Li/MgO catalysts: II. A DTA and TG study of precursors

The thermal decomposition of precursors of Li/MgO catalysts prepared from different Mg and Li compounds is reported. Dehydration and dehydroxylation is observed in both cases, in addition to decomposition of LiNO₃, but not of Li₂CO₃. The properties of the solids are related to the melting and spreading of LiNO₃ or Li₂CO₃ before or after Mg(OH)₂ dehydroxylation.

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Li/MgO, Mg Li. LiNO₃, Li₂CO₃, . LiNO₃ Li₂CO₃ Mg(OH)₂.

     

Design of oxygen reduction bimetallic catalysts: ab-initio-derived thermodynamic guidelines

The Gibbs free energies of key elementary steps for the electrocatalytic oxygen reduction reaction (ORR) are calculated with B3LYP type of density functional theory: O2 + M + H+ + e- (0 eV) --> HOO-M (deltaG1), HOO-M + M --> HO-M + O-M (deltaG2), O2 + 2M + H+ + e- (0 eV) --> O-M + HO-M (deltaG3), and HO-M + O-M + 3H+ + 3e- (0 eV) --> 2H2O + 2M (deltaG4), where H+ is modeled as H3(+)O(H2O)3 and M stands for the adsorption site of a metal catalyst modeled by a single metal atom as well as by an M3 cluster. Taking Pt as a reference, deltaG4 is plotted against deltaG1 for 17 metals from groups V to XII. It is found that no single metal has both deltaG1 and deltaG4 more negative than Pt, although some of them have either more negative deltaG1 or more negative deltaG4. This enables us to explain thermodynamically why no other single metal catalyzes the ORR as effectively as Pt does. Moreover, a thermodynamic analysis reveals that the signs of delta deltaG (the difference between deltaG of other metals and deltaG of Pt) strongly correlate with the valence electronic structure of metals, i.e., delta deltaG1 < 0 and delta deltaG4 > 0 for metals M with vacant valence d orbitals, whereas delta deltaG1 > 0 and delta deltaG4 < 0 for metals M' with fully occupied valence d orbitals. Thus, a simple thermodynamic rule for the design of bimetallic catalysts for the ORR is proposed: couple a metal M (delta deltaG1 < 0) with a second metal M' (delta deltaG4 < 0) to form an alloy catalyst MM'3. The rationale behind this selection is based on M being more efficient for the rate-determining step, i.e., for the formation of the adsorbed species M-OOH, while M' can enhance the reductions of O and OH in the last three electron-transfer steps.     

Phosphorylated silica/polyamide 6 nanocomposites synthesis by in situ sol–gel method in molten conditions: Impact on the fire-retardancy

Polyamide 6 (PA6)/phosphorylated silica nanocomposites were synthesized during PA6 extrusion through in situ formation of the inorganic phase without solvent. This synthesis is based on the hydrolysis-condensation reactions of diethylphosphatoethyltriethoxysilane (SiP) as a functional inorganic precursor in combination with or without tetraethoxysilane (TEOS) dispersed in the molten PA6. This synthesis is carried out during PA 6 matrix extrusion that means at high temperature and under shear. The characterization of the in situ synthesized PA6/phosphorylated silica nanocomposites by solid ²⁹Si Nuclear Magnetic Resonance (NMR), Small Angle X-ray Scattering (SAXS) and Transmission Electron Microscopy (TEM) coupled with Energy Dispersive X-ray spectroscopy (EDX) demonstrated the possibility to directly create in less than 5 min at 220 °C a phosphorylated silica uniformly dispersed in the PA6, i.e. in the form of well dispersed particles or aggregates of sub-micron range. The influence of silicon and phosphorus on the thermal and fire retardant behaviour was investigated by thermogravimetric analysis (TGA), cone calorimeter and UL94 tests. The fire retardant behaviour was modified with a formation of a char and a peak heat release rate (PHRR) decrease by more than 50% for the SiP based nanocomposite compared to the pure PA6.     

[Pd(Fmes)2(tmeda)]: A Case of Intermittent C?H⋅⋅⋅F?C Hydrogen‐Bond Interaction in Solution

The X‐ray structure of the title compound [Pd(Fmes)₂(tmeda)] (Fmes=2,4,6‐tris(trifluoromethyl)phenyl; tmeda=N,N,N′,N′‐tetramethylethylenediamine) shows the existence of uncommon C? H???F? C hydrogen‐bond interactions between methyl groups of the TMEDA ligand and ortho‐CF₃ groups of the Fmes ligand. The ¹⁹F NMR spectra in CD₂Cl₂ at very low temperature (157 K) detect restricted rotation for the two ortho‐CF₃ groups involved in hydrogen bonding, which might suggest that the hydrogen bond is responsible for this hindrance to rotation. However, a theoretical study of the hydrogen‐bond energy shows that it is too weak (about 7 kJ mol^?1) to account for the rotational barrier observed (ΔH^≠=26.8 kJ mol^?1), and it is the steric hindrance associated with the puckering of the TMEDA ligand that should be held responsible for most of the rotational barrier. At higher temperatures the rotation becomes fast, which requires that the hydrogen bond is continuously being split up and restored and exists only intermittently, following the pulse of the conformational changes of TMEDA.     

Flammability and morphology of HDPE/clay nanocomposites

High-density polyethylene/modified bentonite clay/polar compatibilizer nanocomposites were prepared through the melt intercalation process. The clay was organophilizated using different percentages of quaternary ammonium salt 100, 125, and 150 % based cation exchange capacity of the clay. The nanocomposites were prepared in a counter-rotating twin-screw extruder and then specimens were injection molded. For the evaluation of flammability of the test system was used for burning in the horizontal position according to the norm (Underwriters Laboratories, UL94HB) and to the method of cone calorimeter. The thermal behavior of nanocomposites was evaluated by thermogravimetry and X-ray diffraction techniques, and transmission electron microscopy were used to characterize the morphology and analyze the degree of expansion of the clays prepared and the degree of exfoliation of nanocomposites. It was observed that the percentage of ammonium salt and the compatibilizer polar influence on the final properties of the systems and consequently improving the thermal stability and reducing the flammability of the matrix.     

Mechanism of fire retardance in poly(2,6-dimethyl-1,4-phenylene ether)-high impact polystyrene

Preliminary results are presented of a study concerning the mechanism of action of triphenyl phosphate (TPP) added to blends of poly(phenylene ether) (PPE) and high impact polystyrene (HIPS), 65/35 w/w. Comparison of effectiveness of TPP in increasing either the oxygen index or the nitrous oxide index of the polymeric blend, indicates that the fire retardant may act by a mixed gas-condensed phase mechanism. The thermogravimetric behaviour of the fire retarded blend is compatible with this suggestion.     

Mechanisms of fire retardance in glass fibre polymer composites

It is shown that the introduction of glass fibres in the poly(butylene terephthalate) (PBT) matrix, increases its flammability. The mechanism of action of a typical fire retardant for PBT which is a mixture of a brominated organic compound and antimony trioxide, seems to involve both the condensed and the gas phase.     

Characterisation of fire retardant poly(phenylene ether) high impact polystyrene in the UL-94 test

The distribution of the temperature and the morphology of the charred material formed in the combustion of blends of poly(phenylene ether) (PPE) with high impact polystyrene (HIPS), carried out in the UL94 test, were examined. The effect of the fire retardant triphenyl phosphate is shown to be the decrease of time of burning, of temperature of the specimen and of zone involved in combustion, without apparent modification of the char structure. Hypothesis on gas and condensed phase fire retardant mechanisms are discussed.     

Mechanistic aspects of intumescent fire retardant systems

The mechanism of intumescence is studied in mixtures of ammonium polyphosphate (APP) with several polycondensates as a part of a systematic study of intumescent fire retardants. It is shown that APP reacts on heating with the polycondensate to form a precursor of the intumescent char which is obtained on further heating. The introduction of the intumescent system in polypropylene does not modify the structure of the char formed on heating. However, the polymer modifies the foaming behaviour of the system. The thermal decomposition of the char occurs with volatilisation of phosphorus moieties and formation of a relatively thermally stable residue. Effects of the thermal behaviour of the char, on fire retardance, are discussed.     

On the girth of extremal graphs without shortest cycles

Let EX(ν;{C₃,…,C_n}) denote the set of graphs G of order ν that contain no cycles of length less than or equal to n which have maximum number of edges. In this paper we consider a problem posed by several authors: does G contain an n+1 cycle? We prove that the diameter of G is at most n−1, and present several results concerning the above question: the girth of G is g=n+1 if (i) ν≥n+5, diameter equal to n−1 and minimum degree at least 3; (ii) ν≥12, ν∉{15,80,170} and n=6. Moreover, if ν=15 we find an extremal graph of girth 8 obtained from a 3-regular complete bipartite graph subdividing its edges. (iii) We prove that if ν≥2n−3 and n≥7 the girth is at most 2n−5. We also show that the answer to the question is negative for ν≤n+1+⌊(n−2)/2⌋.