Estudo da reação de modificação química da poliacrilonitrila com grupos 2-oxazolina

Neste trabalho a reação de modificação química da poliacrilonitrila pela incorporação de grupos 2-oxazolina foi estudada através da interação dos grupos nitrila do polímero com 2-amino-etanol catalisada por acetato de cádmio. Os copolímeros foram obtidos em diferentes condições reacionais para alcançar a reação de incorporação do heterocíclico preferencialmente à reação de ciclização dos grupos nitrila que ocorre na presença de catalisador. O grau de modificação química obtido foi relacionado às alterações nas propriedades dos polímeros modificados, que foram caracterizados por espectroscopias na região do infravermelho com transformada de Fourier, do ultravioleta-visível e de ressonância magnética nuclear de hidrogênio, e por calorimetria diferencial de varredura e termogravimetria. As condições ótimas de reação foram alcançadas a 70C após 35h. E o polímero obtido a partir destas condições foi avaliado como inibidor de corrosão para aço-carbono em solução de ácido clorídrico. Sob estas condições experimentais, uma eficiência de inibição de 63 % foi obtida

STUDY OF TI/LNP INTERFACE BY PES

The interface of Ti/InP(110) was studied by X-ray photoelectron spectroscopy (XPS) and ultraviolet photoelectron spectroscopy (UPS). It is evident that deposition of Ti on the surface of InP(110) at room temperature introduced a break of the In-P bond and a diffusion of In atoms into the Ti film. The interaction of Ti and P occurred at a temperature of 350-degrees-C.

Kinetics of dissociative water adsorption on stepped Si(001), on Si(115), Si(113), Si(5,5,12) and Si(112)

We present photoelectron spectroscopic and low energy electron diffraction measurements of water adsorption on flat Si samples of the orientations (001), (115), (113), (5,5,12) and (112) as well as on curved samples covering continuously the ranges (001)-(117) and (113)-(5,5,12)-(112). On all orientations, water adsorption is dissociative (OH and H) and non-destructive. On Si(001) the sticking coefficient S and the saturation coverage Theta(sat) are largest. On Si(001) and for small miscuts in the [110]-azimuth, S is constant nearly up to saturation which proves that the kinetics involves a weakly bound mobile precursor state. For (001)-vicinals with high miscut angles (9-13 degrees), the step structure breaks down, the precursor mobility is affected and the adsorption kinetics changed. On (115), (113), (5,5,12) and (112), the values of S and Theta(sat) are smaller which indicates that not all sites are able to dissociate and bind water. For (113) the shape of the adsorption curves Theta versus exposure shows the existence of two adsorption processes, one with mobile precursor kinetics and one with Langmuir-like kinetics. On (5,5,12), two processes with mobile precursor kinetics are observed which are ascribed to adsorption on different surface regions within the large surface unit cell. From the corresponding values of S and Theta(sat), data for structure models are deduced. (C) 1997 Elsevier Science B.V.

Chemisorption and reaction characteristics of methyl radicals on Cu(110)

Methyl radicals are generated by pyrolysis of azomethane, and the condition for achieving neat adsorption on Cu(110) is described for studying their chemisorption and reaction characteristics. The radical-surface system is examined by X-ray photoemission spectroscopy, ultraviolet photoemission spectroscopy, temperature-programmed desorption, low-energy electron diffraction (LEED), and high-resolution electron energy loss spectroscopy under ultrahigh vacuum conditions. It is observed that a small fraction of impinging CH3 radicals decompose into methylene possibly on surface defect sites. This type of CH2 radical has no apparent effect on CH3(ads) surface chemistry initiated by dehydrogenation to form active CH2(ads) followed by chain reactions to yield high-mass alkyl products. All thermal desorption products, such as H-2, CH4, C2H4, C2H6, and C3H6, are detected with a single desorption peak near 475 K. The product yields increase with surface coverage until saturation corresponding to 0.50 monolayer of CH3(ads). The mass distribution is, however, invariant with initial CH3(ads) coverage, and all desorbed species exhibit first-order reaction kinetics. LEED measurement reveals a c(2 x 2) adsorbate structure independent of the amount of gaseous exposure. This strongly suggests that the radicals aggregate into close-packed two-dimensional islands at any exposure. The islanding behavior can be correlated with the reaction kinetics and is deemed to be essential for the chain propagation reactions. Some relevant aspects of the CH3/Cu(111) system are also presented. The new results are compared with those of prior studies employing methyl halides as radical sources. Major differences are found in the product distribution and desorption kinetics, and these are attributed to the influence of surface halogen atoms present in those earlier investigations.

Facile synthesis of poly(o-phenylenediamine) microfibrils using cupric sulfate as the oxidant

A rapid, templateless, surfactantless approach is proposed to prepare microfibrils by simply mixing of aqueous cupric sulfate and o-phenylenediamine (oPD) solutions at room temperature. The as-prepared poly(o-phenylenediamine) (PoPD) microfibrils have been characterized by optical microscope, transmission electron microscope (TEM), X-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy (FTIR), ultraviolet-visible spectroscopy (UV-vis) and X-ray diffraction (XRD).

The role of molybdenum oxide as anode interfacial modification in the improvement of efficiency and stability in organic light-emitting diodes

It has been experimentally found that molybdenum oxide (MoO3) as the interfacial modification layer on indium-tin-oxide (ITO) in organic light-emitting diodes (OLEDs) significantly improves the efficiency and lifetime. In this paper, the role of MoO3 and MoO3 doped N,N '-di(naphthalene-1-yl)-N,N '-diphenyl-benzidine (NPB) as the interface modification layer on ITO in improvement of the efficiency and stability of OLEDs is investigated in detail by atomic force microscopy (AFM), polarized optical microscopy, transmission spectra, ultraviolet photoemission spectroscopy (UPS) and X-ray photoemission spectroscopy (XPS).

Electrostatic layer-by-layer a of platinum-loaded multiwall carbon nanotube multilayer: A tunable catalyst film for anodic methanol oxidation

A simple layer-by-layer (LBL) electrostatic adsorption technique was developed for deposition of films composed of alternating layers of positively charged poly(diallyldimethylammonium chloride) (PDDA) and negatively charged multiwall carbon nanotubes bearing platinum nanoparticles (Pt-CNTs). PDDA/Pt-CNT film structure and morphology up to six layers were characterized by scanning electron microscopy and ultraviolet-visible spectroscopy, showing the Pt-CNT layers to be porous and uniformly deposited within the multilayer films.

Efficient inverted top-emitting organic light-emitting diodes using ultrathin MoO3/C-60 bilayer structure to enhance hole injection

Efficient inverted top-emitting organic light-emitting diodes with aluminum (Al) as both the cathode and semitransparent anode are investigated. It is found that introduction of the ultrathin molybdenum trioxide (MoO3)/fullerene (C-60) bilayer structure between the low work function Al top anode and the hole-transporting layer dramatically enhances the device performance as compared to the devices with sole MoO3 or C-60 buffer layer. The ultraviolet photoemission spectroscopy and x-ray photoelectron spectroscopy indicate that the hole injection barrier between Al anode and hole-transporting layer is effectively reduced via strong dipole effect at Al/MoO3/C-60 interfaces with its direction pointing from Al to C-60.

Origin of improvement in device performance via the modification role of cesium hydroxide doped tris(8-hydroxyquinoline) aluminum interfacial layer on ITO cathode in inverted bottom-emission organic light-emitting diodes

It has been found that cesium hydroxide (CsOH) doped tris(8-hydroxyquinoline) aluminum (Alq(3)) as an interfacial modification layer on indium-tin-oxide (ITO) is an effective cathode structure in inverted bottom-emission organic light-emitting diodes (IBOLEDs). The efficiency and high temperature stability of IBOLEDs with CsOH:Alq(3) interfacial layer are greatly improved with respect to the IBOLEDs with the case of Cs2CO3:Alq(3). Herein, we have studied the origin of the improvement in efficiency and high temperature stability via the modification role of CsOH:Alq(3) interfacial layer on ITO cathode in IBOLEDs by various characterization methods, including atomic force microscopy (AFM), ultraviolet photoemission spectroscopy (UPS), X-ray photoemission spectroscopy (XPS) and capacitance versus voltage (C-V). The results clearly demonstrate that the CsOH:Alq(3) interfacial modification layer on ITO cathode not only enhances the stability of the cathode interface and electron-transporting layer above it. which are in favor of the improvement in device stability, but also reduces the electron injection barrier and increases the carrier density for current conduction, leading to higher efficiency.

Efficient top-emitting organic light-emitting diodes with a V2O5 modified silver anode

We fabricated efficient top-emitting organic light-emitting diodes (OLEDs) with silver (Ag) as an anode and samarium (Sm) as a semi-transparent cathode. The hole-injection barrier at the Ag anode/hole transporter interface is reduced by inserting a buffer layer of vanadium oxide (V2O5) between them. The ultraviolet photoelectron spectroscopy analysis shows that the hole-injection barrier is reduced by 0.5 eV. Both the V2O5 thickness and the organic layer thickness are optimized. The optimized device achieves a maximum current efficiency of 5.46 cd A(-1) and a power efficiency of 3.90 lm W-1, respectively.

Interfacial electronic structure of copper phthalocyanine and copper hexadecafluorophthalocyanine studied by photoemission

Electronic structures of the heterojunction between copper phthalocyanine (CuPc) and copper hexadecafluorophthalocyanine (F16CuPc) were studied with ultraviolet photoemission spectroscopy. Band bending and an interface dipole were observed at the interface due to the formation of an electron accumulation layer and a depletion layer in F16CuPc and CuPc, respectively. Such an energy level alignment leads to interesting ambipolar characteristics for application of the CuPc/F16CuPc junction in organic field-effect transistors.

Catalytic oxidization polymerization of aniline in an H2O2-Fe2+ system

Polyaniline is prepared by chemical polymerization of aniline in an acidic solution using H2O2 as an oxidant and ferrous chloride as a catalyst. A wide variety of synthesis parameters are studied, such as the amount of the catalyst, reaction temperature, reaction time, initial molar ratio of oxidant, monomer and catalyst, and aniline and HCl concentrations. The polymerization of aniline can be initiated by a very small amount of catalyst. The yield and the conductivity of product depend on the initial molar ratio of the oxidant and monomer. The polyaniline with a conductivity of about 10 degrees S/cm and a yield of 60% is prepared under optimum conditions. The process of polymerization was studied by in situ ultraviolet-visible spectroscopy and open-circuit potential technology. Compared to the polymerization process in a (NH4)(2)S2O8 system, the features of the H2O2-Fe2+ system are pointed out, and the chain growth mechanism is proposed. (C) 1999 John Wiley & Sons, Inc.

Coadsorption of nitric oxide and oxygen on the Ag(110) surface

The coadsorption of NO and O-2 on Ag(110) surface has been studied by X-ray photoelectron spectroscopy (XPS), ultraviolet photoelectron spectroscopy (UPS) and in situ Raman spectroscopy. The existence of oxygen enhances the adsorption of NO by forming the NOx species, that is, NO2 and NO3, and the NO in turn as a promotor facilitates the cleavage of the dioxygen bond, forming the surface atomic oxygen species having the same spectral characteristics as those produced using oxygen at high pressure. The oxygen species generated by the interaction is composed of two parts. One is produced directly by the decomposition of surface NO-O-2 complex at ca 625 K, which raised an O 1s feature at 530.5 eV and is absent at ca 800 K, while the another with an O 1s binding energy of 529.2 eV emerges at higher temperatures and shows similar properties as the reported gamma-state oxygen which bound tightly on restructured silver surface. The exposure to NO and O-2 causes noticeable changes in the morphology of the Ag(110) surface and the flat terraces superseded by small (ca 0.1 mu m) pits, and particles with typical diameters of a few micrometres were formed at elevated temperatures. (C) 1999 Elsevier Science B.V. All rights reserved.

Probing near-infrared photorelaxation pathways in eumelanins and pheomelanins.

Ultraviolet-visible spectroscopy readily discerns the two types of melanin pigments (eumelanin and pheomelanin), although fundamental details regarding the optical properties and pigment heterogeneity are more difficult to disentangle via analysis of the broad featureless absorption spectrum alone. We employed nonlinear transient absorption spectroscopy to study different melanin pigments at near-infrared wavelengths. Excited-state absorption, ground-state depletion, and stimulated emission signal contributions were distinguished for natural and synthetic eumelanins and pheomelanins. A starker contrast among the pigments is observed in the nonlinear excitation regime because they all exhibit distinct transient absorptive amplitudes, phase shifts, and nonexponential population dynamics spanning the femtosecond-nanosecond range. In this manner, different pigments within the pheomelanin subclass were distinguished in synthetic and human hair samples. These results highlight the potential of nonlinear spectroscopies to deliver an in situ analysis of natural melanins in tissue that are otherwise difficult to extract and purify.