Using an effective surface charge to explain surface potentials of Langmuir monolayers from dialkyldimethylammonium halides with the Gouy-Chapman theory

The use of an effective surface charge density has allowed the Gouy-Chapman (CC) theory to explain surface potential isotherms of Langmuir monolayers of dioctadecyldimethylammonium bromide (DODAB). The effective surface charge density of DODAB monolayer increases with the electronegativity of the counterions in the subphase. The pressure-area isotherms indicate a very condensed monolayer for DODAB spread on an I--containing subphase, which exhibits the lowest surface charge density, whereas the monolayer on a F-containing subphase is extremely expanded owing to the high surface charge density or electrostatic repulsion between headgroups. (C) 2001 Published by Elsevier B.V. B.V.

Influência dos defeitos cristalinos nas propriedades dielétricas e não-ôhmicas do 'CA' 'CU IND.3' 'TI IND.4' 'O IND.12'(CCTO)

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Surface potentials of corona-charged ferroelectric P(VDF-TrFE) copolymer samples

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Enhanced stabilization of aerosol-OT surfactant monolayer upon interaction with small amounts of bovine serum albumin at the air-water interface

An investigation is made of the influence from small amounts of the protein bovine serum albumin (BSA) on the lateral organization of low molecular weight surfactant sodium bis-2-ethylhexyl sulfosuccinate (AOT) at the air-water interface. Surface pressure (pi - A), surface potential (DeltaV - A) and Brewster angle microscopy (BAM) experiments were carried out, with particular emphasis on the monolayer stability under successive compression-expansion cycles. AOT monolayer is not stable at the air-water interface, which means that the majority of AOT molecules go into the aqueous subphase as monomers and/or normal micelles. When a waiting time elapses between spreading and compression, the surfactant monolayer tends to reorganize partially at the air-water interface, with a monolayer expansion being observed for waiting times as large as 12 h. The incorporation of very small amount of BSA (10(-9) M) at the interface, also inferred from BAM, increases the monolayer stability as revealed by pi - A and DeltaV - A results. For a waiting time of circa 3 h, the mixed monolayer reaches its maximum stability. This must be related to protein (and/or protein-surfactant complexes) adsorbed onto the AOT monolayer, thus altering the BSA conformation to accommodate its hydrophobic/hydrophilic residues. Furthermore, the effects from such small amounts of BSA in the monolayer formation and stabilization mean that the AOT monolayer responds cooperatively to BSA. (C) 2004 Elsevier B.V. All rights reserved.

Synthesis of poly(styrene-co-methyl methacrylate)-based ionomers and their Langmuir and Langmuir-Blodgett (LB) film formation

Poly(styrene-co-methyl methacrylate) (PS-PMMA) ionomers with several degrees of sulfonation were synthesized and characterized by infrared, UV-vis, and NMR spectroscopies, elemental analysis, and differential scanning calorimetry (DSC). Stable Langmuir films could be produced with PS-PMMA with 3 and 6 mol % of sulfonation, while PS-PMMA 8% exhibited material loss to the water subphase, probably due to its higher solubility. Surface pressure and surface potential isotherms with PS-PMMA 3% spread onto salt-containing subphases pointed to a film behavior characteristic of the polyelectrolyte effect, where charge repulsion governs the film properties. The Langmuir-Blodgett films of this ionomer were successfully transferred onto various substrates, as confirmed by UV-vis and FTIR spectroscopies. Using cycling voltammetry, we show that LB films from PS-PMMA 3% can be applied in selective sensing of dopamine, even in the presence of interferents such as ascorbic acid.

Langmuir and Langmuir-Blodgett (LB) films of tetrapyridyl metalloporphyrins

We report on the formation of Langmuir films of 5,10,15,20-tetra(4-pyridyl) 21H,23H-porphine,hereafter named tetrapyridyl porphyrins with distinct central ions (2H(+), Zn(2+), Cu(2+), Ni(2+)). The films were characterized with surface pressure and surface potential isotherms and in situ UV-vis absorbance. The measurements indicated strong aggregation of porphyrin monomers at the air-water interface, with a red shift of the Soret band in comparison with the spectrum obtained from CHCl(3) solutions. The shift was larger for the non-substituted H(2)TPyP, and depended on the metal ion. Significantly, aggregation occurred right after spreading of the Langmuir film, with on further shifts in the UV-vis spectra upon compression of the film, or even after transferring them onto solid substrates in the form of Langmuir-Blodgett (LB) films. The buildup of LB films from H(2)TPyP and ZnTPyP was monitored with UV-vis spectroscopy, indicating an equal amount of material deposited in each deposition step. Using FTIR in the transmission and reflection modes, we inferred that the H(2)TPyP molecules exhibit no preferential orientation in the LB films, while for ZnTPyP there is preferential orientation, with the porphyrin molecules anchored to the substrate by the lateral pyridyl groups. (C) 2008 Elsevier B.V. All rights reserved.

Técnicas de caracterização para investigar interações no nível molecular em filmes de Langmuir e Langmuir-Blodgett (LB)

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Periodic study on the structural and electronic properties of bulk, oxidized and reduced SnO2(110) surfaces and the interaction with O-2

The structural and electronic properties of bulk and both oxidized and reduced SnO2(110) surfaces as well as the adsorption process of O-2 on the reduced surface have been investigated by periodic DFT calculations at B3LYP level. The lattice parameters, charge distribution, density of states and band structure are reported for the bulk and surfaces. Surface relaxation effects have been explicitly taken into account by optimizing slab models of nine and seven atomic layers representing the oxidized and reduced surfaces, respectively. The conductivity behavior of the reduced SnO2(110) surface is explained by a distribution of the electrons in the electronic states in the band gap induced by oxygen vacancies. Three types of adsorption approaches of O-2 on the four-fold tin at the reduced SuO(2)(110) surface have been considered. The most exothermic channel corresponds to the adsorption of O-2 parallel to the surface and to the four-fold tin row, and it is believed to be associated with the formation of a peroxo O-2(2-) species. The chemisorption of O-2 on reduced SnO2(110) surface causes a significant depopulation of states along the band gap and it is shown to trap the electrons in the chemisorbed complex producing an electron-depleted space-charge layer in the inner surface region of the material in agreement with some experimental evidences. (C) 2002 Elsevier B.V. B.V. All rights reserved.

Colloidal particles: Spherical yttrium iron garnet

The purpose of this work is to obtain spherical particles YIG from micrometric to nanometric scales. The spherical particles were obtained from cation hydrolysis in acid medium by adding urea or ammonia in order to carry out a homogeneous nucleation process up to 90 degrees C. Different composition and morphology were achieved by changing reactant concentrations, precipitation agent and stabilizing agent. X-ray diffractometry, electrophoretic mobility, transmission and scanning electron microscopies were carried out on these particles to investigate the phase identification, mobility, morphology and particle size. Crystalline YIG, with spherical characteristics, was obtained. The surface potential presented different characteristics for different dispersion media.

Water at interfaces and its influence on the electrical properties of adsorbed films

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Langmuir and langmuir-blodgett films of polyfluorenes and their use in polymer light-emitting diodes

The Langmuir and Langmuir-Blodgett (LB) film properties of two polyfluorene derivatives, namely poly(2,7-9,9'-dihexylfluorene-dyil) (PDHF) and poly(9,9 dihexylfluorene-dyil-vynilene-alt-1,4-phenylene-vyninele) (PDHF-PV), are reported. Surface pressure (Pi-A) and surface potential (Delta V-A) isotherms indicated that PDHF-PV forms true monolayers at the air/water interface, but PDHF does not. LB films could be transferred onto various types of substrate for both PDHF and PDHF-PV. Only the LB films from PDHF-PV could withstand deposition of a layer of evaporated metal to form a light-emitting diode (PLED), which had typical rectifying characteristics and emitted blue light. It is inferred that the ability of the polymer to form true monomolecular layers at the air/water interface seems to be associated with the viability of the LB films in PLEDs.

Preparation, characterization and taste sensing properties of Langmuir-Blodgett Films from mixtures of polyaniline and a ruthenium complex

Langmuir-Blodgett (LB) films from a ruthenium complex, mer-[RuCl3(dppb)(py)] (dppb = PPh2(CH2)(4)PPh2; py = pyridine) (Rupy), and from mixtures with varied amounts of polyaniline (PANi) were fabricated. Molecular-level interactions between the two components are investigated by surface potential, dc conductivity and Raman spectroscopy measurements, particularly for the mixed film with 10% of Rupy. For the latter, the better miscibility led to an interaction with Rupy inducing a decrease in the conducting state of PANi, as observed in the Raman spectra and conductivity measurement. The interaction causes the final film properties to depend on the concentration of Rupy, and this was exploited to produce a sensor array made up of sensing units consisting of 11-layer LB films from pure PANi, pure Rupy and mixtures with 10 and 30% of Rupy. It is shown that the combination of only four non-specific sensing units allows one to distinguish the basic tastes detected by biological systems, viz. saltiness, sweetness, sourness and bitterness, at the muM level. (C) 2003 Elsevier B.V. Ltd. 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].

Structural and electronic properties of PbTiO3 slabs: a DFT periodic study

Structural and electronic properties of the bulk and relaxed surfaces (TiO2 and PbO terminated) of cubic PbTiO3 are investigated by means of periodic quantum-mechanical calculations based on density functional theory. It is observed that the difference in surface energies is small and relaxations effects are most prominent for Ti and Ph surface atoms. The electronic structure shows a splitting of the lowest conduction bands for the TiO2 terminated surface and of the highest valence bands for the PbO terminated slab. The calculated indirect band gap is: 3.18, 2.99 and 3.03 eV for bulk, TiO2 and PbO terminations, respectively. The electron density maps show that the Ti-O bond has a partial covalent character, whereas the Pb-O bonds present a very low covalency. (C) 2004 Elsevier B.V. All rights reserved.

MEASURING HYSTERESIS LOOPS OF FERROELECTRIC POLYMERS USING THE CONSTANT CHARGING CURRENT CORONA TRIODE

A novel method is proposed for measuring the hysteresis loops of ferroelectric polymers. The samples need to have only one electrode and are poled by corona discharge in a constant current corona triode. It is shown how the sample surface potential and the charging current are related to the remanent polarization and coercive field, so that the hysteresis loops can be obtained. An illustrative example is given for samples of beta-PVDF for which the hysteresis cycles were remarkably close to those obtained with the traditional Sawyer-Tower circuit. Values of 80 MV/m and 70 mC/m2 were estimated for the coercive field and remanent polarization, respectively.