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  • 1
    Electronic Resource
    Electronic Resource
    Springer
    Calcified tissue international 10 (1972), S. 82-90 
    ISSN: 1432-0827
    Keywords: Calcium ; Phosphate ; Precipitation ; Kinetics ; Chemistry
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine , Physics
    Description / Table of Contents: Résumé La cinétique de la formation et de la transformation des précipités de phosphate de calcium, obtenus en mélangeant de volumes égaux de solutions à 6×10−3 M de calcium total et/ou phosphate total est étudiée à 25°C. Les solutions de phosphate sont préajustées à un pH de 7.4. Les changements de pH et de turbidité des solutions sont suivis simultanément en fonction du temps. Les précipités sont isolés à des intervalles de temps variables et caractérisés par diverses méthodes physico-chimiques. Initialement un précipité avec un rapport molaire Ca/P de 1.5, amorphe aux rayons X et en diffraction électronique, est formé. Le spectre IR indique la présence de PO 4 3− et de HPO 4 2− . Après une période métastable, on observe la précipitation d'un matériel cristallin dans ou sur la phase amorphe. Vingt quatre heures après préparation de l'échantillon les précipités présentent surtout les caractères du phosphate octocalcique.
    Abstract: Zusammenfassung Die Kinetik der Bildung und Transformation von Calciumphosphat-Niederschlägen wurde bei 25°C untersucht. Es wurden dazu gleiche Volumen von Lösungen gemischt, bei einer Konzentration von 6×10−3M totales Calcium und/oder totales Phosphat. Die Phosphatlösungen wurden zuerst auf pH 7,4 eingestellt. Veränderungen des pH und Trübung der Lösungen wurden gleichzeitig als eine Funktion der Zeit aufgezeichnet. Niederschläge wurden in verschiedenen Zeitintervallen isoliert und mit verschiedenen physiko-chemischen Methoden charakterisiert. Am Anfang wurde ein Niederschlag mit einem molaren Ca/P-Verhältnis von 1,5, im Röntgenbild und in der Elektronendiffraktion amorph, gebildet. Infrarotspektren deuteten die Anwesenheit von PO 4 3− - und HPO 4 2− -Ionen an. Nach einer metastabilen Periode erfolgte ein Niederschlag aus kristallinem Material innerhalb oder auf der amorphen Substanz. 24 Std nach der Herstellung der Proben zeigten die Niederschläge in der Hauptsache die Charakteristiken von Octocalciumphosphat.
    Notes: Abstract The kinetics of the formation and transformation of calcium phosphate precipitates obtained by mixing equal volumes of solutions, 6×10−3 M in total calcium and/or total phosphate was investigated at 25°. The phosphate solutions were preadjusted to pH 7.4. Changes of the pH and turbidity of the solutions were followed simultaneously as a function of time. Precipitates were isolated at various time intervals and characterized by different physicochemical methods. Initially a precipitate with a molar Ca/P ratio of 1.5, amorphous to X-ray and electron diffraction was formed. IR spectra indicated the presence of PO 4 3− and HPO 4 2− ions. After a period of metastability, precipitation of a crystalline material within or upon the amorphous matter occurred. Twenty four hours after sample preparation the precipitates showed mainly the characteristics of octacalcium phosphate.
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  • 2
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    Meccanica 33 (1998), S. 445-468 
    ISSN: 1572-9648
    Keywords: Turbulence ; Wall-bounded turbulent shear flows ; Scaling laws in turbulence ; Local structure of turbulence ; Fluid mechanics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Abstract Turbulence at very large Reynolds numbers (often called developed turbulence) is widely considered to be one of the happier provinces of the turbulence realm, as it is widely thought that two of its basic results are well-established, and have a chance to enter, basically untouched, into a future complete theory of turbulence. These results are the von Kármán-Prandtl universal logarithmic law in the wall-region of wall-bounded turbulent shear flow, and the Kolmogorov-Obukhov scaling laws for the local structure of developed turbulent flow.However, doubts have been expressed over the years about the fluid mechanical assumptions that underlie these laws. After a concise review of the problem of turbulence as a whole we will show in the present paper that the von Kármán–Prandtl universal logarithmic law is based on an assumption which,though plausible, in fact is not quite correct. We will come to the conclusion, based on theoretical considerations and on processing of experimental data, that the universal logarithmic law does not describe the real features of developed turbulent wall-bounded flow of viscous fluid; it should be jettisoned and replaced by a different law, a scaling law. Experimental evidence for the local structure of turbulent flows is now not sufficiently well-established to allow a similarly definite conclusion. However, the application of the new approach presented here makes it very plausible that the classical, non-modified version of Kolmogorov–Obukhov ‘K-41’ laws gives an adequate description of the local features of developedturbulent flows. Sommario.La turbolenza agli altissimi numeri di Reynolds (spesso chiamata turbolenza sviluppata) è largamente ritenuta una delle regioni felici del regno della turbolenza: si pensa infatti che due suoi risultati fondamentali siano ben assodati e che abbiano speranza di entrare senza rilevanti modifiche in una futura teoria completa della turbolenza.Questi risultati sono la legge logaritmica universale di Kármán–Prandtl per la regione di parete dei flussi turbolenti confinati e la legge di simulitudine di Kolmogorov–Obukhov per la struttura locale del flusso turbolento sviluppato. Nel corso degli anni sono stati tuttavia espressi dubbi sulle ipotesi fluidodinamiche che sottendono queste leggi. Nel presente lavoro, dopo un breve esame del problema della turbolenza nel suo insieme,dimostreremo che la legge logaritmica universale di Kármán–Prandtl è basata su un'assunzione che, per quanto plausibile, non è del tutto corretta. Giungeremo alla conclusione, basata su considerazioni teoriche esull'elaborazione di dati sperimentali, che la legge logaritmica universale non descrive le caratteristiche reali del flusso turbolento di un fluido viscoso sviluppato e confinato da una parete; essa dovrebbe essere sostituita de una legge differente, una legge di similitude. L'evidenza sperimentale per la stzuttura locale di flusso turbolento non è al momento sufficientemente assodata perpermettere una conclusione altrettanto definita. L'impiegodel nuovo approccio qui presentato, tuttavia, rende assai plausible che la classica versione non modificata della legge ‘K-41’ di Kolmogorov-Obukhov fornisca una adeguata descrizione delle caratteristiche locali del flussoturbolento sviluppato.
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  • 3
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    Meccanica 33 (1998), S. 29-46 
    ISSN: 1572-9648
    Keywords: Finite difference methods ; Free shear layers ; Turbulence ; Fluid mechanics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Abstract A computational formulation is proposed for second-moment closure turbulence models, especially suited to models intended to ensure physical realizability. It enables to cast the quite complicated model equations in a compact form. It is specifically applied here to a two-dimensional parabolized flow, though it lends itself to extension to more complex flows. An effective computational algorithm is proposed, based on a staggered grid and a block tridiagonal solver. The algorithm is applied to a turbulent mixing layer, and the comparison between the predictions obtained by standard modelling tools and a realizable second-moment closure clearly points out the superiority of the latter.
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  • 4
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    Meccanica 33 (1998), S. 503-516 
    ISSN: 1572-9648
    Keywords: Flow visualization ; Speckle photography ; Particle image velocimetry ; Turbulence ; Fluid mechanics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Abstract Modern developments in laser and computer technology, electronic cameras, and digital image processing techniques allow to generate planar distributions of quantitative data in turbulent flows. Large amounts of data can be processed easily and analyzed statistically. With these tools, it is possible to quantitatively visualize turbulent coherent structures, even in flows of high Reynolds number, and measure characteristic spatial quantities like vorticity, length scales, spatial correlation functions, etc. These potentials in analyzing spatial characteristics of turbulent flows are demonstrated with two different methods of quantitative flow visualization: speckle photography as a representative of the line-of-sight methods, and particle image velocimetry belonging to the methods that rely on the scattering of laser light from tracer particles. Sommario.I moderni sviluppi nelle tecnologie del laser e dei computers, delle telecamere elettroniche e le tecniche di analisi digitale delle immagini permettono di ottenere distribuzioni quantitative, in un piano, di dati relativi a flussi turbolenti. Una gran quantità di dati può essere con facilità analizzata statisticamente. Con questi mezzi è possibile visualizzare quantitativamente strutture coerenti turbolente anche in flussi da alto numero di Reynolds, e misurare caratteristiche spaziali, come vorticità scale e funzioni di correlazione. Questa potenzialità di studiare caratteristiche spaziali di flussi turbolenti viene qui mostrata per due differenti metodi di visualizzazione quantitativa: fotografia ‘speckle’ e PIV (particle image velocimetry).
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  • 5
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    Space science reviews 83 (1998), S. 75-86 
    ISSN: 1572-9672
    Keywords: Solar wind ; Heliosphere ; Ulysses ; SOHO ; MHD waves ; Turbulence
    Source: Springer Online Journal Archives 1860-2000
    Topics: Physics
    Notes: Abstract The solar wind in the inner heliosphere, inside ~ 5 AU, has been almost fully characterized by the addition of the high heliographic latitude Ulysses mission to the many low latitude inner heliosphere missions that preceded it. The two major omissions are the high latitude solar wind at solar maximum, which will be measured during the second Ulysses polar passages, and the solar wind near the Sun, which could be analyzed by a Solar Probe mission. Here, existing knowledge of the global solar wind in the inner heliosphere is summarized in the context of the new results from Ulysses.
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  • 6
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    Calcified tissue international 10 (1972), S. 171-197 
    ISSN: 1432-0827
    Keywords: Amorphous ; Crystalline ; Calcium phosphate ; Chemistry ; Composition
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine , Physics
    Description / Table of Contents: Résumé Des échantillons non lavés de phosphate de calcium amorphe (ACP) contiennent une fraction labile, non remplaçable, riche en phosphate acide avec un rapport Ca/P faible: cette fraction est perdue de façon irréversible au cours du lavage. De l'ACP frais, précipité entre pH 6.6–10.6, varie dans un rapport molaire Ca/P de 1.18 à 1.50 et dans un rapport HPO 4 2− /P total de 33.0% à 10.1%. A pH 7.40, de l'ACP frais a un rapport molaire Ca/P de 1.36±0.02 et contient 22.8 (±2.2)% HPO 4 2− . Les résultats obtenus avec du précipité non lavé ne peuvent s'expliquer par du Ca2+ emprisonné et de l'HPO 4 2− ou du Na+, Cl− et CO 3 2− exogènes. Les phosphates de calcium amorphes constituent une classe de sels ayant des caractères chimiques variables et des propriétés physiques identiques, comparables au verre. Le CaHPO4·xH2O non cristallin peut être un ACP, surtout au cours des phases précoces de formation. A des pH physiologiques, l'ACP se transforme en petits cristaux applatis contenant de fortes quantités de phosphate acide facilement remplaçable. Le fait de laver la couche de surface produit un changement chimique dans les nouveaux cristaux: des cristaux non lavés donnent des diagrammes de diffraction d'apatite peu cristallins, ainsi que des spectres infra-rouges peu nets, intermédiaires entre des apatites et du phosphate octocalcique. Des explications structurales sont proposées et les compositions minérales amorphe/cristalline de l'os et du cartilage sont recalculées.
    Abstract: Zusammenfassung Ungewaschene Proben von amorphem Calciumphosphat (ACP) enthalten eine unersetzliche labile Fraktion, welche reich an saurem Phosphat ist und ein niederes Ca/P-Verhältnis hat und welche während des Waschprozesses unwiderruflich verloren geht. Natives ACP, welches im pH-Bereich 6,6–10,6 ausgefällt wurde, variierte im molaren Ca/P-Verhältnis zwischen 1,18 und 1,50 und in HPO 4 2− /totales P zwischen 33,0 und 10,1%. Bei pH 7,40 hatte natives ACP ein molares Ca/P-Verhältnis von 1,36±0,02 und enthielt 22,8 (±2,2)% HPO 4 2− . Die Werte beim ungewaschenen Niederschlag rühren weder von aus dem Überstand aufgenommenem Ca2+ und HPO2−, noch von außen kommendem Na+, Cl− und CO 3 2− her. Die amorphen Calciumphosphate werden als eine Klasse von Salzen erkannt, welche veränderliche chemische, aber identische glasartige physicochemische Eigenschaften haben. Nicht kristallines CaHPO4·xH2O kann auch ein ACP sein, besonders in den frühen Bildungsstadien. Bei physiologischem pH verwandelt sich ACP in kleine plattenförmige Kristalle, welche große Mengen von leicht ersetzbarem saurem Phosphat enthalten. Das Waschen dieser Oberflächenschicht erzeugte chemische Veränderungen in den resultierenden Kristallen; ungewaschene Kristalle zeigten ein Diffraktionsmuster, das nur schwach demjenigen des kristallinen Aspatites glich, aber ein schlecht aufgelöstes Infrarotspektrum, welches zwischen Apatit und Octocalciumphosphat war. Es werden strukturelle Erklärungen für alle diese Phenomena diskutiert, und revidierte amorph/kristalline Mineralzusammensetzungen von Knochen und Knorpel wurden neu berechnet.
    Notes: Abstract Unwashed samples of amorphous calcium phosphate (ACP) contain an irreplaceable labile fraction, rich in acid phosphate and low in Ca/P ratio, which is irreversibly lost during the washing process. Native ACP precipitated in the pH range 6.6–10.6 varied in Ca/P molar ratio from 1.18 to 1.50 and in HPO 4 2− /total P from 33.0% to 10.1%. At pH 7.40, native ACP had a Ca/P molar ratio of 1.36±0.02 and contained 22.8 (±2.2)% HPO 4 2− . Unwashed precipitate data could not be attributed to either trapped supernatant Ca2+ and HPO 4 2− or extraneous Na+, Cl−, and CO 3 2− . The amorphous calcium phosphates are recognized as a class of salts having variable chemical but identical glass-like, physicochemical properties. Non-crystalline CaHPO4·xH2O may also be an ACP, especially during early formative stages. At physiological pH, ACP transforms to small platy crystals containing large amounts of readily-replaceable acid phosphate. Washing this surface layer produced chemical alterations in the resultant crystals; unwashed crystals had poorly-crystalline apatitic diffraction patterns but exhibited poorly-resolved infrared spectra intermediate between apatite and octacalcium phosphate. Structural explanations for all these phenomena are discussed, and revised bone and cartilage amorphous/crystalline mineral compositions have been re-calculated.
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  • 7
    ISSN: 1432-1254
    Keywords: Key words Meteorology ; Turbulence ; Modelling ; Spray drift ; Wind
    Source: Springer Online Journal Archives 1860-2000
    Topics: Geography , Physics
    Notes: Abstract  An insight into the nature of prevailing meteorological conditions and the manner in which they interact with spraying parameters is an important prerequisite in the analysis of the dynamics of agrochemical sprays. Usually, when these sprays are projected from hydraulic nozzles, their initial velocity is greater than that of the ambient wind speed. The flowfield therefore experiences changes in speed and direction which are felt upstream as well as downstream of the spray droplets. The pattern of the droplet flow, i.e. the shape of the streamlines marking typical trajectories, will be determined by a balance of viscous forces related to wind speed, inertial forces resulting from the acceleration of the airstream and pressure forces which can be viewed in terms of the drag forces exerted on the spray droplets themselves. At a certain distance in the ensuing motion, when the initial velocity of the spray droplets has decreased sufficiently for there to be no acceleration, their trajectories will be controlled entirely by the random effects of turbulence. These two transport processes in the atmosphere can be modelled mathematically using computers. This paper presents a model that considers the velocity of spray droplets to consist of a ballistic velocity component superimposed by a random-walk velocity component. The model is used to study the influence of meteorological and spraying parameters on the three-dimensional dynamics of spray droplets projected in specified directions in neutral and unstable weather conditions. The ballistic and random-walk velocity components are scaled by factors of (1–ξ) and ξ respectively, where ξ is the ratio of the sedimentation velocity and the relative velocity between the spray droplets and the surrounding airstream. This ratio increases progressively as the initial velocity of the spray droplet decreases with air resistance and attains a maximum when the sedimentation velocity has been reached. As soon as this occurs, the random-walk process predominates. The computed effects of the release height of spray droplets, atmospheric turbulence intensity, evaporation, drop size spectrum, wind velocity and wind direction on the transport process have been studied and an analysis of spray drift is provided.
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  • 8
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    Boundary layer meteorology 87 (1998), S. 459-480 
    ISSN: 1573-1472
    Keywords: Coherence model ; Spatial coherence ; Turbulence
    Source: Springer Online Journal Archives 1860-2000
    Topics: Geosciences , Physics
    Notes: Abstract Wind speed measurements from the test site at Rutherford Appleton Laboratory have been evaluated with respect to the spatial coherence function. The experimental arrangement provides coherence information for separation distances of 62, 80 and 102 m. These are at least three times greater than the measurement heights of 18 m and 18.7 m. Based on these experimental data and data published in the literature, different theoretical formulations are compared and a new, but simple, model for longitudinal and lateral coherence is proposed. At large separations the turbulent wind field is not isotropic, theoretical models to describe the coherence function for such distances are not available. The new model we propose builds on the classical exponential approach. It takes into account the influence of turbulence intensity and models the angular dependence of horizontal coherence. It is found that, for constant turbulence intensity, the lateral coherence decay becomes independent of the mean wind speed.
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  • 9
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    Boundary layer meteorology 89 (1998), S. 285-316 
    ISSN: 1573-1472
    Keywords: Boundary layer ; Heterogeneous terrain ; Roughness length ; Surface fluxes ; Turbulence
    Source: Springer Online Journal Archives 1860-2000
    Topics: Geosciences , Physics
    Notes: Abstract The aim of this work is to present experimentally evaluated effective roughnesses (zoe) of a partly forested landscape. Although the ratio of boundary-layer height to obstacle size was only of the order of 50, there still seemed to exist a height range of 75–200 m where surface-layer similarity was approximately valid. Attempts were made to use conventional wind profile analysis to evaluate zoe, but the small height range and the large number of variables initially led to unacceptable uncertainties. Fixing the displacement height zd, rather than fitting it, reduced the data scatter to an acceptable level. The profile-derived roughness lengths zop obtained in this way were in good agreement with previous work, and with an alternative roughness length estimate zof for which flux-derived profile parameters u* and θ* were used. This implies that the profile-derived roughnesses were consistent with the measured surface-layer momentum flux. Comparison of both roughness estimates also yielded an improved estimate of the displacement height. Besides this, the authors tested a landscape roughness evaluation method which makes use of the gustiness parameter Tu = σu/U in the surface layer. The results obtained by this method were in fair agreement with the profile-derived data. In previous work, the gustiness method was advocated because it could be used at relatively low levels, perhaps even within the roughness sub-layer. At the present measuring site, this was not the case as the gustiness method was only valid in an approximate way, and for a limited height range.
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  • 10
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    Boundary layer meteorology 86 (1998), S. 63-87 
    ISSN: 1573-1472
    Keywords: Stratocumulus ; Mass flux ; Lateral entrainment ; Turbulence ; Conditional sampling
    Source: Springer Online Journal Archives 1860-2000
    Topics: Geosciences , Physics
    Notes: Abstract A mass-flux approach is applied to observational data obtained in a convective boundary layer topped with stratocumulus clouds. The observational data were obtained from aircraft measurements during the Atlantic Stratocumulus Transition Experiment (ASTEX). A conditional sampling method is used to calculate average updraft and downdraft values. The vertical fluxes calculated with the mass-flux approach are found to be proportional to the real (measured) fluxes, with a proportionality factor being about 0.6. This value is predicted by theory for two variables having a joint Gaussian distribution function; proportionality factor = 2π-1 ≈ 0.637. The horizontal fractional entrainment and detrainment rates calculated from the data (ε ≈ 1–2 × 10-2 m-1) are an order of magnitude higher than the rates obtained by large eddy simulations for cumulus convection (ε ≈ 2–3 × 10-3 m-1) and two orders of magnitude higher than those used in modelling cumulus convection with a mass-flux scheme in an operational weather forecast model (ε ≈ 3 × 10-4 m-1). A numerical mass-flux model for the thermodynamics was developed and showed that results are in good agreement when compared with measured profiles of the liquid water content.
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  • 11
    ISSN: 1573-1472
    Keywords: Turbulence ; Surface temperature ; Surface inhomogeneity ; Source area
    Source: Springer Online Journal Archives 1860-2000
    Topics: Geosciences , Physics
    Notes: Abstract Turbulence characteristics, vertical profiles of wind velocity u(z) and air temperature T(z), and also spatial variations in steppe surface radiation temperature Tr(x) are measured simultaneously. A marked effect of Tr(x) characteristics on the turbulence characteristics and T(z) profiles is observed in the lower part of the atmospheric surface layer. We suggest that variability in Tr(x) noticeably influences the surface-layer temperature field and leads to scatter in the values of the universal functions obtained by different authors; effects of Tr(x) are not accounted for in similarity theory. The introduction of the value of temperature zero-plane displacement dT in the calculation formulae (to determine temperature flux) noticeably improves the agreement between calculated and measured (by eddy-correlation method) results. The influence of footprint (or Source Area) on the obtained results leads to noticeable scatter in the data obtained from measurements of atmospheric turbulence.
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  • 12
    ISSN: 1573-1472
    Keywords: Turbulence ; Convective boundary layer ; Clear air radar observations ; Coherent organizations ; Radar-aircraft joint observations
    Source: Springer Online Journal Archives 1860-2000
    Topics: Geosciences , Physics
    Notes: Abstract The scientific objective of the TRAC experiment (Turbulence Radar Aircraft Cells) was to investigate the respective roles played by small-scale turbulence and coherent structures in the vertical transfer within the atmospheric boundary layer (ABL). Field research held in June 1993 in France was based on coupled aircraft and Doppler radar measurements. The results discussed here are mainly focused on the evaluation of the performance of the radar in the 3D description of the clear air ABL, which was the technical goal of TRAC. During the experiment, the radar was able to provide continuous and coherent echo fields over a range of several tens of kilometres, extending up to about 3 km. Good agreement was obtained in the ABL between the radar-derived turbulent quantities and airborne measurements. As depicted by the reflectivity fields, coherent organizations were found to be a common feature of the eleven ABL cases analyzed. These organizations evolved during the day between a banded structure and a cellular pattern. A very weak correlation was found between the reflectivity field and the atmospheric parameters measured by the aircraft. However, in terms of characteristic scale, the reflectivity field appeared to be strongly related to the water vapour field. The inhomogeneity induced by the coherent circulations questions the representativity of one-dimensional sampling of these 3D fields and suggests the need to adapt the traditional statistical approach of the ABL.
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  • 13
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    Boundary layer meteorology 86 (1998), S. 233-256 
    ISSN: 1573-1472
    Keywords: Lidar ; Remote sensing ; Turbulence ; Velocity statistics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Geosciences , Physics
    Notes: Abstract Coherent Doppler lidar measurements of wind statistics in the boundary layer are presented. The effects of the spatial averaging by the lidar pulse are removed using theoretical corrections and computer simulations. This permits unbiased estimates of velocity variance, spatial velocity structure functions, energy dissipation rate, and other point statistics of the velocity field.
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  • 14
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    Boundary layer meteorology 86 (1998), S. 333-344 
    ISSN: 1573-1472
    Keywords: Turbulence ; Dispersion model ; Non-uniqueness ; Plant canopy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Geosciences , Physics
    Notes: Abstract Lagrangian stochastic models, quadratic in velocity and satisfying the well-mixed condition for two-dimensional Gaussian turbulence, are used to make predictions of scalar dispersion within a model plant canopy. The non-uniqueness associated with satisfaction of the well-mixed condition is shown to be non-trivial (i.e. different models produce different predictions for scalar dispersion). The best agreement between measured and predicted mean concentrations of scalars is shown to be obtained with a small sub-class of ‘optimal’ models. This sub-class of ‘optimal’ models includes Thomson's model (J. Fluid Mech. 180, 529–556, 1987), the simplest model that satisfies the well-mixed condition for Gaussian turbulence, but does not include two other models identified recently as being in optimal agreement with the measured spread of tracers in a neutral boundary layer. It is therefore demonstrated that such models are not universal, i.e. applicable to a wide range of flows without readjustment of model parameters. Predictions for scalar dispersion in the model plant canopy are also obtained using the model of Flesch and Wilson (Boundary-Layer Meteorol. 61, 349–374, 1992). It is shown that, when used with a Gaussian velocity distribution or a maximum-missing-information velocity distribution, which accounts for the measured skewness and kurtosis of velocity statistics, the agreement between predictions obtained using the model of Flesch and Wilson and measurements is as good as that obtained using Thomson's model.
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  • 15
    ISSN: 1573-1472
    Keywords: Lagrangian decorrelation time scales ; Structure function constant ; Turbulence ; Lagrangian spectrum constant
    Source: Springer Online Journal Archives 1860-2000
    Topics: Geosciences , Physics
    Notes: Abstract A new method for deriving the Lagrangian decorrelation time scales for inhomogeneous turbulence is described. The expression for the time scales here derived for the convective boundary layer is compared to those estimated by Hanna during the Phoenix experiment. Then the values of C0, the Lagrangian velocity structure function constant, and of Bi, the Lagrangian velocity spectrum constant, were evaluated from the Eulerian velocity spectra and from the Lagrangian time scales derived, under unstable conditions, from Taylor's statistical diffusion theory. The numerical coefficient of the lateral and vertical Lagrangian spectra in the inertial subrange was found equal to 0.21, in good agreement with previous experimental estimates.
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  • 16
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    Boundary layer meteorology 87 (1998), S. 1-25 
    ISSN: 1573-1472
    Keywords: Kites ; Atmospheric measurements ; Turbulence ; Profiling ; Ozone
    Source: Springer Online Journal Archives 1860-2000
    Topics: Geosciences , Physics
    Notes: Abstract This paper presents the capabilities and limitations of using state-of-the-art kites for atmospheric research. A brief historical review of the subject is first presented, followed by an outline of the current status of kite-borne measurement technology. The utility of the technique is then illustrated by presenting a series of recent measurements made using kite-borne technology. A summary of the advantages and limitations of kite-based measurements relative to other technologies is provided for reference.
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    Studia geophysica et geodaetica 42 (1998), S. 382-390 
    ISSN: 1573-1626
    Keywords: Magnetohydrodynamics (MHD) ; Turbulence ; Magnetic fields ; Galaxies
    Source: Springer Online Journal Archives 1860-2000
    Topics: Architecture, Civil Engineering, Surveying , Geosciences , Physics
    Notes: Abstract We present simulations of the 3D nonlinear induction equation in order to investigate the temporal evolution of large-scale magnetic fields in spiral galaxies. Our model includes differential rotation, ambipolar diffusion and, based on small-scale turbulence, eddy diffusivity and the tensorial α-effect with magnetic feedback. The nonaxisymmetric spiral pattern and – if considered – the vertical stratification of the galaxy are represented in its density and turbulence profile. Neglecting vertical stratification the lifetime and geometry of an initial magnetic field depend on the correlation time of interstellar turbulence τ corr . Short correlation times increase the lifetime of the initial magnetic field, but the field is rapidly wound up. Its pitch-angles develop to zero. The magnetic field has disappeared after at most 1 to 1.5 Gyr. A resonance like phenomenon is found by tuning the pattern velocity of the galactic spiral. The simulations then show an exceptional amplification of the magnetic field in the case that the pattern speed and a magnetic drift velocity have similar values. Considering a vertical stratification we achieve sufficiently long living grand-designed magnetic fields excited by dynamo action. The behaviour and geometry of the resulting field is again significantly influenced by the correlation time τ corr . Small values of τ corr lead to axisymmetric fields with small pitch-angles and field-concentration between the spiral arms. Increasing the correlation time the solutions show larger pitch-angles; and depending on very large correlation times the galactic dynamo rather generates fields clearly within the spiral arms and having a bisymmetric structure.
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    Boundary layer meteorology 88 (1998), S. 211-237 
    ISSN: 1573-1472
    Keywords: Aircraft measurements ; Compositing ; Rayleigh-Bénard convection ; Spectral energetics ; Thermals ; Turbulence
    Source: Springer Online Journal Archives 1860-2000
    Topics: Geosciences , Physics
    Notes: Abstract A turbulence data set collected by the research aircraft Hercules and Falcon in the planetary boundary layer (PBL) over the North Sea during Rayleigh-Bénard convection (RBC) is analysed. Altogether nearly three hundred cell passages at different levels and in two different flight directions were sampled. The convective boundary-layer height (H) was about 1 km, and the RBC cells had a diameter D of roughly 2–3 km, resulting in an aspect ratio A = D/H ≈ 2–3. This value is also found in the case of RBC in laboratory-scale flows, whereas most of the recent PBL experimental work reports convection PBL rolls with A ≈ 3 and mesoscale cellular convection (MCC) with A ≈ 10–40 over the oceans. The large number of RBC cell passages made it possible to composite their average structure. Due to the more complex three-dimensional structure and the importance of thermals to the RBC dynamics, spectral, temporal and spatial decompositions and model calculations were necessary to illuminate structure, dynamics, energetics and organisation. The final impression is that the structure of RBC in the PBL is given by a honeycomb-like arrangement of short-lived mixed-layer thermals with more passive downward motions in between. The regularity of the Cu-cloud cover results partly from the more stationary flow in the cloud-free cell centres. On the other hand it is shown that active as well as inactive clouds contribute to the cloud cover. Thus, the PBL flow and the cloud cover are decoupled, at least temporarily and locally. Due to sparse observational and measured information about RBC occurrence and structure in the PBL, additional material was gathered, resulting in the impression that RBC is one additional realised mode of organised convection in the PBL, as has already been clarified for PBL rolls and MCC by recent investigations.
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    ISSN: 1573-1472
    Keywords: Heterodyne Doppler lidar ; Organized large eddies ; Planetary boundary laye ; Turbulence
    Source: Springer Online Journal Archives 1860-2000
    Topics: Geosciences , Physics
    Notes: Abstract In an experiment investigating the planetary boundary layer (PBL) wind and temperature fields, and PBL inversion height recorded by various instruments, the results reveal the presence of organized large eddies (OLE) or rolls. The measurements by lidars, anemometers, soundings and sodar gave an overview of the characteristics of the rolls and sources of energy production that maintain them. The experimental results obtained on two consecutive days are compared to model outputs. The agreement is excellent, showing that thermal stratification and wind shear are important factors in the structure and dynamics of OLE. A heterodyne Doppler lidar (HDL) is shown to be a useful tool in the study of OLE.
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    Boundary layer meteorology 89 (1998), S. 47-74 
    ISSN: 1573-1472
    Keywords: Canopy closure model ; Pine forest ; Turbulence
    Source: Springer Online Journal Archives 1860-2000
    Topics: Geosciences , Physics
    Notes: Abstract Simultaneous triaxial sonic anemometer velocity measurements vertically arrayed at six levels within and above a uniform pine forest were used to examine two parameterization schemes for the triple-velocity correlation tensor employed in higher-order closure models. These parameterizations are the gradient-diffusion approximation typically used in second-order closure models, and the full budget for the triple-velocity correlation tensor typically employed in third-order closure models. Both second- and third-order closure models failed to reproduce the measured profiles of the triple-velocity correlation within and above the canopy. However, the Reynolds stress tensor profiles (including velocity variances) deviated greatly from the measurements only within the lower levels of the canopy. It is shown that the Reynolds stresses are most sensitive to the parameterization of the triple-velocity correlation in these lower canopy regions where local turbulent production is negligible and turbulence is mainly sustained by the flux transport term. The failure of the third-order closure model to reproduce the measured third moments in the upper layers of the canopy-top contradicts conclusions from a previous study over shorter vegetation but agrees with another study for a deciduous forest. Whether the third-order closure model failure is due to the zero-fourth-cumulant closure approximation is therefore considered. Comparisons between measured and predicted quadruple velocity correlations suggest that the zero-fourth-cumulant approximation is valid close to the canopy-atmosphere in agreement with recent experiments.
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    Boundary layer meteorology 89 (1998), S. 141-159 
    ISSN: 1573-1472
    Keywords: Radiation ; Stable conditions ; Turbulence
    Source: Springer Online Journal Archives 1860-2000
    Topics: Geosciences , Physics
    Notes: Abstract The interaction between longwave radiation and temperature fluctuations plays a role in the dissipation of temperature variance. This interaction is most easily described by spectral models of atmospheric turbulence and a spectral radiative dissipation function which gives the intensity of the damping at each radiative wavelength λ and wavenumber k. We have used a Corrsin–Pao closure for the spectral budgets of turbulent kinetic energy and temperature to study the coupling of radiation to turbulence. The spectral radiative dissipation function and a related integral have been fitted by analytical approximations with the correct asymptotic behavior. This resulted in a simple analytical formula for the dimensionless temperature spectrum as a function of Monin-Obukhov stability, and a new dimensionless parameter describing the relative importance of radiation in the temperature spectral budget. The radiative effects both on the temperature spectrum and on the dimensionless temperature variance can then be calculated. Based on typical values of the radiative dimensionless parameters for the surface layer, we conclude that radiative dissipation is probably negligible there.
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    Boundary layer meteorology 89 (1998), S. 109-140 
    ISSN: 1573-1472
    Keywords: BOREAS ; Eddy correlation ; Eddy covariance ; Turbulence ; Understory
    Source: Springer Online Journal Archives 1860-2000
    Topics: Geosciences , Physics
    Notes: Abstract Turbulent flux measurements both above and beneath the canopy of a boreal aspen forest are described. Velocity skewness showed that, beneath the aspen canopy, turbulence was dominated by intermittent, downward penetrating gusts. Eulerian horizontal length scales calculated from integration of the autocorrelation function or spectral peaks were 9.0 and 1.4 times the mean aspen height of 21.5 m respectively. Above-canopy power spectral slopes for all velocity components followed the -2/3 power law, whereas beneath-canopy slopes were closer to -1 and showed a spectral short cut in the horizontal and vertical components. Cospectral patterns were similar both above and beneath the canopy. The Monin–Obukhov similarity function for the vertical wind velocity variance was a well-defined function of atmospheric stability, both above and beneath the canopy. Nocturnal flux underestimation and departures of this similarity function from that expected from Monin–Obukhov theory were a function of friction velocity. Energy balance closure greater than 80% was achieved at friction velocities greater than 0.30 and 0.10 m s-1, above and below the aspen canopy, respectively. Recalculating the latent heat flux using various averaging periods revealed a minimum of 15 min were required to capture 90% of the 30-min flux. Linear detrending reduced the flux at shorter averaging periods compared to block averaging. Lack of energy balance closure and erratic flux behaviour led to the recalculation of the latent and sensible heat fluxes using the ratio of net radiation to the sum of the energy balance terms.
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    ISSN: 1572-9613
    Keywords: Turbulence ; universal statistics ; anomalous scaling ; multi-fractals
    Source: Springer Online Journal Archives 1860-2000
    Topics: Physics
    Notes: Abstract We develop a consistent closure procedure for the calculation of the scaling exponents ζ n of the nth-order correlation functions in fully developed hydro-dynamic turbulence, starting from first principles. The closure procedure is constructed to respect the fundamental rescaling symmetry of the Euler equation. The starting point of the procedure is an infinite hierarchy of coupled equations that are obeyed identically with respect to scaling for any set of scaling exponents ζ n . This hierarchy was discussed in detail in a recent publication by V. S. L'vov and I. Procaccia. The scaling exponents in this set of equations cannot be found from power counting. In this paper we present in detail the lowest non-trivial closure of this infinite set of equations, and prove that this closure leads to the determination of the scaling exponents from solvability conditions. The equations under consideration after this closure are nonlinear integro-differential equations, reflecting the nonlinearity of the original Navier–Stokes equations. Nevertheless they have a very special structure such that the determination of the scaling exponents requires a procedure that is very similar to the solution of linear homogeneous equations, in which amplitudes are determined by fitting to the boundary conditions in the space of scales. The renormalization scale that is necessary for any anomalous scaling appears at this point. The Hölder inequalities on the scaling exponents select the renormalization scale as the outer scale of turbulence L. We demonstrate that the solvability condition of our equations leads to non-Kolmogorov values of the scaling exponents ζ n . Finally, we show that this solutions is a first approximation in a systematic series of improving approximations for the calculation of the anomalous exponents in turbulence.
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    Journal of Polymer Science: Macromolecular Reviews 6 (1972), S. 179-250 
    ISSN: 0076-2083
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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    ISSN: 0076-2083
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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    Journal of Applied Polymer Science 16 (1972), S. 1-14 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The radiation-induced graft copolymerization of styrene and various kraft softwood lignins was studied. Expression of the results as the usual “per cent graft” was impossible, because grafting caused the lignin to become extractable in solvents for the styrene homopolymer. However, evaluation of the effects of various solvents on the degree of reaction was made through an indirect, and possibly more characteristic, measure. Grafting was least pronounced under conditions of low lignin accessibility (e.g., when less than 10% methanol was present), but increased with the addition of better lignin solvents or with higher methanol concentrations. The precipitating nature of the latter conditions was also found to contribute to an accelerated rate of grafting. Surprisingly, the graft copolymer was found to degrade at higher doses. Proof of grafting is offered in a fractionation scheme. Measurement of the molecular weight of the polystyrene separated from the lignin backbone allows the estimation of approximately one polystyrene graft per lignin molecule in benzene-extractable copolymers. Two glass transition temperatures could be detected in several fractionated copolymers.
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    Journal of Applied Polymer Science 16 (1972), S. 61-68 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Color stability in irradiated PVC may be achieved by (1) structural modification to block dehydrochlorination, (2) addition of radiation protectors, or (3) addition of radical scavengers. This study explores the latter approaches. Twenty-six compounds representing a variety of structural types were screened for their effectiveness as measured by subsequent color development. Fifteen of the compounds imparted partial or complete postirradiation stability. Possible stabilizer mechanisms are discussed.
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    Journal of Applied Polymer Science 16 (1972), S. 83-97 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The ultraviolet degradation of poly(vinyl chloride) films was studied in a photoreactor which supplied energy near 3000 Å. It was noted that the rate of degradation and color development was increased when the level of residual solvent in the cast films was increased. Two solvents were employed in the study: tetrahydrofuran and dichloroethane. The amount of residual solvent was correlated with the height of a characteristic peak at 2800 Å for tetrahydrofuran and 1900 Å for dichloroethane. Films which had very small traces of solvent showed excellent resistance to ultraviolet degradation, even in the absence of ultraviolet stabilizers. The analysis of solubility data showed that chain scission was controlling in the early stages of exposure, while crosslinking was controlling at later stages. As a result, it was not possible to apply Charlesby's treatment of radiation-induced degradation. Comparison with the results obtained by other workers for degradation at 2537 Å showed that degradation at this wavelength was much faster than degradation at 3000 Å. Furthermore, degradation at 2537 Å appeared to be controlled by crosslinking at all stages of exposure.
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    Journal of Applied Polymer Science 16 (1972), S. 139-155 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: In this paper we define a new structural parameter of polymers, and show how this may be employed. This parameter, for which only the structure and the density are needed, is the relative number of network bonds per unit volume; it is written Ner (basis 1 cm3), and it is used in conjunction with the average connectivity or connection number CN of the network atoms, where the word connection also refers only to network bonds. The relationship of these two numbers makes it possible to present a unified picture of all polymers, organic and inorganic, including such highly condensed networks as diamond. By plotting Ner against CN, the region in which inorganic and organic polymers occur can be seen. This is called the polymer zone, and it is evident that carbon polymers occupy only a small part of it. From this graph, an arbitrary measure of bond packing efficiency can be deduced for carbon polymers. In addition, the process of graphitization and carbonization can be followed graphically within the polymer zone. Ner is also related to certain physical properties such as bulk modulus, hardness, and cubical coefficient of expansion, which depend (among other things) on the tightness of bond arrangement. The resultant correlations can be used to predict the value of Ner required to achieve given values of these properties for the more rigid structures.
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    Journal of Applied Polymer Science 16 (1972), S. 191-202 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
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    Notes: Poly(ethylene terephthalate) has been irradiated with UV light of different wavelengths and in various atmospheres. The extent of degradation was monitored by measuring the tensile strength, molecular weight, carboxylic acid endgroups, and fluorescence emission of the polymer. The importance of wavelengths 〈315 nm in causing deterioration was demonstrated to be mainly due to strong surface absorption which results in surface crazing and ultimate fracture under stress. Irradiation in nitrogen and under vacuum were found to give similar results, but with oxygen present in the system several significant differences were observed. In nonoxidative irradiations, crosslinking and discoloration of the polymer occurred. Under oxidative conditions, chain scissions and fluorescent material build-up resulted, whereas no crosslinking and only slight discoloration was observed. The possibility of a photo-oxidation reaction has thus been suggested, involving hydroperoxide formation, to explain the discrepancy in results obtained for the two types of environments.
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    Journal of Applied Polymer Science 16 (1972), S. 345-352 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The preparation of 3,3′-dichloro-5,5′-diaminobenzidine and its polymeric reaction products with pyromellitic dianhydride and 3,4,3′,4′-benzophenonetetracarboxylic dianhydride are described. The soluble amine-acid-amide form of the polymer is stable at higher concentrations than the corresponding polymers from 3,3′-diaminobenzidine or 3,3′,4,4′-tetraaminodiphenyl ether. Infrared spectra indicate that polybenzimidazopyrrolone structure is formed after cure. The preparation and properties of films and glass-reinforced laminates prepared from the polymers are described.
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    Journal of Applied Polymer Science 16 (1972), S. 395-406 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: A variance range analysis of the x-ray line profiles for seven cottons (native, ureatreated, and mercerized) has been carried out to get two estimates of the crystallite size from (1) the slope and (2) the variance intercept. Assuming the crystallite length of cellulose to be the same in ramie and native cottons under ideal conditions of growth, the relative fluctuation of the repeat length along the b-axis has been calculated for all the samples. This degree of paracrystalline lattice distortions is negatively correlated with the fiber bundle strength at zero gauge and appears to be the same as the imperfections referred to in the weak link theories of fiber strength. While the orientation parameters are also well correlated with strength, the degree of crystallinity does not seem to have any influence. Wilson's rigorous mathematical treatment of the number-average particle size, in relation to the two estimates from the variance slope and intercept as well as the particle size distribution, has been successfully applied for the first time to cotton fibers leading to a clearer understanding of crystallite size-strength relationship.
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    Journal of Applied Polymer Science 16 (1972), S. 449-460 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: A copolymer (MW = 1800) of styrene (St) and maleic anhydride (MAn) was esterified with an excess amount of an alcohol mixture, and then the relation between the esterification rates of the individual alcohols and the contents of the esters in the esterific copolymer was examined. At first, the rate constant of an individual esterification was obtained for four different alcohols (n-butanol, i-amylalcohol, and benzylalcohol) in a noncatalyst system. Then, the mixed esterification of n-butanol and i-amylalcohol was carried out; from the analysis of the ester contents, the following equation was obtained: $$ {{\left[ {{\rm P}_{\rm 1} } \right]} \mathord{\left/ {\vphantom {{\left[ {{\rm P}_{\rm 1} } \right]} {\left[ {{\rm P}_{\rm 2} } \right]}}} \right. \kern-\nulldelimiterspace} {\left[ {{\rm P}_{\rm 2} } \right]}} = {{k_1 \left[ {{\rm B}_{\rm 1} } \right]_0 } \mathord{\left/ {\vphantom {{k_1 \left[ {{\rm B}_{\rm 1} } \right]_0 } {k_2 \left[ {{\rm B}_{\rm 2} } \right]_0 .}}} \right. \kern-\nulldelimiterspace} {k_2 \left[ {{\rm B}_{\rm 2} } \right]_0 .}} $$ From this result, it was concluded that, in esterification with alcohols involving n species, the content of the individual ester can be expressed by the following equation: $$ {{\left[ {{\rm P}_j } \right]} \mathord{\left/ {\vphantom {{\left[ {{\rm P}_j } \right]} {\sum\limits_{i = 1}^n {\left[ {{\rm P}_i } \right]} }}} \right. \kern-\nulldelimiterspace} {\sum\limits_{i = 1}^n {\left[ {{\rm P}_i } \right]} }} = {{k_j \left[ {{\rm B}_j } \right]_0 } \mathord{\left/ {\vphantom {{k_j \left[ {{\rm B}_j } \right]_0 } {\sum\limits_{i = 1}^n {k_i \left[ {{\rm B}_i } \right]_0 } }}} \right. \kern-\nulldelimiterspace} {\sum\limits_{i = 1}^n {k_i \left[ {{\rm B}_i } \right]_0 } }} $$ where [P] = concentration of esters in the copolymer, [B]0 = initial concentration of alcohols, and k = rate constant of esterification (i,j = 1,2…,n).
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    Journal of Applied Polymer Science 16 (1972), S. 539-543 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
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    Journal of Applied Polymer Science 16 (1972), S. 865-870 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
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    Notes: The difference between the hydraulic permeability K under a pressure gradient and the diffusive permeability P under a concentration gradient can be explained by the incipient viscous flow at high degree of swelling. This flow is opposed by the friction resistance of the macromolecules of the highly swollen membrane. It comes to an end at a critical swelling Hc when the number of permeant molecules is not more sufficient for a complete solvation of the macromolecules of the membrane. Below this swelling, K equals PV1/RT, where V1 is the molar volume of the permeant, and above it the difference K - PV1/RT is proportional to H/(1 - H) - Hc/(1 - Hc). The proportionality factor depends on the friction coefficient of the macromolecular segments and on the average lateral chain clustering. The data on poly(glycerol methacrylate) suggest that on the average the aggregates contain two chains.
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    Journal of Applied Polymer Science 16 (1972), S. 917-920 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
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    Notes: A two-component reactive system consisting of a poly(chromium(III) bisphosphinate) and dioctylphosphinic acid reacts to form a poly(chromium(III) trisphosphinate). Extensive thermomechanical hysteresis is displayed throughout the temperature range -180°C to 〉300°C by specimens containing filaments of glass. Thermal pretreatment to about 400°C (the limit of thermal stability) eliminated these instabilities. These results correlate with the reported brittle and tough character of films of the poly(chromium (III) bisphosphinate) and poly(chromium (III) trisphosphinate), respectively. Regardless of thermal history (between 200°C and 400°C), the polymer system displayed three major transition regions: the glass transition centered at about 0°C, another centered at about 230°C, and a third at about -200°C.
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    Journal of Applied Polymer Science 16 (1972), S. 945-954 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Sorption kinetics and equilibria for CO2 in polycarbonate were studied over a range of temperatures from 35° to 65°C and pressures from 3 to 22 atm. The dual mode sorption model of Vieth et al. was used to test the data, and a comparison was made with previous work on glassy polystyrene. Further evidence of the validity of generality of the model in providing a consistent picture of small-molecule diffusion in glassy polymers was thereby provided. The technical feasibility of membrane separation of H2 from a H2/CO2 mixture by selective permeation through polycarbonate was examined at 50°C.
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    Journal of Applied Polymer Science 16 (1972), S. 987-1008 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Statistical analysis of inherent viscosities (LVN), shear modulus (G*), and melting temperature (Tm) interval data for isotactic polypropylene-linear polyethylene (HDPE) blends was performed in order to verify their microheterogeneity. High shear measurements in viscometric (Poiseuille's) flow were carried out on four replicated compositions of the blends. Least-squares treatment of the results yielded power law parameters for the blends differing in composition. The significance of differences between the blends of various HDPE content was tested using the multiple-range (Duncan's) test, and tentative conclusions are drawn on the composition dependence of the melt flow viscosities of the blends.
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    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The radiation-induced graft copolymerization of styrene to cellulose has been studied in vacuo at 30°C and at dose rates from (0.37 to 8.73) × 10-2 W/kg. Dioxan was used as solvent for monomer and polystyrene homopolymer, and water (2% total volume) was incorporated as swelling agent for cellulose. The concentration of styrene in the bulk medium was varied from 0.432 to 3.46 moles/l., and the rates of both grafting and homopolymerization were shown to be proportional to [monomer] · [intensity]1/2. The value of 3.3 × 10-4 l. mole-1 sec-1 derived for kp2/kt in homopolymerization is similar to that for normal free-radical polymerization of styrene. However, reduced termination during grafting yielded a much higher value (58 l. moles-1 sec-1). Degradation of cellulose in the absence of monomer was followed viscometrically, and values of 13.5 and 24.6 were derived for G (scission) in vacuo and in air, respectively.
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  • 40
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The separation of various liquid mixtures including systems of chloroform-hydrocarbons or ethyl ether, water-alcohols and water-nucleophilic organic solvents have been investigated by the pervaporation technique. Membranes were obtained by grafting Lewis base onto poly(tetrafluoroethylene) (PTFE) films. The PTFE backbone has been chosen for its mechanical and chemical resistance. N-Vinylpyrrolidone and 4-vinylpyridine were selected because of their great affinity for the electrophilic compounds. In all cases, the compound which has the greatest affinity for the membrane pervaporates selectively through modified PTFE films. Selectivity and rates were studied. It is concluded that because selectivity is very important, total separation of different mixtures is possible at a good yield, with a faster rate when the temperature is increased or the thickness of the membrane is decreased.
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  • 41
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    Journal of Applied Polymer Science 16 (1972), S. 1109-1123 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Polybutadiene rubbers of well-defined and varying molecular weight were prepared by anionic polymerization and used in the preparation of mass-polymerized polystyrene blends. The particle size of the dispersed rubber phase was varied by (1) controlling the relative viscosity, at phase inversion, of the two liquid phases composed of polystyrene and polybutadiene in styrene monomer; (2) by varying the intensity of mixing, and (3) by adding preformed polystyrene to the prepolymer, prior to phase inversion. The mechanical and dynamic properties of the resulting blends are found to be determined mainly by the particle size of the dispersed rubber phase, independently from the method used to obtain such size. The weight fraction of rubber phase, rather than the weight fraction of rubber charged, is found to correlate with the blend modulus and may also affect its level of toughness. Low molecular weight rubbers are found capable of efficient blend reinforcement, if the excessively small rubber particle size obtained by conventional processes is enlarged by incorporation of preformed polystyrene prior to phase inversion.
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  • 42
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    Journal of Applied Polymer Science 16 (1972), S. 1155-1166 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: This paper describes the results of simultaneous dynamic measurements in tension and torsion made on propellant samples. The complex dynamic moduli E′, E″, G′, and G″ at low frequencies were determined within a temperature range from room temperature to -90°C. Time temperature shift factors and reduced master curves for both tension and shear properties are discussed. The effect of dewetting on the dynamic properties in tension and shear was also investigated. A preliminary attempt is made to compute the degree of dewetting in a propellant by applying Beer-Lambert's law.
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  • 43
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    Journal of Applied Polymer Science 16 (1972), S. 1191-1212 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: A change in the degree of vulcanization in a carbon black-filled rubber is shown not to affect the change of in-phase shear modulus with strain amplitude, provided the amount of filler is kept constant. Similar results are found with the change of out-of-phase modulus and phase angle with strain amplitude. A similar value of change of in-phase shear modulus with strain amplitude (G′0 - G′∞) is found for a vulcanized and unvulcanized tire tread rubber; this behavior is attributed for the breakdown of the secondary three-dimensional carbon black aggregated network. Detailed consideration is given to other factors such as hydrodynamic, shape factor, and relaxation effects which contribute to the difference between the shear modulus of the gum rubber and the filled rubber when all the carbon black structure has been broken down. The consequence of the breakdown of the secondary aggregated structure of carbon black are considered in terms of factors affecting heat build-up in tires.
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  • 44
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    Journal of Applied Polymer Science 16 (1972), S. 1281-1293 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: A semiempirical model for estimation of viscosities of concentrated polymer solutions1 can be applied to mixtures of polymers in a common solvent. The data required for estimation of mixture viscosity are: solvent viscosity, polymer molecular weight, density, concentration, and intrinsic viscosity in the particular solvent. Calculated and experimental viscosities agree to within a few per cent for the relatively nonpolar systems for which comparative data are available. The model does not appear to be adequate for mixtures in which there are extensive hydrogen-bonding interactions.Results of the new model are equivalent to those of an empirical equation2 reported to be effective for fairly concentrated binary polymer mixtures.Specific interactions between polymeric solutes can be conveniently assessed by comparing measured mixture viscosity to that calculated from the model presented. It is not clear, however, that such assessments have any fundamental significance, since the interactions which are calculated depend on the assumptions inherent in the estimation of the “ideal” mixture viscosity. The same reservations apply to other models which have been proposed for this purpose.
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  • 45
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    Journal of Applied Polymer Science 16 (1972), S. 1911-1924 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Equipment and techniques are described which have been developed for determining the drawing behavior of fibers from novel polymers which are available only in very small quantities. Emphasis is placed upon information obtained from the stress-strain diagrams of the fibers during drawing. A parameter, the reinforcement factor, is described which reflects the degree of orientation induced by drawing short lengths of fiber in a discontinuous manner. This parameter exhibits maxima at various combinations of temperature and draw rate, and the relationship between the corresponding temperatures and draw rates is shown to be logarithmic. The parameter is used to predict temperatures and draw rates which will give fibers having a high degree of orientation and good tensile properties when drawn continuously. The application of these techniques to give acceptable fibers from poly(m-phenylene adamantane-1,3-dicarboxamide) is described. This material is of interest as one possessing a high degree of thermal stability, and the best fibers produced to date have a tenacity of 4.0 g per denier, an initial modulus of 60 g per denier, and a break extension of 16.0%.
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  • 46
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    Journal of Applied Polymer Science 16 (1972), S. 1925-1935 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Styrene-grafted nylon 6 fibers which had been prepared by the UV irradiation method were investigated by dynamic viscoelasticity and dilatometry. It was found that nylon 6 is relaxed and polystyrene is simultaneously plasticized by nylon 6 during grafting. These phenomena are interpreted as follows. The grafting process causes nylon 6 to have a lower glass transition temperature and increases grafting frequency of polystyrene to nylon 6 by increasing the chemical junctions between the two components, so that they necessarily become more compatible.
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  • 47
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    Journal of Applied Polymer Science 16 (1972), S. 1947-1952 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
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    Notes: The grafting of isoprene as well as a comonomer mixture of isoprene and acrylonitrile onto a backbone of high molecular weight poly(propylene oxide) with tertiary-butyl peroctoate gave a gumstock which is sulfur curable to a product having interesting elastomeric properties.
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  • 48
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    Journal of Applied Polymer Science 16 (1972), S. 1937-1946 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Starch xanthates with degrees of substitution (D.S.) ranging from 0.08 to 0.58 were reacted with high or low molecular weight polyethylenimine (PEI, two of six times the stoichiometric amount) to form starch poly(ethylenimino thiourethanes). Aqueous thiourethane solutions were mixed with commercial styrene-butadiene and acrylonitrile-butadiene latices, and the solids were coprecipitated by adding 1M ZnSO4 and 1N H2SO. The master batches (filtered, dried at 70°C), having 15 to 50 parts of starch (equivalent) per 100 parts of rubber (phr), were masticated and compounded in a sulfur-accelerator recipe and press cured to yield vulcanizates of improved physical characteristics compared to control vulcanizates. About 0.22 D.S. produced best results. With this D.S. xanthate and a 3.5 ratio of 100,000 MW PEI, a 25 phr starch loading gave maximum tensile strength (2720 psi) in a styrene-butadiene vulcanizate. Hardness generally increased with increasing D.S. and starch contents. The thiourethane decreased compression set and increased abrasion resistance. The former was lowest and the latter highest at ca. 0.20 D.S. and 25 phr starch. Both set and abrasion were lowest with thiourethane prepared from xanthate made in a “Roto-feed” process rather than a “Ko-Kneader” operation. Rebound was not appreciably changed, and increase of volume swelling in water was small upon thiourethane incorporation.
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    Journal of Applied Polymer Science 16 (1972), S. 1953-1958 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: A series of epoxy resins based on the diglycidyl ethers of bisphenol A have been characterized by nuclear magnetic resonance and gel permeation chromatography. The ratio of molecular volume of a lightly branched molecule to that of a linear molecule of the same weight was found to vary as the square root of the ratio of the average maximal dimensions of the chain. At high degrees of chain branching, the ratio of the latter was to the power of three halves.
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    Journal of Applied Polymer Science 16 (1972), S. 1959-1965 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
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    Notes: The kinetics of primary crystallization from the melt of nylon 6-piperazine adipate and nylon 6-piperazine terephthalate copolyamides were measured dilatometrically. It was found that the crystallization rate of the samples under investigation decreases with increase in the percentage comonomer content and rigidity of molecules over the entire temperature range investigated. The Avrami exponent n varied with temperature, values being from 2 to 4.
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    Journal of Applied Polymer Science 16 (1972), S. 2091-2104 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
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    Notes: The thermomechanical spectra of two series of amorphous polyolefins represented by $\rlap{--} [{\rm CH}_2 )_m {\rm - C}\left( {{\rm CH}_3 } \right)_2 \rlap{--} ]_n$ and $\rlap{--} [\left( {{\rm CH}_2 } \right)_m \bond {\rm C}\left( {{\rm CH}_3 } \right)\left( {{\rm C}_2 {\rm H}_5 } \right)\rlap{--} ]_n$, where m = 1, 2, and 3, are presented from -180°C to above the glass transition temperatures. The polymers were obtained by cationic polymerization of α-olefins. The mechanical spectra show a maximum in glass transition temperature and secondary transition temperature for the second member of each series. This maximum is interpreted in terms of a proposed geometrical intermolecular interlocking which is considered to be at a maximum for the second member of the series and serves to restrict the submolecular motions associated with the transitions. The proposal is discussed in terms of its consequences upon free volume, density, cohesive energy density, and chain flexibility.
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    Journal of Applied Polymer Science 16 (1972), S. 2131-2139 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The proton spin-lattice relaxation and dielectric relaxation were studied in some polymers at the solid-polymer interface was constructed from several filled polymers. A useful model of surface layer which can be considered as consisting of a great number of small solid particles covered with a polymer layer. The following systems were studied: polystyrene, poly(methyl methacrylate), their copolymers and cellulose acetate in the presence of different content of fine particles of aerosil and Teflon. It was established that the decrease of surface layer thickness shifts the minimum of spin-lattice relaxation time T1 of high temperature process to higher temperature and minimum T1 of low temperature process to lower temperature. The same was found for dielectric losses reflecting the motion of side groups and of segments. From temperature dependence of T1 and tan δ for both relaxation processes the apparent energies of activation were calculated. On the base of dielectric relaxation data the circular diagram of complex dielectric constant was constructed and by the Cole-Cole method the dispersion parameter α for polymers at the interface was calculated. These data also show the broadening of relaxation spectra in surface layers. The results are discussed in terms of the restriction of possible conformation of chains at the interface and their interaction with surface. It was established that character of molecular motion changes at the interface is dependent on the mode of molecular motion.
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    Journal of Applied Polymer Science 16 (1972), S. 2153-2155 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
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    Journal of Applied Polymer Science 16 (1972), S. 2175-2184 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Capillary flow data were obtained for a 27.5% solution of cellulose acetate in acetone. The solution temperature was 50°C, and the range of apparent shear rates investigated was 1.7 × 105 to 1.7 × 106 sec-1. Capillaries having tapered entrance angles of 37.88° to 120.63° were used. A power-law model was adequate to describe the shear stress at the wall (τw) and the corrected shear rate \documentclass{article}\pagestyle{empty}\begin{document}$(\dot \gamma )$\end{document} relationship. Entrance angle affected the entrance pressure drop corrected for kinetic energy, (ΔP0,c); ΔP0,c increased as the angle widened. Treating the entrance flow as an elongational flow situation facilitated superposition of the Delta;P0,c data on a single curve. Estimated elongational viscosities decreased with increasing applied stress.
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    Journal of Applied Polymer Science 16 (1972), S. 2159-2173 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Differential thermal analysis, or DTA, is a technique for determining the properties of materials from the thermodynamic and kinetic points of view. Dielectric measurement is also a powerful tool for probing the structure of materials, but from another direction. Dielectric analysis is a measure of the dipole response within dielectric materials to an applied electric field. This response is controlled by the spatial arrangement and viscoelastic properties of dielectric materials. Dielectric thermal analysis is being increasingly used in research and process control, offering the advantages of being nonobtrusive and easily instrumented and having a broad theoretical basis which can be correlated with results from other methods such as dynamic mechanical relaxation measurements, NMR, neutron relaxation, birefringence, and, of course, DTA. Because of the nonobtrusive nature of dielectric measurement, it can be run concurrently with other analytical techniques without disturbing their results. When dielectric analysis is run concurrently with other methods of analysis such as DTA, we often receive fresh insights and cross-checking on such behavior as polymeric crosslinking, molecular weight increase, and Tg - viscoelastic behavior in general. The results and conclusions drawn for such investigations are described.
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    Journal of Applied Polymer Science 16 (1972), S. 2207-2213 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Contact angles are reported for the systems ethanol-water, n-propanol-water, and benzene-cyclohexane measured at atmospheric pressure and 25.0°C, in equilibrium with their vapors, on poly(tetrafluoroethylene) surfaces of known roughness. Comparison of the data with those reported by other workers has shown that the discordancy in values can be attributed solely to the various preparation techniques producing surfaces of differing roughnesses.
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  • 57
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    Journal of Applied Polymer Science 16 (1972), S. 2239-2247 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The compatibility of the mixtures poly(vinyl chloride) - ethylene vinyl acetate copolymer and poly(vinyl chloride) - chlorinated ethylene vinyl acetate copolymer was studied by the method of dynamic mechanical testing. The character of G′ and G″ was confronted with the Takayanagi model. In all cases a limited compatibility of the components was observed.
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    Journal of Applied Polymer Science 16 (1972), S. 2249-2255 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The applicability of the formula f(t) = n(t)RT(α - α-2) suggested by Tobolsky as the basis of chemorheology has been discussed. In this expression, f(t) is the stress after t hours, n(t) is the crosslinking density (mole/cc) after t hours, R is the gas constant, T is the absolute temperature, and α is the extension ratio. We have discussed the applicability of this formula, in another words, whether the degraded stress f(t) calculated from this formula would be consistent with the initial stress ft(0) of other polymer if the degraded crosslinking density values n(t) are equal to those of nt(0), the initial density values n(0) of other polymer. Natural rubber vulcanizates and SBR vulcanizates were used as samples in these experiments. Assuming n(t) = σ(t) n(0), α(t′) = 1, the applicability of the above formula was recognized from our experimental results.
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    Journal of Applied Polymer Science 16 (1972), S. 2257-2268 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The effects of the combination of solvent and nonsolvent on the column fractionation of polypropylene were investigated. Decalin, kerosene, and α-chloronaphthalene were employed as the solvents, whereas ethyl and butyl carbitol were employed as the nonsolvents. It was found that the molecular weight distribution of the fractions was not very significantly affected by the combination of solvent and nonsolvent. By applying Caplan's theory, namely, that M̄-1/2 is a linear function of the weight fraction of solvent contained in the eluent (where M is the average molecular weight of a fraction), we concluded that to conduct a good fractionation both the solvent and the nonsolvent should be poorer solvents for the polymer.
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    Journal of Applied Polymer Science 16 (1972), S. 2291-2315 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: An apparatus was constructed which would allow vinyl-type monomers (and others) to polymerize at ambient temperatures in the presence of an inductively coupled RF field. The details of the construction of the system are reported along with preliminary results obtained from nine monomers: styrene, methylvinyldichlorosilane, vinyl acetate, acrylonitrile, vinyl fluoride, 1,1-difluoroethylene, vinyl chloride, ethylene, and 1,3-butadiene.
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    Journal of Applied Polymer Science 16 (1972), S. 2317-2341 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: A study has been made on the plasma polymerization of styrene monomer in a cold, low-power, inductively coupled RF plasma. Styrene monomer yielded an insoluble, crosslinked film which was slightly colored. A kinetic study is reported for styrene. The effects of power level, bleed rate of monomer, pressure, and reactor geometry on the rate of polymer formation are reported. A mechanism is postulated for plasma polymerization. It was found that the initiation step was the rate controlling step and that the reaction followed a cationic polymerization scheme. Both crosslinking and discoloration of the polymers occur at the time of polymerization and are not a result of exposure of the reacted polymer to the plasma. The polymerization was shown to take place in the bulk phase as well as on the reaction wall surfaces.
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    Journal of Applied Polymer Science 16 (1972), S. 2269-2290 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The phenomenon of plasticizer acceptance by poly(vinyl chloride) (PVC) in hotprocess dry blending is examined via scanning electron microscopy, mercury intrusion porosimetry, and torque rheometer measurements. The effects of granule porosity, resin molecular weight, and synthesis recipe in PVC manufacture by the suspension process are related to the rate of plasticizer acceptance. For a PVC resin to dry blend, i.e., to become a free-flowing powder when mixed with plasticizer under hot-processing conditions, the resin granules must be porous. Porosity arises from interstices between primary PVC particles. At a given granule porosity, an increase in primary particle agglomeration adversely affects dry blend performance. At constant molecular weight and for resins manufactured by a given recipe, dry-blend performance is quantitatively described by granule porosity. With an increase in resin molecular weight, a greater granule porosity is required to maintain an equivalent dry-blend time (DBT). Accordingly, for most suspending agent recipes, DBT is dependent directly upon granule porosity and inversely upon molecular weight. However, if the suspending agent used in resin manufacture is an excessively rapid film former, dry-blend performance with molecular weight variation is dependent upon the suspending agent's concentration, not upon granule porosity, which must be adequate, nor upon the resin's molecular weight. An interfacial film-forming suspending agent enhances fusion of primary PVC particles at the suspension granule - water interface, increasing the granule's “pericellular membrane” thickness. This membrane, a PVC skin, does not significantly influence dry-blend performance with low- or intermediate-viscosity plasticizers. The particle skin does impede dry-blend rates with high-viscosity, poorly solvating plasticizers, but this effect can be negated in part by increasing the diameter of pore openings in the topographical skin. Dry blending occurs below the glass transition temperature (Tg) of PVC with low-viscosity plasticizers and above the Tg with high-viscosity, poorly solvating modifiers. The influence of resin and plasticizer variables indicates the dry-blend phenomenon to be a diffusion-controlled process. The rate of dry blending is dependent upon two mechanisms: (1) the rate of pore penetration - which exposes the plasticizer to a much greater surface area than if it remained exterior, encapsulating the granule - and (2) the rate of plasticizer diffusion into the PVC matrix.
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  • 63
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    Journal of Applied Polymer Science 16 (1972), S. 2353-2359 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: A high-density polyethylene prepared at low pressures is characterized with respect to density, microscopic examination, mechanical properties, and diffusion. The data for the slowly cooled, nonisothermally crystallized polymer clearly indicate that the method of preparation grossly affects the final properties of the polymer.
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  • 64
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    Journal of Applied Polymer Science 16 (1972), S. 3003-3016 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Osmotic pressure experiments were conducted with PVC samples of different molecular weights dissolved in THF, using both a block osmometer and a Hewlett-Packard automatic osmometer equipped alternately with Schleicher and Schuell 07 and 08 membranes to optimize the procedure for accurate osmotic pressure measurements. It was found that, provided a flow of solvent could be maintained through the membrane and into the solution, an osmotic pressure of good accuracy was obtained even though the membrane was nominally much too coarse for the polymer analyzed.
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  • 65
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    Journal of Applied Polymer Science 16 (1972), S. 3035-3038 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
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  • 66
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    Journal of Applied Polymer Science 16 (1972), S. 3039-3040 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
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  • 67
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    Journal of Applied Polymer Science 16 (1972), S. 3041-3046 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
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  • 68
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    Journal of Applied Polymer Science 16 (1972), S. 3017-3034 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Earlier work revealed that the internal plasticization of polyacrylonitrile by the higher n-alkyl acrylates or N-n-alkylacrylamides yielded only brittle copolymers. This difficulty was circumvented in the present work by starting with copolymers of acrylonitrile and ethyl acrylate, over the range of compositions, and further modifying these by incrementally displacing the ethyl acrylate in each recipe by n-octadecyl acrylate through terpolymerization. In this way, the stepwise small reduction in Tg for the base ethyl acrylate-acrylonitrile copolymers was greatly increased for each of the terpolymers. Compositions were obtained ranging from glassy, brittle terpolymers, with glass transitions above room temperature, to soft plasticized polymers having sufficient polar networks retained from the nitrile to confer useful properties. The decline in the glass temperature was shown to be dependent on the free volume conferred by the side-chain methylene groups of each acrylate ester. In contrast, the decline in tensile and flexural strengths and moduli for the terpolymers having glass transitions above room temperature was produced entirely by the presence of the methylene groups of the 18-carbon ester. The glass transition region corresponded to room temperature when the acrylonitrile content of the base copolymer had been reduced to 50 mole-%. Terpolymers of this nitrile content and lower had the low moduli and large elongations of plasticized compositions. An equation was developed which correlated empirically the glass transitions and the mechanical properties with the weight fraction of the acrylate esters for the glassy terpolymers.
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    Journal of Applied Polymer Science 16 (1972), S. 3047-3062 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The problem of drag reduction in a helically coiled tube is examined experimentally. The general problems involved in the correlation of drag reduction data are analyzed critically, and some important recommendations are made based on the findings of this work. A phenomenological approach is suggested for correlating the drag reduction data. An examination of the straight-tube data from the literature and the coiledtube data obtained in this work shows that for a variety of aqueous polymer solutions the data could be uniquely correlated by the following equation: \documentclass{article}\pagestyle{empty}\begin{document}$ \beta = 0.2 + \frac{{0.8}}{{1 + \left( {{\rm De'}} \right)^{0.8} }} $\end{document} where β = reduced friction factor and De′ = modified Deborah number.
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    Journal of Applied Polymer Science 16 (1972), S. 3063-3071 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The ultraviolet absorption spectra of Cadoxen solutions of hydrocellulose and hydrocellulose phenylosazones are described. With solutions of hydrocellulose no simple relationship between D.P. and absorbance was found. Solutions of hydrocellulose phenylosazone in Cadoxen show well-defined maxima at 277 nm and 390 nm and do not change over 1 hr when oxygen is excluded. The absorbance of the phenylosazone at 390 nm may be used to determine the D.P. of the hydrocellulose samples.
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  • 71
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    Journal of Applied Polymer Science 16 (1972), S. 3073-3094 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The thermomechanical spectra of two new carborane-siloxane polymers containing five-boron carborane cages in the backbones are reported and discussed. The polymers are the homopolymer, HO—[Si(CH3)2—CB5H5C—Si(CH3)2—O—]nH, and the random copolymer with 20 mole-% of the ten-boron meta-carborane analogue, —[Si(CH3)2—CB10H10C—Si(CH3)2—O—]. The mechanical spectra (∼1 cps) were determined from -180° → +625° → -180°C (ΔT/Δl = 3.6°C/min for T 〉 25°C and 2°C/min for T 〈 25°C) using the semimicro thermomechanical technique, torsional braid analysis. In nitrogen, both polymers displayed secondary transitions at -140°C. The glass transition (Tg) for the homopolymer was -60°C and for the copolymer was -52°C. The homopolymer had a melting point of +70°C. The copolymer was amorphous. The high-temperature stability in nitrogen of both polymers appeared to be identical; thermal stiffening commenced at 400°C, continued to 625°C, and resulted in materials that were typical of highly crosslinked resins. In air, the homopolymer began to stiffen catastrophically near 270°C, while the copolymer began to stiffen similarly nearly 50°C higher. The intrinsic elastomeric nature together with the thermomechanical results prompted further study of the copolymer. Thermomechanical cycling studies in nitrogen and air are reported for the copolymer. Some correlating TGA and DTA are also discussed.
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  • 72
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    Journal of Applied Polymer Science 16 (1972), S. 3095-3103 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Nine linear poly(carborane-siloxane) high-temperature elastomers which differ systematically in chemical structure were investigated by torsional braid analysis. The structural variations include two different carborane cage structures in the polymer chain (—CB10H10C— and —CB5H5C—) and the stepwise increase in the number of —Si(CH3)2—O— linkages associated with each cage in the repeat unit. Poly(dimethylsiloxane) was studied as the compositional limit of both series. The dynamic mechanical relaxations (at about 1 cps) of the materials are reported. These include the melting points of the semicrystalline polymers and the glass transitions and secondary transitions of all the polymers. The glass transition temperatures in each series were systematized using the well-known copolymer composition-versus-glass transition temperature relationship 1/Tg = W1/Tg1 + W2/Tg2.
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    Journal of Applied Polymer Science 16 (1972), S. 3113-3121 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The interaction of the acid dye Biebrich Scarlet (C.I. Acid Red 66) with α-, β-, and γ-keratoses obtained from wool fiber by performic acid oxidation was studied. The extrapolated saturation values of dye bound to protein and the association constants for the interactions were obtained. Maximum dye uptake was found for α-keratose, followed by γ- and β-keratoses, in that order. Incorporation of varying amounts of m-cresol in the dye solutions showed no significant effect. There was no indication of an interaction between m-cresol and the keratoses from direct studies.
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  • 74
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    Journal of Applied Polymer Science 16 (1972), S. 3123-3131 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
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    Notes: The thermal stabilities of polybutadienyllithium, polyisoprenyllithium, and polystyryllithium solutions have been determined in hydrocarbon solvents. Kinetic analysis indicated that a complex mechanism was involved in the thermolysis of polybutadienyllithium. The thermal stability was observed to increase with increasing lithium concentration, suggesting the presence of competitive reactions in addition to the expected elimination of lithium hydride. The thermal stability of the three systems studied was consistent with their reported degrees of association: dimeric polystyryllithium was less stable than tetrameric polyisoprenyllithium or hexameric polybutadienyllithium.
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  • 75
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    Journal of Applied Polymer Science 16 (1972), S. 3133-3144 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
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    Notes: In addition to the expected elimination of lithium hydride, metalation and addition reactions have been observed as competitive, thermolytic reactions of polybutadienyllithium. The importance of these reactions at temperatures frequently utilized for the polymerization of butadiene was illustrated and the effect of these reactions on the macrostructure of polybutadiene determined.
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  • 76
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    Journal of Applied Polymer Science 16 (1972), S. 3207-3221 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The products obtained on degradation of poly(p-N,N-dimethylaminostyrene) in vacuo are described. The effects of molecular weight and pyrolysis temperature are discussed and the behavior compared with polystyrene under similar conditions. Product analysis has revealed significant differences between the products of degradation obtained from the two polymers, and mechanisms involving methyl-group migration have been proposed and discussed to account for the anomalous behavior of poly(p-N,N-dimethyl-aminostyrene). The liquid products of pyrolysis have been separated and identified by gas-liquid chromatography using the Kovats retention index, and quantitative analysis is also described. Analysis of the gaseous fraction by mass spectrometry is described.
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  • 77
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    Journal of Applied Polymer Science 16 (1972), S. 3223-3236 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The effect of the extent of degradation of poly(p-N,N-dimethylaminostyrene) on the quantity and composition of the residue and the effect of pyrolysis temperature on the fraction volatile at pyrolysis temperature are discussed. The behavior of poly(p-N,N-dimethylaminostyrene) is compared to that of polystyrene. A significant difference has been found for the behavior of the residue from poly(p-N,N-dimethylaminostyrene), which is ascribed to a crosslinking reaction involving the dimethylamino substitutent. Mechanisms to account for the observed products of degradation have been suggested and are discussed.
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  • 78
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    Journal of Applied Polymer Science 16 (1972), S. 3237-3244 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
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    Notes: Fibers were spun from six different, wholly aromatic copolyamides of limited order. Tensile properties of the fibers were obtained at standard conditions and, for selected fibers, at elevated temperatures and after heat-aging at 300°C in air. The dry-heat shrinkage determined up to 400°C on selected fibers was relatively low; zero-strength temperatures ranged from 375°C to 495°C. Resistance to numerous chemical reagents was determined for one of the fibers and found to be comparable to that of the fibers from other wholly aromatic polyamides. Resistance to ultraviolet light appeared to be of the same order as that of unstabilized nylon 66.
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    Journal of Applied Polymer Science 16 (1972), S. 3245-3251 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: On the basis of Mooney scorch measurements at 120°C and of continuous measurements of vulcanization in a Vuremo curemeter at 145°C, sulfenamides which function as inhibitors of the sulfur-free thiuram vulcanization have been investigated. It was found that the actual prevulcanization inhibitor is 2-mercaptobenzothiazole. Its formation from sulfenamides is activated by zinc dimethyldithiocarbamate since the vulcanization of rubber by thiuram disulfides in the presence of zinc oxide is always accompanied by the formation of zinc dithiocarbamate. It seems probable that the inhibition effect of 2-mercaptobenzothiazole is attributable to the formation of a complex with zinc dimethyldithiocarbamate which decreases the reaction rate in the initial steps of the sulfur-free thiuram vulcanization and thus causes the scorch delay.
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    Journal of Applied Polymer Science 16 (1972), S. 3265-3274 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The thermal decomposition and resultant disposal of waste poly(vinyl chloride) (PVC) is facilitated by preliminary exposure to ionizing radiation, such as energetic electrons, in an oxygen atmosphere. The results of isothermal and temperature-programmed thermogravimetry, differential thermal analysis, and effluent gas analysis in nitrogen and in oxygen indicate that the major effect of irradiation is to render PVC increasingly susceptible to oxidation. The presence of oxygen during heating enhances the decomposition. Crystalline order in PVC is destroyed by irradiation.
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  • 81
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    Journal of Applied Polymer Science 16 (1972), S. 3253-3263 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The kinetics of simultaneous thermal and hydrolytic degradation of poly(1,4-cyclohexylenedimethylene terephthalate) (PCHDT) were evaluated by using a 1.5-in.-diam. melt extruder (≈20/1 length/diameter ratio) as a reactor. The effects of extrusion temperature (295°-330°C), residence time (2.6-17.5 min), and moisture content (〈0.001% to 0.2%) of the supply polymer on degradation were determined. The rate of degradation was measured in terms of the rate at which inherent viscosity (I.V.) decreased and the rate at which carboxyl endgroup concentration increased. The contributions of both thermal and hydrolytic degradation to the total degradation of PCHDT could be separated because the hydrolysis was rapid enough that it could be considered as occurring prior to thermal degradation. Thus, the hydrolysis merely adjusted the initial properties of the supply polymer, which was then subjected to thermal degradation. Equations were developed from an analysis of the kinetic data based on a random chain scission mechanism. The activation energies for decrease in I.V. and increase in carboxyl endgroup concentration of PCHDT from thermal degradation were determined as 33.5 and 41 kcal/mole, respectively.
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    Journal of Applied Polymer Science 16 (1972), S. 3353-3360 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Two independently derived distribution function methods validate both the calibration curve and the dispersion correction of the “effective linear calibration” method used in gel permeation chromatography (GPC). Experimental conditions are specified for making the method more useful by permitting linear extrapolation of the calibration line, \documentclass{article}\pagestyle{empty}\begin{document}$ V_R = C_1 + C_2 \log M, $\end{document} and for using a minimum number of standards. The independent methods quantitatively relate known differential of integral distribution functions for standard samples to their respective chromatograms. As such, they are useful calibration methods also, but are limited in scope and range.
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    Journal of Applied Polymer Science 16 (1972), S. 3381-3385 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
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  • 84
    ISSN: 0894-3230
    Keywords: Menschutkin reaction ; duality of SN1, SN2 mechanisms ; benzyl tosylates ; Yukawa-Tsuno equation ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The rate data for the Menschutkin reaction between strongly activated Z-substituted benzyl p-toluenesulfonates and Y-substituted N,N-dimethylanilines in acetonitrile at 35 °C fit the equation, kobs  =  k1 + k2 [DMA], which is consistent with concurrent first- and second-order processes. The k1 and k2 values for each substrate were separated based on the above equation. The SN1 rate constant, k1, is unaffected by the nature of the nucleophile, whereas the SN2 rate constant, k2, increased with the electron-donating substituent of the N,N-dimethylaniline. The substituent effect on the k1 values is linearly correlated by the Yukawa-Tsuno equation with ρ  =  -5.2 and r  =  1.3. The unimolecular reaction can be regarded as a classical SN1 mechanism. In contrast, that on the k2 values shows an upward curvature when analyzed by the Brown σ+ treatment. These results are ascribed to the simultaneous and independent occurrence of SN1 and SN2 mechanisms in the present Menschutkin reaction. © 1998 John Wiley & Sons, Ltd.
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    Journal of Physical Organic Chemistry 11 (1998), S. 231-231 
    ISSN: 0894-3230
    Keywords: Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: No Abstract
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  • 86
    ISSN: 0894-3230
    Keywords: calorimetry ; IR spectra ; ketones ; solvation ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Solution enthalpies of n-hexane, acetone, butan-2-one and octan-2-one in a series of tetrachloromethane-acetonitrile mixtures and the carbonyl stretching absorption frequencies in the IR spectra of these ketones were determined. It was found that over the whole range of concentrations (varying from neat tetrachloromethane up to neat acetonitrile) the solvation enthalpy of these compounds can be obtained additively from the contributions of the alkyl and carbonyl fragments. The solvent effect on the solvation enthalpy of the carbonyl group was found to be satisfactorily correlated with the corresponding IR frequency shifts of the C=O group. It was also found that the sensitivities of the carbonyl IR frequencies to the solvent composition are different for various ketones. From both IR and calorimetric data, the preferential solvation parameters were evaluated. The differences between the IR spectroscopic and calorimetric data are discussed. © 1998 John Wiley & Sons, Ltd.
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  • 87
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    Journal of Physical Organic Chemistry 11 (1998), S. 261-272 
    ISSN: 0894-3230
    Keywords: 1-substituted 2-pyrrolidinones ; C=O stretching frequencies ; solvent effects ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: In an effort to model solute-solvent interactions, the C=O stretching frequencies of five 1-substituted 2-pyrrolidinones and four other carbonyl-containing compounds were measured for 30 common solvents. These were then correlated with four empirical parameter sets and one theoretical (computational) parameter set. While an empirical parameter set gave the best correlation equations, the theoretical parameter equations are physically and statistically significant. Solvent volume, polarizability and hydrogen bond donor acidity (capacity) terms are significant in the correlation equations. © 1998 John Wiley & Sons, Ltd.
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    Journal of Physical Organic Chemistry 11 (1998), S. 232-240 
    ISSN: 0894-3230
    Keywords: P - S bond cleavage ; hydroperoxidolysis ; nerve agent VX ; molecular orbital calculations ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The P - S bond cleavage process in the hydroperoxidolysis of a model system for the nerve agent VX was studied using ab initio and semiempirical molecular orbital methods. Aqueous solvation effects were included through single-point calculations using the semiempirical SM5.2PD/A continuum solvation model and geometries optimized at the HF/MIDI! level of theory. The predominant pathway for P - S bond cleavage involves pseudorotation of a low-energy trigonal bipyramidal intermediate followed by apical ligand ejection. In aqueous solution, the free energy barriers for these processes are found to be 14.3 and 4.6 kcal mol-1, respectively, with electronic energies calculated at the MP2/cc-pVDZ//HF/MIDI! level of theory. By comparison with another continuum model of solvation (PCM), it is concluded that the SM5.2PD/A model performs well even for hypervalent phosphorus species, in spite of not having included any such molecules in the model's parameterization set. © 1998 John Wiley & Sons, Ltd.
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  • 89
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    Journal of Physical Organic Chemistry 11 (1998), S. 407-410 
    ISSN: 0894-3230
    Keywords: gas-phase thermolysis ; N-methyl-N-phenyl-tert-butylsulfenamide ; morpholinyl-tert-butylsulfenamide ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: N-Methyl-N-phenyl-tert-butylsulfenamide (MPSA) and morpholinyl-tert-butylsulfenamide (MOSA) were thermolyzed in a stirred-flow reactor at temperatures of 340-390 °C and pressures of 7-13 Torr, using toluene as carrier gas, at residence times of 0.3-1.3 s. Isobutene was formed in 99% yield through first-order reactions having the following Arrhenius parameters (A,s-1, Ea, kJ mol-1): MPSA, log A  =  12.41 ± 0.02, Ea  =  158.8 ± 0.2; MOSA, log A  =  12.91 ± 0.22, Ea  =  159 ± 3. It is proposed that the elimination of isobutene takes place by unimolecular reaction mechanisms involving polar, four-center cyclic transition states, forming S-unsubstituted thiohydroxylamines as co-products. Thermochemical parameters, estimated by semiempirical AM1 calculations, are reported for the latter and for the parent molecules. © 1998 John Wiley & Sons, Ltd.
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  • 90
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    Journal of Physical Organic Chemistry 11 (1998), S. 411-418 
    ISSN: 0894-3230
    Keywords: 2,2′-bisbenzimidazolyl ; tautomerism ; NMR ; semi-empirical calculations ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A dynamic NMR study of the tautomerism of 2,2′-bisbenzimidazolyl in DMSO-d6 and a mechanistic interpretation of the process, based on a stepwise, single-proton transfer and formation of a zwitterionic intermediate, are presented. This interpretation is substantiated by semi-empirical calculations of the postulated intermediate and transition state, that yield results which are compared with previous studies on related aliphatic systems. © 1998 John Wiley & Sons, Ltd.
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  • 91
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    Journal of Physical Organic Chemistry 11 (1998), S. 397-406 
    ISSN: 0894-3230
    Keywords: bond dissociation energy ; acidity ; phenylsulfenylamides ; phenylsulfenylanilides ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Acidities and bond dissociation energies (BDEs) of the N-H bond in two phenylsulfenylamides, PhSNHBz and PhSNH-t-Bu, and four phenylsulfenylanilides, 4-GC6H4NHSPh, where G  =  MeO, H, Br and CN, were measured in order to compare the effects of substituents on acidities and BDEs of N - H bonds with those of C - H bonds. The effects of PhS groups on acidities and BDEs in a series of C - H acids were found to be comparable to those on acidities and BDEs of PhS in a similar series of N - H acids. Comparisons were also made of the effects of changing the oxidation state of sulfur in the series PhS, PhSO and PhSO2 on the acidities and BDEs of adjacent N - H and C - H bonds in weak acids. Hammett-type plots of pKHA values for phenyl benzyl sulfones (4-GC6H4CH2SO2Ph) and phenylsulfenylanilides (4-GC6H4NHSPh) were linear vs σp- values. A linear plot was obtained and explained for a plot of BDE of the N - H bonds in remotely substituted phenylsulfonylanilides with σ+ values. Plots of BDEs vs Eox(A-) were also linear for 4-substituted phenylsulfenylanilides (4-GC6H4NHSPh), phenylsulfonylanilides (4-GC6H4NHSO2Ph) and phenyl benzyl sulfones (4-GC6H4CH2SO2Ph). © 1998 John Wiley & Sons, Ltd.
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  • 92
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    Journal of Physical Organic Chemistry 11 (1998), S. 387-391 
    ISSN: 0894-3230
    Keywords: α-diamides ; 17O NMR ; conformation ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: 17O NMR spectra of several α-diamides were obtained at natural isotopic abundance in acetonitrile solution in order to study the conformations of these compounds in solution. The 17O NMR shifts vary with the intercarbonyl dihedral angle α in a sense opposite to that observed for α-diketones. © 1998 John Wiley & Sons, Ltd.
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  • 93
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    Journal of Physical Organic Chemistry 11 (1998), S. 392-396 
    ISSN: 0894-3230
    Keywords: 8-azaadenine ; tautomerism ; theoretical study ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The prototropic tautomerism of 8-azaadenine (azaade) was studied theoretically by means of ab initio methods, in both the gas phase and aqueous solution. A number of tautomeric forms were not included in the calculations after applying a stepwise elimination procedure based on both AM1 and HF/6-31G* energy values. The tautomers 9H-azaade, 8H-azaade and 7H-azaade survived to this elimination and their optimized geometries and energies were calculated at the MP2/6-31*//HF/6-31G* level. To include the solvent effects, two self-consistent reaction field method were used: (1) Onsager's SCRF with multipolar expansion up to the hexadecapolar term and (2) the isodensity polarizable continuum method (IPCM). Both methods produce similar results, although the latter represents better the situation in aqueous solution. The stability order in solution, 8H- 〉 9H- 〉 7H-azaade, differs slightly from that found in the gas phase, implying that in general the electrostatic effects in solution are important, but the intrinsic stability of these species in the gas phase overcomes the solvent effect. © 1998 John Wiley & Sons, Ltd.
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  • 94
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    Journal of Physical Organic Chemistry 11 (1998), S. 377-377 
    ISSN: 0894-3230
    Keywords: Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: No abstract.
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  • 95
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    Journal of Physical Organic Chemistry 11 (1998), S. 419-425 
    ISSN: 0894-3230
    Keywords: 5-nitro-5′-dimethylamino-2,2′-bisthiophene ; π* probe dye ; cyclic voltammetry ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Cyclic voltamograms of the solvatochromic dye 5-nitro-5′-dimethylamino-2,2′-bisthiophene (1), introduced recently as a sensitive π* probe, were recorded in different solvents. An EPR spectrum of the anionic radical of 1 in DMSO was obtained and compared with other spectra of analogous substituted bisthiophene radicals. It was found that the presence of a donor- acceptor pair of substituents in 1-⋅ reduces significantly the rotational barrier of the radical compared with the unsubstituted bithienyl radical anion 2-⋅. This is the result of an electronic repulsion between the donor ring fragment and the added electron in the coplanar radical, which does not exist in 2-⋅. © 1998 John Wiley & Sons, Ltd.
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  • 96
    ISSN: 0894-3230
    Keywords: calix[4]resorcinarenes ; organophosphorus compounds ; solvatophobic interactions ; host-guest complexation ; high-performance liquid chromatography ; x-ray analysis ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Reversed-phase high-performance liquid chromatography [LiChrosorb RP-18,UV detection at 254 nm and acetonitrile-water (86:14,v/v) as mobile phase] was applied to studies of the host-guest complexation of tetraalkylcalix[4]resorcinareneoctols and their upper rim phosphoryl, sulfonyl and dialkylaminomethyl derivatives with some aromatic guests in the mobile phase. It was shown that the formation of the inclusion complexes results in changes in the retention of aromatic guests and improves their separation. Stability constants of the complexes were calculated from the dependences of the l/k′ values of the aromatic guest on the concentration of the calix[4]resorcinarene in the mobile phase. The molecular structure of 4,6,16,18-tetrahydroxy-10,12,22,24-tetrakis(dipropoxyphosphoryloxy)-2,8,14,20-tetramethylcalix[4]resorcinarene (12) was determined. Crystal data for 12 are P21/n, a  =  16.708(9) Å, b  =  18.683(6) Å, c  =  20.243(5) Å, β  =  95.75(3)°, V  =  6287(4) Å3 and Z  =  4. Compound 12 exists in a boat conformation, in which two opposite unsubstituted resorcinol rings of the macrocyclic skeleton lie in the plane formed by four methine bridges and two diphosphorylated rings are perpendicular to the plane. © 1998 John Wiley & Sons, Ltd.
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  • 97
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    Journal of Physical Organic Chemistry 11 (1998), S. 378-386 
    ISSN: 0894-3230
    Keywords: alkylboronic acids ; arylboronic acids ; ab initio ; MM3 ; molecular mechanics ; force field parameters ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The boronic acid functional group has been incorporated into various biologically important compounds. In order to study this class of compounds better with molecular mechanics, five alkyl- and arylboronic acids were calculated using ab initio methods (Spartan) at the RHF/6-31G* level. MM3 force field parameters were developed based on the theoretically calculated geometries, vibrational spectra, and torsional profiles. © 1998 John Wiley & Sons, Ltd.
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  • 98
    ISSN: 0894-3230
    Keywords: γ-lactones ; base-catalysed hydrolysis ; reactivity-structure correlations ; isobenzofuranones ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Rate coefficients were measured for the base-catalysed hydrolysis of a series of substituted 3-(phenoxy- or thiophenoxymethylene)-(Z)-1(3H)-isobenzfuranones (3-phenoxy- or thiophenoxymethylenephthalides) in 70% (v/v) aqueous dioxane at 30.0 °C, in addition to the carbonyl stretching frequencies in chloroform and tetrachloromethane following deconvolution and band separation, when required. The Hammett reaction constants for the alkaline hydrolysis of the 3-/4-substituted phenoxy and thiophenoxy series are ca 0.75 and 1.10, respectively. These results are related to electrostatic field and resonance effects. Successful correlations between the carbonyl stretching frequencies and substituent constants and the rates of alkaline hydrolysis were found. Computational studies using the semi-empirical AM1 method correctly model both the details of the mechanistic pathway and the substituent effects. © 1998 John Wiley & Sons, Ltd.
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  • 99
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    Journal of Physical Organic Chemistry 11 (1998), S. 437-447 
    ISSN: 0894-3230
    Keywords: inductive constants ; theoretical estimation ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A new model of the inductive effect is proposed, allowing highly accurate theoretical calculations of inductive constants for a diversity of substituents, using a simple and readily available system of mathematics. According to this approach, the inductive effect of a substituent is considered in terms of the additive influence of its constituent atoms. A constant inherent capacity for inductive interaction with a reactive center (with a four-coordinate carbon atom chosen for such a center), represented by an atomic constant σA, is ascribed to each atom. Values of σA for a wide variety of atoms are determined, and their physical meaning is revealed to elucidate to a certain extent the physical nature of the inductive effect. In addition, the proposed model permits the convenient use in calculations of group constants σG characterizing the inductive power of groups. Values of σG are determined for molecular fragments that are most widely dealt with in organic chemistry, and the use of σA or σG constants and of their superposition is shown to have, in most cases, little or no effect on the accuracy and reproducibility of the results obtained. It is also shown that, in terms of the developed approach, the inductive effect of a substituent is closely associated with its conformation. Theoretical inductive constants were calculated for 427 organic, aromatic, organometallic and charged substituents, and they showed perfect correlation with the corresponding experimental values. © 1998 John Wiley & Sons, Ltd.
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  • 100
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    Journal of Physical Organic Chemistry 11 (1998), S. 448-454 
    ISSN: 0894-3230
    Keywords: mandelic acid ; alkaline permanganate ; oxidation ; kinetics ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The kinetics of the oxidation of mandelic acid (MA) by permanganate in aqueous alkaline medium at a constant ionic strength of 1.0 mol dm-3 were studied spectrophotometrically. The reaction shows first-order kinetics in [permanganate ion] and fractional order dependences in [MA] and [alkali]. Addition of products, manganate and aldehyde have no significant effect on the reaction rate. An increase in ionic strength and a decrease in dielectric constant of the medium increase the rate. The oxidation process in alkaline medium under the conditions employed in the present investigation proceeds first by formation of an alkali permanganate complex, which combines with mandelic acid to form another complex. The latter decomposes slowly followed by a fast reaction between the free radical of mandelic acid and another molecule of permanganate to give products. The reaction constants involved in the mechanism were derived. There is good agreement between the observed and calculated rate constants under different experimental conditions. The reaction was studied at different temperatures and activation parameters were computed with respect to the slow step of the proposed mechanism. © 1998 John Wiley & Sons, Ltd.
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