Rheological characterization oscillatory shear measurements

It was clear that low concentrations of hnear contaminants had a large influence on the melt rheology of rings. The extent to which this is tme was revealed in a recent report on the stress-relaxation behavior of PS rings (161 and 198 kg/mol) that were purified by LCCC (Section 26.1) and characterized as pure as currently possible (Kapnistos et al, 2008). Kapnistos et al conducted small-amphtude oscillatory shear measurements at different... 

The rheological behaviour of molten polymers is of prime importance as it relates to their microstructure and governs their processing characteristics [1]. Rotational rheometers, specifically cone-plate, parallel plate, and sliding plate rheometers are routinely used to characterize the linear viscoelastic properties of polymer melts. Small amplitude oscillatory shear experiments are employed to measure the storage (G ) and loss moduli (G"), which are related to the elastic and viscous character of the material, respectively, and the complex viscosity (77 ) as functions of angular frequency (a). 

Frequently used single-point viscosity tests in the starch plant are orifice pipettes,56 orifice funnels,57 the Hot Scott viscometer, and various methods to determine alkaline fluidity.58 For absolute measurements of the rheological properties, rotating viscometers with coaxial cylinders are used.59 The paper industry uses mainly the Brookfield viscometer and the Hercules viscometer for determining shear-dependent viscosity, pseudoplasticity, and thixotropy. Oscillatory and capillary viscometers are used for more detailed viscosity characterization, such as yield value, elastic properties, and viscoelasticity.60... 

Another well documented, but less widely used method for formulation development is the measurement of electrokinetic properties [14]. These tests require more disdnc-tive/elaborate sample preparation and are mosdy restricted to use during development. Also widely used and relied on are rheological measurements. The scope of rheological measurements ranges from viscosity measurements to the determination of yield points or oscillatory properties, such as the G and G -modules [15]. Since suspoemulsions are not ideal viscous but mostly viscoelastic or dilatant, a wide range of characterization techniques exists. Instrumentation required for this are simple rotary viscosimeters (Brookfield) or more sophisticated stress or shear controlled rotational viscosimeters. 

Steady shear flow measnrements, however, can measure only viscosity and the first normal stress difference, and it is difficult to derive information abont fluid structure from such measurements. Instead, dynamic oscillatory rheological measurements are nsed to characterize both enhanced oil recovery polymer solutions and polymer crosslinker gel systems (Prud Homme et al., 1983 Knoll and Pmd Homme, 1987). Dynamic oscillatory measurements differ from steady shear viscosity measnrements in that a sinusoidal movement is imposed on the fluid system rather than a continnons, nnidirectional movement. In other words, the following displacement is imposed ... 

Dynamic shear rheology involves measuring the resistance to dynamic oscillatory flows. Dynamic moduli such as the storage (or solid-like) modulus (G ), the loss (or fluid-like) modulus (G"), the loss tangent (tan 8 = G"IG ) and the complex viscosity ( / ) can all be used to characterize deformation resistance to dynamic oscillation of a sinusoidally imposed deformation with a characteristic frequency of oscillation (o). 

From R D to quality control, rheology measurements for each phase of the product development life cycle involve raw materials, premixes, solutions, dispersions, emulsions, and full formulations. Well-equipped laboratories with stress- and strain-controlled oscillatory/steady shear rheometers and viscometers can generally satisfy most characterization needs. When necessary, customized systems are designed to simulate specific user or process conditions. Rheology measurements are also coupled with optic, thermal, dielectric, and other analytical methods to further probe the internal microstucture of surfactant systems. New commercial and research developments are briefly discussed in the following sections. 

Several researches have reported on transient and/or steady shear rheology of TLCPs (Isayev and Nicolais 2011 Han et al. 2001). However, very few studies have been reported on the oscillatory flow of TLCPs. The measurements of oscillatory flow properties have certain advantages over the steady flow properties (Seung and Chang 1993). Viscoelastic parameters are directly related to the structure of the materials and these information are mainly used for characterizing the molecules in their equilibrium state to compare different resins, for quality control by the resin manufacturers (Dealy and Wissbum 1990). Many useful information that can be derived from the dynamic shear rheology is elastic (storage, G ) modulus, viscous (loss, G") modulus and complex viscosity ( / ). 

Rheological studies can provide useful information on the stability and internal microstructure of the multiple emulsions. Some attention was given to this subject in recent years, and the results help clarify certain aspects of stability and release properties of the multiple emulsions (Benichou et al., 2002b). Oscillatory dynamic tests and steady-state analyses, and parameters such as shear or complex modulus (G ), the lag phase between stress and strain (5), the storage modulus (G ), and the loss modulus (G"), provide quantitative characterization of the balance between the viscous and elastic properties of the multiple emulsions. Oscillatory measurements generally indicate that multiple emulsions are predominantly viscous in that the loss modulus... 

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