Kinetic features of ethylene polymerization over supported catalysts [2,6‐bis(imino)pyridyl iron dichloride/magnesium dichloride] with AlR3 as an activator

The effects of polymerization temperature, polymerization time, ethylene and hydrogen concentration, and effect of comonomers (hexene‐1, propylene) on the activity of supported catalyst of composition LFeCl₂/MgCl₂‐Al(i‐Bu)₃ (L = 2,6‐bis[1‐(2,6‐dimethylphenylimino)ethyl] pyridyl) and polymer characteristics (molecular weight (MW), molecular‐weight distribution (MWD), molecular structure) have been studied. Effective activation energy of ethylene polymerization over LFeCl₂/MgCl₂‐Al(i‐Bu)₃ has a value typical of supported Ziegler–Natta catalysts (11.9 kcal/mol). The polymerization reaction is of the first order with respect to monomer at the ethylene concentration >0.2 mol/L. Addition of small amounts of hydrogen (9–17%) significantly increases the activity; however, further increase in hydrogen concentration decreases the activity. The IRS and DSC analysis of PE indicates that catalyst LFeCl₂/MgCl₂‐Al(i‐Bu)₃ has a very low copolymerizing ability toward propylene and hexene‐1. MW and MWD of PE produced over these catalysts depend on the polymerization time, ethylene and hexene‐1 concentration. The activation effect of hydrogen and other kinetic features of ethylene polymerization over supported catalysts based on the Fe (II) complexes are discussed. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 5057–5066, 2007     

Protection of iron corrosion by stearic acid and stearic imidazoline self-assembled monolayers

A type of stearic imidazoline (IM) inhibitor was prepared using stearic acid (SA) and diethylenetriamine (DETA) as raw materials. The monolayers of IM and SA were assembled on the iron surface. The electrochemical characterization of stearic acid (SA) and stearic imidazoline (IM) on an oxide free iron surface had been studied. The monolayers of IM inhibitor were characterized by electrochemical impedance spectroscopy (EIS), electrochemical polarization curves, double layer capacitance, X-ray photoelectron spectroscopy (XPS) and molecular simulation. The results of electrochemical studies had illustrated that the inhibition efficiency of IM was higher than SA. XPS showed that the IM molecules adsorbed on the iron surface. The molecular simulation calculations showed that the IM molecules were tilted at an angle on the iron surface.     

Slow positron beam study of corrosion-related defects in pure iron

Corrosion-related defects of pure iron were investigated by measuring Doppler broadening energy spectra (DBES) of positron annihilation and positron annihilation lifetime (PAL). Defect profiles of the S-parameter from DBES as a function of positron incident energy up to 30 keV (i.e. ∼1 μm depth) were analyzed. The DBES data show that S-parameter increases as a function of positron incident energy (mean depth) after corrosion, and the increase in the S-parameter is larger near the surface than in the bulk due to corrosion. Furthermore, information on defect size from PAL data as a function of positron incident energy up to 10 keV (i.e. ∼0.2 μm depth) was analyzed. In the two-state trapping model, the lifetime τ₂ = 500 ps is ascribed to annihilation of positrons in voids with a size of the order of nanometer. τ₁, which decreases with depth from the surface to the bulk, is ascribed to the annihilation of positrons in dislocations and three-dimensional vacancy clusters. The corroded samples show a significant increase in τ₁ and the intensity I₂, and near the surface the corroded iron introduces both voids and large-size three-dimensional vacancy clusters. The size of vacancy clusters decreases with depth.     

Electrophoretic study of the effect of ultradisperse iron powder on cotton seed proteins

The protein composition of seeds treated with a suspension of ultradisperse iron was studied using electrophoresis on PAAG. Changes were noted in the fractions with relative electrophoretic mobility (REM) 0.11 of water-soluble and REM 0.37 of buffer-soluble An-9 cotton seed proteins. __________ Translated from Khimiya Prirodnykh Soedinenii, No. 4, pp. 384–385, July–August, 2006.     

The dehydration of copper(II) acetate monohydrate

The thermal dehydration of copper(II) acetate hydrate has been studied between 353 and 406 K, over a range of humidities. The dehydration is controlled by nucleation-and-growth kinetics at low temperatures, with an activation energy of 154 kJ·mol⁻¹, which changes to contracting-disc kinetics at higher temperatures with a lower activation energy of 76 kJ·mol⁻¹. Frequency factors have also been derived; the value for the high temperature process is low (10⁷s⁻¹) and that for the low temperature step is high (10¹⁷s⁻¹). Optical microscopy has been used to clarify the bulk kinetics; there is evidence for a reactive layer at the surface of the decomposing solid. In celebration of the 60^th birthday of Dr Andrew K. Galwey     

Surface-enhanced Raman scattering study of polymer on metals. III. Chemisorbed polybenzimidazole and its corrosion-inhibiting properties at high temperature

Chemisorption of polybenzimidazole on silver and copper etched with nitric acid has been observed by surface-enhanced Raman scattering (SERS). The polymer is found to react chemically with silver, forming a complexed film on the surface. The SERS spectra show that polybenzimidazole film inhibits oxidation of the metal at high temperature, unlike chemisorbed benzimidazole, benzotriazole, and poly(4-vinyl pyridine). © 1992 John Wiley & Sons, Inc.     

Influence of poly(aminoquinone) on corrosion inhibition of iron in acid media

The inhibitor performance of chemically synthesized water soluble poly(aminoquinone) (PAQ) on iron corrosion in 0.5 M sulphuric acid was studied in relation to inhibitor concentration using potentiodynamic polarization and electrochemical impedance spectroscopy measurements. On comparing the inhibition performance of PAQ with that of the monomer o-phenylenediamine (OPD), the OPD gave an efficiency of 80% for 1000 ppm while it was 90% for 100 ppm of PAQ. PAQ was found to be a mixed inhibitor. Besides, PAQ was able to improve the passivation tendency of iron in 0.5 M H₂SO₄ markedly.     

Matrix-Untersuchungen zu monomerem Kupfer(I)-chlorid und seinen Komplexen mit N2 und PN IR-spektroskopische Nachweise und ab-initio Rechnungen

Matrix-Investigations on Monomeric Copper(I) Chloride and its Complexes with N₂ and PN Ligands. IR Spectroscopic Results and ab-initio Calculation In solid argon the reaction of monomeric CuCl with N₂ yields ClCuN₂. On the basis of two absorptions in the ir-spectrum and their corresponding isotopic shifts (_14/15N) and with the help of a normal coordinate analysis, linearity of the molecule has been deduced. These results are confirmed by large scale ab-initio Calculations (CPF, MP2). Reaction of monomeric CuCl with molecular PN under matrix condition is shown to give rise to new absorptions in the IR spectrum which arev assigned to a linear molecule ClCuNP.     

甲基百里(香)酚蓝新负载树脂的特 性及应用

本文以金属指示剂甲基百里(香)酚蓝作为鳌合剂制得具有相应鳌合基团的负载树脂.研究了该树脂的某些分析特性及其在富集天然水中微量铜、钻、镍、锌中的应用.     

Sulfur adsorption on Fe(1 1 0): a DFT study

The adsorption of atomic S on the Fe(1 1 0) surface is examined using density functional theory (DFT). Three different adsorption sites are considered, including the atop, hollow and bridge sites and the S is adsorbed at a quarter monolayer coverage in a p(2 × 2) arrangement. The hollow site is found to be the most stable, followed by the bridge and atop sites. At all three sites, S adsorption results in relatively minor surface reconstruction, with the most significant being that for the hollow site, with lateral displacements of 0.09 Å. Comparisons between S-adsorbed and pure Fe surfaces revealed reductions in the magnetic moments of surface-layer Fe atoms in the vicinity of the S. At the hollow site, the presence of S causes an increase in the surface Fe d-orbital density of states between 4 and 5 eV. However, S adsorption has no significant effect on the structure and magnetic properties of the lower substrate layers.