2,547 research outputs found
The crystallization of tough thermoplastic resins in the presence of carbon fibers
The crystallization kinetics of the thermoplastic resins poly(phenylene sulfide) (PPS) and poly(aryl-ether-ether-ketone) (PEEK) in the presence and in the abscence of carbon fibers was studied. How carbon fiber surfaces in composites affect the crystallization of tough thermoplastic polymers that may serve as matrix resins were determined. The crystallization kinetics of such substances can provide useful information about the crystallization mechanisms and, thus, indicate if the presence of carbon fibers cause any changes in such mechanisms
The crystallization and crystalline properties of LARC-TPI
LARC-TPI, a thermoplastic polyimide, has been studied in order to develop an understanding of its crystalline phase transition. Our experiments suggest that samples synthesized in different laboratories apparently had different degrees of imidization and their thermal behaviors differed accordingly. When the most crystalline of these polyimides was studied in some detail, we found that it melted irreversibly in that once a sample was completely melted it would not recrystallize. A polymer that did not recrystallize displayed a glass transition, which increased in temperature upon subsequent cooling and reheating. Solubility experiments indicated that heating above the crystalline melting temperature led to network formation in the polymer, a conclusion that is consistent with other behavior just mentioned. Differential calorimetric studies revealed that annealing at slow heating rates or under isothermal conditions resulted in dual melting transitions. These studies, supported by X-ray diffraction results, strongly indicate that the annealing process involves a solid-liquid-solid transformation. From an existing phenomenological model for the kinetics of phase transitions, kinetic parameters for these crystallizations have been evaluated. The Avrami exponents n increased with the annealing temperature in the protocol used in this study. Their values were about 2 or lower, thus indicating that crystallization may have followed a mechanism that included heterogeneous nucleation of a low dimensional order in which all the embryonic crystallites formed at the beginning of the process. A positive temperature coefficient for these crystallizations indicated that diffusion may have had a rate controlling influence and affected the values of n
The crystallization of tough thermoplastic resins in the presence of carbon fibers
The presence of carbon fibers increased the crystallization rates of both PEEK and PPS thermoplastic polymers. The effect was most pronounced at higher crystallization temperatures. Isothermal crystallization rates were analyzed by applying classical phenomenological nucleation theory. Unusually high values of the so-called Avrami exponent were found for neat PEEK. Isothermal crystallization of PEEK and PPS polymers produced crystalline samples having a wide variety of melting temperatures. The melting as observed by differential scanning calorimetry occurred as dual endotherms which were called primary (higher temperature) and secondary melting peaks. Each primary peak accounted for most of the crystallinity present. The secondary peaks represented the melting of crystallites formed later than those attributable to the primary endotherms. The presence of carbon fibers increased the thermal stability of both PEEK and PPS crystallites as manifested by higher temperatures for the primary melting peaks. This may be attributable to increased crystallite size, greater crystallite perfection, and/or favorable modification of the crystallite interface. Over the range studied, crystallization temperature strongly influenced the positions of the secondary peaks but not the primary peaks
Optimal uncertainty quantification for legacy data observations of Lipschitz functions
We consider the problem of providing optimal uncertainty quantification (UQ)
--- and hence rigorous certification --- for partially-observed functions. We
present a UQ framework within which the observations may be small or large in
number, and need not carry information about the probability distribution of
the system in operation. The UQ objectives are posed as optimization problems,
the solutions of which are optimal bounds on the quantities of interest; we
consider two typical settings, namely parameter sensitivities (McDiarmid
diameters) and output deviation (or failure) probabilities. The solutions of
these optimization problems depend non-trivially (even non-monotonically and
discontinuously) upon the specified legacy data. Furthermore, the extreme
values are often determined by only a few members of the data set; in our
principal physically-motivated example, the bounds are determined by just 2 out
of 32 data points, and the remainder carry no information and could be
neglected without changing the final answer. We propose an analogue of the
simplex algorithm from linear programming that uses these observations to offer
efficient and rigorous UQ for high-dimensional systems with high-cardinality
legacy data. These findings suggest natural methods for selecting optimal
(maximally informative) next experiments.Comment: 38 page
Alter Patient - (k)ein Grund zur Sorge?: Ethische Fragen im Lichte empirischer Daten
Zusammenfassung: Hintergrund: Die vorliegende Arbeit befasst sich mit der Frage, ob und inwiefern das Alter des Patienten bei Therapieentscheidungen eine Rolle spielt. Material und Methoden: Als empirische Grundlage werden aktuelle Daten aus 2Interviewstudien zu ethischen Fragen in der Rettungs- und Intensivmedizin bzw. der Geriatrie herangezogen sowie eine Fragebogenstudie bei Allgemeinärzten und Internisten (ambulant und stationär tätig) in 4 europäischen Ländern. Ergebnisse: Demnach besteht Evidenz, dass das Alter des Patienten faktisch durchaus ein wirksamer Faktor bei der Therapieentscheidung bis hin zum Vorenthalten adäquater Maßnahmen ist. Zu unterscheiden ist dabei zwischen einer Wirksamkeit des Faktors Alter einerseits und der Legitimation, Therapie nach dem Alter des Patienten zuzuteilen oder vorzuenthalten. Ob eine solche Unterscheidung nach Alter ethisch akzeptabel ist, wird international kontrovers beurteilt. Die Daten der Studien werden im Lichte ethischer Argumente diskutiert. Schlussfolgerung: Nach einer Übersicht über das Für und Wider der Altersrationierung wird die Schlussfolgerung vertreten, dass die Argumente gegen eine Diskriminierung nach Alter überwiegen. Die Arbeit schließt mit (ethischen) Empfehlungen für die Praxi
Dynamic rotor mode in antiferromagnetic nanoparticles
We present experimental, numerical, and theoretical evidence for a new mode
of antiferromagnetic dynamics in nanoparticles. Elastic neutron scattering
experiments on 8 nm particles of hematite display a loss of diffraction
intensity with temperature, the intensity vanishing around 150 K. However, the
signal from inelastic neutron scattering remains above that temperature,
indicating a magnetic system in constant motion. In addition, the precession
frequency of the inelastic magnetic signal shows an increase above 100 K.
Numerical Langevin simulations of spin dynamics reproduce all measured neutron
data and reveal that thermally activated spin canting gives rise to a new type
of coherent magnetic precession mode. This "rotor" mode can be seen as a
high-temperature version of superparamagnetism and is driven by exchange
interactions between the two magnetic sublattices. The frequency of the rotor
mode behaves in fair agreement with a simple analytical model, based on a high
temperature approximation of the generally accepted Hamiltonian of the system.
The extracted model parameters, as the magnetic interaction and the axial
anisotropy, are in excellent agreement with results from Mossbauer
spectroscopy
Oxidation of guanines in the iron-responsive element RNA: similar structures from chemical modification and recent NMR studies
AbstractBackground: The translation or stability of the mRNAs from ferritin, m-aconitase, erythroid aminoevulinate synthase and the transferrin receptor is controlled by the binding of two iron regulatory proteins to a family of hairpin-forming RNA sequences called iron-responsive elements (IREs). The determination of higher-solution nuclear magnetic resonance (NMR) structures of IRE variants suggests an unusual hexaloop structure, leading to an intra-loop G-C base pair and a highly exposed loop guanine, and a special internal loop/bulge in the ferritin IRE involving a shift in base pairing not predicted with standard algorithms.Results: Cleavage of synthetic 55- and 30-mer RNA oligonucleotides corresponding to the ferritin IRE with complexes based on oxoruthenium(IV) shows enhanced reactivity at a hexaloop guanine and at a guanine adjacent to the internal loop/bulge with strong protection at a guanine in the internal loop/bulge. These results are consistent with the recent NMR structures. The synthetic 55-mer RNA binds the iron-regulatory protein from rabbit reticulocyte lysates. The DNA analogs of the 55- and 30-mers do not show the same reactivity pattern.Conclusions: The chemical reactivity of the guanines in the ferritin IRE towards oxoruthenium(IV) supports the published NMR structures and the known oxidation chemistry of the metal complexes, The results constitute progress towards developing stand-alone chemical nucleases that reveal significant structural properties and provide results that can ultimately be used to constrain molecular modeling
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