Study of Ti-modified columbite route and the effect of lithium doping in 0.9PMN-0.1PT ceramics

The influence of lithium on the structural characteristics of PMN-PT ceramic was studied. The synthesis of PMN-PT powders using this precursor leads to the formation of high amount of perovskite phase. The insertion of Li(+) ions in B-site affects the microstructure because the rise in mass transport changes the mechanical characteristics of sintered ceramic. Higher values of K(m) and T(m) were gotten when lithium is inserted into perovskite phase. Secondary phase was found when lithium content increase beyond 1 mol%, besides the occurrence of transgranular fractures in sintered ceramic. Also, the additive acts increasing the relaxor behavior.

Wet-chemical synthesis of magnesium niobate nanoparticles powders

Nanosized and highly reactive magnesium mobate (MgNb2O6) powders were successfully synthesized by a new wet-chemical method by means of the dissolution of Nb2O5 center dot 5H(2)O and in a solution of oxalic acid followed by the addition of stoichiometric amounts of magnesium carbonate. The Nb-Mg-oxalic acid solution was evaporated resulting in a dry and amorphous powder that was calcined in the temperature range from 200 to 900 degrees C for 2 h. The crystallization process from the amorphous state to the crystalline MgNb2O6 was followed by thermal analysis. The calcined powders characterized by FT-Raman spectroscopy, X-ray diffraction (XRD) and their morphology examined by high resolution scanning electron microscopy (HR-SEM). Pure MgNb2O6, free from the second phases and obtained at 800 degrees C was confirmed by a combined analysis using XRD and FT-Raman. The average diameter of the particles was calculated from the HR-SEM image as 70 urn approximately. This technique allows a better mixing of the constituent elements and thus a better reactivity of the mixture to obtain pre-reaction products with high purity at lower temperatures and reducing cost. It can offer a great advantage in the PMN-PT formation with respect to the solid-state synthesis. (c) 2006 Elsevier Ltd and Techna Group S.r.l. All rights reserved.

Synthesis and characterization of 0.9PMN-0.1PT powders by the use of a modified columbite precursor

The complex perovskite compound 0.9PbMg 1/3Nb 2/3O 3-0.1PbTiO 3 is one of the most promising relaxor ceramic because the addition of lead titanate increases T m, by about 5°C/mol% from intrinsic T m value for pure PMN (near -7 to -15°C). A Ti-modified columbite precursor was used to prepare PMN-PT powders containing single perovskite phase. This variation on columbite route includes Ti insertion in MgNb 2O 6 orthorhombic structure so that individual PT synthesis becomes unnecessary. Furthermore, effects of Li additive on columbite and PMN-PT structures were studied by XRD to verify the phase formation at each processing step. XRD data were also used for the structural refinement by Rietveld method. The additive acts increasing columbite powders crystallinity, and the amount of perovskite phase was insignificantly decreased by lithium addition. By SEM micrographs it was observed that Li presence in PMN-PT powders leads to the formation of rounded primary particles and for lmol% of additive, the grain size is not changed, different from when this concentration is enhanced to 2mol%.

Physical characterization of K-doped 0.9PMN-0.1PT synthesized by an association of the columbite route and the polymeric precursor method

The solid solution 0.9PbMg 1/3Nb 2/3O 3-0.1PbTiO 3 is one of the most widely investigated relaxor ceramic, because of its high dielectric constant and low sintering temperatures. PMN-PT powders containing single perovskite phase were prepared by using a Timodified columbite precursor obtained by the polymeric precursor method. Such precursor reacts directly with stoichiometric amount of PbO to obtain pyrochlore-free PMN-PT powders. The structural effects of K additive included in the columbite precursor and 0.9PMN-0.1PT powders were also studied. The phase formation at each processing step was verified by XRD analysis, being these results used for the structural refinement by the Rietveld method. It was verified the addition of K in the columbite precursor promotes a slight increasing in the powder crystallinity. There was not a decrease in the amount of perovskite phase PMN-PT for 1mol% of K, and the particle and grain size were reduced, making this additive a powerful tool for grain size control.

Charge induced enhancement of adsorption for hydrogen storage materials

The rising concerns about environmental pollution and global warming have facilitated research interest in hydrogen energy as an alternative energy source. To apply hydrogen for transportations, several issues have to be solved, within which hydrogen storage is the most critical problem. Lots of materials and devices have been developed; however, none is able to meet the DOE storage target. The primary issue for hydrogen physisorption is a weak interaction between hydrogen and the surface of solid materials, resulting negligible adsorption at room temperature. To solve this issue, there is a need to increase the interaction between the hydrogen molecules and adsorbent surface. In this study, intrinsic electric dipole is investigated to enhance the adsorption energy. The results from the computer simulation of single ionic compounds with hydrogen molecules to form hydrogen clusters showed that electrical charge of substances plays an important role in generation of attractive interaction with hydrogen molecules. In order to further examine the effects of static interaction on hydrogen adsorption, activated carbon with a large surface area was impregnated with various ionic salts including LiCl, NaCl, KCl, KBr, and NiCl and their performance for hydrogen storage was evaluated by using a volumetric method. Corresponding computer simulations have been carried out by using DFT (Density Functional Theory) method combined with point charge arrays. Both experimental and computational results prove that the adsorption capacity of hydrogen and its interaction with the solid materials increased with electrical dipole moment. Besides the intrinsic dipole, an externally applied electric field could be another means to enhance hydrogen adsorption. Hydrogen adsorption under an applied electric field was examined by using porous nickel foil as electrodes. Electrical signals showed that adsorption capacity increased with the increasing of gas pressure and external electric voltage. Direct measurement of the amount of hydrogen adsorption was also carried out with porous nickel oxides and magnesium oxides using the piezoelectric material PMN-PT as the charge supplier due to the pressure. The adsorption enhancement from the PMN-PT generated charges is obvious at hydrogen pressure between 0 and 60 bars, where the hydrogen uptake is increased at about 35% for nickel oxide and 25% for magnesium oxide. Computer simulation reveals that under the external electric field, the electron cloud of hydrogen molecules is pulled over to the adsorbent site and can overlap with the adsorbent electrons, which in turn enhances the adsorption energy Experiments were also carried out to examine the effects of hydrogen spillover with charge induced enhancement. The results show that the overall storage capacity in nickel oxide increased remarkably by a factor of 4.

Metal-oxide film and photonic structures for integrated device applications

The application of photonic crystal technology on metal-oxide film is a very promising field for future optical telecommunication systems. Band gap and polarization effects in lithium niobate (LiNbO3) photonic crystals and bismuth-substituted iron garnets (BiYIG) photonic crystals are investigated in this work reported here. The design and fabrication process are similar for these two materials while the applications are different, involving Bragg filtering in lithium niobate and polarization rotation in nonreciprocal iron garnets. The research of photonic structures in LiNbO3 is of high interest for integrated device application due to its remarkable electro-optical characteristics. This work investigated the photonic band gap in high quality LiNbO3 single crystalline thin film by ion implantation to realize high efficiency narrow bandwidth filters. LiNbO3 thin film detachment by bonding is also demonstrated for optical device integration. One-dimensional Bragg BiYIG waveguides in gyrotropic system are found to have multiple stopbands and evince enhancement of polarization rotation efficiency. Previous photon trapping theory cannot explain the phenomena because of the presence of linear birefringence. This work is aimed at investigating the mechanism with the support of experiments. The results we obtained show that selective suppression of Bloch states in gyrotropic bandgaps is the key mechanism for the observed phenomena. Finally, the research of ferroelectric single crystal PMN-PT with ultra high piezoelectric coefficient as a biosensor is also reported. This work presents an investigation and results on higher sensitivity effects than conventional materials such as quartz and lithium niobate.

Non-Linear Dielectric Properties of PLMN-PT Relaxor Ferroelectrics

Recent investigations on the non-linear (NL) dielectric properties of relaxor ferroelectrics systems, not only as ceramic bodies, but also, in thin films, have showed a significant technological and scientific interest. The most common practical applications of relaxors include multilayer capacitors and actuators. In this work, non-linear dielectric properties of hot-pressed (1-x)[Pb1 -(3/2) yLayMg1/3Nb2/3O3]-xPbTiO3 (PLMN-PT) ferroelectric ceramics were investigated. The NL properties were obtained by using the measurements of the dielectric permittivity of the material as a function of the AC electric field with variable amplitude in the frequency and temperature range of 100 Hz-1 MHz and 50-450 K, respectively. An anomalous behavior of the non-linear dielectric response was observed when submitted to high electric fields levels. The obtained results were analyzed concerning one of the models for the dielectric response of relaxors ferroelectrics materials currently discussed in the literature.

Electronic And Structural Study Of Pt-modified Au Vicinal Surfaces: A Model System For Pt-au Catalysts.

Two single crystalline surfaces of Au vicinal to the (111) plane were modified with Pt and studied using scanning tunneling microscopy (STM) and X-ray photoemission spectroscopy (XPS) in ultra-high vacuum environment. The vicinal surfaces studied are Au(332) and Au(887) and different Pt coverage (θPt) were deposited on each surface. From STM images we determine that Pt deposits on both surfaces as nanoislands with heights ranging from 1 ML to 3 ML depending on θPt. On both surfaces the early growth of Pt ad-islands occurs at the lower part of the step edge, with Pt ad-atoms being incorporated into the steps in some cases. XPS results indicate that partial alloying of Pt occurs at the interface at room temperature and at all coverage, as suggested by the negative chemical shift of Pt 4f core line, indicating an upward shift of the d-band center of the alloyed Pt. Also, the existence of a segregated Pt phase especially at higher coverage is detected by XPS. Sample annealing indicates that the temperature rise promotes a further incorporation of Pt atoms into the Au substrate as supported by STM and XPS results. Additionally, the catalytic activity of different PtAu systems reported in the literature for some electrochemical reactions is discussed considering our findings.

Influence Of Substrate Steps On The Catalytic Properties Of Pt Layers: The Ethanol Electrooxidation Reaction.

The ethanol oxidation reaction (EOR) is investigated on Pt/Au(hkl) electrodes. The Au(hkl) single crystals used belong to the [n(111)x(110)] family of planes. Pt is deposited following the galvanic exchange of a previously deposited Cu monolayer using a Pt(2+) solution. Deposition is not epitaxial and the defects on the underlying Au(hkl) substrates are partially transferred to the Pt films. Moreover, an additional (100)-step-like defect is formed, probably as a result of the strain resulting from the Pt and Au lattice mismatch. Regarding the EOR, both vicinal Pt/Au(hkl) surfaces exhibit a behavior that differs from that expected for stepped Pt; for instance, the smaller the step density on the underlying Au substrate, the greater the ability to break the CC bond in the ethanol molecule, as determined by in situ Fourier transform infrared spectroscopy measurements. Also, we found that the acetic acid production is favored as the terrace width decreases, thus reflecting the inefficiency of the surface array to cleave the ethanol molecule.

Ethanol electrooxidation on Pt-Sn and Pt-Sn-W bulk alloys

Ethanol oxidation has been studied on Pt-Sn and Pt-Sn-W electrodes prepared in an arc-melting furnace. Different electrochemical techniques like cyclic voltammetry and chronoamperometry were used to evaluate the catalytic activity of these materials. The electro-oxidation process was also investigated by in situ infrared reflectance spectroscopy in order to determine adsorbed intermediates and reaction products. Experimental results indicated that Pt-Sn and Pt-Sn-W alloys are able to oxidize ethanol mainly to acetaldehyde and acetic acid. Adsorbed CO was also detected, demonstrating the viability of splitting the C-C bond in the ethanol molecule during the oxidation process. The adsorbed CO was further oxidized to CO2.This reaction product was clearly detected by SNIFTIRS. Pt-Sn-W catalyst showed a better electrochemical performance than Pt-Sn that, in it turn, is better than Pt-alone.

Density functional theory and ab initio molecular dynamics study of NO adsorption on Pd(111) and Pt(111) surfaces

The origin of the unique geometry for nitric oxide (NO) adsorption on Pd(111) and Pt(111) surfaces as well as the effect of temperature were studied by density functional theory calculations and ab initio molecular dynamics at finite temperature. We found that at low coverage, the adsorption geometry is determined by electronic interactions, depending sensitively on the adsorption sites and coverages, and the effect of temperature on geometries is significant. At coverage of 0.25 monolayer (ML), adsorbed NO at hollow sites prefer an upright configuration, while NO adsorbed at top sites prefer a tilting configuration. With increase in the coverage up to 0.50 ML, the enhanced steric repulsion lead to the tilting of hollow NO. We found that the tilting was enhanced by the thermal effects. At coverage of 0.75 ML with p(2 x 2)-3NO(fcc+hcp+top) structure, we found that there was no preferential orientation for tilted top NO. The interplay of the orbital hybridization, thermal effects, steric repulsion, and their effects on the adsorption geometries were highlighted at the end.

Influence of Poly(Vinyl Alcohol) (PVA) on the Cyclic-Voltammetry Behavior of Single-Crystal Pt Surfaces in Aqueous H(2)SO(4)

In the present work we investigated the electrochemical behavior of PVA on polycrystalline Pt and single-crystal Pt electrodes. PVA hampered the characteristic hydrogen UPD and anion adsorption on all investigated surfaces, with the processes on Pt(110) being the most affected by the PVA presence. Several oxidation waves appeared as the potential was swept in the positive direction and the Pt(111) was found to be the most active for the oxidation processes. (C) 2011 The Electrochemical Society. [DOI: 10.1149/1.3615965] All rights reserved.

Autocatalysis in the open circuit interaction of alcohol molecules with oxidized Pt surfaces

We studied the open circuit interaction of methanol and ethanol with oxidized platinum electrodes using in situ infrared spectroscopy. For methanol, it was found that formic acid is the main species formed in the initial region of the transient and that the steep decrease of the open circuit potential coincides with an explosive increase in the CO(2) production, which is followed by an increase in the coverage of adsorbed CO. For ethanol, acetaldehyde was the main product detected and only traces of dissolved CO(2) and adsorbed CO were found after the steep potential decay. In both cases, the transients were interpreted in terms of (a) the emergence of sub-surface oxygen in the beginning of the transient, where the oxide content is high, and (b) the autocatalytic production of free platinum sites for lower oxide content during the steep decay of the open circuit potential.

Electrochemical and spectroscopic studies of ethanol oxidation on Pt stepped surfaces modified by tin adatoms

Ethanol oxidation on platinum stepped surfaces vicinal to the (111) pole modified by tin has been studied to determine the role of this adatom in the oxidation mechanism. Tin has been slowly deposited so that the initial stages of the deposition take place on the step, and deposition on the terrace only occurs when the step has been completely decorated. Voltammetric and chronoamperometric experiments demonstrate that tin on the step catalyzes the oxidation. The maximum enhancement is found when the step is completely decorated by tin. FTIR experiments using normal and isotopically labeled ethanol have been used to elucidate the effect of the tin adatoms in the mechanism. The obtained results indicate that the role of tin is double: (i) when the surface has sites capable of breaking the C-C bond of the molecule, that is, when the step sites are not completely covered by tin, it promotes the oxidation of CO formed from the molecular fragments to CO(2) through a bifunctional mechanism and (ii) it catalyzes the oxidation of ethanol to acetic acid.

Reconstruction of core and surface nanoparticles: The example of Pt(55) and Au(55)

Cuboctahedron (CUB) and icosahedron (ICO) model structures are widely used in the study of transition-metal (TM) nanoparticles (NPs), however, it might not provide a reliable description for small TM NPs such as the Pt(55) and Au(55) systems in gas phase. In this work, we combined density-functional theory calculations with atomic configurations generated by the basin hopping Monte Carlo algorithm within the empirical Sutton-Chen embedded atom potential. We identified alternative lower energy configurations compared with the ICO and CUB model structures, e. g., our lowest energy structures are 5.22 eV (Pt(55)) and 2.01 eV (Au(55)) lower than ICO. The energy gain is obtained by the Pt and Au diffusion from the ICO core region to the NP surface, which is driven by surface compression (only 12 atoms) on the ICO core region. Therefore, in the lowest energy configurations, the core size reduces from 13 atoms (ICO, CUB) to about 9 atoms while the NP surface increases from 42 atoms (ICO, CUB) to about 46 atoms. The present mechanism can provide an improved atom-level understanding of small TM NPs reconstructions.