Oxygen/nitrogen ordering in lanthanum new phase (La3Si8N11O4)

High-resolution ¹⁷O NMR spectra have been collected for crystalline samples of lanthanum new phase, La₃Si₈N₁₁O₄. In conjunction with previously published ²⁹Si and ¹⁵N spectra obtained for this phase, and in the light of the high-quality crystal structure data reported recently, a more detailed interpretation of the NMR spectra is presented than was possible in previous studies. The non-bridging oxygens in the structure are responsible for the single sharp peak seen in the ¹⁷O spectrum at 188 ppm; the remaining oxygens, occupying bridging sites shared with nitrogen, show up only weakly on the ¹⁷O spectrum as a broad diffuse band centered around zero ppm. The peak at −57.3 ppm on the ²⁹Si spectrum is believed to correspond to an overlap of [SiN₄] and [SiON₃] environments, with the −68.2 ppm peak corresponding to an [SiO₂N₂] environment.     

Synthesis and Characterization of Novel Methacrylate Monomers Having Pendant Oxime Esters and Their Copolymerization with Styrene

New methacrylate monomers, 2‐{[(diphenylmethylene)amino]oxy}‐2‐oxoethyl methacrylate (DPOMA) and 2‐{[(1‐phenylethylidene)ami no]oxy}‐2‐oxoethyl methacrylate (MMOMA) were prepared by reaction of sodium methacrylate with diphenylmethanone O‐(2‐chloroacetyl) oxime and 1‐phenylethanone O‐(2‐chloroacetyl) oxime, respectively. They were obtained from a reaction of chloroacetyl chloride with benzophenone oxime or acetophenone oxime. The free‐radical‐initiated copolymerization of (DPOMA) and (MMOMA) with styrene (St) were carried out in 1,4‐dioxane solution at 65°C using 2,2‐azobisisobutyronitrile (AIBN) as an initiator with different monomer‐to‐monomer ratios in the feed. The monomers and copolymers were characterized by FTIR, ¹H‐ and ¹³C‐NMR spectral studies. The copolymer compositions were evaluated by nitrogen content in polymers. The reactivity ratios of the monomers were determined by the application of Fineman–Ross and Kelen–Tüdös methods. The molecular weights (M¯_w and M¯_n) and polydispersity index of the polymers were determined by using gel permeation chromatography. Thermogravimetric analysis of the polymers reveals that the thermal stability of the copolymers increases with an increase in the mole fraction of St in the copolymers. The activation energies of the thermal degradation of the polymers were calculated with the MHRK method. Glass transition temperatures of the copolymers were found to decrease with an increase in the mole fraction of DPOMA or MMOMA in the copolymers. The antibacterial and antifungal effects of the monomers and polymers were also investigated on various bacteria and fungi. The photochemical properties of the polymers were investigated by UV and FTIR spectra.     

A nonstandard numerical method for the modified KdV equation

A linearly implicit nonstandard finite difference method is presented for the numerical solution of modified Korteweg–de Vries equation. Local truncation error of the scheme is discussed. Numerical examples are presented to test the efficiency and accuracy of the scheme.     

Measurements of Propanal Ignition Delay Times and Species Time Histories Using Shock Tube and Laser Absorption

Propanal is an aldehyde intermediate formed during the hydrocarbon combustion process. Potentially, the use of oxygenated biofuels reduces greenhouse gas emissions; however, it also results in increased toxic aldehyde by‐products, mainly formaldehyde, acetaldehyde, acrolein, and propanal. These aldehydes are carcinogenic, and therefore it is important to understand their formation and destruction pathways in combustion systems. In this work, ignition delay times were measured behind reflected shock waves for stoichiometric (Φ = 1) mixtures of propanal (CH₃CH₂CHO) and oxygen (O₂) in argon bath gas at temperatures of 1129 K < T < 1696 K and pressures around 1 and 6 atm. Measurements were conducted using the kinetics shock tube facility at the University of Central Florida. Current results were compared to available data in the literature as well as to the predictions of three propanal combustion kinetic models: Politecnico di Milano (POLIMI), National University of Ireland at Galway, and McGill mechanisms. In addition, a continuous wave‐distributed feedback interband cascade laser centered at 3403.4 nm was used for measuring methane (CH₄) and propanal time histories behind the reflected shock waves during propanal pyrolysis. Concentration time histories were obtained at temperatures between 1192 and 1388 K near 1 atm. Sensitivity analysis was carried for both ignition delay time and pyrolysis measurements to reveal the important reactions that were crucial to predicting the current experimental results. Adjustments to the POLIMI mechanism were adopted to better match the experimental data. Further research was suggested for the H abstraction reaction rates of propanal. In addition to extending the temperature and pressure region of literature ignition delay times, we provide the first high‐temperature species concentration time histories during propanal pyrolysis.     

Silicon/aluminum and oxygen/nitrogen ordering in lanthanum U−phase (La3Si3Al3O12N2)

High-resolution ²⁹Si, ²⁷Al, ¹⁵N, and ¹⁷O MAS NMR spectra have been obtained for both glass and crystalline samples of lanthanum U-phase, La₃Si₃Al₃O₁₂N₂. Previous X-ray single-crystal studies have shown that this phase is iso-structural with rare-earth gallogermanates of the type Ln₃Ga₅GeO₁₄, the atomic arrangement consisting of layers of [(Si,Al)(O,N)₄] tetrahedra in the x, y plane of the hexagonal unit cell, linked together in the z-direction by [AlO₆] octahedra, with rare-earth cations occupying the large holes in this network. However, previous studies obtained only a limited amount of information about cation and anion ordering, mainly deduced from bond-length data. NMR spectra have not only enabled the change in structure from glass to crystalline ceramic to be monitored, but have also given detailed ordering information about the latter, indicating partial disorder of both (Si,Al) and (O,N) on their respective sites in the tetrahedra.