Polymer growth mode on the heterogeneous Ziegler–Natta catalyst: active sites at the bottom of the growing polymer layer

By alternating the supply of propylene and ethylene monomers, alternating polypropylene and polyethylene films were produced on one model Ziegler–Natta catalyst. This way, we could show that the active polymerization sites remain under the growing polymer films and thus the monomer molecules must transport through the growing polymer to the active sites. This revised version was published online in July 2006 with corrections to the Cover Date.     

Acid–base interactions and covalent bonding at a fiber–matrix interface: contribution to the work of adhesion and measured adhesion strength

The work of adhesion, W _A, and the practical adhesion in terms of the interfacial shear strength, τ, in some polymer-fiber systems were determined to establish a correlation between these quantities. An attempt was made to analyze the contributions of various interfacial interactions (van der Waals forces, acid-base interaction, covalent bonding) to the 'fundamental' and 'practical' adhesion. The surface free energies of the fibers were altered using different coupling agents. To characterize the strength of an adhesion contact, the ultimate adhesion strength, τ_ult, was determined for the onset of contact failure. The adhesion of non-polar polymers occurs through van der Waals interaction only; therefore, fiber sizing does not affect the adhesion strength. For polar polymers, such as poly(acrylonitrile butadiene styrene) and polystyrene, adhesion is sensitive to fiber treatments: suppression of the acid-base interaction by using an electron-donor sizing agent γ-aminopropyltriethoxysilane results in a decrease of both 'fundamental' and 'practical' adhesion. In the case of epoxy resins, the main contribution to the work of adhesion is made by covalent bonds. Since the process of their formation is irreversible, the work of adhesion determined from micromechanical tests seems to be more reliable than indirect estimations, such as from wetting and inverse gas chromatography techniques. Fiber treatment by sizing agents results in considerable changes in the intensity of adhesional interaction with the epoxy matrix. A correlation between the work of adhesion, the ultimate interfacial shear strength, and the strength of macro-composites has been found.     

Interplay of coordination and hydrogen bonding modes in the self-assembly of the supramolecular network in copper(II) phthalate–trimethoprim complex (0.5:1:1)

Trimethoprim cations forming self complementary hydrogen-bonded DADA arrays interact with the copper–phthalate supramolecular frameworks through extensive hydrogen bonding.     

The direct influence of the support on the electronic structure of the active sites in supported metal catalysts: evidence from Pt–H anti-bonding shape resonance and Pt–CO FTIR data

The catalytic activity and spectroscopic properties of supported noble metal catalysts are strongly influenced by support properties such as the presence of protons, type of charge compensating cations, Si/Al ratio and/or presence of extra-framework Al. The metal–support interaction is relatively independent of the metal (Pd or Pt) or the type of support (microporous zeolites such as LTL and Y or macroporous supports such as SiO₂). As the alkalinity of the support increases (i.e., with increasing electronic charge on the support oxygen ions), the TOF of the metal particles for neopentane hydrogenolysis decreases. At the same time, there is a systematic shift from linear to bridge bonded CO as indicated by the IR spectra. This is a strong indication of a change in the electronic structure of the catalytically active Pt surface atoms. Analysis of the Pt–H anti-bonding shape resonance present in the Pt X-ray absorption spectra of the L₃ edge indicates that the difference in energy between the Pt–H anti-bonding orbital and the Fermi level decreases as the alkalinity of the support increases. The results from the IR and Pt–H shape resonance data directly show that the support influences the position in energy of the metal valence orbitals. The ionisation potential of the catalytically active Pt surface atoms decreases with increasing support alkalinity, i.e., with increasing electron charge on the support oxygen ions. This shift leads to a weakening of the Pt–H bond.     

Relationship of the different Ca sites in the matrix with luminescence properties of orange‒red emitting Li0.04Ca0.96-xSiO3:Smx phosphors

Li_0.04Ca_0.96-xSiO₃:Sm_x orange?red emitting phosphors were synthesized using the sol-gel method. X-ray diffraction, Rietveld refinement of XRD patterns, Fourier transform infrared spectroscopy and ?uorescence spectrophotometry were used to characterize the crystal structure, sites of cationic Ca and luminescence properties of the prepared phosphors. The relationship of the different Ca sites in the matrix with the luminescence properties was analysed. The results indicate that the prepared phosphors reveal a β-CaSiO₃ phase with a monoclinic crystal structure and space Group P21/a. As the Sm³⁺ concentration increases, the unit cell volume of phosphors and the Ca–O band lengths of different Ca sites decrease due to substitution of Ca²⁺ by smaller Sm³⁺ ions. By excitation at 404 nm, Li_0.04Ca_0.96-xSiO₃:Sm_x phosphors exhibit warm orange?red light, corresponding to the electron transitions from ⁴G_5/2 → ⁶H_5/2 (567 nm), ⁴G_5/2 → ⁶H_7/2 (605 nm) and ⁴G_5/2 → ⁶H_9/2 (651 nm) of Sm³⁺. The concentration quenching phenomenon appears at Sm³⁺ concentrations beyond 0.02. The refinement results demonstrate that three cationic Ca sites, named Ca1, Ca2 and Ca3, exist in the β-CaSiO₃ host lattice. The Ca²⁺ ions at Ca1 and Ca2 sites are coordinated with six oxygen ions, leading to the same coordination number (CN). The Ca²⁺ ion located at Ca3 site has seven coordination numbers. The Ca1 site possesses a smaller lattice distortion and better symmetry than those of Ca2 and Ca3 sites. However, the Ca3 site exhibits the largest lattice distortion and poor symmetry. The Sm³⁺ present in symmetric Ca1 sites in the matrix illustrates the strong emission intensity, long luminescence lifetimes and good thermal stability.     

Modifier–substrate interactions of various types in the Orito reaction: Reversal of the enantioselection in the hydrogenation of ketopantolactone on Pt modified by β-isocinchonine and O-phenylcinchonidine

The enantioselective hydrogenation of ketopantolactone (KPL) on Pt–alumina catalyst modified by β-isocinchonine (β-ICN) and O-phenylcinchonidine (PhOCD) in toluene, acetic acid and their mixtures under otherwise identical experimental conditions was studied. Reversal of the enantioselection was obtained dependent on the concentration of acetic acid (ee_max = 17% (S) on Pt–PhOCD and 50% (R) on Pt–β-ICN, respectively). The possible role in enantioselection of adducts forming in the reaction mixture and the stability of PhOCD under the conditions of the hydrogenation was investigated by ESI-MS. The results of the nonlinear phenomenon measurements on β-ICN + PhOCD mixtures suggest that the intermediate surface complexes β-ICN–KPL and PhOCD–KPL responsible for the opposite enantioselection include different types of interactions and the enantioselection is directed by the competition between these interactions.     

The role of the solvent in TS-1 chemistry: active or passive? An early study revisited

The oxidation of n-hexane with hydrogen peroxide, catalyzed by TS-1 in various solvents, is reported. The initial rate of reaction decreases in the order: t-butanol > t-butanol/water > methanol acetonitrile water, whereas the reverse trend was observed for the adsorption of n-hexane in the catalyst. A dual function is postulated for the solvent in relation to its effects on kinetics. It assists the sorption/desorption of reagents/products in TS-1 (passive role) and participates in the catalytic cycle, through interactions with polar species involved in it (active role). A mechanistic pathway for the hydroxylation of paraffinic and aromatic C–H bonds is suggested.     

Interfacial interactions in calcium carbonate–polypropylene composites. 2: Effect of compounding on the dispersion and the impact properties of surface-modified composites

This study was carried out to investigate the influences of compounding process and surface treatment on calcium carbonate (CaCO₃) filled polypropylene. The compounding process is discussed with reference to a twin-screw extruder and an internal mixer. The calcium carbonate filler was surface-treated with a liquid titanate coupling agent (LICA 12) and stearic acid. Composites of different weight fractions were prepared by both compounding processes, and their impact properties were evaluated. The notched Izod impact strength increased with CaCO₃ content up to a maximum at about 10 vol%, and then decreased. Surface treatment of CaCO₃ filler generally yielded composites of higher impact strength than untreated system. Though LICA 12 was more effective than stearic acid in modifying the filler, the low-cost stearic acid proved to be more effective when dealing with the impact properties of composites. Moreover, the composites from a Brabender Plasti-corder exhibited better gross uniformity than that from the twin-screw extruder. However, good filler dispersion and uniform microscopic morphology, as revealed by SEM microscopy, was observed in the samples from the twin-screw extruder. Polym. Compos. 25:451–460, 2004. © 2004 Society of Plastics Engineers.     

Investigation of the anticorrosion efficiency of ferrites Mg1−xZnxFe2O4 with different particle morphology and chemical composition in epoxy-ester resin-based coatings

Mixed metal oxides with the ferrospinel structure ZnFe₂O₄, Mg_0.2Zn_0.8Fe₂O₄ and MgFe₂O₄ were synthesised by the high-temperature solid-phase process. A series of pigments containing the metals Mg–Zn–Fe was prepared from 4 different starting iron oxides: viz. goethite (FeOOH), hematite (Fe₂O₃), magnetite (FeO·Fe₂O₃) and specularite (Fe₂O₃). The properties of the ferrites as pigments were examined in a solvent-based epoxy-ester resin-based coating material at a pigment volume concentration PVC_ferrite = 10%. The anticorrosion efficiency of the paints with the ferrites was examined by exposing panels coated with the paints to atmospheres with SO₂, NaCl, or condensed moisture. Furthermore, the physico-mechanical properties of paint films containing the pigments were evaluated by standardised tests. Ferrites prepared from the needle-shaped FeOOH or lamellar Fe₂O₃ emerged as pigments with the best anticorrosion properties. From the aspect of chemical composition, the paint films containing Mg_0.2Zn_0.8Fe₂O₄, i.e. combinations of the cations Mg–Zn, were assessed as the best.     

Problems of spectrophotometry of glass-forming melts: II. A technique for measuring the absorption spectra of glasses and melts in the red and near-infrared ranges at temperatures from 20 to 1500°C

A technique for measuring the absorption spectra of glasses and glass-forming melts in the red visible and near IR ranges, the experimental setup, and the measuring cell intended for use over a wide range of temperatures are described. The main problems concerning the acquisition of reliable data on the absorption spectra of glass-forming melts at high temperatures and the basic sources of errors in measurements of the spectra are considered.     

Stability of rare earth oxides in a moist environment at elevated temperatures—Experimental and thermodynamic studies: Part II: Comparison of the rare earth oxides

Volatilisation tests enabled to quantify the stability of different rare earth sesquioxides, RE₂O₃ (where RE = Sc, Dy, Er, Yb) and to understand the corrosion process. These tests were carried out at temperatures ranging from 1000 to 1400 °C in moist air with 50 kPa of water at atmospheric pressure, under a flowing gas velocity of 5 cm s^?1. Besides the volatilisation rate, the nature of the volatile gaseous species was determined. The proposed experimental method allowed too to assess the Gibbs free energy of formation of these gaseous volatile species. Finally, the stability of each rare earth oxide under a moist environment at high temperature was compared.     

Photodegradation of Natural Organic Matter in Water with UV Irradiation at 185 and 254 nm: Importance of Hydrodynamic Conditions on the Decomposition Rate

Abstract

The kinetic investigation of photodegradation of the natural organic matter (NOM) in natural lake water was conducted using two low‐pressure mercury lamps of the same nominal power: a) with suprasil quartz envelope emitting at both wavelengths ?254 nm and 185 nm (hereafter VUV); b) with standard quartz envelope emitting only at 254 nm (hereafter UV). In comparison to the UV process, the addition of 185 nm irradiation (VUV process) increased the degradation rate ten‐fold overall at lower and seventeen‐fold at higher Reynolds numbers, respectively. The hydrodynamic characteristics of the photoreactor are of crucial importance for total energy efficiency for VUV processes.     

A unique supramolecular sandwich structure of a tetrabromocatechol-chelated iron(III) complex: Mutual reinforcement of H-bonding and π⋯π stacking interactions in the crystal lattice

A unique supramolecular sandwich structure of a tetrabromocatecholate chelated mononuclear iron(III) complex, [H₃ntb]₂[Fe(Br₄Cat)₃](ClO₄)₃·4CH₃OH·4H₂O (1) [ntb = tris(2-benzimidazolylmethyl)amine and Br₄CatH₂ = tetrabromocatechol], is reported. The most interesting feature of the crystal structure of 1 is that the central [Fe(Br₄Cat)₃]^3 − anion is sandwiched by the triply-protonated two ntb ligands in which mutual reinforcement of the π⋯π stacking and hydrogen bonding interactions play significant role to stabilize the structural motif. Electrochemical studies disclose both the noninnocent ligand and metal based redox processes.     

Stereo-Preference in the Degradation of the Erythro and Threo Isomers of β‐O‐4‐Type Lignin Model Compounds in Oxidation Processes: Part 1: In the Reaction with Active Oxygen Species Under Oxygen Delignification Conditions

We examined whether or not active oxygen species (AOS) stereo-preferentially attack the erythro or threo isomer of non-phenolic β-O-4 -type lignin model compounds under oxygen delignification conditions. When AOS were generated in situ by the reaction between O₂ and co-existing 4-hydroxy-3-methoxybenzyl alcohol (vanillyl alcohol), the obtained results could be explained on the basis of the hypothesis that an electrostatic repulsion exists between the negatively charged oxyl anion radical and the side-chain of the erythro isomer carrying the α-alkoxide anion. This repulsion prevents the reaction between the two species and, consequently, the erythro isomer is degraded less than the threo isomer. When 2,4,6-trimethylphenol (TMPh) was used to generate AOS, the reverse stereo-preference was observed. This reversal could be attributed to the neutral nature of a peroxyl radical that is an important AOS in the TMPh system and can attack the side-chain of the erythro isomer carrying the negatively charged α-alkoxide anion.