Investigation of the effect of SSP in stabilizing the structure of condensation polymer blends via rheological measurements

We investigated the influence of solid-state polymerization (SSP) process on the reactions that could be taken place at the interphase of polycondensation polymer blends to stabilize the structure obtained after melt mixing. Polyethylene terephthalate (PET) and polyamide 66 (PA66) were melt blended in a mixer, and subsequent SSP process was performed for each sample. FTIR spectra indicated reactions between two polymers. Viscosity behavior and interfacial slip were investigated by measuring shear viscosity of components and blends before and after SSP and then compared with the viscosity calculated from the log-additivity model. The results showed that after SSP, there was no sign of interfacial slip, the slope of viscosity reduction with increasing shear rate became smaller, and the viscosity of blends showed positive deviation at all examined shear rate from the log-additivity model while this deviation was negative at higher shear rate before SSP. SEM micrographs, which were taken after shear stress was imposed on the samples, also indicated the morphological stability after SSP. Furthermore, we studied the effect of functional groups concentration on the reactions at the interphase by using hydrolyzed PET as a precursor for blends. The results showed that slip at the interface would decrease with increasing functional groups of the precursors. These results are particularly valuable for using recycled polymers.     

Some general rheological properties of dilute polymer solutions predicted from intrinsic viscosity measurements

Expressions for the rheological properties of dilute polymer solutions at low and moderate deformation rates are established through the computation and analysis of exact Zimm's eigenvalues. It is shown that they can be expressed in terms of measurable parameters from intrinsic viscosity data. Under moderate deformation rates one needs to introduce a slippage between the solvent and the smoothed polymer to be able to describe shear-thinning behaviour.     

Quasi-linear rheological behaviour of polymer melts: Comparison between mechanical and improved flow birefringence measurements

Summary The latest improvement of the rotor unit (cone- and plate-type) for the measurement of the flow-birefringence of polymer melts is described. As a consequence of this improvement, the influence of parasitic birefringences, as produced in the corners near the windows, is minimized. It is shown that the limitation of the range of available rates of shear, as experienced with previous versions of the apparatus, was due to those parasitic birefringences which predominated at rates of shear where the main birefringence caused an optical path difference of one, two or more whole wavelengths (fringes) and was, as a consequence, virtually zero. This explains why great troubles were experienced in particular with polymers possessing a high back-bone anisotropy. The validity of the linear stress-optical rule up to shear rates, where melt fracture occurs in capillary flow, is well understood in terms of the wriggling motion of chain molecules. Comparison with direct mechanical measurements was very satisfactory.

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Zusammenfassung Eine Beschreibung der jüngsten Verbesserung an der Rotorzelle (Kegel-Platte-Typ) für die Messung der Strömungsdoppelbrechung polymerer Schmelzen wird gegeben. Als Folge dieser Verbesserung wird der Einfluß der parasitären Doppelbrechung, die in den Ecken neben den Fenstern auftritt, minimalisiert. Es wird gezeigt, daß die Begrenzung des Bereiches der verfügbaren Schergeschwindigkeiten, wie sie in früheren Versionen des Apparates gefunden wurde, auf das Vorherrschen der parasitären Doppelbrechungen bei Schergeschwindigkeiten zurückzuführen ist, bei denen die Hauptdoppelbrechung optische Weglängen von einer, zwei oder mehreren ganzen Wellenlängen verursacht und daher effektiv null wird. Dies erklärt, warum große Schwierigkeiten gerade bei solchen Polymeren auftraten, die eine stärkere Kettenanisotropie aufweisen. Die Gültigkeit der linearen spannungsoptischen Regel bis zu Schergeschwindigkeiten, bei denen in der Kapillaren Schmelzbruch auftritt, kann man aufgrund der Ringelbewegung der Makromoleküle gut verstehen. Ein Vergleich mit direkten mechanischen Messungen ergab sehr befriedigende Ergebnisse.

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With 8 figures and 2 tables     

Suspension-based rheological modeling of crystallizing polymer melts

The applicability of suspension models to polymer crystallization is discussed. Although direct numerical simulations of flowing particle-filled melts are useful for gaining understanding about the rheological phenomena involved, they are computationally expensive. A more coarse-grained suspension model, which can relate the parameters in a constitutive equation for the two-phase material to morphological features, such as the volume fractions of differently shaped crystallites and the rheological properties of both phases, will be more practical in numerical polymer processing simulations. General issues, concerning the modeling of linear and nonlinear viscoelastic phenomena induced by rigid and deformable particles, are discussed. A phenomenological extension of linear viscoelastic suspension models into the nonlinear regime is proposed. A number of linear viscoelastic models for deformable particles are discussed, focusing on their possibilities in the context of polymer crystallization. The predictions of the most suitable model are compared to direct numerical simulation results and experimental data.     

In-line measurement of rheological properties of polymer melts

Shear viscosity (), first normal stress difference (N ₁), and extensional viscosity ( _E ) of polymer melts measured under processing conditions are important in process modeling, quality control, and process control. A slit rheometer that could simultaneously measure , N ₁, and the planar extensional viscosity ( _p ) was designed and tested by attaching it in-line to a laboratory model single-screw extruder. A tube (circular cross-section) rheometer to measure and the uniaxial extensional viscosity ( _u ) simultaneously was also designed and tested. Two commercial grades of LDPE (low density polyethylene) with melt index values of 6 and 12 were used as test materials for the study. Exit and hole pressure methods were used to estimate N ₁, and the entrance pressure drop method using the analyses of Cogswell, Binding, and Gibson (the last analysis used with the axisymmetric case only) was used to estimate _E .The hole pressure method was considered better than the exit pressure method to estimate N ₁ (due to the greater susceptibility of the latter to experimental errors). From the hole pressure method N ₁ was obtained from 100 kPa to 500 kPa over a range of shear rates from 40 s^–1 to 700 s^–1. Among the analyses used to estimate the extensional viscosity, Cogswell's is recommended due to its simpler equations without loss of much information compared to the other analyses. The range of extension rates achieved was 1 to 30 s^–1. The combination of the hole pressure and entrance pressure drop methods in a slit rheometer is a feasible design for a process rheometer, allowing the simultaneous measurement of the shear viscosity, first normal stress difference and planar extensional viscosity under processing conditions. Similarly, combining the entrance pressure drop measurements with a tube rheometer is also feasible and convenient.     

Dynamic and transient rheological properties of glass filled polymer melts

The dynamic and transient rheological properties of a low density polyethylene melt and a plasticized polyvinylchloride melt filled with glass beads were measured at 200 °C and 180 °C respectively in a modified Weissenberg Rheogoniometer R-17. Its main modification consisted of the use of a piezoelectric transducer instead of the conventional torsion bar, and of the interfacing of a microcomputer Apple II plus to the Rheogoniometer for data acquisition and analysis. The glass beads were pretreated with silane and titanate coupling agents to observe the effect of the chemical modification of the polymer filler interface on these properties. It was observed that both the dynamic viscosity and the storage modulus increased with the weight fraction, but this last parameter did appreciably affect the stress growth and stress relaxation curves of the polymeric matrices at low shear rates. The effect of coupling agents on these properties was varied.     

Some thermal and rheological properties of homogeneous interpenetrating polymer networks

Summary Homogeneous interpenetrating polymer networks, (IPNs), consisting of methacrylic and epoxy networks, were obtained at various compositions from a simultaneous polymerization of DGEBAMA and DGEBA. For each composition, the glass transition occurs at a well-defined temperature which is lower than the weighted average of the glass transition temperatures of each component. Tensile experiments showed a change of mechanical behaviour above some critical strain value. This phenomenon was corroborated by stress relaxation tests which allowed the determination of a complete relaxation below a critical strain. This strain is increasing with the temperature and decreasing with the crosslink density. Such a property disappeared after the addition of grafting molecules which prevented both networks from any relative sliding. In this way this behaviour appears to be a specific property of interpenetrating networks.With 10 figures     

Experimental study of stratified jet by simultaneous measurements of velocity and density fields

Stratified flows with small density difference commonly exist in geophysical and engineering applications, which often involve interaction of turbulence and buoyancy effect. A combined particle image velocimetry (PIV) and planar laser-induced fluorescence (PLIF) system is developed to measure the velocity and density fields in a dense jet discharged horizontally into a tank filled with light fluid. The illumination of PIV particles and excitation of PLIF dye are achieved by a dual-head pulsed Nd:YAG laser and two CCD cameras with a set of optical filters. The procedure for matching refractive indexes of two fluids and calibration of the combined system are presented, as well as a quantitative analysis of the measurement uncertainties. The flow structures and mixing dynamics within the central vertical plane are studied by examining the averaged parameters, turbulent kinetic energy budget, and modeling of momentum flux and buoyancy flux. At downstream, profiles of velocity and density display strong asymmetry with respect to its center. This is attributed to the fact that stable stratification reduces mixing and unstable stratification enhances mixing. In stable stratification region, most of turbulence production is consumed by mean-flow convection, whereas in unstable stratification region, turbulence production is nearly balanced by viscous dissipation. Experimental data also indicate that at downstream locations, mixing length model performs better in mixing zone of stable stratification regions, whereas in other regions, eddy viscosity/diffusivity models with static model coefficients represent effectively momentum and buoyancy flux terms. The measured turbulent Prandtl number displays strong spatial variation in the stratified jet.     

Quantitative description of rheological properties of dilute polymer solutions

The Rouse-Zimm model has been generalized to describe the rheology of dilute polymer solutions at moderate shear rates by allowing for a reduced-shear-rate dependent slippage of the carrier solvent in the neighbourhood of the polymer coil with respect to the macroscopic continuum. A comparison of the theoretical predictions with published viscosity data for monodisperse polymer systems shows good agreement. Thus it appears to be sufficient to measure the intrinsic viscosity in order to estimate all the material functions of interest for the steady and dynamic shear flow of dilute polymer solutions.     

Investigation of aeroacoustic noise generation by simultaneous particle image velocimetry and microphone measurements

A correlation technique is tested, which enables the identification of flow structures that are involved in sound generation processes. At first, the method is applied to the problem of induced noise from flow over a cylinder. The velocity field around a circular cylinder is measured by particle image velocimetry (PIV), while the radiated sound is recorded with a microphone. Both measurements are conducted in a synchronized manner so as to enable the calculation of the cross-correlation between velocity or vorticity fluctuations and the acoustic pressure. The therewith obtained coefficient matrix provides time- and space-resolved information about the statistical dependency between flow structures and the acoustic pressure. Furthermore, a proper orthogonal decomposition (POD) is applied to the velocity field. Then the correlation between dominating modes and the acoustic pressure is computed to identify which modes are mainly involved in the sound generation. Finally, the developed method is applied to the more applied problem of the flow-field inside a leading-edge slat-cove. The results show that, in this case, the signal-to-noise ratio is too low to allow an identification of noise-relevant flow structures, as opposed to the case of the cylinder wake flow, where 5,000 PIV recordings were sufficient to identify the flow structures, which are involved in the noise-generation process. A maximum in spatial distribution of the cross-correlation coefficient is observed 1.6 diameters downstream of the cylinder; its value decreases as one moves further downstream. In this area of maximal correlation, a rapid acceleration of the released vortices takes place. The cross-correlation coefficient fluctuates over time in a sine-type oscillation with maximum values of about and show a periodic behavior with a phase shift of π/2 with respect to each other. These regular oscillations can be explained by coherent periodic structures in the flow-field. These structures generate a sound field with the same periodicity, which is perceived as tone. Hence, the correlation between the velocity fluctuations and the acoustic pressure show oscillations identical to those of the input signals. A filtering of uncorrelated noise can be observed; this being caused by the averaging process during the cross-correlation calculation. The correlation with the eigenmodes of a POD gives correlation coefficients, which are no larger than the correlation with a local near-field quantity.     

On-line measurements of the rheological properties of fermentation broth

The paper is concerned with measurements of rheological properties of fermentation broth. An on-line rheometer, Rheohelix-1, based on the application of a helical screw impeller rotating in a draught tube has been constructed. The instrument was used for measurements of the rheological parameters of fermentation broth of Aspergillus niger in a submerged fermentation process. The results of rheological and some standard measurements have been compared and proved the applicability of the instrument.Presented at the Golden Jubilee Conference of the British Society of Rheology and Third European Rheology Conference, Edinburgh, 3–7 September, 1990.     

Flow birefringence and rheological measurements on shear induced micellar structures

Aqueous solutions of cationic surfactant systems with strongly binding counterions show the striking phenomenon of shear induced phase transitions. At low shear rates or angular frequencies, the solutions exhibit Newtonian flow. At high rates of shear, however, the rheological properties change dramatically. Above a well defined threshold value of the velocity gradient, a supermolecular structure can be formed from micellar aggregates. This shear induced structure (SIS) behaves like a gel and exhibits strong flow birefringence. The formation of the shear induced structure is very complicated and depends on the specific conditions of the surfactant system. In this paper we discuss new results which have been obtained from rheological measurements and from flow birefringence data. We examine the stability of the shear induced state as a function of temperature, surfactant concentration and salt concentration and we analyse the effect of solubilisation of alcohols and hydrocarbons. The results are interpreted in terms of a kinetic model which accounts for the observed behavior.Dedicated to the 60. birthday of Prof. H. Harnisch, Hoechst AGPartly presented at the 2nd Conference of European Rheologists, Prague, June 17–20, 1986     

Phase morphology and rheological behavior of polymer/layered silicate nanocomposites

Rheological behavior of polymer/layered silicate nanocomposites are strongly dependent not only upon their microstructure but also upon the interfacial characteristics. Different phase morphology (intercalated or exfoliated) of polymer/clay is obtained according to interfacial characteristics between polymer chains and clay. In intercalated structure, the presence of randomly oriented anisotropic stacks of silicate layers is responsible for the enhancement of both moduli. The PS/clay nanocomposites exhibit a slight enhancement at low frequency because of its simple intercalated structure and little interaction. On the other hand, the PS-co-ma/clay nanocomposites have a similar intercalated structure but exhibit a distinct plateau-like behavior at low frequency since the PS-co-ma has a strong attractive interaction with the silicate layers. Finally, PE-g-ma/clay nanocomposites display an exfoliated structure, which exhibit both a distinct plateau-like behavior at low frequency and enhanced moduli at high frequency. Percolation structure as well as large interfacial area between polymer chains and clay are responsible for the rheological behavior. Received: 20 March 2000   Accepted: 11 September 2000     

The effect of instrument compliance on dynamic rheological measurements

The effect of instrument compliance on ERD and forced oscillation experiments is examined. A relationship for the determination of correct experimental conditions in ERD measurements is presented. It is concluded that the applicability of shear compliance corrections is doubtful whenever their magnitude is over 50% of the measured quantity and |G ^*| > 5 × 10⁵ Pa. Compressive compliance is found to have a negligible effect in all practical cases. Torsional compliance can be important in oscillatory experiments when sample torsional stiffness is high relative to instrument stiffness. Numerical values for Rheometrics equipment are used throughout the discussion.     

Measurement of rheological and ultrasonic properties of food and synthetic polymer melts

A slit die viscometer has been used in conjunction with a co-rotating twin screw extruder to study the rheological behaviour of maize grits, potato powder and low density polyethylene, as a function of feed rate, screw speed and temperature. The shear viscosity of both maize and potato decreased with increasing feed rate. Increasing the temperature or screw speed at any given feed rate also reduced the viscosity. The ultrasonic velocity through the material has also been shown to be sensitive to the extruder operating conditions. Overall, the ultrasonic velocity decreased as screw speed and temperature increased and feed rate decreased.     

Zero-shear-rate viscosity measurements for polymer solutions by falling ball viscometry

Falling ball viscometry experiments were carried out for three polymer solutions. The data were analyzed following eight different methods available in the literature for obtaining the zero-shear-rate viscosity.It is concluded that the procedures involving extrapolation of the natural logarithm of the apparent viscosity to zero characteristic shear stress is the most reliable technique for obtaining an estimate of the zero-shear-rate viscosity.     

Dynamic measurements on polymer solutions and melts

Summary An apparatus for the measurement of the dynamic viscosity is described. In a coaxial cylinder geometry forced vibrations are executed in the frequency region from 2·10^–4 to 50 cycles/sec. Fluids with a wide range of viscosities (10^–1 to 10⁷ poise) can be measured. A number of experimental results obtained on dilute solutions and melts of polymers are given and compared with results of the molecular theories.

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Zusammenfassung Es wird ein Gerät für die Messung der dynamischen Viskosität beschrieben. Innerhalb eines koaxialen Zylindersystems werden im Frequenzgebiet von 2 · 10^–4 bis 50 Hz erzwungene Schwingungen ausgeführt. Messungen an Flüssigkeiten sind in einem weiten Viskositätsbereich (10^–1 bis 10⁷ Poise) möglich. Einige Messungen an verdünnten Lösungen oder Schmelzen von Hochpolymeren werden mitgeteilt und mit Voraussagen molekularer Theorien verglichen.

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Paper read at the Annual Meeting of the German Rheologits, Berlin-Dahlem, May 20–21, 1968).     

Determination of molar mass polydispersity index from dynamic rheological measurements

The polydispersity of the molar mass of a material influences the behaviour of its dynamic rheological propertiesG () andG (). This is exemplified by the deviation from unity of the indexI = [2 – (d logG/d log)]/[1 – (d logG/d log)] in the terminal zone, i.e. at low frequencies. For a normal logarithmic distribution of species, a quantitative correlation may be established between the rheological properties and the parameter that is characteristic of the polydispersity for these species. This correlation can, in certain cases, be drawn from measurements in just the terminal zone or it may require measurements both in the terminal zone and at the beginning of the plateau zone. In each case, the parameter of dispersion can be determined by simple graphical or numerical methods. Finally, an example of the application of these methods to entangled liquid polymers is presented.