High-Modulus Wholly Aromatic Fibers. II. Partially Ordered Polyamide-Hydrazides

Partially ordered polyarnide-hydrazides were produced by the poly condensation of diacid chlorides with aminobenz-hydrazides, the order that results being a consequence of the considerably more rapid reaction of a diacid chloride with the hydrazide group in competition with the aromatic amine group of the aminobenzhydrazide. Fibers were produced from a series of such polymers containing from 50 mole % meta-oriented phenylene rings to 100 mole % para-oriented ones. Fiber from the wholly para-oriented type of polymer exhibited very high strength and modulus: 12.5 and 468 g/den, respectively, at 4.3% elongation-to-break. Although the crystallinity and density observed for hot-drawn fibers of partially ordered completely para-oriented polyarnide-hydrazides were comparable to the crystallinity and density of fibers of the isomeric wholly ordered polymer, the partially ordered polymers were more readily spun to the ultra-high strength and high modulus type fibers, probably because their greater solubility made them easier to spin.     

High-Modulus Wholly Aromatic Fibers. I. Wholly Ordered Polyamide-Hydrazides and Poly-1,3,4-oxadiazole—Amides

Several completely ordered polyamide-hydrazide copolymers were prepared via low temperature poly condensation of aromatic diacid chlorides with symmetrical aromatic diamines containing preformed dihydrazide linkages. Highly crystalline, hot-drawn fibers of the polyamide-hydrazide containing only para-oriented phenylene units showed unusually high strength and exceptionally high initial modulus: 10.8 and 508 g/den, respectively, at 2.9% elongation-to-break. The as-spun fibers also exhibited rather high tensile strength and unusually high initial modulus: 8.2 and 291 g/den, respectively, at 9.4% elongation-to-break. The hot-drawn fiber retained considerable strength at elevated temperatures, exhibiting a tenacity of 1.4 g/den and an initial modulus of 169 g/den at 350°C. Heat-aging of the as-spun fiber at 185°C in air showed that 66% of the original tenacity, 41% of the elongation, and 86% of the modulus were retained even after 336 hr. Substitution of as little as 25 mole % meta-oriented phenylene rings for para-oriented ones resulted in loss of the ultra-high strength and modulus, giving tensile properties comparable to those of fibers from wholly aromatic polyamides of the meta-oriented type. Fibers from the polyamide-hydrazides containing 50 mole % meta-oriented rings showed similar properties. Although ordered oxadiazole-amide copolymers were obtained from diamines containing two preformed oxadiazole linkages separated by m-phenylene rings, fibers could not be spun from them. Fiber of an ordered oxadiazole-amide copolymer was obtained, however, by heat treatment of the wholly p-phenylene ordered poly amide-hydrazide copolymer precursor fiber. Such a fiber exhibited a tenacity of 15.3 g/den, 3.6% elongation-to-break, and 564 g/den initial modulus.     

Highly luminescent europium(III) complexes with naphtoiltrifluoroacetone and dimethyl sulphoxide

The synthesis, luminescence properties, experimental determination and theoretical calculation of the emission quantum yield of Eu(NTA)₃.2L complexes, where NTA is naphtoiltri-fluroacetone and L denotes H₂O or DMSO (dimethyl sulphoxide), were reported. The compounds were characterized by elemental analysis (carbon, hydrogen and europium), thermal analysis, UV-visible absorption and photoluminescence spectroscopies. The experimental quantum yields were determined based on a method previously proposed by Bril and collaborators. The Eu(NTA)₃.2DMSO compound shows a high value for the Ω₂ intensity parameter (35.8 × 10^?20 cm²), reflecting the hypersensitive nature of the ⁵D₀ → ⁷F₂ transition and indicating that the lanthanide ion is in a highly polarizable chemical environment. The experimental quantum yield measured for that compound, 0.75, is one of the highest so far reported for solid-state europium complexes. The theoretical calculations of the quantum yield were carried out by solving an appropriate set of rate equations and by using empirical spectroscopic parameters and energy transfer rates. The theoretical results agree well with the experimental data for both complexes. The photostability of Eu(NTA)₃.2DMSO at 358K was evaluated in order to verify whether this complex can be applied as a phosphor for blue light emitting devices.     

Ionic conductivity of sodium beta″-alumina

Measurements of the electrical conductivity of Na ß″-alumina show that the low-temperature activation energies are 0.3337 ± 0.0055 eV for MgO stabilized crystals grown at 1700°C, 0.275 ± 0.015 eV for crystals with the same starting composition position grown at 1650°C, and 0.1716 ± 0.0093 eV for crystals stabilized with ZnO and grown at 1700°C. The conductivities of almost all crystals at 500°C were found to be 1.3 ± 0.6 Ω^?1 cm^?1. In addition to the growth conditions, the presence of a dc electric field, the type of electrode material, the type of conducting ion, and the concentration of stabilizing ion are important in determining the electrical conductivity. These factors are believed to affect the nature of the ordering of vacancies in the ß″-aluminas, leading to variations in the activation energy.     

Adsorption, desorption, and diffusion of nitrogen in a model nanoporous material. II. Diffusion limited kinetics in amorphous solid water

The adsorption, desorption, and diffusion kinetics of N2 on thick (up to approximately 9 microm) porous films of amorphous solid water (ASW) films were studied using molecular beam techniques and temperature programmed desorption. Porous ASW films were grown on Pt(111) at low temperature (<30 K) from a collimated H2O beam at glancing incident angles. In thin films (<1 microm), the desorption kinetics are well described by a model that assumes rapid and uniform N2 distribution throughout the film. In thicker films (>1 microm), N2 adsorption at 27 K results in a nonuniform distribution, where most of N2 is trapped in the outer region of the film. Redistribution of N2 can be induced by thermal annealing. The apparent activation energy for this process is approximately 7 kJ/mol, which is approximately half of the desorption activation energy at the corresponding coverage. Preadsorption of Kr preferentially adsorbs onto the highest energy binding sites, thereby preventing N2 from trapping in the outer region of the film which facilitates N2 transport deeper into the porous film. Despite the onset of limited diffusion, the adsorption kinetics are efficient, precursor mediated, and independent of film thickness. An adsorption mechanism is proposed, in which a high-coverage N2 front propagates into a pore by the rapid transport of physisorbed second layer N2 species on top of the first surface bound layer.     

Characterization of bacterial lipooligosaccharides by delayed extraction matrix-assisted laser desorption ionization time-of-flight mass spectrometry

Matrix-assisted laser desorption ionization (MALDI) with a time-of-flight analyzer has been used to analyze bacterial lipooligosaccharides (LOS). Crude LOS preparations from pathogenic strains of Haemophilus influenzae and Haemophilus ducreyi and a commercial preparation of lipopolysaccharide from Salmonella typhimurium were treated with hydrazine to remove O-linked fatty acids on the lipid A moiety. The resulting O-deacylated LOS forms were water soluble and more amenable to cocrystallization with standard MALDI matrices such as 2,5-dihydroxybenzoic acid and 1-hydroxyisoquinoline. Under continuous extraction conditions, O-deacylated LOS yielded broad peaks with abundant salt adducts as well as forming prompt fragments through β-elimination of phosphoric acid, that is, [M-H₃PO₄-H]. However, when a time delay was used between ionization and extraction (“delayed extraction”) a significant improvement was seen in both mass resolution and the stability of the molecular ions against β-elimination of phosphoric acid, especially in the negative-ion mode. Both an external two-point calibration and an internal single-point calibration were used to assign masses, the latter of which provided the highest degree of accuracy (better than 0.01% in most cases). At higher laser powers, the LOS molecules cleave readily between the oligosaccharide and lipid A moieties yielding a number of prompt fragments. Postsource decay (PSD) analysis of selected molecular ions provided a set of fragments similar to those seen in the linear spectra, although they were more limited in number because they were derived from a single LOS-glycoform. Both the prompt and PSD fragments provided important structural information, especially in assigning the phosphate and phosphoethanolamine substitution pattern of the lipid A and oligosaccharide portions of LOS. Last, with the addition of ethylenediaminetetraacetic acid followed by pulsed sonication, the relatively insoluble (and impure) LOS preparations yielded MALDI spectra similar to the O-deacylated LOS, although these intact LOS preparations required higher laser powers to ionize and were generally more affected by competing impurities.     

Ab initio calculations of the reaction mechanisms for metal-nitride deposition from organo-metallic precursors onto functionalized self-assembled monolayers

An atomistic mechanism has been derived for the initial stages of the adsorption reaction for metal-nitride atomic layer deposition (ALD) from alkylamido organometallic precursors of Ti and Zr on alkyltrichorosilane-based self-assembled monolayers (SAMs). The effect of altering the terminal functional group on the SAM (including -OH, -NH2, -SH, and -NH(CH3)) has been investigated using the density functional theory and the MP2 perturbation theory. Reactions on amine-terminated SAMs proceed through the formation of a dative-bond complex with an activation barrier of 16-20 kcal/mol. In contrast, thiol-terminated SAMs form weak hydrogen-bonded intermediates with activation barriers between 7 and 10 kcal/mol. The deposition of Ti organometallic precursors on hydroxyl-terminated SAMs proceeds through the formation of stronger hydrogen-bonded complexes with barriers of 7 kcal/mol. Zr-based precursors form dative-bonded adducts with near barrierless transitions. This variety allows us to select a kinetically favorable substrate for a chosen precursor. The predicted order of reactivity of differently terminated SAMs and the temperature dependence of the initial reaction probability have been confirmed for Ti-based precursors by recent experimental results. We predict that the replacement of methyl groups by trifluoromethyl groups on the SAM backbone decreases the activation barrier for amine-terminated SAMs by 5 kcal/mol. This opens a route to alter the native reactivities of a given SAM termination, in this case making amine termination energetically viable. The surface distribution of SAM molecules has a strong effect on the adsorption kinetics of Ti-based precursors. Unimolecular side decomposition reactions were found to be kinetically competitive with adsorption at 400 K.     

Graft Copolymerizations of Polysaccharides. II. Acrylamide Grafting to Yellow Dextrin

Graft copolymers of acrylamide and yellow dextrin were prepared using cerium(IV) as initiator. The yellow dextrin had a very broad molecular weight distribution but was fractionated utilizing dialysis and ultrafiltration membranes. Initiator efficiencies were determined using size exclusion chromatography and were found to be between 2.4 and 34%. Initiator efficiency increased with acrylamide concentration at constant cerium (IV) and yellow dextrin concentrations, and decreased with increasing cerium(IV) concentration at constant acrylamide and yellow dextrin concentrations. Plots of acrylamide conversion and intrinsic viscosity vs initial acrylamide concentration at constant yellow dextrin and ceric ion concentrations showed a maximum at about 2.0 M.