Fractal approach to ac impedance spectroscopy studies of ceramic materials

A novel fractal model for grain boundary regions of ceramic materials was developed. The model considers laterally inhomogeneous distribution of charge carriers in the vicinity of grain boundaries as the main cause of the non-Debye behaviour and distribution of relaxation times in ceramic materials. Considering the equivalent circuit the impedance of the grain boundary region was expressed. It was shown that the impedance of the grain boundary region has the form of the Davidson-Cole equation. The fractal dimension of the inhomogeneous distribution of charge carriers in the region close to the grain boundaries could be calculated based on the relation ds = 1 + β, where β is the constant from the Davidson-Cole equation.

A method for the digital image analysis of ceramic grains based on shape factor segmentation

A very simple and robust method for ceramics grains quantitative image analysis is presented. Based on the use of optimal imaging conditions for reflective light microscopy of bulk samples, a digital image processing routine was developed for shading correction, noise suppressing and contours enhancement. Image analysis was done for grains selected according to their concavities, evaluated by perimeter ratio shape factor, to avoid consider the effects of breakouts and ghost boundaries due to ceramographic preparation limitations. As an example, the method was applied for two ceramics, to compare grain size and morphology distributions. In this case, most of artefacts introduced by ceramographic preparation could be discarded due to the use of perimeter ratio exclusion range.

Ceramic Crucible Corrosion by Heavy Metal Oxide Glasses, Part II: Diffusion Study

Due to their low cost and high resistance to corrosion, ceramic crucibles can be used for the melting of PBG glasses (PbO-BiO 1.5GaO 1.5). These glasses present good window transmission from ultra-violet to infrared, making their use as optical fibres promising. However, their disadvantage is the high reactivity, leading to the corrosion of different crucibles, including gold and platinum ones. In this work, the corrosion of Al 2O 3, SnO 2 and ZrO 2 crucibles after melting at temperatures varying from 850 to 1000°C, was evaluated by Scanning Electronic Microscopy (SEM) in conjunction with microanalysis by EDS. The lead diffusion profile in the crucible material was obtained. Diffusion coefficients were calculated according to the Fick and Fisher theories. Results indicated that the different crucibles presented similar behaviour: in the region near the interface, diffusion occurs in the volumetric way and in regions away from the interface, diffusion occurs through grain boundary.

Influence of oxygen atmosphere on LiNbO3 thin films prepared by Pechini process

Thin films of lithium niobate were deposited on the Pt/Ti/SiO2 (111) substrates by the polymeric precursor method (Pechini process). Annealing in static air and oxygen atmosphere was performed at 500°C for 3 hours. The films obtained were characterized by X-ray diffraction, scanning electron microscopy and transmission electron microscopy. The dielectric constant, dissipation factor and resistance were measured in frequency region from 10 Hz to 10 MHz. Electrical characterizations of the films pointed to ferroelectricity via hysteresis loop. The influence of oxygen atmosphere on crystallization and properties of LiNbO3 thin films is discussed.

Effect of Boron powder purity on superconducting properties of bulk MgB2

In order to study the influence of the amorphous Boron powder on the superconducting properties, MgB2 bulk samples were prepared using 96% and 99% pure commercial Boron powder as well as 92% commercial Boron powder after purification process. The results showed that the original 96% and the purified 92% powders have larger particle size compared to the pure 99% Boron powder, which leads to reduce magnetic critical current densities. In order to get higher performance MgB2, the purified low grade Boron powder need further control of their microstructure such as smaller particle size to enhance flux pinning from the grain boundaries which represent effective pinning centers. © 2007 Elsevier B.V. All rights reserved.

Microstructure evolution during warm deformation of low carbon steel with dispersed cementite

The microstructure evolution and mechanical behavior during large strain of a 0.16%C-Mn steel has been investigated by warm torsion tests. These experiments were carried out at 685°C at equivalent strain rate of 0.1 s . The initial microstructure composed of a martensite matrix with uniformly dispersed fine cementite particles was attained by quenching and tempering. The microstructure evolution during tempering and straining was performed through interrupted tests. As the material was reheated to testing temperature, well-defined cell structure was created and subgrains within lath martensite were observed by TEM; strong recovery took place, decreasing the dislocation density. After 1 hour at the test temperature and without straining, EBSD technique showed the formation of new grains. The flow stress curves measured had a peculiar shape: rapid work hardening to a hump, followed by an extensive flow-softening region. 65% of the boundaries observed in the sample strained to ε = 1.0 were high angle grain boundaries. After straining to ε = 5.0, average ferrite grain size close to 1.5 μm was found, suggesting that dynamic recrystallization took place. Also, two sets of cementite particles were observed: large particles aligned with straining direction and smaller particles more uniformly dispersed. The fragmentation or grain subdivision that occurred during reheating and tempering time was essential for the formation of ultrafine grained microstructure.

Analytical model for heterogeneous crystallization kinetics of spherical glass particles

An analytical model developed to describe the crystallization kinetics of spherical glass particles has been derived in this work. A continuous phase transition from three-dimensional (3D)-like to 1D-like crystal growth has been considered and a procedure for the quantitative evaluation of the critical time for this 3D-1D transition is proposed. This model also allows straightforward determination of the density of surface nucleation sites on glass powders using differential scanning calorimetry data obtained under different thermal conditions. © 2009 The American Ceramic Society.

Observation of piezoelectric response on tungsten doped barium zirconium titanate ceramics

This study describes observation of piezoelectric response of Ba(Zr 0.10Ti 0.90.O3 ceramics modified with tungsten (BZT:2W) by the mixed oxide method. According to X ray diffraction analysis, the ceramics are free of secondary phases. Transmission electron microscopy (TEM) analyses reveals the absence of segregates in the grain boundaries indicates the high solubility of WO3 in the BZT matrix. The dielectric permittivity measured at a frequency of 10 KHz was equal to 6500 with dieletric loss of 0.15. A typical hysteresis loop was observed at room temperature. Electron Paramagnetic Resonance (EPR) analyses reveals that substitution of W6+ by Ti4+ causes distortion in the crystal structure changing lattice parameter. Polarization reversal was investigated by applying dc voltage through a conductive tip during the area scanning. Piezoelectric force microscopy images reveals that in-plane response may not change its sign upon polarization switching, while the out-of-plane response does. Copyright © 2010 American Scientific Publishers.

Optical and transport properties of rare-earth trivalent ions located at different sites in sol-gel SnO2

Photoluminescence and photo-excited conductivity data as well as structural analysis are presented for sol-gel SnO2 thin films doped with rare earth ions Eu3+ and Er3+, deposited by sol-gel-dip-coating technique. Photoluminescence spectra are obtained under excitation with various types of monochromatic light sources, such as Kr+, Ar+ and Nd:YAG lasers, besides a Xe lamp plus a selective monochromator with UV grating. The luminescence fine structure is rather different depending on the location of the rare-earth doping, at lattice symmetric sites or segregated at the asymmetric grain boundary layer sites. The decay of photo-excited conductivity also shows different trapping rate depending on the rare-earth concentration. For Er-doped films, above the saturation limit, the evaluated capture energy is higher than for films with concentration below the limit, in good agreement with the different behaviour obtained from luminescence data. For Eu-doped films, the difference in the capture energy is not so evident in these materials with nanoscocopic crystallites, even though the luminescence spectra are rather distinct. It seems that grain boundary scattering plays a major role in Eu-doped SnO2 films. Structural evaluation helps to interpret the electro-optical data. © 2010 IOP Publishing Ltd.

SnO 2 ceramics with low electrical resistivity obtained by microwave sintering

The main aim of this study was to develop dense and conducting SnO 2 ceramics without precipitated phases on the grain boundaries, which was verified using field emission scanning microscopy (FE-SEM) coupled with an energy-dispersive X-ray spectroscopy (FE-SEM/EDS). Two sample groups were investigated, where the first sample group was doped with zinc while the second one was doped with cobalt. The ceramics were prepared using the oxides mixture method and the sintering was carried out in a conventional muffle oven as well as in microwave oven. The results obtained were found to be similar regarding the relative density for the two sintering methods while time and temperature gains were observed for the microwave sintering method. The relative densities obtained were nearly 95%, for the two sintering methods. Concerning the electrical characterization measurements-electric field x current density as well as the environment temperature, the ceramics obtained through the conventional sintering method presented non-ohmic behavior. For the microwave sintered ceramics, we observed an ohmic behavior with electrical resistivity of 1.3 Ωcm for the samples doped with ZnO/Nb 2O 5 and 2.5 Ωcm for that of the samples doped with CoO/Nb 2O 5. The FE-SEM/EDS results for the microwave sintered ceramics indicated a structure with a reduced number of pores and other phases segregated at the grain boundaries, which leads to a better conductive ceramic than the conventional oven sintered samples. The dilatometry analysis determined the muffle sintering temperature and the difference between the densification of cobalt and zinc oxides. The addition of niobium oxide resulted in the decrease in resistivity, which thus led us to conclude that it is possible to obtain dense ceramics with low electrical resistivity based on SnO 2 using commercial oxides by the oxides mixture technique and the microwave oven sintering method. Copyright © 2011 American Scientific Publishers All rights reserved.

Decay of photo-induced conductivity in Sb-doped SnO2 thin films, using monochromatic light of about bandgap energy

Doping tin dioxide (SnO2) with pentavalent Sb5+ ions leads to an enhancement in the electrical conductivity of this material, because Sb5+ substitutes Sn4+ in the matrix, promoting an electronic density increase in the conduction band, due to the donor-like nature of the doping atom. Results of computational simulation, based on the Density Functional Theory (DFT), of SnO2:4%Sb and SnO2:8%Sb show that the bandgap magnitude is strongly affected by the doping concentration, because the energy value found for 4 at%Sb and 8 at%Sb was 3.27 eV and 3.13 eV, respectively, whereas the well known value for undoped SnO2 is about 3.6 eV. Sb-doped SnO2 thin films were obtained by the sol-gel-dip-coating technique. The samples were submitted to excitation with below theoretical bandgap light (450 nm), as well as above bandgap light (266 nm) at low temperature, and a temperature-dependent increase in the conductivity is observed. Besides, an unusual temperature and time dependent decay when the illumination is removed is also observed, where the decay time is slower for higher temperatures. This decay is modeled by considering thermally activated cross section of trapping centers, and the hypothesis of grain boundary scattering as the dominant mechanism for electronic mobility. © 2012 Elsevier B.V. All rights reserved.

Use of conventional electrochemical techniques to produce crystalline FeRh alloys induced by Ag seed layer

By combining galvanic displacement and electrodeposition techniques, an ordered Fe20Rh80 structure deposited onto brass was investigated by X-ray diffractometry, Mössbauer spectroscopy and magnetization measurements. Mössbauer and X-ray diffraction analyses suggest that the Fe-Rh alloy directly electrodeposited onto brass displays a nanocrystalline state while a similar alloy deposited onto Ag/brass shows a faced centered cubic-like structure, with dendrites-like features. These results directly indicate that the presence of Ag seed layer is responsible for the Fe-Rh alloy crystallization process. In addition, room temperature Mössbauer data indicate firstly paramagnetic states for two Fe-species. In the dominant Fe-species (major fraction of the Mössbauer spectra), Fe atoms are situated at a cubic environment and it can be attributed to the γ-Fe20Rh80 alloy based on their hyperfine parameters. In the second species, Fe atoms are placed in a non-local symmetry, which can be related to Fe atoms at the grain boundaries or/and Fe small clusters. These Fe-clusters are in superparamagnetic state at room temperature, but they may be ordered below 45 K, as suggested by magnetization data. © 2013 Elsevier B.V. All rights reserved.

Effect of yttrium doping in barium zirconium titanate ceramics: A structural, impedance, modulus spectroscopy study

In the current article, we studied the effect of yttrium [Y3+] ions' substitution on the structure and electric behavior of barium zirconate titanate (BZT) ceramics with a general formula [Ba1-x Y 2x/3](Zr0.25Ti0.75)O3 (BYZT) with [x = 0, 0.025, 0.05] which were prepared by the solid-state reaction method. X-ray diffraction patterns indicate that these ceramics have a single phase with a perovskite-type cubic structure. Rietveld refinement data confirmed [BaO 12], [ZrO6], [TiO6], [YO6] clusters in the cubic lattice. The Y3+ ions' effects on the electric conductivity behavior of BZT ceramics as a function of temperature and frequency are described, which are based on impedance spectroscopy analyses. The complex impedance plots display a double semicircle which highlights the influences of grain and grain boundary on the ceramics. Impedance analyses showed that the resistance decreased with the increasing temperature and resulted in a negative temperature coefficient of the resistance property in all compositions. Modulus plots represent a non-Debye-type dielectric relaxation which is related to the grain and grain boundary as well as temperature-dependent electric relaxation phenomenon and an enhancement in the mobility barrier by Y3+ ions. Moreover, the electric conductivity increases with the replacement of Ba 2+ by Y3+ ions may be due to the rise in oxygen vacancies. © 2013 The Minerals, Metals & Materials Society and ASM International.

Estudo de propriedades anelásticas de MgB2

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Influência do óxido de cromo nas propriedades varistoras do óxido de estanho

Pós-graduação em Química - IQ