Investigation of phase transition in ferroelectric Pb0.70Sr0.30TiO3 thin films

We have carried out dielectric and Raman spectroscopy studies at the 298-623 K temperature range in polycrystalline Pb0.70Sr0.30TiO3 thin films grown by a soft chemical method. The diffuse phase-transition behavior of the thin films was observed by means of the dielectric constant versus temperature curves, which show a broad peak. Such behavior was confirmed later by Raman spectroscopy measurements up to 823 K, indicating that a diffuselike phase transition takes place at around 548-573 K. The damping factor of the E(1TO) soft mode was calculated using the damped simple harmonic oscillator model. on the other hand, Raman modes persist above the tetragonal to cubic phase transition temperature although all optical modes should be Raman inactive. The origin of these modes was interpreted in terms of a breakdown of the microscopic local cubic symmetry by chemical disorder. The lack of a well-defined transition temperature and the presence of broad bands at some temperature interval above the ferroelectric-paraelectric phase-transition temperature suggested a diffuse nature of the phase transition. This result corroborates the dielectric constant versus temperature data, which showed a broad ferroelectric phase transition in this thin film. (C) 2004 American Institute of Physics.

Absence of relaxor-like ferroelectric phase transition in (Pb,Sr)TiO3 thin films

We have performed dielectric and micro-Raman spectroscopy measurements in the 298 - 673 K temperature range in polycrystalline Pb0.50Sr0.50TiO3 thin films prepared by a soft chemical method. The phase transition have been investigated by dielectric measurements at various frequencies during the heating cycle. It was found that the temperature corresponding to the peak value of the dielectric constant is frequency-independent, indicating a non-relaxor ferroelectric behavior. However, the dielectric constant versus temperature curves associated with the ferroelectric to paraelectric phase transition showed a broad maximum peak at around 433 K. The observed behavior is explained in terms of a diffuse phase transition. The obtained Raman spectra indicate the presence of a local symmetry disorder, due to a higher strontium concentration in the host lattice. The monitoring of some modes, conducted in the Pb0.50Sr0.50TiO3 thin films, showed that the ferroelectric tetragonal phase undergoes a transition to the paraelectric cubic phase at around 423 K. However, the Raman activity did not disappear, as would be expected from a transition to the cubic paraelectric phase. The strong Raman spectrum observed for this cubic phase is indicative that a diffuse-type phase transition is taking place. This behavior is attributed to distortions of the perovskite structure, allowing the persistence of low-symmetry phase features in cubic phase high above the transition temperature. This result is in contrast to the forbidden first-order Raman spectrum, which would be expected from a cubic paraelectric phase, such as the one observed at high temperature in pure PbTiO3 perovskite.

Oxygen stoichiometry effects in spinel-type NiMn2O4-delta samples

We report the effects of oxygen stoichiometry in the structure and magnetic response of spinel-type NiMn2O4-delta polycrystalline samples controlled by heat-treatments in different atmospheric conditions.The post-annealed samples were analyzed by Scanning Electron Microscopy associated to X-ray Energy Dispersion Spectrometry, X-ray Photoelectron Spectroscopy and AC/DC magnetic measurements.Results indicate that the oxygen stoichiometry highly influences the magnetic interactions between the ferromagnetic, and antiferromagnetic sublattices in these compounds due to the presence of manganese in three possible valence states. (c) 2005 Elsevier Ltd. All rights reserved.

Detection of cracks in scratching tests in ceramic materials through acoustic emission

The mechanisms of material removal and the interactions among scratches performed in ceramic materials were investigated using acoustic emission signals, and scanning electron microscopy, in scratching experiments. Several testing conditions were used to produce different types of removing mechanism on a glass as well as on a polycrystalline alumina sample composed by heterogeneous grain size. It is known that the material removing process on a polycrystalline ceramic involves intergranular microfracture and grain dislodgement, unlike the chipping produced by the extension of lateral cracks in non-granular materials, such as glass. Distinct settings for velocities, loads, and two types of diamond indenter were tested. The material removal was carried out by three different methods of scratching: single passes, repeated overlapping passes, and parallel scratches. As a general result, there was a clear relationship between the acoustic emission signals and the damage intensity occurred in the material removal. More specifically, there were differences in the acoustic emission signal levels in the scratches made on the alumina and on the glass owing to the material removal mechanisms associated with the structure of these materials. A gradual increase in the acoustic emission levels was observed when the number of repeated passes was increased as a result of the damage accumulation process followed by severe material removal. It was also noticed that the acoustic emission signals were capable of reflecting the interactions between two parallel scratches.

Metamorphism and PGE-Au content of chromitite from the Ipanema mafic/ultramafic Complex, Minas Gerais, Brazil

The Santa Cruz massif, which forms part of the Ipanema mafic/ultramafic Complex, Minas Gerais, Brazil, has an exposed upward sequence of metadunite, metaharzburgite (including three separate chromitite layers), metapyroxenite, metagabbro, and metaanorthosite. Primary igneous chromite grains in the main chromitite layer are poikiloblastic and tectonically fragmented, and have a narrow (10-20 mum) margin of chromian spinel. Cataclased chromite fragments are extensively replaced and mantled by chromian spinel; they have a composite margin comprised of an inner zone of more aluminous spinel and an euhedral outer zone of more Cr-rich spinel, representing granulite and amphibolite facies metamorphic events, respectively. The contents of platinum-group elements (PGE) and Au in chromite separates are relatively high (Os 45, Ir 23, Ru 136, Rh 19, Pt 98, Pd 63, and Au 83 ppb), and significantly enriched (similar to 4x) over whole rock values. Platinum-group minerals are not observed and micrometre-sized inclusions of sulfide minerals (chalcopyrite and pentlandite) in relict chromite are rare. However, comparison of mineral proportions in the separated chromite and whole rock shows that the precious metals are hosted predominantly in the relict igneous chromite grains, rather than the secondary chromian spinel and primary and secondary Mg-rich silicates. The major element composition and average chondrite-normalized PGE pattern of the separated chromite correspond to S-poor stratiform chromitite. We suggest that the precious metals accumulated with chromite during crystallization of a S-poor magma, and were not remobilized in the relict chromite during the subsequent high grade metamorphism.

Preparation and properties of ferroelectric Pb1-xCaxTiO3 thin films produced by the polymeric precursor method

Pb1- xCaxTiO3 thin films with x = 0.24 composition were prepared by the polymeric precursor method on Pt/Ti/SiO2/Si substrates. The surface morphology and crystal structure, and the ferroelectric and dielectric properties of the films were investigated. X-ray diffraction patterns of the films revealed their polycrystalline nature. Scanning electron microscopy (SEM) and atomic force microscopy (AFM) analyses showed the surface of these thin films to be smooth, dense and crack-free with low surface roughness. The multilayer Pb1-xCaxTO3 thin films were granular in structure with a grain size of approximately 60-70 nm. The dielectric constant and dissipation factor were, respectively, 174 and 0.04 at a 1 kHz frequency. The 600-nm thick film showed a current density leakage in the order of 10(-7) A/cm(2) in an electric field of about 51 kV/cm. The C-V characteristics of perovskite thin films showed normal ferroelectric behavior. The remanent polarization and coercive field for the deposited films were 15 muC/cm(2) and 150 kV/cm, respectively. (C) 2001 Kluwer Academic Publishers.

Microstructural investigation of the PZT films prepared from the suspension of nanocrystalline powders

PZT thin films of composition Pb(Zr0.52Ti0.48)O-3 were prepared by a novel method from the suspension of nanocrystalline PZT powders. The powders were obtained by mechanochemical synthesis. Films were deposited on silicon (100) and platinum covered silicon substrates (Pt (111) /Ti/SiO2/Si) Using spin-on technique. Substrate type has influence on films crystallinity, orientation and can react with the films changing its phase composition. Films microstructure strongly depends on thermal treatment conditions due to phase and compositional changes of the films. (C) 2003 Elsevier Ltd. All rights reserved.

Stoichiometry unbalance and photoluminescence emission in Ga1-XAsX films prepared by flash evaporation

Both narrow and broad photoluminescence bands were observed in Ga1-XAsX films prepared by flash evaporation of polycrystalline GaAs containing native C impurities. The observed narrow crystalline-like bands are similar to band-to-band and C acceptor impurity emissions in crystalline GaAs. The narrow bands are evidence that the As excess favors the PL active GaAs crystallite formation in films deposited onto silicon (10 0) substrate, even when the As excess is very large (X = 0.84). This favoring is not observed in twin samples grown on silica glass substrates nor on Ga rich samples, indicating the important role of the combined effect of the As excess and Si substrate in the GaAs crystallite formation. The broad amorphous-like bands were observed in Ga rich and in moderately As rich samples. The photoluminescence emission is compared with the microstructure of the material as determined from the micro-Raman, absorption edge and reflectance measurements. The volume fraction of the crystallites formed is small and PL emission indicates that the crystallite electronic quality is much better than the ones formed heat treating films grown on silica glass substrates. (C) 2004 Elsevier B.V. All rights reserved.

Total secondary-electron yield of metals measured by a dynamic method

The secondary electron emission of dielectrics usually is measured by the pulse method, in which the dielectric is irradiated with short pulses of electrons. Attempts to use a dynamic method, in which the dielectric is irradiated continuously, have failed because the dielectric becomes charged and this charge interferes with the emission process. The dynamic method can, however, be applied to metals where volume charges are prevented. This article reports dynamic measurements of the total secondary emission yield from stainless steel, platinum, and aluminum and compares them with results from the current pulse method. In order to apply the dynamic method to metals a simple but important change in the setup was introduced: a dielectric slab was placed between the electrode and the metallic sample, which permitted the sample surface potential and therefore the energy of the incident electrons to change continuously. Unlike for dielectrics, the emission curves for metals are identical when obtained by the two methods. However, for a sample with deliberately oxidized surfaces the total secondary emission yield is smaller when measured with the dynamic method as compared with the pulse method, just as happens for dielectrics. (C) 2000 American Institute of Physics. [S0021-8979(00)03413-7].

Room-temperature photoluminescence in structurally disordered SrWO4

Intense and broad visible photoluminescent (PL) band in structurally disordered SrWO4 compounds was observed at room temperature. The polycrystalline scheelite strontium tungstate (SrWO4) samples prepared by the polymeric precursor method at different temperatures of annealing were structurally characterized by x-ray diffraction and Fourier transform Raman spectroscopy measurements. Quantum-mechanical calculations showed that the local disorder in the cluster of the network modifiers Sr has a very important role in the charge transfer. The experimental and theoretical results are in good agreement, indicating that the generation of the intense visible PL band can be related to short-range order-disorder degree in the scheelite structure. (c) 2006 American Institute of Physics.

Voltammetric determination of persulfate anions using an electrode modified with a Prussian blue film

Prussian blue [PB, iron(III) hexacyanoferrate(II)] films are effective for the electrocatalysis of the persulfate (peroxodisulfate)/sulfate redox system. This has been exploited in the voltammetric determination of persulfate anions using a PB-modified platinum disc electrode. A linear correlation between electrocatalytic current and persulfate concentration was found for the range 5 x 10(-5) to 3 x 10(-3) mol dm(-3), using 0.100 mol dm(-3) potassium chloride as supporting electrolyte at pH 4. This analytical method has the advantages of speed and ease of operation in relation to traditional titrimetric methods for persulfate determination. The applicability of the method to the determination of persulfate in a commercial hair bleaching 'booster' product is demonstrated. (C) 2000 Elsevier B.V. B.V. All rights reserved.

Microstructural and ferroelectric properties of PbZr1-xTi(x)O(3) thin films prepared by the polymeric precursor method

The polymeric precursor method was employed in the preparation of PZT thin films on Pt(111)Ti/SiO2/Si(100) substrates. X-ray diffraction patterns revealed the polycrystalline nature of the PZT (53:47) thin films, which had a granular structure and a grain size of approximately 70 nm. A 350-nm thick film was obtained by running three cycles of the dip-coating/heating process. Atomic force microscopy (AFM) analyses showed the surface of these thin films to be smooth, dense and crack-free with low surface roughness (= 2.0 nm). The PZT (53:47) thin films annealed at 700 degreesC showed a well-saturated hysteresis loop. The C-V curves of perovskite thin film displayed normal ferroelectric behavior, while the remanent polarization (2P(r)) and coercive field (E-e) of the film deposited and measured at room temperature were 40 muC/cm(2) and 110 kV/cm, respectively. (C) 2001 Elsevier B.V. B.V. All rights reserved.

SrBi2Ta2O9 ferroelectric thick films prepared by electrophoretic deposition using aqueous suspension

SrBi2Ta2O9 ferroelectric thick films were prepared by electrophoretic deposition (EPD). For that, ceramic powders were prepared by chemical method in order to obtain compounds with chemical homogeneity. The polymeric precursor method was used for the synthesis of the SrBi2Ta2O9 powder. The crystallographic structure of the powder was examined by X-ray diffraction, and the surface area was determined by single point BET adsorption. The 0.03 vol.% suspension was formed by dispersing the powder in water using two different polymers as dispersants: an ester polyphosphate (C213) and an ammonium polyacrilate (Darvan 821-A). It was investigated the influence of the different dispersants in the surface properties of the powder by zeta potential measurements. The films were deposited on platinum-coated alumina and Pt/Ti/SiO2/Si substrates by a 4 mA constant current, for 10 min, using two parallel electrodes placed at a separation distance of 3 min in the suspension. Several cycles of deposition-drying of the deposit were carried out until reaching the desired thickness. After thermal treatment at temperatures ranging from 700 to 1000 degreesC, the films were characterized by X-ray diffraction and scanning electron microscopy for the microstructure observation. (C) 2003 Elsevier Ltd. All rights reserved.

High Curie point CaBi2Nb2O9 thin films: A potential candidate for lead-free thin-film piezoelectrics

CaBi2Nb2O9 (CBNO) thin films deposited on platinum coated silicon substrates by the polymeric precursor method exhibited good structural, dielectric, and piezoelectric characteristics. Capacitance-voltage measurements indicated good ferroelectric polarization switching characteristics. Remanent polarization and drive voltage values were 4.2 mu C/cm(2) and 1.7 V for a maximum applied voltage of 10 V. The film has a piezoelectric coefficient d(33) equal to 60 pm/V, current density of 0.7 mu A/cm(2), and Curie temperature of 940 degrees C. The polar-axis-oriented CBNO is a promising candidate for use in lead-free high Curie point in ferroelectric and piezoelectric devices. (c) 2006 American Institute of Physics.

Renewable drops electrochemical sensor for sulfide ions detection

The design and characteristics of a novel electrochemical system, which uses a drop as a renewable electroanalytical sensor, are described. This article describes the performance of the electrochemical system, the coupling of the experimental arrangement with flow injection technique and a demonstration of its applicability for the measurement of sulfide. The method is based on renewable drops of ferricyanide ions, buffered by borate. The ferrocyanide ions, product of the reaction between ferricyanide and sulfide ions, are oxidized on a platinum microelectrode and the current measured is related to sulfide concentration. The measurements can be done in continuous or static flow mode. In continuous mode, the detection limit is 5.0 x 10(-5) mol L-1.