Ethylene polymerization with a catalyst system titanium tetrachloride—diethylaluminium chloride—diphenylmagnesium in the presence of hydrogen

A study was made of ethylene polymerization with the catalyst system titanium tetrachloride-diethylaluminium chloride—diphenylmagnesium in the presence of hydrogen. The system is highly active even at high content of hydrogen in the system and at high reaction temperatures (90–130°). In the presence of hydrogen, polyethylene was obtained with high density and a full commercial melt index range (0–50 g/10 min), i.e. a wide range of molecular weights. At higher reaction temperatures, some activation of the catalyst system was observed.     

Trace Metal Speciation and Research in Marine Geochemistry

Abstract

In order to precise the origin and behaviour of trace metals associated with coastal marine sediments, marine geochemists frequently utilize various methods of sequential extraction. The main objective is to test the potential mobility / stability of particulate metals in the natural environments. Several examples are presented in the article, namely: i/ Exchangeable Pb from podzolic soils of the drainage basin of a lagoon which sediments and phreatic waters are for a large part inherited from the surrounding soils; ii/ Evolution of particulate metals in an estuary; iii/ Mobility of metals at the sea bottom interface; iv/ Role of amorphous components of estuarine sediments and suspended matter; v/ Effects of dredging activities on solubility of metals in an estuary; vi/ Behaviour of heavy metals in lagoons.

Main results obtained from the extraction procedures are described, as well as particular difficulties encountered when applying some classical methods.     

Improvement of Analytical Measurements within the BCR-Programme: Single and Sequential Extraction Procedures Applied to Soil and Sediment Analysis

Abstract

The determination of extractable trace metal contents in soil and sediment, using respectively single and sequential extraction procedures, is currently performed in many laboratories to assess the bioavailable metal fraction (and related phyto-toxic effects) and the accessability to the environment (e.g. contamination of ground waters).

Owing to the need for validation of the extraction schemes used and of the analytical techniques, the Community Bureau of Reference (BCR) decided to organize a project for the improvement of the quality of determinations of extractable trace metal contents in soil and sediment. The implementation of this project follows a stepwise approach involving feasibility studies, intercomparisons to detect and remove sources of errors in the application of the analytical methods, and the certification of the extractable compounds. This paper describes the organization of the work completed so far (feasibility studies and first intercomparison) and discusses its further development.     

Improvement of EEPROM cell reliability by optimization of signal programming

This paper presents an optimization study of electrically erasable programmable read-only memory (EEPROM) cell programming to increase the long-term reliability of the device. Based on a charge-sheet model of the memory cell, we suggest that our result show that it is possible to decrease the electric field across the tunnel oxide of approximately 0.8 MV/cm, when using a particular programming waveform with a double rise ramp. We get the same simulated injected charge in write mode (+15 fC) and in erase mode (−12 fC) with the optimized programming signal rather than with the standard one. Threshold voltage measurements confirm the simulation results. Moreover, the endurance test shows that this new programming signal improves the endurance of the memory cell without any change in the device technology, memory cell lifetime becomes four times longer.     

From anisotropic dots to smooth RFe 2 (110) single crystal layers (R = rare earth)

Single crystal RFe₂(110) films were grown by molecular beam epitaxy to a total thickness of 1000 ? at different substrate temperatures ranging from 450 ^° C to 660 ^° C. The first stages of growth and the surface morphology of the deposited layers have been studied using Reflection High Energy Electron Diffraction (RHEED) and Atomic Force Microscopy (AFM). The growth is first strained but further deposit induces the formation of three-dimensional fully relaxed islands. Subsequently, the morphology of the RFe₂(110) nanosystems evolves from anisotropic dots to a smooth surface, as a function of the preparation parameters, i.e. nominal thickness and substrate temperature. It also depends on the rare earth involved in the compound. Received 29 June 2000     

Quantitative determination of inorganic minor cations in sodium-, calcium-, magnesium-matrix simulated samples by capillary electrophoresis

The analysis of ammonium, alkali and alkaline-earth trace cations (0.5 ppm) in samples with a calcium, sodium or magnesium matrix (500 ppm) has been achieved using 10 mM imidazole (pH 4.5) electrolyte to which a complexing agent (15-crown-5, oxalic acid or dipicolinic acid) has been specifically added in order to decrease the electrophoretic mobility of the matrix cation and thus to allow the separation of higher mobility cations at sub-ppm concentrations. The influence of several experimental parameters (complexing agent concentration, buffer pH and temperature) have been studied in order to optimize the separation. The complexing agent concentration appears to be the main parameter governing the selectivity of the cations during the analysis of matrix samples. In optimized conditions, we have checked that the separation between minor inorganic cations is not significantly altered by an increase in the matrix cation concentration. As the concentration of the matrix cation increases, the migration times of minor cations remain unchanged even for a 1000 ppm concentration of the matrix cation. Finally, these optimized buffers allow the quantitation of minor cations down to 0.05% (w/w) for calcium- or magnesium- matrix simulated samples and 0.2% (w/w) for sodium-matrix simulated samples.     

Improvement of oxygen transfer coefficient duringPenicillium canescens culture

To improve xylanase productivity fromPenicillium canescens 10–10c culture, an optimization of oxygen supply is required. Because the strain is sensitive to shear forces, leading to lower xylanase productivity as to morphological alteration, vigorous mixing is not desired. The influence of turbine design, agitation speed, and air flow rate on K₁a (global mass transfer coefficient, h^-1) and enzyme production is discussed. K₁a values increased with agitation speed and air flow rate, whatever the impeller, in our assay conditions. Agitation had more influence on K₁a values than air flow, when a disk-mounted blade’s impeller (DT) is used; an opposite result was obtained with a hub-mounted pitched blade’s impeller (PBT). Xylanase production appeared as a function of specific power (W/m³), and an optimum was found in 20 and 100 L STRs fitted with DT impellers. On the other hand, the use of a hub-mounted pitched blade impeller (PBT8), instead of a disk-mounted blade impeller (DT4), reduced the lag time of hemicellulase production and increased xylanase productivity 1.3-fold.

     

Investigation of polymer miscibility by spectroscopic methods V. Effect of molecular weight and block copolymerization of syndiotactic poly(methyl methacrylate) on its miscibility with poly(vinyl chloride)

Investigated by nonradiative energy transfer (NRET), the state of mixing of PVC and s.PMMA which is on the dimensional scale of a few nanometers is significantly affected by the chain length. When PVC is blended with s.PMMA of increasing molecular weight (MW), the longest chains of s.PMMA are likely to segregate from a homogeneous blend formed by PVC and low-MW s.PMMA. The phase separation should therefore be of purely entropic origin and strongly dependent on both the relative percentage and the chain length of each component. These results are in qualitative agreement with conclusions previously drawn from DSC and transmission electron microscopy. NRET is a more powerful tool in probing heterogeneities compared to DSC and the thermally stimulated depolarization current method; it provides evidence against the previously suggested model of a 1:1 PVC/s.PMMA aggregate.     

Adsorption of acetic acid on ice: experiments and molecular dynamics simulations

Adsorption study of acetic acid on ice surfaces was performed by combining experimental and theoretical approaches. The experiments were conducted between 193 and 223 K using a coated wall flow tube coupled to a mass spectrometric detection. Under our experimental conditions, acetic acid was mainly dimerized in the gas phase. The surface coverage increases with decreasing temperature and with increasing concentrations of acetic acid dimers. The obtained experimental surface coverages were fitted according to the BET theory in order to determine the enthalpy of adsorption deltaH(ads) and the mololayer capacity N(M(dimers)) of the acetic acid dimers on ice: deltaH(ads) = (-33.5 +/- 4.2) kJ mol(-1), N(M(dimers)) = (l1.27 +/- 0.25) x 10(14) dimers cm(-2). The adsorption characteristics of acetic acid on an ideal ice I(n)(0001) surface were also studied by means of classical molecular dynamics simulations in the same temperature range. The monolayer capacity, the configurations of the molecules in their adsorption sites, and the corresponding adsorption energies have been determined for both acetic acid monomers and dimers, and compared to the corresponding data obtained from the experiments. In addition, the theoretical results show that the interaction with the ice surface could be strong enough to break the acetic acid dimers that exist in the gas phase and leads to the stabilization of acetic acid monomers on ice.