Electron spectroscopies and their use for materials characterization

We present here a general overview of electron spectroscopies from a practical point of view. The most frequently used ones are described and the type of structural information they can provide on materials is explained in relation to the physical processes on which they are based. Furthermore, we explore critically and in detail various tools that have been developed to allow a systematic solving of structures by these spectroscopies.     

Oxidation of oleuropein studied by EPR and spectrophotometry

The autoxidation at alkaline pH and enzymatic oxidation by mushroom tyrosinase of oleuropein, the dominant biophenol present in the fruits and leaves of Olea europea, was followed by both electron paramagnetic resonance (EPR) and absorption spectroscopy. For comparison, the same oxidation processes were applied to 4‐methylcatechol, a simple polyphenol present in olive mill wastewaters. EPR spectra of stable o‐semiquinone radicals produced during autoxidation at pH 12 and short‐lived o‐semiquinone free radicals produced during autoxidation at pH 9.0 or tyrosinase action and stabilized by chelation with a diamagnetic metal ion (Mg²⁺) were recorded for both polyphenols, and the corresponding hyperfine splitting constants were determined. The UV‐Vis spectral characteristics of the oxidation of polyphenols were highly dependent on the type of polyphenol, oxidant type and the pH of the reaction. The kinetic behavior of tyrosinase in the presence of oleuropein and 4‐methylcatechol was followed by recording spectral changes at 400 nm (absorption maximum) over time. The tysosinase activity with oleuropein showed a pronounced pH optimum at pH 6.5 and a minor one around pH 8. From the data analysis of the initial rate at pH 6.5, the kinetic parameters K_m = 0.34 ± 0.03 mM and V_max = 0.029 ± 0.002 ΔA₄₀₀ min^–1 were determined for oleuropein.     

Influence of the surface conditions on permeation in the deuterium–MANET system

The condition of the surfaces is of crucial importance for the deuterium permeation through materials. In this work a study of the surface constants for the adsorption (σk₁) and release (σk₂) of deuterium under different surface conditions on the martensitic steel DIN 1.4914 (MANET) has been carried out. The growth of an oxide surface layer (Cr₂O₃) of about 25–30 nm in a MANET sample, heat treated in an oxidizing environment, compared to the bare MANET that have a ‘natural' oxide of about 5 nm has provoked a reduction of both the permeation rate and the recombination coefficient (about 3 orders of magnitude). In addition, the permeation governing process has changed from diffusion-limited to surface-limited. The measurements of the permeation rate of deuterium were performed by a gas-phase permeation technique over the temperature range 574–746 K and for deuterium driving pressures in the range from 3 to 10⁵ Pa.     

金属表面柴油机油沉积物的反射红外光谱法研究

利用镜反射红外光谱法研究了ＣＣ级柴油机油中添加剂对成漆板板面漆膜组成的影响：考察了成漆板漆膜组成与Ｃａｔ．１Ｈ２活塞环台漆膜组成的相关性。试验结果对柴油机油的研制和应用有一定指导作用。     

Evaluation of different coating systems by electrochemical methods

Corrosion protection of organic coated steel is determined by free corrosion potential measurements and impedance spectroscopy. The results are classified by means of very basic considerations and evaluation figures are developed. These electrochemical data are correlated with the extent of the corrosion for each coating system. The evaluation figures are used for ranking coating systems and this ranking is correlated with the ranking with reference to the results of standardized and exposure tests.     

Electrochemical,FTIR and morphological study of polypyrrole—Polystyrenesulphonate conducting films

The electrochemical behaviour, FTIR spectrum and the morphology of polypyrrole-polystyrenesulphonate (PPy-PSS) films obtained potentiostatically at 0.6 V in a 0.05m Py + 1.7 × 10^?2m NaPSS medium have been analysed. Different electrochemical parameters have been modified in order to establish the first polaron formation, the reversibility of the redox process and the doping mechanism. The FTIR spectrum confirms the existence of C?O groups in the film structure and two possible explanations are suggested. SEM reveals a higher homogeneity in these films than in PPy films doped with smaller counterions.     

The origin of the band at 1462 cm−1 generally appearing upon desorption of pyridine from acidic solids. Steps towards a more comprehensive understanding

The pyridine adsorption-desorption method, followed by IR spectroscopy, is generally applied for acidity determination of solid catalysts. A peculiar band at 1462 cm^–1 was observed by several authors upon pyridine desorption at higher temperatures and was interpreted in various ways. A new complex between Lewis framework acid sites and pyridine is proposed and several evidences are reported.     

The Structure of the Irreversibly Bound Adhesion Promoter-Substrate Interfacial Layer of γ-Aminopropylsilanetriol on Crystalline Si, as Measured by XPS and FTIR

The irreversibly bound interfacial layer deposited by the γ-aminopropysilanetriol adhesion promoter onto a crystalline silicon substrate, which remains even after profuse washing, was found by XPS to have resulted from the fragmentation and rearrangement of the original γ-aminopropylsilanetriol molecule. A mechanism is proposed, involving the homolytic scission of the terminal N-C bond. One of the subsequent reactions is believed to involve hydrogen loss by abstraction and the formation of a terminal vinyl group, which bonds to the substrate. Support for this mechanism is found in IR spectroscopy of this layer.