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  • 1
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 107 (1997), S. 4658-4667 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The Brownian motion in connection to anharmonic oscillations of particles is taken as a basic property associated with a liquid state. The Tg, Tm transitions are discussed in this context. It is shown that consideration of anharmonicity leads to the strong fluctuations in amplitudes and densities, as well as to the coexistence of double values of amplitudes and strong vibrational pulses randomly distributed in a liquid matrix. The analyses of Tg, Tm, or TB transitions by use of the anharmonic oscillator approach allow us to use similar mathernatical tools which are so successfully used in the Voltera–Prigogine type of thermodynamics. In spite of the fact that the anharmonicity effect has already been investigated before, the full impact of "S" shaped amplitude hystereses on the partition function is worked out in more detail in the present paper. © 1997 American Institute of Physics.
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  • 2
    Electronic Resource
    Electronic Resource
    Springer
    Colloid & polymer science 251 (1973), S. 108-116 
    ISSN: 1435-1536
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Description / Table of Contents: Zusammenfassung Eine vorangehende Analyse der Konfigurationsphänomene eines Makromoleküls bei Scher- und Dehnungsfließen wird erweitert auf die Voraussage von viskoelastischen Effekten. Bei Scherung stellen qualitative Vergleiche der viskoelastischen Funktionen eines Modells das Verhalten des realen Materials korrekt über den ganzen Bereich der Deformationsgeschwindigkeiten dar. Beim Dehnungsfließen, das einen strengen Test der Verallgemeinerung des Modells darstellt, werden sehr hochviskose und sehr starke Orientierungseffekte vorausgesagt. Die Ergebnisse für das Dehnungsfließen dürften, obgleich sie bisherigen Theorien, die auf dem Brechen von Netzwerken basieren, widersprechen, doch als realistisch im Hinblick auf die erfolgreichen Voraussagen über die normalen viskoelastischen Funktionen angesehen werden.
    Notes: Summary A previous analysis of configurational phenomena of a macromolecule in shear and elongational flows has been extended to include predictions of viscoelastic effects. In shear flow qualitative comparisons of the viscoelastic functions show the model correctly predicts the behavior of real materials over the entire range of deformation rates that are likely to be of practical interest. In elongational flow, which provides a severe test of the generality of the model, very large viscous and orientation effects are predicted. The results for elongational flow, although disagreeing with recent theories based on network rupture arguments, are believed realistic in view of the successful predictions of the ordinary viscoelastic functions.
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  • 3
    Electronic Resource
    Electronic Resource
    Springer
    Colloid & polymer science 251 (1973), S. 474-482 
    ISSN: 1435-1536
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Summary A consideration from a continuum point of view of the state of polymer molecules in solution shows that linear and non-linear functions differ according to the elastic energy content of the molecules. Consequently for large gradients $$\eta (\dot \gamma ) = \alpha \eta '(\omega )|_{\omega = \dot \gamma }$$ and $$P_{11} - P_{22} = \alpha ^2 2G'|_{\omega = \dot \gamma }$$ in whichα is the molecular elongation. The shift in spectra between linear and non-linear behavior, previously determined empirically, is simply related to the molecular elongation. The theory also provides a mechanistic interpretation of the relaxation time in theGraessley theory. The theory predicts any two of the functionsη, η',P 11-P 22 provided one of them is known. If there is negligible influence of the solvent, the theory is in excellent agreement with experimental normal stress and shear viscosity determined fromη′.
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  • 4
    Electronic Resource
    Electronic Resource
    Springer
    Rheologica acta 13 (1974), S. 602-607 
    ISSN: 1435-1528
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Summary We have considered the optimal conditions for the determinations of relaxation spectra. The numerical process should be based on a well-posted method and should be free of artificial stability conditions. Such artificial conditions are those which restrict or prescribe the shape of the spectra. From the practical point of view we found that simple numerical processes which do not contain matrix inversion are convenient.
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  • 5
    Electronic Resource
    Electronic Resource
    Springer
    Rheologica acta 14 (1975), S. 812-815 
    ISSN: 1435-1528
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Summary The multiparametric models of non-linear viscoelasticity, as typified by theBird-Carreau model, are ill-posed which leads to the practical impossibility of accurately determining the parameter values. This, in turn, makes it hazardous to infer the molecular behaviour of the material although the inaccurate parameters may correctly predict the bulk material behaviour. Instead, it is proposed that models which are defined directly in terms of the measured data be employed. One such model has been briefly described and this model is also well-posed, i.e. the error does not propagate uncontrollably in the calculation when one attempts to improve the accuracy or resolution of the model.
    Notes: Abstract Integral models in non-linear viscoelasticity
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  • 6
    Electronic Resource
    Electronic Resource
    Springer
    Rheologica acta 6 (1967), S. 288-294 
    ISSN: 1435-1528
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Summary An iteration method has been proposed for the calculation of relaxation spectrum. TheRoesler-Twyman solution of an integral equation of a convolution type has been used to obtain the spectrum from the third approximation ofStaverman andSchwarzl (in which the basic function is represented by the real part of the dynamic modulus). The proposed method enables one to calculate the relaxation spectrum with a high accuracy from data obtained in a much narrower frequency range than was required by the originalRoesler-Twyman method. In comparison with theSchwarzl-Staverman approximation our method has a much higher resolution power of discrete relaxation times. Two examples of the calculation are given. It is further shown that the relaxation spectrum may be calculated in a similar way from the loss modulus data when use is made of the first and second approximation ofFujita, or of the second approximation ofSchwarzl-Staverman.
    Notes: Zusammenfassung Es wurde eine Iterationsmethode ausgearbeitet, die auf der mathematischen Lösung der Integralgleichung des Faltungstyps vonRoesler-Twyman beruht, aber von der dritten Näherung des Relaxationsspektrums vonSchwarzl-Staverman aus den Angaben des Realteiles des dynamischen Moduls als Grundfunktion ausgeht. Die Methode ermöglicht es, das Relaxationsspektrum mit hoher Genauigkeit aus einem engeren Frequenzbereich zu bestimmen als die ursprünglicheRoeslers-Twymansche Methode. In der Arbeit wurde weiter gezeigt, daß man auf ähnliche Weise das Relaxationsspektrum auch bei der Angabe des Imaginärteiles des dynamischen Moduls mit Hilfe der ersten und zweiten NäherungFujitas oder der zweiten Näherung vonSchwarzl-Staverman berechnen kann.
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  • 7
    Electronic Resource
    Electronic Resource
    Springer
    Colloid & polymer science 243 (1971), S. 32-41 
    ISSN: 1435-1536
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Description / Table of Contents: Zusammenfassung Ausgehend von der Grundüberlegung vonRouse, daß Polymermoleküle aus n-Reibungszentren in einem sphärischen Bereich bestehen, wird ein neues Modell entwickelt, das die molekularen Konfigurationsphänomene beschreibt. Ursprünglich nimmt das Modell an, daß bei einfacher Scherung die Reibungszentren sich entlang der Oberfläche einer Ellipse bewegen, die eine feste Orientierung relativ zur Fießrichtung aufrechterhalten. Die Orientierung und die Maße der Ellipse werden durch das Fließfeld und die Steifheit des Makromoleküls bestimmt. Die Rechnungen weisen darauf hin, daß das Nettoergebnis, obgleich stark abweichend in der Geschwindigkeit der Rotation und der Dissipation, wie sie verursacht wird durch die Reibungszentren, die mit ihrer Entwicklung entlang der stark verlängerten Ellipse auftreten, wenig von denjenigen Berechnungen abweicht, die im wesentlichen differentielle Deformationen der Makromoleküle annehmen. Gemeinsam mit einer Zahl anderer Untersuchungen sagt das Modell hohe Geschwindigkeitsabhängigkeit der Dehnungsviskosität voraus. Obgleich diese Voraussagen für Längsfluß als halbquantitativ betrachtet werden müssen, so konzentrieren sie das Interesse auf wichtige molekulare Parameter und lassen ahnen, wo weitere Untersuchungen für große Deformationen von Makromolekülen aufgegriffen werden sollten.
    Notes: Summary Starting from the basic notion ofRouse that a polymer molecule consists of n-friction centers in a spherical array, a new model describing molecular configurational phenomena is developed. Basically the model assumes that in simple shear the friction centers move along the surface of an ellipse which maintains a fixed orientation relative to the flow direction. The orientation and dimensions of the ellipse are determined by the flow field and basic stiffness of the macromolecule. The calculations indicate that although gross deviations occur in the rate of rotation and in the dissipation caused by the friction centers moving along a highly elongated ellipse, the net result deviates little from those calculations assuming essentially differential deformations of the macromolecule. In common with a number of other studies, the model predicts a highly rate sensitive elongational viscosity. Although these predictions for elongational flow should be viewed as semi-quantitative, they do focus attention on the important molecular parameters and thereby suggest areas where future work is necessary to define in greater detail the response of the molecules to large deformations.
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  • 8
    Electronic Resource
    Electronic Resource
    Springer
    Rheologica acta 9 (1970), S. 312-317 
    ISSN: 1435-1528
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Summary The spectral distribution function of viscosity has been introduced. Examples are given for its utility. An iteration process is proposed for the calculation of this spectral function from the relaxation modulus. This process is applicable even to the solution of other types of integral equations of the first kind, for which the intensity function is an approximation toDirac's delta function.
    Notes: Zusammenfassung Die Verteilungsfunktion der Viskosität wird als neuer Begriff eingeführt, und es werden Beispiele für die Zweckmäßigkeit dieses Begriffes gegeben. Zur Berechnung dieser Funktion aus dem Relaxationsmodul wird ein Iterationsprozeß vorgeschlagen. Dieser Iterationsprozeß ist auch zur Lösung anderer Typen von Integralgleichungen der ersten Art anwendbar, welche in der Theorie der linearen Viskoelastizität benützt werden, deren Kern eine Näherung für den Einheitsoperator darstellt.
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  • 9
    ISSN: 1435-1528
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Summary A numerical method has been proposed for the conversion of one of the following functions (relaxation modulus, real and imaginary part of dynamic modulus) into the remaining two ones. The method enables a very precize calculation even when using a limited range of the independent variable. Several illustrative examples are given. Analogous relations could be used for the mutual interconversion of the creep function and of the real and imaginary part of dynamic compliance.
    Notes: Zusammenfassung Es wurde eine numerische Methode der wechselseitigen Umrechung folgender Größen vorgeschlagen: des Relaxationsmoduls, der realen und der imaginären Komponente des dynamischen Moduls. Diese Methode ermöglicht ihre sehr genaue wechselseitige Umrechnung auf den unvollständigen Bereich der unabhängig veränderlichen ρöße. Einige illustrative Beispiele werden angeführt. Analoge Beziehungen gelten auch für die wechselseitige Umrechnung der Kriechfunktion, der realen und der imaginären Komponente der dynamischen Nachgiebigkeit.
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  • 10
    Electronic Resource
    Electronic Resource
    Springer
    Mechanics of time-dependent materials 3 (1999), S. 351-370 
    ISSN: 1573-2738
    Keywords: dynamical heterogeneity of liquid state ; glass transition ; phase change in amorphous bodies ; vibrational amplitude jumps
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The behavior of amorphous solids below Vogel's (T V ) or the glass transition (T g ) temperature, as well as the solid-liquid transition, have been analyzed taking into consideration the anharmonicity of motion of microparticles forming the amorphous bodies. The T g transition is explained within the logical association of this transition with the higher-temperature transitions, which can eventually involve the process of particle release into the gas phase through the process of a sudden vibrational amplitude growth. It follows from the mathematical solution of the anharmonicity problems that the pulses and the double amplitudes will always be present in aliquid matrix. The T g temperature is considered as the boundary point for the liquid state at which the dynamical microcracks of a solid state matrix start to proceed. The processes at T g are accompanied by appearance of new, highly agitated spots and the first microcracks (vacancies) filled up with the ‘semi-evaporated’ particles. In the mechanical sense, these vacancies form a new particle species characterized by quite different properties (different thermal expansion coefficient) as compared with the particles of the original matrix. It is assumed that a number of new mechanical units are growing up to the critical temperature when the original liquid frame, bonding the particles to lower amplitudes, is completely destroyed. The approach proposed does not contradict the traditional views reflected in the famous Adam-Gibbs-Di Marzio or WLF approaches, but allows a different approach to these theories.
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