Plasticization and cocrystallization in LLDPE/wax blends

The structure and thermal properties of linear low‐density polyethylene (LLDPE)/medium soft paraffin wax blends, prepared by melt mixing, were investigated by differential scanning calorimetry (DSC) and small‐ and wide‐angle X‐ray scattering (SAXS and WAXS). The blends form a single phase in the melt as determined by SAXS. Upon cooling from the melt, two crystalline phases develop for blends with more than 10 wt % wax characterized by widely different melting points. The wax acts as an effective plasticizer for LLDPE, decreasing both its crystallization and melting temperature. The higher melting point crystalline phase is formed by less branched LLDPE fractions. On the other hand, the lower melting point crystalline phase is a wax‐rich phase constituted by cocrystals of extended chain wax and short linear sequences of highly branched LLDPE chains. The presence of cocrystals was evidenced by standard DSC results, successive self‐nucleation and annealing (SSA) thermal fractionation and by the detection of a new SAXS signal attributed to the lamellar long period of the cocrystals. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 1469–1482     

Progress on the development of uniform distributed Pd electroless based catalysts on MEA for PEMFC application

Envisaging the scale-up production of fuel cell electrodes, it was established an electrode manufacturing method that enables a uniform distribution of Pd-based catalyst over the MEA, ensuring simultaneously a low catalyst loading. The new procedure relies on the direct immobilization of the catalyst on the gas diffusion substrate by the electroless deposition after substrate activation by the electrodeposition of metal nucleus of Pd using the galvanostatic mode. The effect of the novel method on the catalyst distribution uniformity, morphology, and electrocatalytic activity towards the oxygen reduction reaction (ORR) in 0.1 M HClO₄ solution is compared to samples prepared by the conventional Sn/Pd sensitization—activation route. The performance of the PEMFC containing the same Pd load (0.09 mg cm^?2) reveals to be slightly higher on depositing the Pd nucleus by the galvanostatic electrodeposition than by the conventional sensitization/activation method. The new method opens up new approaches to extend the electroless deposition to the preparation of a wide range of alloy catalysts for the cathode and anode sides of PEMFCs.     

Synthesis and Characterization of a Novel Addition-Fragmentation Reactive Surfactant (TRANSURF) for Use in Free-Radical Emulsion Polymerizations

The synthesis and characterization of a new type of chain-transfer-active surfactant (i.e., TRANSURF) is reported. The compound was designed on the basis of the chemistry of macromers, which undergo free-radical chain-transfer addition-fragmentation reactions. In effect this allows incorporation of the surfactant molecule into the polymer backbone, and thus reduces the influence of surfactant migration during film formation. Surfactants of this type, containing two hydrophilic head groups, can have a marked influence on the polymer and latex properties (e.g., molecular weight distributions and particle size). Characterization of the physical properties of this surfactant was therefore carried out using surface tension, conductivity, and fluorescence techniques. Because of the surfactant's unusual "bolaform" (alpha, omega) (Zana, R., in "Structure-Performance Relationships in Surfactants" (K. Esumi and M. Ueno, Eds.), Surfactant Science Series 70, Dekker, New York, 1997) structure the micelle formation process has been found to be quite different from that of the conventional surfactant, sodium dodecyl sulfate (SDS). From the surface tension data a flat molecular conformation was evident at 1x10(-3) mol dm(-3) (131 ?(2) surface area), which we assumed to correspond to the low aggregation number of premicellar aggregates. There is evidence to suggest formation of a larger volume of the microdomains in these micelles compared to that in SDS. At higher TRANSURF concentrations, however, we find no clear indication of a switch to a "wicket"-type conformation, although such conformational changes cannot be ruled out. Copyright 2001 Academic Press.     

Effect of the conformation of the alkyl chain on the catalytic miniemulsion copolymerization of ethylene and acrylates

The catalytic copolymerization of ethylene and acrylic monomers is a promising way of incorporating polar functionality into polyolefins and therefore enlarging the range of properties of these materials. This work shows that for the copolymerization of ethylene and C4 acrylates using a sterically encumbered Pd catalyst, the degree of incorporation of the acrylic monomer decreases with the degree of branching of the alkyl chain of the acrylate, the main reason being the difficulty for coordination of bulky acrylates to the catalytic site. This strongly affects the polymerization rate as well as the molecular weight, crystallinity and melting point temperature of the copolymers.     

Theoretical study of the complex-forming CH + H2 --> CH2 + H reaction

The complex-forming CH + H2 --> CH2 + H reaction is studied employing a recently developed global potential energy function. The reaction probability in the total angular momentum J = 0 limit is estimated with a four-atom quantum wave packet method and compared with classical trajectory and statistical theory results. The formation of complexes from different reactant internal states is also determined with wave packet calculations. While there is no barrier to reaction along the minimum energy path, we find that there are angular constraints to complex formation. Trajectory-based estimates of the low-pressure rate constants are made and compared with experimental results. We find that zero-point energy violation in the trajectories is a particularly severe problem for this reaction.     

Planning annualised hours with a finite set of weekly working hours and cross-trained workers

Annualising working hours (i.e., the possibility of irregularly distributing the total number of working hours over a year) permits companies to adapt capacity to fluctuations in demand, thus reducing overtime, temporary workers and inventory costs. Since annual hours can lead to a worsening of the staff’s working conditions, many laws and collective bargaining agreements contain constraints that affect the distribution of working time. This paper proposes a MILP model to solve an annualised working hours planning problem in which workers are considered to be cross-trained, and in which the number of weekly working hours must belong to a previously agreed finite set. A computational experiment demonstrates the effectiveness of the model.     

Capture and dissociation in the complex-forming CH(v = 0,1) + D2 → CHD + D, CD2 + H, CD + HD reactions and comparison with CH(v = 0,1) + H2

Rate coefficients for the CH(v = 0,1) + D(2) reaction have been determined for all possible channels (T: 200-1200 K), using the quasiclassical trajectory method and a suitable treatment of the zero point energy. Calculations have also been performed on the CH(v = 1) + H(2) reaction and the CH(v = 1) + D(2) → CH(v = 0) + D(2) process. Most of the results can be understood considering the key role played by the deep minimum of the potential energy surface (PES), the barrierless character of the PES, the energy of the reaction channels, and the kinematics. The good agreement found between theory and experiment for the rate coefficients of the capture process of CH(v = 0) + D(2), the total reactivity of CH(v = 1) + D(2), H(2), as well as the good agreement observed for the related CH(v = 0) + H(2) system (capture and abstraction), gives confidence on the theoretical rate coefficients obtained for the capture processes of CH(v = 1) + D(2), H(2), the individual reactive processes of CH(v = 1) + D(2), H(2), the abstraction and abstraction-exchange reactions for CH(v = 0) + D(2), and the inelastic process mentioned above, for which there are no experimental data available, and that can be useful in combustion chemistry and astrochemistry.     

Assessing the suitability of 1,2,3-triazole linkers for covalent immobilization of chiral ligands: application to enantioselective phenylation of aldehydes

Alkynyl-functionalized amino alcohols have been covalently supported on azidomethylpolystyrene resins with different levels of functionalization through Cu(I)-catalyzed 1,3-dipolar cycloadditions ("click chemistry"). The resulting 1,2,3-triazole-substituted resins, characterized by different levels of ligand loading and, depending on the nature of the alkynyl-functionalized amino alcohol, the presence of a one-carbon, four-carbon, or eight-carbon linear spacer, have been tested as catalysts in the enantioselective phenyl transfer from zinc to aldehydes. High catalytic activities and enantioselectivities (up to 82% ee) have been recorded. The influence of structural characteristics of the resin on enantioselectivity are discussed, and the limitations in enantiocontrol inherent to the use of a 1,2,3-triazole linker have been rationalized with the help of DFT calculations on model systems.     

Coexistence of five different copper(II)-phenanthroline species in the crystal packing of inorganic-metalorganic hybrids based on Keggin polyoxometalates and copper(II)-phenanthroline-oxalate complexes

Reaction of in situ generated copper(II)-monosubstituted Keggin polyoxometalates and copper(II)-phenanthroline-oxalato complexes in ammonium or rubidium acetate buffers led to the formation of the hybrid inorganic-metalorganic compounds E4[Cu(phen)(H2O)4]2[Cu4(phen)4(H2O)4(ox)3]0.6[Cu2(phen)2(H2O)4(ox)]0.4[Cu(phen)(ox)]0.8[{SiW11O39Cu(H2O)}2{Cu2(phen)2(ox)}].20H2O [E: Rb (1), NH4 (2)]. The two compounds have been characterized by means of elemental analysis, thermogravimetry, infrared and electron paramagnetic resonance spectroscopies, and magnetic susceptibility measurements, and their structures have been established by single-crystal X-ray diffraction. Both compounds are isostructural, and they contain a discrete bimolecular hybrid polyanion and several types of copper-phenanthroline complexes of variable nuclearity. The main structural features of these compounds are the presence of the new hybrid POM [{SiW11O39Cu(H2O)}2{Cu2(phen)2(mu-ox)}]10-, where the dinuclear copper-oxalato complex is sandwiched by two copper-monosubstituted POMs, and the coexistence of five different copper-phenanthroline species with nuclearities ranging from one to four.     

Catalytic ethylene polymerisation in carbon dioxide as a reaction medium with soluble nickel(II) catalysts

A series of neutral Ni(II)-salicylaldiminato complexes substituted with perfluorooctyl- and trifluoromethyl groups, [Ni{kappa(2)-N,O-6-C(H)==NAr-2,4-R'(2)C(6)H(2)O}(Me)(pyridine)] (6 a: Ar=2,6-{4-(F(17)C(8))C(6)H(4)}(2)C(6)H(3), R'=I; 6 b: Ar=2,6-{4-(F(3)C)C(6)H(4)}(2)C(6)H(3), R'=I; 6 c: Ar=2,6-{3,5-(F(3)C)(2)C(6)H(3)}(2)C(6)H(3), R'=3,5-(F(3)C)(2)C(6)H(3); 6 d: Ar=2,6-{4-(F(17)C(8))C(6)H(4)}(2)C(6)H(3), R'=3,5-(F(3)C)(2)C(6)H(3); 6 e: Ar=2,6-{3,5-(F(3)C)(2)C(6)H(3)}(2)C(6)H(3), R'=I) were studied as catalyst precursors for ethylene polymerisation in supercritical CO(2). Catalyst precursors 6 a and 6 c, which are soluble in scCO(2), afford the highest polymer yields, corresponding to 2 x 10(3) turnovers. Semicrystalline polyethylene (M(n) typically 10(4) g mol(-1)) is obtained with variable degrees of branching (11 to 24 branches per 1000 carbon atoms, predominantly Me branches) and crystallinities (54 to 21 %), depending on the substitution pattern of the catalyst.