Molecular Evolution of Polymers through Photoageing: A New UV in situ Viscoelastic Technique

Summary: Dienic elastomers are highly sensitive towards oxidation. During UV exposure, both scission and/or recombination reactions compete which involves an evolution of the molecular structure of the material. We developed an in situ technique to monitor the viscoelastic property changes upon UV irradiation of polymers in a single experiment. We illustrated this photorheology technique in the case of two kinds of elastomers. From our findings, this method is assumed to bring significant new advantages.

Photograph of the photorheometer used in this study.     

Study of the chemical derivatization of zearalenone and its metabolites for gas chromatography-mass spectrometry analysis of environmental samples

This study compares different silylation procedures of zearalenone and its metabolites: alpha-zearalenol, beta-zearalenol, zearalanone, alpha-zearalanol and beta-zearalanol for gas chromatography-mass spectrometry (GC-MS) analysis. Four silylating agents among the most frequently used to derivatize polar organic compounds were tested: N,O-bis(trimethylsilyl)trifluoroacetamide (BSTFA), N-methyl-N-trimethylsilyltrifluoroacetamide (MSTFA), N,N-diethyltrimethylsilylamine (TMSDEA) and a commercial mixture of N,O-bis(trimethylsilyl)acetamide, trimethylchlorosilane and N-trimethylsilyimidazole. Previous studies showed that the addition of polar and/or basic solvents can significantly improve the yield of a reaction of derivatization. In this work, four solvents were tested: pyridine, dimethylformamide, acetonitrile and acetone. The influence of each solvent was studied as a function of the silylating agent/solvent ratio. The influences of the temperature and of the reaction time on the reaction yields were also evaluated. A GC-MS quantitation method associating methanol chemical ionization and selected ion storage with three ions was developed and successfully tested on a reconstituted sediment spiked in zearalenone and its metabolites.     

Group 2 metal salts of pyromellitic acid: [Mg(H2O)6](C10H4O8) and [Ba(C10H4O8)(H2O)5]

Structural determinations of the magnesium(II) and barium(II) salts of pyromellitic acid (benzene‐1,2,4,5‐tetra­carboxyl­ic acid) are presented. Hexa­aqua­magnesium(II) benzene‐1,2,4,5‐tetra­carboxyl­ate(2−), [Mg(H₂O)₆](C₁₀H₄O₈), (I), and penta­aqua­[benzene‐1,2,4,5‐tetra­carboxyl­ato(2−)]­barium(II), [Ba(C₁₀H₄O₈)(H₂O)₅], (II), are both centrosymmetric and both possess a 1:1 metal–ligand ratio, but the two structures are found to differ in that the magnesium salt contains a hexaaqua cation and possesses only hydrogen‐bonding interactions between cations and anions, while the barium salt exhibits coordination of the carboxyl­ate ligand to the nine‐coordinate metal centre. In (I), both ions sit on a 2/m site symmetry, and in (II), the cation and anion are located on m and i site symmetries, respectively.     

Impact of the Atmosphere on the Reactivity of Peroxidic Species upon Photooxidation of Polymers

Summary: This paper gives an account of preliminary results about the impact of an oxidative atmosphere on peroxidation. Attention is focused on the level, nature, and reactivity of (hydro)peroxides with respect to the oxidative component concentration. Our main result is surprising: a lower peroxidation rate occurs, but a higher content of hydroperoxides are formed in air than in pure oxygen atmospheres. The results may lead to an approach to understand the influence of atmospheric factors on the outdoor weathering of polymers.

The device used to measure the oxygen uptake of the systems studied here.     

Stationary availability of a semi‐Markov system with random maintenance

We consider a reparable system with a finite state space, evolving in time according to a semi‐Markov process. The system is stopped for it to be preventively maintained at random times for a random duration. Our aim is to find the preventive maintenance policy that optimizes the stationary availability, whenever it exists. The computation of the stationary availability is based on the fact that the above maintained system evolves according to a semi‐regenerative process. As for the optimization, we observe on numerical examples that it is possible to limit the study to the maintenance actions that begin at deterministic times. We demonstrate this result in a particular case and we study the deterministic maintenance policies in that case. In particular, we show that, if the initial system has an increasing failure rate, the maintenance actions improve the stationary availability if and only if they are not too long on the average, compared to the repairs ( a bound for the mean duration of the maintenance actions is provided). On the contrary, if the initial system has a decreasing failure rate, the maintenance policy lowers the stationary availability. A few other cases are studied. Copyright © 2000 John Wiley & Sons, Ltd.