Al-Mn-Ce quasicrystalline composites: Phase formation and mechanical properties

Aluminium-based composites with quasicrystalline particles as reinforcements were synthesized via the powder metallurgy processing route. In order to obtain bulk samples with a nanoscale microstructure most equivalent to that resulting from rapid solidification, powders of Al-Mn-Ce alloys were prepared by pulverization of melt-spun ribbons using a planetary ball mill. Significant differences in the phase formation upon quenching, composite microstructure and thermal stability of the microstructure were found for different alloy compositions. Severe grain growth during the subsequent consolidation by hot extrusion caused the formation of a micrometre-scale composite instead of the nanoscale phase mixture initially existing after rapid solidification. After hot extrusion, the specimens were deformed by compression at a constant compression rate at room temperature. With an ultimate strength of up to 975 MPa and a ductility of more than 4% the material yields excellent properties compared with conventionally produced aluminium-based alloys.     

Electron energy-loss spectroscopy at incommensurately modulated crystalline and glassy Ba2TiGe2O8

Based on cluster molecular orbital calculations, high-energy resolution (ΔE?～ 0.4?eV) Ti–L_2,3 electron energy loss near-edge structures of single-crystalline and glassy Ba₂TiGe₂O₈ are interpreted. The finding that the Ti–L_2,3 near-edge structure of the Ba₂TiGe₂O₈ single crystal possesses less pronounced peaks than the glass under identical experimental conditions can be attributed to distinct distortions of the titanium environment caused by the very strong one-dimensional structural modulation hosted by the Ba₂TiGe₂O₈ crystal lattice. As lattice periodicity is absent in the glass, the titanium environment is more regular in the vitreous surroundings. Moreover, the modulation in crystalline Ba₂TiGe₂O₈ is responsible for the virtually indiscernible O–K near-edge structures of the glassy and crystalline samples.     

Poly(lactic acid) composites with poly(lactic acid)‐modified carbon nanotubes

This work reports the study of the effect of chemical functionalization of carbon nanotubes on their dispersion in poly(lactic acid). The nanotubes were functionalized by the 1,3‐dipolar cycloaddition reaction, generating pyrrolidine groups at the nanotube surface. Further reaction of the pyrrolidine groups with poly(lactic acid) was studied in solution and in the polymer melt. The former involved refluxing the nanotubes in a dimethylformamide/polymer solution; the latter was carried out by direct melt mixing in a microcompounder. The carbon nanotubes collected after each process were characterized by thermogravimetry and by X‐ray photoelectron spectroscopy, showing evidence of polymer bonded to the nanotube surface only when the reaction was carried out in the polymer melt. The composites with polymer modified nanotubes present smaller average agglomerate area and a narrower agglomerate area distribution. In addition, they show improved tensile properties at low CNT concentration and present lower electrical resistivity. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 3740–3750     

Giant Fullerene Polyelectrolytes Composed of C60 Building Blocks with an Octahedral Addition Pattern and Discovery of a New Cyclopropanation Reaction Involving Dibromomalonates

We report here on the facile synthetic access of a new family of bis‐, tetra‐, hexa‐, and heptafullerenes (prototypes I–IV), which can be easily converted into very water soluble polyelectrolytes with up to 60 charges located on their periphery. Their very regioselective formation is based on the use of C_2v‐symmetrical pentakisadducts 3 and hexakisadducts 2 as key intermediates. All fullerene moieties incorporated in these macromolecular structures involve a complete or partial octahedral addition pattern. Tripod‐shaped tetrafullerenes 9 a , b (type II), which can accumulate up to thirty positive or negative charges, are very soluble in acidic or basic water, respectively. Hexafullerenes 13 a , b (type III) were synthesized via isoxazolinofullerenes 10 followed by photolytic cleavage of the isoxazoline group. The giant heptafullerene 1 b (type IV) representing the anionic counterpart of the previously synthesized polyelectrolyte 1 a can store up to 60 negative charges on its periphery within a defined three‐dimensional structure. We also discovered a new cyclopropanation reaction of C₆₀ involving dibromomalonates and 1,8‐diazabicyclo[5.4.0]undec‐7‐ene (DBU). This reaction allows even for the highly regioselective formation of hexakisadducts with an octahedral addition pattern without requiring activation with reversibly binding addends such as 9,10‐dimethylanthracene (DMA).