The mechanism of protection of molten magnesium by cover gas mixtures containing sulphur hexafluoride

Experimental studies have been undertaken, involving in situ observations of the interaction between cover gas mixtures and molten magnesium. It has been shown that, in the presence of sulphur hexafluoride (SF6), the contact angle between solid MgO and molten magnesium is reduced, resulting in the wetting of MgO by magnesium metal. In contrast, it was observed that the absence of SF6 results in a large contact angle, poor wetting of the MgO by magnesium metal and a non-adherent surface film. It is proposed that the formation of an adherent, protective surface film under a cover gas mixture containing SF6 is due to capillary forces acting within the film.

Conformational changes in monolayers of a cationic amphiphilic porphyrin on saline subphases

Langmuir monolayer films of the tetracationic porphyrin tetrakis(octadecyl-4-pyridin ium)porphyrinatozinc(II) bromide on various salt containing subphases were analyzed using surface pressure-area isotherms and X-ray reflectivity. The use of these complementary techniques showed that the porphyrin molecules undergo changes in conformation upon compression. Two main phases were identified, one in which the porphyrin moiety is parallel to the subphase and one in which the porphyrin moiety is tilted out of the plane. The addition of different salts into the subphase brought about changes in film behaviour, which are explained in terms of a lyotropic series. Copyright (C) 2002 Society of Porphyrins,& Phthalocyanines.

Porphyrin profiles in blood and urine as a biomarker for exposure to various arsenic species

A sensitive method using HPLC with fluorescence detection has been established for the measurement of porphyrins in biological materials. The assay recoveries were 88.0 +/- 1.8% for protoporphyrin IX in the blood, and ranged from 98.3 +/- 2.7% to 111.1 +/- 7.4% for various porphyrins in the urine. This method was employed to investigate the altered porphyrin profiles in rats after a single dose of various arsenicals including soluble sodium arsenate and sodium arsenite, and the relatively insoluble calcium arsenite, calcium arsenate and arsenic-contaminated soils at dose rates of 5 mg/kg or 0.5 mg/kg body weight. Porphyrin concentrations increased within 24-48hr after the arsenic treatment in blood and urine. Protoporphyrin IX is the predominant porphyrin in the blood. In rats administered 5 mg As(III)/kg body weight, protoporphyrin IX concentration elevated to 123% of them control values in rats, 24 hr after the treatment. Higher increases were recorded in the urinary protoporphyrin IX (253% at 24 hr; 397% on day 2), uroporphyrin (121% at 24 hr; 208% on day 2) and coproporphyrin 111 (391% at 24 hr; 304% on day 2), while there was no significant increase (109% on day 3) observed in the urinary coproporphyrin I excretion. In rats administered 5 mg As(V)/kg, urinary excretion of protoporphyrin IX, uroporphyrin, coproporphyrin Ill and coproporphyrin I elevated to the maximum levels by 48 hr with the corresponding percentage values compared to the control being 177%, 158%, 224% and 143%, respectively. In rats dosed with 5 mg As(III)/kg, the increases (expressed as % of the control values) of protoporphyrin IX in the blood were in the order: sodium arsenite (144%) > sodium arsenate (125%) greater than or equal to calcium arsenite (123%) > calcium arsenate. In contrast, there was no significant increase of protoporphyrin K when the six arsenic-contaminated cattlei dip soils and nine copper chrome arsenate (CCA-contaminated) soils were administered to the rats. Probable explanations are discussed.

Thin films of a tetracationic porphyrin

Langmuir-Blodgett films of the tetracationic porphyrin tetrakis( octadecyl-4-pyridinium) porphinatozinc(ii) bromide transferred from subphases containing different salts were studied using X-ray photoelectron spectroscopy (XPS) and X-ray reflectometry. In contrast to previous results at the air/water interface, we found that the porphyrin adopted a fixed conformation at the air/solid interface regardless of composition of the subphase or whether the films were transferred above or below the primary phase transition. This conformation was assigned to the formation of an interdigitated bilayer structure.

Method for determining reaction rate of mild steel containers during melting of magnesium-aluminium alloys and effect of aluminium content on directionally solidified microstructures

A magnesium alloy of eutectic composition (33 wt-'%Al) was directionally solidified in mild steel tubes at two growth rates, 32 and 580 mum s(-1,) in a temperature gradient between 10 and 20 K mm(-1). After directional solidification, the composition of each specimen varied dramatically, from 32'%Al in the region that had remained solid to 18%Al (32 mum s(-1) specimen) and 13%Al (580 mum s(-1) specimen) at the plane that had been quenched from the eutectic temperature. As the aluminium content decreased, the microstructure contained an increasing volume fraction of primary magnesium dendrites and the eutectic morphology gradually changed from lamellar to partially divorced. The reduction in aluminium content was caused by the growth of an Al-Fe phase ahead of the Mg-Al growth front. Most of the growth of the Al-Fe phase occurred during the remelting period before directional solidification. The thickness of the Al-Fe phase increased with increased temperature and time of contact with the molten Mg-Al alloy. (C) 2003 Maney Publishing.

Alloying of pure magnesium with Mg-33.3 wt-%Zr master alloy

To capitalise on the strengthening potential of zirconium as a potent grain refiner for magnesium alloys, the mechanisms of adding zirconium to magnesium and its subsequent grain refining action need to be understood. Using a Mg-33.3Zr master alloy (Zirmax supplied by Magnesium Elektron Ltd) as a zirconium alloying additive, the influence of different alloying conditions on the dissolution of zirconium in magnesium was investigated. It was found that owing to the highly alloyable microstructure of Zirmax, the dissolution of zirconium was generally complete within a few minutes in the temperature range 730 to 780degreesC. Prolonging and/or intensifying stirring were found to have no conspicuous influence on further enhancing the dissolution of zirconium. In all cases studied, the average grain size increased with increasing holding time at temperature while the total zirconium content decreased. The finest grain structure and highest total zirconium content corresponded to sampling immediately after stirring. Pick up of iron by molten magnesium from the mild steel crucibles used for melting and holding, was significantly delayed or avoided in the temperature range 730 to 780degreesC by coating the crucibles with boron nitride. It is therefore feasible to conduct zirconium alloying at 730degreesC without the need of a considerable excess of Zirmax addition using a properly coated or lined steel crucible.

Understanding magnesium corrosion - A framework for improved alloy performance

The purpose of this paper is to provide a succinct but nevertheless complete mechanistic overview of the various types of magnesium corrosion. The understanding of the corrosion processes of magnesium alloys builds upon our understanding of the corrosion of pure magnesium. This provides an understanding of the types of corrosion exhibited by,magnesium alloys, and also of the environmental factors Of most importance. This deep understanding is required as a foundation if we are to produce magnesium alloys much more resistant to corrosion than the present alloys. Much has already been achieved, but there is vast scope for improvement. This present analysis can provide a foundation and a theoretical framework for further, much needed research. There is still vast scope both for better fundamental understanding of corrosion processes, engineering usage of magnesium, and also on the corrosion protection of magnesium alloys in service.

Studies of the interaction of Potassium(I), Calcium(II), Magnesium(II), and Copper(II) with Cyclosporin A

Metal ion binding properties of the immunosuppressant drug cyclosporin A have been investigated. Complexation studies in acetonitrile solution using H-1 NMR and CD spectroscopy yielded 1:1 metal-peptide binding constants (log(10)K) for potassium(l), < 1, magnesium(II), 4.8 +/- 0.2. and calcium(II), 5.0 +/- 1.0. The interaction of copper(II) with cyclosporin A in methanol was investigated with UV/visible and electron paramagnetic resonance (EPR) spectroscopy. No complexation of copper(II) was observed in neutral solution. In the presence of base, monomeric copper(II) complexes were detected. These results support the possibility that cyclosporin A has ionophoric properties for biologically important essential metal ions. (C) 2003 Elsevier Inc. All rights reserved.