy, which determined that the incorporation of Mg in the structure improves the ionic conductivity by three orders of magnitude, obtaining conductivities of 1.6 mS/cm at 900 °C for x = 0.2. Although the improvement in conductivity is considerable, many challenges such as densification, the segregation of impurities, and the study of mechanical and thermal properties must be carried out on these materials to endorse them as solid electrolytes in SOFC.
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To complement previous results, an analysis of the chemical and morphological properties of babassu fibers (Attalea speciosa Mart. ex Spreng.) was conducted in order to evaluate their potential as reinforcements in the production of composites with epoxy matrix. The diameter distribution was analyzed in a sample of one hundred fibers, allowing the verification of its variation. The determination of the chemical properties involved experimental analyses of the constituent index and X-ray diffraction. The diffractogram was used to calculate the crystallinity index and the microfibril angle, which are crucial parameters that indicate the consistency of the mechanical properties of babassu fibers and the feasibility of their use in composites. The results revealed that babassu fiber has a chemical composition, with contents of 28.53% lignin, 32.34% hemicellulose, and 37.97% cellulose. In addition, it showed a high crystallinity index of 81.06% and a microfibril angle of 7.67°. These characteristics, together with previous results, indicate that babassu fibers have favorable chemical and morphological properties to be used as reinforcements in composites, highlighting its potential as an important material for applications in technology areas.
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The dissolution rate of the anti-HIV drug saquinavir base (SQV), a poorly water-soluble and extremely low absolute bioavailability drug, was improved through a eutectic mixture formation approach. A screening based on a liquid-assisted grinding technique was performed using a 1:1 molar ratio of the drug and the coformers sodium saccharinate, theobromine, nicotinic acid, nicotinamide, vanillin, vanillic acid, and piperine (PIP), followed by differential scanning calorimetry (DSC). Given that SQV-PIP was the only resulting eutectic system from the screening, both the binary phase and the Tammann diagrams were adapted to this system using DSC data of mixtures prepared from 0.1 to 1.0 molar ratios in order to determine the exact eutectic composition. The SQV-PIP system formed a eutectic at a composition of 0.6 and 0.40, respectively. Then, a solid-state characterization through DSC, powder X-ray diffraction (PXRD), including small-angle X-ray scattering (SAXS) measurements to explore the small-angle region in detail, Fourier transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), and a powder dissolution test were performed. The conventional PXRD analyses suggested that the eutectic mixture did not exhibit structural changes; however, the small-angle region explored through the SAXS instrument revealed a change in the crystal structure of one of their components. FT-IR spectra showed no molecular interaction in the solid state. Finally, the dissolution profile of SQV in the eutectic mixture was different from the dissolution of pure SQV. After 45 min, approximately 55% of the drug in the eutectic mixture was dissolved, while, for pure SQV, 42% dissolved within this time. Hence, this study concludes that the dissolution rate of SQV can be effectively improved through the approach of using PIP as a coformer.
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PyDDT is a free Python package of computer codes for exploiting X-ray dynamic multiple diffraction in single crystals. A wide range of tools are available for evaluating the usefulness of the method, planning feasible experiments, extracting phase information from experimental data and further improving model structures of known materials. Graphical tools are also useful in analytical methodologies related to the three-dimensional aspect of multiple diffraction. For general X-ray users, the PyDDT tutorials provide the insight needed to understand the principles of phase measurements and other related methodologies. Key points behind structure refinement using the current approach are presented, and the main features of PyDDT are illustrated for amino acid and filled skutterudite single crystals.
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Formulations of biodegradable films using macrocarpa peach palm flour (low amylose starch), chitosan and glycerol, were developed and the effects of the drying temperature on films by assessing their physicochemical, mechanical, barrier, optical, structural, antioxidant properties, and the biodegradability in soil were evaluated. Chitosan enhanced the mechanical properties of the films, but they showed no antimicrobial activity against the tested food-borne pathogens, except for Listeria monocytogenes, for which the inhibition zone was from 0.1 to 0.6 cm. Films with higher concentrations of peach palm flour are opaquer, with better antioxidant characteristics and content of phenolic compounds compared to films made with lower concentrations of flour. The films presented a yellowish color because of the carotenoids found in peach palm flour, 29.63 µg 100 g-1, and exhibited a C-type X-ray pattern, characteristic peak of materials where amylose and amylopectin are present. After 15 days in soil, the films lost 30% of their initial weight. Therefore, these results suggest that the development of films as food preservative is a promising field and that the material used in the study are suitable for their formulation.
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Arecaceae , Quitosana , Antioxidantes , Amilose , Quitosana/química , Arecaceae/química , SoloRESUMO
A compilation of articles with a strong teaching element published since 2018 is presented alongside an overview of the articles in the special issue on this topic.
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The current study compares the antibacterial activity of zinc oxide nanostructures (neZnO). For this purpose, two bacterial strains, Escherichia coli (ATCC 4157) and Staphylococcus aureus (ATCC 29213) were challenged in room light conditions with the aforementioned materials. Colloidal and hydrothermal methods were used to obtain the quasi-round and quasi-diamond platelet-shape nanostructures. Thus, the oxygen vacancy (VO ) effects on the surface of neZnO are also considered to assess its effects on antibacterial activity. The neZnO characterization was achieved by X-ray diffraction (XRD), a selected area electron diffraction (SAED) and Raman spectroscopy. The microstructural effects were monitored by scanning electron microscopy (SEM) and transmission electron microscopy (TEM). Furthermore, optical absorption ultraviolet visible spectrophotometry (UV-Vis) and X-ray photoelectron spectroscopy (XPS) analyses complement the physical characterization of these nanostructures; neZnO caused 50 % inhibition (IC50 ) at concentrations from 0.064 to 0.072â mg/mL for S. aureus and from 0.083 to 0.104â mg/mL for E. coli, indicating an increase in activity against S. aureus compared to E. coli. Consequently, quasi-diamond platelet-shaped nanostructures (average particle size of 377.6±10â nm) showed enhanced antibacterial activity compared to quasi-round agglomerated particles (average size of 442.8±12â nm), regardless of Vo presence or absence.
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Nanopartículas Metálicas , Nanoestruturas , Óxido de Zinco , Óxido de Zinco/farmacologia , Óxido de Zinco/química , Escherichia coli , Staphylococcus aureus , Espectroscopia de Infravermelho com Transformada de Fourier , Testes de Sensibilidade Microbiana , Antibacterianos/farmacologia , Antibacterianos/química , Nanoestruturas/química , Difração de Raios X , Nanopartículas Metálicas/químicaRESUMO
Human tooth enamel (HTE) is the hardest tissue in the human body and its structural organization shows a hierarchical composite material. At the nanometric level, HTE is composed of approximately 97% hydroxyapatite [HAP, Ca10(PO4)6(OH)2] as inorganic phase, and of 3% as organic phase and water. However, it is still controversial whether the hexagonal HAP phase crystallizes in P63/m or another space group. The observance in HTE of Ca2+, Mg2+ and Na+ ions using X-ray characteristic energy-dispersive spectroscopy in the scanning electron microscope has been explained by substitutions in the HAP unit cell. Thus, Ca2+ can be replaced by Na+ and Mg2+ ions; the PO43- group can be replaced by CO32- ions; and the OH- ions can also be replaced by CO32-. A unit-cell model of the hexagonal structure of HTE is not fully defined yet. In this work, density functional theory calculations are performed to study the hexagonal HAP unit cell when substitution by OH-, CO32-, Mg2+ and Na+ ions are carried out. An approach is presented to study the crystallographic unit cell of HTE by examining the changes resulting from the inclusion of these different ions in the unit cell of HAP. Enthalpies of formation and crystallographic characteristics of the electron diffraction patterns are analysed in each case. The results show an enhancement in structural stability of HAP with OH defects, atomic substitution of Mg2+, carbonate and interstitial Na+. Simulated electron diffraction patterns of the generated structures show similar characteristics to those of human tooth enamel. Hence, the results explain the indiscernible structural changes shown in experimental X-ray diffractograms and electron diffraction patterns.
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Maleic acid was studied by Raman spectroscopy and powder synchrotron X-ray diffraction (XRD) under high pressure conditions by using a diamond anvil cell. The Raman spectroscopy measurements were performed from ambient pressure up to 9.2 GPa in the 100-3200 cm-1 spectral range. While the XRD measurements were performed up to 10.1 GPa. Here we present the pressure-dependence behavior from both the Raman modes and cell parameters. Maleic acid lattice parameters decrease anisotropically as a function of pressure and a reduction of 27% in the volume of the unit cell was observed. Modifications in the material's compressibility were observed at around 2 and 6 GPa.
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The local structural characterization of iron oxide nanoparticles is explored using a total scattering analysis method known as pair distribution function (PDF) (also known as reduced density function) analysis. The PDF profiles are derived from background-corrected powder electron diffraction patterns (the e-PDF technique). Due to the strong Coulombic interaction between the electron beam and the sample, electron diffraction generally leads to multiple scattering, causing redistribution of intensities towards higher scattering angles and an increased background in the diffraction profile. In addition to this, the electron-specimen interaction gives rise to an undesirable inelastic scattering signal that contributes primarily to the background. The present work demonstrates the efficacy of a pre-treatment of the underlying complex background function, which is a combination of both incoherent multiple and inelastic scatterings that cannot be identical for different electron beam energies. Therefore, two different background subtraction approaches are proposed for the electron diffraction patterns acquired at 80â kV and 300â kV beam energies. From the least-square refinement (small-box modelling), both approaches are found to be very promising, leading to a successful implementation of the e-PDF technique to study the local structure of the considered nanomaterial.
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Drying rice in a single layer in a silo-dryer-aerator allows uniform drying. The objective of this study was to evaluate the physical, physicochemical, and morphological quality of rice grain cultivars (IRGA 424, BRS Pampeira, and Guri INTA) in the lower (initial time) and upper (final time) layers in a silo-dryer-aerator, employing single-layer loading at low temperatures, using the methods of near-infrared spectroscopy, X-ray diffraction analysis, scanning electron microscopy, and multivariate statistical analysis. Drying rice in silo-dryer-aerator attenuated the moisture diffusivity in the grains, minimizing its effects on the physical, physicochemical, and morphological properties of the grains. However, the physicochemical constituents and morphology of starch were preserved by the low drying temperatures, mainly in the lower layers throughout the 2-month drying. The rice grains of the Guri INTA and BRS Pampeira cultivars were the most resistant to drying and showed greater uniformity on the final quality.
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Fatty acid binding proteins (FABPs) are responsible for the long-chain fatty acids (FAs) transport inside the cell. However, despite the years, since their structure is known and the many studies published, there is no definitive answer about the stages of the lipid entry-exit mechanism. Their structure forms a ß -barrel of 10 anti-parallel strands with a cap in a helix-turn-helix motif, and there is some consensus on the role of the so-called portal region, involving the second α -helix from the cap ( α 2), ß C- ß D, and ß E- ß F turns in FAs exchange. To test the idea of a lid that opens, we performed a soaking experiment on an h-FABP crystal in which the cap is part of the packing contacts, and its movement is strongly restricted. Even in these conditions, we observed the replacement of palmitic acid by 2-Bromohexadecanoic acid (Br-palmitic acid). Our MD simulations reveal a two-step lipid entry process: (i) The travel of the lipid head through the cavity in the order of tens of nanoseconds, and (ii) The accommodation of its hydrophobic tail in hundreds to thousands of nanoseconds. We observed this even in the cases in which the FAs enter the cavity by their tail. During this process, the FAs do not follow a single trajectory, but multiple ones through which they get into the protein cavity. Thanks to the complementary views between experiment and simulation, we can give an approach to a mechanistic view of the exchange process.
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Proteínas de Ligação a Ácido Graxo , Simulação de Dinâmica Molecular , Proteínas de Ligação a Ácido Graxo/química , Proteínas de Ligação a Ácido Graxo/metabolismo , Raios X , Conformação Proteica , Ácidos Palmíticos/metabolismo , Lipídeos , Ácidos GraxosRESUMO
The plastic phase of cyclohexane (polymorph I) was studied by Kahn and co-workers, without achieving a satisfactory determination of the atomic coord-inates [Kahn et al. (1973). Acta Cryst. B29, 131-138]. The positions of the C atoms cannot be determined directly as a consequence of the disorder in a high-symmetry space group, an inherent feature of plastic materials. Given this situation, the building of a polyhedron describing the disorder was the main tool for determining the molecular structure in the present work. Based on the shape of reflections {111}, {200} and {113} in space group Fm 3 m, we assumed that cyclohexane is disordered through the action of rotation group 432. The polyhedral cluster of disordered molecules is then a rhombic dodecahedron centred on the nodes of an fcc Bravais lattice. The vertices of this polyhedron are the positions of C atoms for the cyclohexane molecule, which is disordered over 24 positions. With such a model, the asymmetric unit is reduced to two C atoms placed on special positions, and an acceptable fit between the observed and calculated structure factors is obtained.
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Photonic crystals (PCs) are nanomaterials with photonic properties made up of periodically modulated dielectric materials that reflect light between a wavelength range located in the photonic band gap. Colloidal PCs (C-PC) have been proposed for several applications such as optical platforms for the formation of physical, chemical, and biological sensors based on a chromatic response to an external stimulus. In this work, a robust protocol for the elaboration of photonic crystals based on SiO2 particle (SP) deposition using the vertical lifting method was studied. A wide range of lifting speeds and particle suspension concentrations were investigated by evaluating the C-PC reflectance spectrum. Thinner and higher reflectance peaks were obtained with a decrease in the lifting speed and an increase in the SP concentrations up to certain values. Seven batches of twelve C-PCs employing a SP 3% suspension and a lifting speed of 0.28 µm/s were prepared to test the reproducibility of this method. Every C-PC fabricated in this assay has a wavelength peak in a range of 10 nm and a peak width lower than 90 nm. Inverse-opal polymeric films with a highly porous and interconnected morphology were obtained using the developed C-PC as a template. Overall, these results showed that reproducible colloidal crystals could be elaborated on a large scale with a simple apparatus in a short period, providing a step forward in the scale-up of the fabrication of photonic colloidal crystal and IO structures as those employed for the elaboration of photonic polymeric sensors.
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Aiming of self-sustainable production, the search for biodegradable and biocompatible materials has brought with it the need to know the physicochemical and dielectric characteristics of polysaccharide-based composite structures, which can be used as important and promising raw materials for biotechnology and electronic industries. Galactomannans are polysaccharides, extracted from seeds and microbiological sources, consisting of mannose and galactose. In this context, this work aimed to extract, purify and characterize by XRD, FTIR and impedance spectroscopy galactomannan obtained from seeds of Adenanthera pavonina L. The purification process was made with ethyl alcohol at concentrations of 70, 80 and 90 %. Polymeric films were prepared by solvent slow evaporation at low temperatures. XRD measurements revealed that Galactomannan from Adenanthera pavonina L., after purification, has a semi-crystalline structure due to the identification of two peaks the first between 5.849° and 6.118° and the second between 20.011° and 20.247°. FTIR spectra showed the functional groups associated with monosaccharides of the galactomannan from Adenanthera pavonina L. seeds, as well as the typical polysaccharide bands and peaks, confirmed by literature data. The impedance results give an increment on the state-of-the-art of this biomaterial by showing the existence of dielectric relaxations, independent of the degree of purification, using the dielectric modulus formalism. The permittivity analysis reveals the presence of water in the structure of the film, whose dipoles contribute to the relatively high value of the dielectric constant. From the results obtained, it can be concluded that purified galactomannan has the potential for possible applications in the electronics industry as a green and eco-friendly dielectric material.
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Fabaceae , Mananas , Mananas/análise , Mananas/química , Fabaceae/química , Polissacarídeos/química , Galactose , Sementes/química , Materiais BiocompatíveisRESUMO
To increase hydration properties and soluble fiber content, okara with different moisture contents (30, 35, and 40%) was extruded in single-screw equipment, keeping the temperature (120 °C) and screw speed (115â rpm) fixed. The physical, chemical, and techno-functional properties of extruded and non-extruded okara (control) were evaluated. The microstructure, color, chemical composition, and techno-functional properties of okara were altered after extrusion. The extruded samples showed general microstructure aspects similar between them, with an irregular and rough surface, striated parts, orifices, and some agglomerated particles with distorted, compact, and amorphous appearance, different from control. Among the modified samples, okara extruded with 30% moisture showed more intense changes in relation to the samples extruded with 35 and 40% moisture. Based on the results, it can be inferred that okara extruded with 35% moisture is the most suitable. Under this condition, there was an increase of 80% in soluble fiber content, 45% in water absorption and holding capacity and 11% in solid stability in water, the maintenance of swelling and oil absorption and holding capacities and the reduction of protein solubility in water. X-ray diffraction analysis showed that crystalline phase was affected by extrusion.