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.     

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Effect of charged and excited states on the decomposition of 1,1-diamino-2,2-dinitroethylene molecules

The authors have calculated the electronic structure of individual 1,1-diamino-2,2-dinitroethylene molecules (FOX-7) in the gas phase by means of density functional theory with the hybrid B3LYP functional and 6-31+G(d,p) basis set and considered their dissociation pathways. Positively and negatively charged states as well as the lowest excited states of the molecule were simulated. They found that charging and excitation can not only reduce the activation barriers for decomposition reactions but also change the dominating chemistry from endo- to exothermic type. In particular, they found that there are two competing primary initiation mechanisms of FOX-7 decomposition: C-NO2 bond fission and C-NO2 to CONO isomerization. Electronic excitation or charging of FOX-7 disfavors CONO formation and, thus, terminates this channel of decomposition. However, if CONO is formed from the neutral FOX-7 molecule, charge trapping and/or excitation results in spontaneous splitting of an NO group accompanied by the energy release. Intramolecular hydrogen transfer is found to be a rare event in FOX-7 unless free electrons are available in the vicinity of the molecule, in which case HONO formation is a feasible exothermic reaction with a relatively low energy barrier. The effect of charged and excited states on other possible reactions is also studied. Implications of the obtained results to FOX-7 decomposition in condensed state are discussed.     

TDPAC study of the ZrCo-hydrogen system

The properties of the ZrCo-hydrogen system as a function of composition ratio H/ZrCo were investigated by combining TDPAC and X-ray diffraction techniques with the full potential linearized augmented plane wave (LAPW) band structure calculations. It was found that during hydrogenation ZrCo transferred directly into ZrCoH₃ and no transition phase existed. The z component V_zz of the efg and the asymmetry parameter η at the Zr and Co sites were calculated for ZrCoH₃ by using the structure parameters of Zr and Co, obtained in the present work, combined with the hydrogen structure parameters obtained from neutron diffraction on ZrNiH₃. The calculations are in good agreement with the measured values for V_zz and η. This agreement is consistent with the proposed 4c and 8f interstitial sites occupancy of the hydrogen atoms in ZrCoH₃. This revised version was published online in August 2006 with corrections to the Cover Date.     

Measurement of the intensity and phase of supercontinuum from an 8-mm-long microstructure fiber

We generate, measure, and model broadband continuum generation from a relatively short 8-mm-long microstructure fiber pumped by 40-fs pulses at 816 nm in the near infrared. Cross-correlation frequency-resolved optical gating is used to measure the spectral intensity and phase of the output continuum, and the results are shown to be in good agreement with numerical simulations. The output temporal intensity exhibits a distinct series of ultra-short sub-40-fs-duration sub-pulses, with these results directly revealing for the first time the temporal pulse breakup and soliton fission that is the dominant initial spectral broadening process underlying supercontinuum generation in microstructure fibers.     

A random evolution related to a Fisher–Wright–Moran model with mutation,recombination and drift

The paper deals with a model of the genetic process of recombination, one of the basis mechanisms of generating genetic variability. Mathematically, the model can be represented by the so‐called random evolution of Griego and Hersch, in which a random switching process selects from among several possible modes of operation of a dynamical system. The model, introduced by Polanska and Kimmel, involves mutations in the form of a time‐continuous Markov chain and genetic drift. We demonstrate asymptotic properties of the model under different demographic scenarios for the population in which the process evolves. Copyright © 2003 John Wiley & Sons, Ltd.     

Minimal surfaces: a geometric three dimensional segmentation approach

Summary. A novel geometric approach for three dimensional object segmentation is presented. The scheme is based on geometric deformable surfaces moving towards the objects to be detected. We show that this model is related to the computation of surfaces of minimal area (local minimal surfaces). The space where these surfaces are computed is induced from the three dimensional image in which the objects are to be detected. The general approach also shows the relation between classical deformable surfaces obtained via energy minimization and geometric ones derived from curvature flows in the surface evolution framework. The scheme is stable, robust, and automatically handles changes in the surface topology during the deformation. Results related to existence, uniqueness, stability, and correctness of the solution to this geometric deformable model are presented as well. Based on an efficient numerical algorithm for surface evolution, we present a number of examples of object detection in real and synthetic images. Received January 4, 1996 / Revised version received August 2, 1996     

Modeling competitive cytokine adsorption dynamics within hemoadsorption beads used to treat sepsis

Extracorporeal blood purification is a promising therapeutic modality for sepsis, a potentially fatal, dysfunctional immunologic state caused by infection. Removal of inflammatory mediators such as cytokines from the blood may help attenuate hyper-inflammatory signaling during sepsis and improve patient outcomes. We are developing a hemoadsorption device to remove cytokines from the circulating blood using biocompatible, porous sorbent beads. In this work, we investigated whether competitive adsorption of serum solutes affects cytokine removal dynamics within the hemoadsorption beads. Confocal laser scanning microscopy (CLSM) was used to quantify intraparticle adsorption profiles of fluorescently labeled IL-6 in horse serum, and results were compared to predictions of a two component competitive adsorption model. Supraphysiologic IL-6 concentrations were necessary to obtain adequate CLSM signal, therefore unknown model parameters were fit to CLSM data at high IL-6 concentrations, and the fitted model was used to simulate cytokine adsorption behavior at physiologically relevant levels which were below the microscopy detection threshold. CLSM intraparticle IL-6 adsorption profiles agreed with predictions of the competitive adsorption model, indicating displacement of cytokine by high affinity serum solutes. However, competitive adsorption effects were predicted using the model to be negligible at physiologic cytokine concentrations associated with hemoadsorption therapy.