A note on the tan δ(T) peak as a glass transition indicator in biosolids

The plasticization of many biosolids can take place over a fairly broad temperature range. The resulting loss of stiffness is primarily expressed by a drastic drop of G(T) whose magnitude is usually higher than G(T) by one or two orders of magnitude. Both G(T) and G(T) have characteristic properties that can vary widely among biomaterials. Consequently, the tan (T) peak need not be a mark of the transition center and it can be observed at temperatures where different materials have undergone a very different degree of plasticization as judged by the magnitude of G(T). This is demonstrated by computer simulations using typical functions that describe G(T) and G(T) at the glass transition region and with published data on the dynamic mechanical behavior of a variety of biosolids.     

Effects of MHD free convection and mass transfer on the flow past an oscillating infinite coaxial vertical circular cylinder

The effects of MHD free convection and mass transfer are taken into account on the flow past oscillating infinite coaxial vertical circular cylinder. The analytical expressions for velocity, temperature and concentration of the fluid are obtained by using perturbation technique.

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Einwirkungen von freier MHD-Konvektion und Stoffübertragung auf eine Strömung nach einem schwingenden unendlichen koaxialen vertikalen Zylinder

Zusammenfassung Die Einwirkungen der freien MHD-Konvektion und Stoffübertragung auf eine Strömung nach einem schwingenden, unendlichen, koaxialen, vertikalen Zylinder wurden untersucht. Die analytischen Ausdrücke der Geschwindigkeit, Temperatur und Fluidkonzentration sind durch die Perturbationstechnik erhalten worden.

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Nomenclature C _p Specific heat at constant temperature - C the species concentration near the circular cylinder - C _w the species concentration of the circular cylinder - C the species concentration of the fluid at infinite - * dimensionless species concentration - D chemical molecular diffusivity - g acceleration due to gravity - Gr Grashof number - Gm modified Grashof number - K thermal conductivity - Pr Prandtl number - r _a ,r _b radius of inner and outer cylinder - a, b dimensionless inner and outer radius - r,r coordinate and dimensionless coordinate normal to the circular cylinder - Sc Schmidt number - t time - t dimensionless time - T temperature of the fluid near the circular cylinder - T _w temperature of the circular cylinder - T temperature of the fluid at infinite - u velocity of the fluid - u dimensionless velocity of the fluid - U ₀ reference velocity - z,z coordinate and dimensionless coordinate along the circular cylinder - coefficient of volume expansion - * coefficient of thermal expansion with concentration - dimensionless temperature - H ₀ magnetic field intensity - coefficient of viscosity - _e permeability (magnetic) - kinematic viscosity - electric conductivity - density - M Hartmann number - dimensionless skin-friction - frequency - dimensionless frequency     

Concentration dependence of the critical viscoelastic properties of gelatin at the gel point

Gelatin gel properties have been studied through the evolution of the storage [G()] and the loss [G()] moduli during gelation or melting near the gel point at several concentrations. The linear viscoelastic properties at the percolation threshold follow a power-law G()G() and correspond to the behavior described by a rheological constitutive equation known as the Gel Equation. The critical point is characterized by the relation: tan = G/G = cst = tan ( · /2) and it may be precisely located using the variations of tan versus the gelation or melting parameter (time or temperature) at several frequencies. The effect of concentration and of time-temperature gel history on its variations has been studied. On gelation, critical temperatures at each concentration were extrapolated to infinite gel times. On melting, critical temperatures were determined by heating step by step after a controlled period of aging. Phase diagrams [T = f(C)] were obtained for gelation and melting and the corresponding enthalpies were calculated using the Ferry-Eldridge relation. A detailed study of the variations of A with concentration and with gel history was carried out. The values of which were generally in the 0.60–0.72 range but could be as low as 0.20–0.30 in some experimental conditions, were compared with published and theoretical values.     

Beschreibung des visko-elastischen Verhaltens des polymeren Mischsystems Phenolnovolakharz-Nitrilkautschuk (PF/NBR) mit Hilfe der Van-der-Poel-Gleichung

Zusammenfassung Morphologische Untersuchungen an dem polymeren Mischsystem Phenolnovolakharz-Nitrilkautschuk haben gezeigt, daß diese Mischungen eine Struktur aufweisen, in der harte kugelige PF-Teilchen in einer Kautschukmatrix bzw. weiche Kautschukteilchen in einer Harzmatrix eingebettet sind. Mit Hilfe der morphologischen und mechanisch-dynamischen Untersuchungen wird versucht, das viskoelastische Verhalten von Polyblends mit der Van-der-Poel-Gleichung zu beschreiben. Es konnte gezeigt werden, daß bis zu ModulwertenGhart/Gweich ~ 100 eine gute Übereinstimmung mit der Van-der-Poel-Gleichung gefunden wird. Hohe Modulverhältnisse der harten Einlagerungskomponente zur weichen KomponentenGhart/Gweich ~ 1000, wie sie im kautschukelastischen Bereich auftreten, zeigen eine Übereinstimmung mit der Van-der-Poel-Gleichung nur bei einer Volumenkonzentration der harten EinlagerungskomponenteV _f < 0,3. Diese Ergebnisse werden mit anderen bekannten theoretischen Überlegungen über den Zusammenhang zwischen Elastizitätsmodul und Zusammensetzung von Verbundwerkstoffen verglichen.Schlüsselwörter Phenolnovolakharz-Nitrilkautschuk-System, viskoelastisches Verhalten, Torsionspendel, Van-der-Poel-Gleichung

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Summary Morphological investigations of the polymer compound-system novolak resin-nitril rubber (PF/NBR) have shown, that these mixtures exhibit structures, in which hard spherical particles are embedded in a rubber matrix, respectively soft rubber particles in a resin matrix.An attempt was made to describe the viscoelastic behaviour of these polyblends by means of morphological and dynamic-mechanical investigations with the relation given by Van der Poel.Up to ratios of the moduliGhard/Gsoft ~ 100 a good agreement with the Van-der-Poel equation was found. In the rubber elastic region at ratiosG hard/G soft ~ 1000 this agreement was found for volume concentrations of the phenolic componentV _f ~ 0.3 only.The results are compared with other existing theories on the correlation between elastic modulus and composition of compound materials.

Mit 7 Abbildungen und 6 Tabellen     

Relations between steady flow and oscillatory shear measurements

Summary Results are given of a comparison between dynamic oscillatory and steady shear flow measurements with some polymer melts. Comparison of the steady shear flow viscosity,, with the absolute value of the dynamic viscosity, ¦¦, at equal values of the shear rate,q, and the circular frequency,, has shown the relation thatCox andHerz had found empirically to be substantially correct.Further, the coefficients of the normal stress differences obtained by streaming birefringence techniques have been compared with 2G () · ^{– 2} in the same range of shear rates as covered by the viscosity measurements (G is the real part of the dynamic shear modulus). Two polystyrenes with narrow molecular weight distribution showed the same shift factor along the orq axis for the normal stress coefficients with respect to 2G () · ^{– 2} and the steady shear flow viscosities with respect to the real part of the dynamic viscosity,. For two polyethylenes the results are not so conclusive owing to the smallness of the shift factor found. An empirical equation is proposed predicting the main normal stress difference from dynamic measurements only.

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Zusammenfassung Die Ergebnisse von Messungen unter erzwungenen Schwingungen und stationärer Scherströmung an einigen Polymerschmelzen werden miteinander verglichen. Der Vergleich der stationären Viskosität mit der absoluten dynamischen Viskosität ¦¦ bei gleichen Werten des Strömungsgradientenq und der Kreisfrequenz zeigt die Gültigkeit der empirischen Beziehung vonCox undHerz.Weiter wurden die Koeffizienten der Normalspannungsdifferenzen, welche durch Messung der Strömungsdoppelbrechung erhalten wurden, mit 2G() · ^–2 verglichen, und zwar wiederum bei gleichen Werten vonq und, wobeiG die Speicherkomponente des dynamischen Schubmoduls ist. Zwei Polystyrole mit enger Molekulargewichtsverteilung zeigen die gleiche Verschiebung entlang der-oderq-Achse für die Normalspannungskoeffizienten in bezug auf2G()· ^–2 und für die stationären Scherviskositäten in bezug auf den Realteil der dynamischen Viskosität. Für zwei Polyäthylene sind die Ergebnisse weniger signifikant, da die entsprechenden Verschiebungen zu klein waren. Eine empirische Beziehung zwischen den Hauptnormalspannungsdifferenzen und den dynamischen Meßwerten wird vorgeschlagen.

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Paper presented at the British Society of Rheology Conference, held at Shrivenham, from 9th–12th September, 1968.     

Flow through a helically coiled annulus

In this paper the flow is studied of an incompressible viscous fluid through a helically coiled annulus, the torsion of its centre line taken into account. It has been shown that the torsion affects the secondary flow and contributes to the azimuthal component of velocity around the centre line. The symmetry of the secondary flow streamlines in the absence of torsion, is destroyed in its presence. Some stream lines penetrate from the upper half to the lower half, and if is further increased, a complete circulation around the centre line is obtained at low values of for all Reynolds numbers for which the analysis of this paper is valid, being the ratio of the torsion of the centre line to its curvature.Nomenclature A =constant - a outer radius of the annulus - b unit binormal vector to C - C helical centre line of the pipe - D rL - g 1000 - K Dean number=Re² - L 1+r sin - M (L ²+ ² r ²)^1/2 - n unit normal vector to C - P, P pressure and nondimensional pressure - p ₀, p pressures of O(1) and O() - Re Reynolds number=aW ₀/ - (r, , s), (r, , s) coordinates and nondimensional coordinates - nonorthogonal unit vectors along the coordinate directions - r ₀ radius of the projection of C - t unit tangent vector to C - V _r, V , V _s velocity components along the nonorthogonal directions - V_r, V, V _s nondimensional velocity components along - W ₀ average velocity in a straight annulus Greek symbols , curvature and nondimensional curvature of C - U, V, W lowest order terms for small in the velocity components along the orthogonal directions t - _r, , _s first approximations to V _r , V, V _s for small - =/=/ - kinematic viscosity - density of the fluid - , torsion and nondimensional torsion of C - , stream function and nondimensional stream function - nondimensional streamfunction for U, V - a inner radius of the annulus After this paper was accepted for publication, a paper entitled On the low-Reynolds number flow in a helical pipe, by C.Y. Wang, has appeared in J. Fluid. Mech., Vol 108, 1981, pp. 185–194. The results in Wangs paper are particular cases of this paper for =0, and are also contained in [9].     

Generalized Rouse model for a dilute solution of clustered polymers

A theory analogue to tha of Rouse is given, to describe the rheological behavior of dilute solutions consisting of clusters of crosslinked polymers. The frequency-dependent behavior of the dynamic moduli of these fluids differs substantially from that of the well-known Rouse-like fluid (GG^1/2). In our case the storage modulus becomes proportional to ^3/2, while the loss modulus is proportional to . The loss modulus dominates the dynamic behavior for frequencies smaller than the largest normal frequency of the clusters.     

Classification of linear viscoelastic solids based on a failure criterion

An isotropic, incompressible linear viscoelastic solid subjected to a step shear displacement fails if the relaxation function G(s) is such that 0<G(0)< and –<G(0)0. In this case, the discontinuity in displacement propagates into the interior of the body. The discontinuity will not propagate however if G(0)= or G(0)=–. In the former case there is a diffusion-like smoothening of discontinuous data characteristic of parabolic equations. The case G(0)= may be achieved by composing the kernel as a sum of a smooth kernel and a delta function at the origin times a viscosity coefficient. If the viscosity is small, the smoothing will take place in a propagating layer which scales with the small viscosity. The case of G(0)=– is interesting in the sense that the solution is C smooth but the boundary of the support of the solution propagates at a constant wave spped. If 0<G(0)< and –<G(0)<0, then the material accomodates stress waves under step traction leading to an elastic steady state.     

Shear softening and thixotropic properties of wheat flour doughs in dynamic testing at high shear strain

Shear softening and thixotropic properties of wheat flour doughs are demonstrated in dynamic testing with a constant stress rheometer. This behaviour appears beyond the strictly linear domain (strain amplitude ₀ 0.2%),G,G and |^*| decreasing with ₀, the strain response to a sine stress wave yet retaining a sinusoidal shape. It is also shown thatG recovers progressively in function of rest time. In this domain, as well as in the strictly linear domain, the Cox-Merz rule did not apply but() and | ^*())| may be superimposed by using a shift factor, its value decreasing in the former domain when ₀ increases. Beyond a strain amplitude of about 10–20%, the strain response is progressively distorted and the shear softening effects become irreversible following rest.     

The virtual origin of riblets in an open channel flow

In this paper, a method using the mean velocity profiles for the buffer layer was developed for the estimation of the virtual origin over a riblets surface in an open channel flow. First, the standardized profiles of the mixing length were estimated from the velocity measurement in the inner layer, and the location of the edge of the viscous layer was obtained. Then, the virtual origins were estimated by the best match between the measured velocity profile and the equations of the velocity profile derived from the mixing length profiles. It was made clear that the virtual origin and the thickness of the viscous layer are the function of the roughness Reynolds number. The drag variation coincided well with other results.Nomenclature f _r skin friction coefficient - f _ro skin friction coefficient in smooth channel at the same flow quantity and the same energy slope - g gravity acceleration - H water depth from virtual origin to water surface - H ⁺ u*H/ - H false water depth from top of riblets to water surface - H ⁺ u*H/ - I _e streamwise energy slope - I _b bed slope - k riblet height - k ⁺ u*k/ - l mixing length - l _s standardized mixing length - Q flow quantity - Re Reynolds number volume flow/unit width/v - s riblet spacing - u mean velocity - u* friction velocity = - u* false friction velocity = - y distance from virtual origin - y distance from top of riblet - y ₀ distance from top of riblet to virtual origin - y _v distance from top of riblet to edge of viscous layer - y ⁺ u*y/ - y ⁺ u*y/ - y ₀ ⁺ u*y ₀/ - u ⁺ u*y/ - shifting coefficient for standardization - thickness of viscous layer=y ₀+y - ⁺ u*/ - ⁺ u*/ - eddy viscosity - ridge angle - v kinematic viscosity - density - shear stress     

The dynamic performance of the Weissenberg rheogoniometer III. Large amplitude oscillatory shearing — harmonic analysis

The harmonic content of the nonlinear dynamic behaviour of 1% polyacrylamide in 50% glycerol/water was studied using a standard Model R 18 Weissenberg Rheogoniometer. The Fourier analysis of the Oscillation Input and Torsion Head motions was performed using a Digital Transfer Function Analyser.In the absence of fluid inertia effects and when the amplitude of the (fundamental) Oscillation Input motion _I is much greater than the amplitudes of the Fourier components of the Torsion Head motion _Tn empirical nonlinear dynamic rheological propertiesG _n (, ⁰),G _n (, ⁰) and/or _n (, ⁰), _n (, ⁰) may be evaluated without a-priori-knowledge of a rheological constitutive equation. A detailed derivation of the basic equations involved is presented.Cone and plate data for the third harmonic storage modulus (dynamic rigidity)G ₃ (, ⁰), loss modulusG ₃ (, ⁰) and loss angle ₃ (, ⁰) are presented for the frequency range 3.14 × 10^–2 1.25 × 10² rad/s at two strain amplitudes, _CP ⁰ = 2.27 and 4.03. Composite cone and plate and parallel plates data for both the third and fifth harmonic dynamic viscosities ₃ (, ⁰), _S (, ⁰) and dynamic rigiditiesG ₃ (, ⁰),G ₅ (, ⁰) are presented for strain amplitudes in the ranges 1.10 _CP ⁰ 4.03 and 1.80 _PP ⁰ 36 for a single frequency, = 3.14 × 10^–1 rad/s. Good agreement was obtained between the results from both geometries and the absence of significant fluid inertia effects was confirmed by the superposition of the data for different gap widths.     

On the localness of the spectral energy transfer in turbulence

By utilizing available experimental data for net energy transfer spectra for homogeneous turbulence, contributions P(, ) to the energy transfer at a wavenumber from various other wavenumbers are calculated. This is done by fitting a truncated power-exponential series in and to the experimental data for the net energy transfer T(), and using known properties of P(, ). Although the contributions P(, ) obtained by using this procedure are not unique, the results obtained by using various assumptions do not differ significantly. It seems clear from the results that for a region where the energy entering a wavenumber band dominates that leaving, much of the energy entering the band comes from wavenumbers which are about an order of magnitude smaller. That is, the energy transfer is rather nonlocal. This result is not significantly dependent on Reynolds number (for turbulence Reynolds numbers based on microscale from 3 to 800). For lower wavenumbers, where more energy leaves than enters a wavenumber band, the energy transfer into the band is more local, but much of the energy then leaves at distant wavenumbers.     

Bursting and structure of the turbulence in an internal flow manipulated by riblets

The buffer layer of an internal flow manipulated by riblets is investigated. The distributions of the ejection and bursting frequency from the beginning to the middle part of the buffer layer, together with high moments of the fluctuating streamwise velocity,u, and its time derivative are reported. The profiles of the ejection and bursting frequency are determined and compared using three single point detection schemes. The effect of the riblets on the bursting mechanism is found confined in a localized region in the buffer layer. The multiple ejection bursts are more affected than the single ejection bursts. The skewness and flatness factors of theu signal are larger in the manipulated layer than in the standard boundary layer. That, also holds true for the flatness factor of the time derivative, but the Taylor and Liepman scales are not affected. The spectrum of theu signal is altered at the beginning part of the viscous sublayer.Nomenclature u Friction velocity - Viscosity - l _v ;f _v wall scalesv/u ;u ² /v - y Vertical distance to the wall - z Spanwise extent - (⁺) Variable normalized with wall scales - u Velocity;u=Turbulence intensity - h, s Height and width of the riblets - f _e Ejection frequency - f _b Bursting frequency - f _BME Frequency of the Bursts with Multiple Ejection - f _BSE Frequency of Single Ejection Bursts - S andS _du/dt Skewness factor ofu and its time derivative - F _u andF _du/dt Flatness factor ofu and its time derivative Abbreviations SBL Standard (non-manipulated) Boundary Layer - MBL Manipulated Boundary Layer - BME Bursts with Multiple Ejections - BSE Bursts with Single Ejections - VITA Variable Interval Time Averaging technique - u–l u-level technique - mu Modifiedu-level technique     

Symplectic approach to the theory of quantized fields. II

We prove that the set D of vector fields on the configuration space B of a field whose 1-parameter groups locally associated are groups of fibre-preserving transformations of B that leave invariant that field in the sense of variational theory, is a Lie algebra with respect to ordinary addition, multiplication by real numbers and Lie brackets. We see that this Lie algebra structure can be carried over to the corresponding set of Noether invariants, which then becomes a Lie algebra in a natural way.Further, we define the n-form of Poincaré-Cartan of a field, and we use it to generalize the Lie algebras D and in a reasonable way. The algebras D and are subalgebras of the new Lie algebras D and introduced. A main result in this connection is the following: the differential d of the n-form of Poincaré-Cartan is –(d+f), where (, d+f) are the field equations on the vertical bundle B.The symplectic manifold of solutions associated with a field is introduced in a formal way and the former Lie algebras D, , D, are interpreted on this manifold. In imitation of the case of analytical dynamics, the main results in this direction are: a) Every vector field of the Lie algebra D defines, in a canonical way, a vector field on the manifold of solutions such that its polar 1-form with respect to the symplectic metric ₂ is the differential of its corresponding Noether invariant, and b) the Lie bracket [, ] of two Noether invariants , is the Noether invariant given by ₂(D, D), where D, D are the vector fields on the manifold of solutions defined, in the sense a), by two infinitesimal generators of , , respectively. This will allow us to regard the Lie algebra as the analogous object in field theory to the Poisson algebra of analytic dynamics.We apply the general formalism to the relativistic theory of non-linear scalar fields, and we compare our results with the formalism developed by I. Segal for this case.     

Effects of MHD free convection and mass transfer on the flow past a vibrating infinite vertical circular cylinder

The effects of MHD free convection and mass transfer are taken into account on the flow past a vibrating infinite isothermal and constant heat flux vertical circular cylinder. The expressions for velocity, temperature, concentration and skin-friction of the fluid are obtained in closed form by using Laplace transform technique. The effects ofPr (Prandtl number),Sc (Schmidt number),Gr (Grashof number,Gr>0 implies cooling andGr<0 heating of the cylinder),Gm (modified Grashof number),M (magnetic field parameter) and variation of time on velocity distribution have been studied graphically. The results presented in this paper agree with the results of Lien and Chen when magnetic parameter approaches zero.

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Effekte der freien MHD Konvektion und der Stoffübertragung auf die Strömung längs eines vibrierenden unendlich langen vertikalen Kreiszylinders

Zusammenfassung Es werden die Effekte der freien MHD Konvektion und der Stoffübertragung auf die Strömung längs eines vibrierenden unendlich langen vertikalen isothermen Kreiszylinders mit konstanter Wärmestromdichte untersucht. Es werden geschlossene Ausdrücke für die Geschwindigkeit, Temperatur, Konzentration und Wandreibung des Fluides mittels der Laplace-Transformation erhalten. Die Effekte der Prandtl-ZahlPr, Schmidt-ZahlSc, Grashof-ZahlGr (Gr>0 bedeutet kühlen,Gr<0 heizen), der modifizierten Grashof-ZahlGm, des ParametersM für das magnetische Feld und das zeitliche Verhalten der Geschwindigkeitsverteilung wurden graphisch untersucht. Die Ergebnisse dieser Untersuchung stimmen mit denen von Lien und Chen überein, wenn der Parameter für das magnetische Feld nahe bei 0 liegt.

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Nomenclature C _p Specific heat at constant temperature - C the species concentration near the circular cylinder - C _w the species concentration of the circular cylinder - C the species concentration of the fluid at infinite - * dimensionless species concentration - D chemical molecular diffusivity - g acceleration due to gravity - Gr Grashof number - Gm modified Grashof number - K thermal conductivity - Pr Prandtl number - r ₀ radius of the circular cylinder - r ₀ dimensionless radius - r, r coordinate and dimensionless coordinate normal to the circular cylinder - Sc Schmidt number - t time - t dimensionless time - T temperature of the fluid near the circular cylinder - T _w temperature of the circular cylinder - T temperature of the fluid at infinite - u velocity of the fluid - u dimensionless velocity of the fluid - U ₀ reference velocity - z, z coordinate and dimensionless coordinate along the circular cylinder - coefficient of volume expansion - * coefficient of thermal expansion with concentration - dimensionless temperature - H ₀ magnetic field intensity - coefficient of viscosity - _e permeability (magnetic) - kinematic viscosity - electric conductivity - density - M Hartmann number - dimensionless skin-friction - frequency - dimensionless frequency     

Optical co-ordinates in general relativity 2 — the problem of distance

Summary Let denote the congruence of null geodesics associated with a given optical observer inV ₄. We prove that determines a unique collection of vector fieldsM₍₎ ( =1, 2, 3) and ₍₀₎ overV ₄, satisfying a weak version of Killing's conditions.This allows a natural interpretation of these fields as the infinitesimal generators of spatial rotations and temporal translation relative to the given observer. We prove also that the definition of the fieldsM₍₎ and ₍₀₎ is mathematically equivalent to the choice of a distinguished affine parameter f along the curves of, playing the role of a retarded distance from the observer.The relation between f and other possible definitions of distance is discussed.

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Sommario Sia la congruenza di geodetiche nulle associata ad un osservatore ottico assegnato nello spazio-tempoV ₄. Dimostriamo che determina un'unica collezione di campi vettorialiM₍₎ ( =1, 2, 3) e ₍₀₎ inV ₄ che soddisfano una versione in forma debole delle equazioni di Killing. Ciò suggerisce una naturale interpretazione di questi campi come generatori infinitesimi di rotazioni spaziali e traslazioni temporali relative all'osservatore assegnato. Dimostriamo anche che la definizione dei campiM₍₎, ₍₀₎ è matematicamente equivalente alla scelta di un parametro affine privilegiato f lungo le curve di, che gioca il ruolo di distanza ritardata dall'osservatore. Successivamente si esaminano i legami tra f ed altre possibili definizioni di distanza in grande.

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Work performed in the sphere of activity of: Gruppo Nazionale per la Fisica Matematica del CNR.     

Die Kennzeichnung der Gelbildung bei PVC-Pasten durch Viskositätsmessung

Zusammenfassung Für hochviskose Pasten und raschen Temperatur-wechsel wird ein Kapillarviskosimeter aus Glas beschrieben, das bei Treibdrucken bis 60 atü einen Bereich der Schubspannung von 100–10000 Dyn cm^–2 und der Schergeschwindigkeit von 2–100 sec^–1 aufweist. Damit wird die Umwandlung des bei 160° gebildeten Solzustandes bei PVC-Pasten in den Gelzustand durch Abkühlung verfolgt. Die Fließkurven lassen sich durch dieOstwald-de Waelesche Beziehung beschreiben, wobei die Konstanten undn bezüglich Zeit, Temperatur und Konzentration über die einfache Gleichung log=an+b (a=A _t , bzw.A _t ,A _c ,b=log fürn=1 bzw. log fürt=160° bzw. log des Weichmachers) zusammenhängen.Die vorliegende Arbeit wurde im Institut für technische Chemie der Technischen Hochschule Hannover angefertigt. Die Verfasser danken herzlich Herrn Prof. Dr.G. Schiemann für das gewährte Gastrecht.     

Viskoelastisches Verhalten von ABS-Polymeren in der Schmelze

Zusammenfassung Mit Hilfe eines Schwingungsviskosimeters mit konzentrischen Zylindern wurde der komplexe SchubmodulG +iG von ABS-Polymeren bei Frequenzen zwischen 10^–3 und 50 Hz und Temperaturen zwischen 130 und 250 °C gemessen. Bei hohen Frequenzen ergeben sich keine wesentlichen Unterschiede im Verlauf der Modulkurven, verglichen mit homogenen Schmelzen. Das viskoelastische Verhalten wird hier vor allem durch das Verschlaufungsnetzwerk der kohärenten Phase bestimmt. Bei tiefen Frequenzen verhalten sich ABS-Polymere in der Schmelze dagegen ähnlich wie vernetzte Kautschuke:G wird frequenzunabhängig, steigt proportional zu ·T an und nimmt wesentlich größere Werte an alsG. Es überwiegen also die elastischen Eigenschaften, während die Schmelzen homogener Polymerer bei tiefen Frequenzen vorwiegend viskos sind. Dieses gummielastische Verhalten ist um so ausgeprägter, je höher der Kautschukgehalt, der Pfropfungsgrad der Kautschukteilchen und, bei gleichem Kautschukgehalt, die Teilchenzahl ist.AusG und G läßt sich die komplexe Schwingungsviskosität ^* berechnen, deren Betrag ¦^*¦ bei vielen Kunststoffschmelzen mit der Viskositätsfunktion () bei stationären Scherströmungen übereinstimmt. Bei ABS-Polymeren wird ¦^*¦ bei tiefen Frequenzen nicht konstant, sondern steigt mit abnehmender Frequenz stark an. Es existiert also offensichtlich keine konstante Nullviskosität ₀ wie bei homogenen Schmelzen.Ein ähnliches viskoelastisches Verhalten wie ABS-Polymere, wenn auch schwächer ausgeprägt, zeigen Kunststoffe mit anorganischen Füllstoffen wie TiO₂.

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Summary The complex shear moduliG +iG of ABS-polymers were measured by means of a dynamic viscometer with concentric cylinders at frequencies between 10^–3 and 50 cps and temperatures between 130 and 250 °C. At high frequencies there are no remarkable differences in the shape of the modulus curves compared with homogeneous melts. The viscoelastic behaviour is here mainly determined by the entanglement network of the coherent phase.At low frequencies molten ABS-Polymers behave like crosslinked rubbers:G becomes independent of frequency, is proportional to ·T and has much greater values thanG. That means that the elastic properties are prevailing, whereas the melts of homogeneous polymers are mainly viscous at low frequencies. This rubberlike behaviour is the more marked, the higher the rubber contents, the degree of grafting of the rubber particles and, with equal rubber contents, the number of particles.FromG andG the complex dynamic viscosity ^* can be evaluated. For many polymer melts the absolute value ¦^*¦ corresponds to the steady-state viscosity (). For ABS-polymers ¦^*¦ does not become constant at low frequencies but rises to much higher values with decreasing frequency. Obviously there is no constant zero — shear viscosity as there is for homogeneous melts.A similar viscoelastic behaviour as shown by ABS-polymers, though less marked, is shown by plastics with anorganic fillers like TiO₂.

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Den Herren Dr.Haaf, Dr.Heinz und Dr.Stein danke ich für die Herstellung der Proben.     

Relations between loss angles in isotropic linear viscoelastic materials

Summary Starting from the relations between complex dynamic moduli simple diagrams are deduced connecting the locus of complex Poisson's ratiov ^* v +iv in the complexv ^* plane with differences between various loss angles. From these diagrams the sequence of magnitudes of several loss angles appearing in linear viscoelastic theory is deduced. Although theoretically this sequence depends on the values ofv andv, it is found experimentally that for polymeric materials, due to the fact that the values ofv andv are constrained to limited ranges, general rules can be given. The sequences deduced are compared with experimental data. Finally some relations are used to illustrate the phase relationships between stress and deformations in an uniaxial stress experiment. From these relations a new method for measuring the loss angle in compression is suggested.

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Zusammenfassung Mit Hilfe der Beziehungen zwischen komplexen dynamischen Moduln wurden einfache Diagramme konstruiert, in denen der geometrische Ort des komplexen Poisson-Verhältnissesv ^* v +iv in der komplexenv ^*-Ebene mit Differenzen zwischen verschiedenen Verlustwinkeln verbunden werden. Aus diesen Diagrammen kann auf die Reihenfolge der Größe mehrerer in der linearen viskoelastischen Theorie auftretender Verlustwinkel gefolgert werden. Obwohl diese Reihenfolge theoretisch von den Werten vonv undv abhängig ist, wird experimentell gefunden, daß für polymere Substanzen allgemeine Regeln gegeben werden können. Dies findet seine Ursache in der Tatsache, daß die Werte vonv undv auf begrenzte Gebiete beschränkt sind. Zum Schluß werden für einen einachsigen Spannungsversuch die Phasenbeziehungen zwischen den Spannungen und den Verformungen illustriert. Mit Hilfe dieser Phasenbeziehungen wird eine neue Methode für die Messung des Verlustwinkels in Kompression vorgeschlagen.

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Part of this study was performed while the author was an employee of TNO, Delft.

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With 16 figures and 1 table     

A third order scheme in the vlasov theory and some consequences in the evolution of few body systems

Summary A set of implemented evolution equations, describing the coherent nonlinear interaction of plasma waves, based on the perturbation method, has been derived, taking into account initial value effects and third order nonlinearities in the modal amplitudes.The equations reduce, in the appropriate limit, to well known stochastic triplets of hydrodynamic type.It is argued that, the stochastization mechanism of the decay instability in strongly damped regime, may be interpreted as a Duffing-type behavior.

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Sommario Si presenta un sistema di equazioni di evoluzione descrivente l'interazione coerente nonlineare di onde di plasma, tenendo conto di effetti di condizioni iniziali e nonlinearità del terzo ordine nelle ampiezze modali. Le equazioni si riducono, nel limite appropriato, a ben noti tripletti stocastici di tipo idrodinamico.Si ipotizza che il processo di stocastizzazione della instabilità di decadimento, in regime di forte dissipazione, possa essere interpretato da un modello dinamico del tipo Duffing.

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Lyst of greek symbols omega (lower case)=frequency - delta (1.c.)=partial derivative - pi (1.c.)=greek pi (=3,14r. units) in (26) - Sigma (Capital case)=Summation symbol - Delta (C.c)=def. as in (14) - epsilon (1.c.) def. as in (10) - sigma (1.c.)=def. as in (36) - gamma (1.c.)=def. as in (37) - beta (1.c.)=def. as in (37) - ro, (1.c.)=def. as in (37) - alfa (1.c.)=def. in connection with _k in (60) - Gamma (C.c.)=def. as in (63) and (66), (67) - delta (1.c.)=def. as in (66) - psi (1.c.)=def. as in (75) - fi (1.c.)=def. in (71) in connection with ₀ - Fi (C.c.)=def. as in (75) - Omega (C.c.)=def. in (78)