Rheological shear viscosity

Thixotropic gels also demonstrate a characteristic shear thinning rheology. Shear viscosities, as a function of shear rate, for PANI solutions of 7.5% and 10% aged for a period of 4 h, are shown in Fig. 18.5. The 7.5%... 

Extensional Viscosity. In addition to the shear viscosity Tj, two other rheological constants can be defined for fluids the bulk viscosity, iC, and the extensional or elongational viscosity, Tj (34,49,100—107). The bulk viscosity relates the hydrostatic pressure to the rate of deformation of volume, whereas the extensional viscosity relates the tensile stress to the rate of extensional deformation of the fluid. Extensional viscosity is important in a number of industrial processes and problems (34,100,108—110). Shear properties alone are insufficient for the characterization of many fluids, particularly polymer melts (101,107,111,112). 

Kalyan et al. [56] have also studied the effect of alpha-olefin comonomers on the rheological properties and processing of LLDPE. The characteristics of the resins are shown in Table 2. It is found that 1-octene-based LLDPE has the lowest shear viscosity as compared to 1-butene- and 1-hexene-based polymers (Fig. 9). Decrease in power consumption, pressure before the die, temperature in the die, and increase in output has also been found according to shear viscosities of the polymers during tubular film extrusion. 

Linear novolac resins prepared by reacting para-alkylphenols with paraformaldehyde are of interest for adhesive tackifiers. As expected for step-growth polymerization, the molecular weights and viscosities of such oligomers prepared in one exemplary study increased as the ratio of formaldehyde to para-nonylphenol was increased from 0.32 to 1.00.21 As is usually the case, however, these reactions were not carried out to full conversion, and the measured Mn of an oligomer prepared with an equimolar phenol-to-formaldehyde ratio was 1400 g/mol. Plots of apparent shear viscosity versus shear rate of these p-nonylphenol novolac resins showed non-Newtonian rheological behavior. 

The rheological behavior of storage XGs was characterized by steady and dynamic shear rheometry [104,266]. Tamarind seed XG [266] showed a marked dependence of zero-shear viscosity on concentration in the semi-dilute region, which was similar to that of other stiff neutral polysaccharides, and ascribed to hyper-entanglements. In a later paper [292], the flow properties of XGs from different plant species, namely, suspension-cultured tobacco cells, apple pomace, and tamarind seed, were compared. The three XGs differed in composition and structural features (as mentioned in the former section) and... 

Taking into account the relevance of the range of semi-dilute solutions (in which intermolecular interactions and entanglements are of increasing importance) for industrial applications, a more detailed picture of the interrelationships between the solution structure and the rheological properties of these solutions was needed. The nature of entanglements at concentrations above the critical value c leads to the viscoelastic properties observable in shear flow experiments. The viscous part of the flow behaviour of a polymer in solution is usually represented by the zero-shear viscosity, rj0, which depends on the con-... 

Many materials are conveyed within a process facility by means of pumping and flow in a circular pipe. From a conceptual standpoint, such a flow offers an excellent opportunity for rheological measurement. In pipe flow, the velocity profile for a fluid that shows shear thinning behavior deviates dramatically from that found for a Newtonian fluid, which is characterized by a single shear viscosity. This is easily illustrated for a power-law fluid, which is a simple model for shear thinning [1]. The relationship between the shear stress, a, and the shear rate, y, of such a fluid is characterized by two parameters, a power-law exponent, n, and a constant, m, through... 

Other schemes have been proposed in which data are fit to a lower, even order polynomial [19] or to specific rheological models and the parameters in those models calculated [29]. This second approach can be justified in those cases when the range of behavior expected for the shear viscosity is limited. For example, if it is clear that power-law fluid behavior is expected over the shear rate range of interest, then it would be possible to calculate the power-law parameters directly from the velocity profile and pressure drop measurement using the theoretical velocity profile... 

Oscillatory shear experiments are the preferred method to study the rheological behavior due to particle interactions because they directly probe these interactions without the influence of the external flow field as encountered in steady shear experiments. However, phenomena that arise due to the external flow, such as shear thickening, can only be investigated in steady shear experiments. Additionally, the analysis is complicated by the different response of the material to shear and extensional flow. For example, very strong deviations from Trouton s ratio (extensional viscosity is three times the shear viscosity) were found for suspensions [113]. 

Galgali and his colleagues [46] have also shown that the typical rheological response in nanocomposites arises from frictional interactions between the silicate layers and not from the immobilization of confined polymer chains between the silicate layers. They have also shown a dramatic decrease in the creep compliance for the PP-based nanocomposite with 9 wt% MMT. They showed a dramatic three orders of magnitude drop in the zero shear viscosity beyond the apparent yield stress, suggesting that the solid-like behavior in the quiescent state is a result of the percolated structure of the layered silicate. 

The dynamic behavior of fluid interfaces is usually described in terms of surface rheology. Monolayer-covered interfaces may display dramatically different rheological behavior from that of the clean liquid interface. These time-dependent properties vary with the extent of intermolecular association within the monolayer at a given thermodynamic state, which in turn may be related directly to molecular size, shape, and charge (Manheimer and Schechter, 1970). Two of these time-dependent rheological properties are discussed here surface shear viscosity and dynamic surface tension. 

The rheological properties of a fluid interface may be characterized by four parameters surface shear viscosity and elasticity, and surface dilational viscosity and elasticity. When polymer monolayers are present at such interfaces, viscoelastic behavior has been observed (1,2), but theoretical progress has been slow. The adsorption of amphiphilic polymers at the interface in liquid emulsions stabilizes the particles mainly through osmotic pressure developed upon close approach. This has become known as steric stabilization (3,4.5). In this paper, the dynamic behavior of amphiphilic, hydrophobically modified hydroxyethyl celluloses (HM-HEC), was studied. In previous studies HM-HEC s were found to greatly reduce liquid/liquid interfacial tensions even at very low polymer concentrations, and were extremely effective emulsifiers for organic liquids in water (6). 

Define rheology, shear force, shear stress, shear rate, Newtonian fluid, dynamic viscosity, centi-poise, kinematic viscosity, centistokes, viscometry, and viscometer. 

Polymer rheology can respond nonllnearly to shear rates, as shown in Fig. 3.4. As discussed above, a Newtonian material has a linear relationship between shear stress and shear rate, and the slope of the response Is the shear viscosity. Many polymers at very low shear rates approach a Newtonian response. As the shear rate is increased most commercial polymers have a decrease in the rate of stress increase. That is, the extension of the shear stress function tends to have a lower local slope as the shear rate is increased. This Is an example of a pseudoplastic material, also known as a shear-thinning material. Pseudoplastic materials show a decrease in shear viscosity as the shear rate increases. Dilatant materials Increase in shear viscosity as the shear rate increases. Finally, a Bingham plastic requires an initial shear stress, to, before it will flow, and then it reacts to shear rate in the same manner as a Newtonian polymer. It thus appears as an elastic material until it begins to flow and then responds like a viscous fluid. All of these viscous responses may be observed when dealing with commercial and experimental polymers. 

Performing numerical simulations of the extrusion process requires that the shear viscosity be available as a function of shear rate and temperature over the operating conditions of the process. Many models have been developed, and the best model for a particular application will depend on the rheological response of the resin and the operating conditions of the process. In other words, the model must provide an acceptable viscosity for the shear rates and temperatures of the process. The simple models presented here include the power law. Cross, and Carreau models. An excellent description of a broad range of models was presented previously by Tadmor and Gogos [4]. 

Extensional viscosity that results purely from shear deformation seems to be of less interest, but has been measured (108). The rheology of several different polymer melts in terms of shear viscosity and uniaxial and biaxial extensional viscosity has been compared (231). Additional information on the measurement of extensional viscosity are also available (105,238—240). 

Rheological properties of filled polymers can be characterised by the same parameters as any fluid medium, including shear viscosity and its interdependence with applied shear stress and shear rate elongational viscosity under conditions of uniaxial extension and real and imaginary components of a complex dynamic modulus which depend on applied frequency [1]. The presence of fillers in viscoelastic polymers is generally considered to reduce melt elasticity and hence influence dependent phenomena such as die swell [2]. 

This article reviews the following solution properties of liquid-crystalline stiff-chain polymers (1) osmotic pressure and osmotic compressibility, (2) phase behavior involving liquid crystal phasefs), (3) orientational order parameter, (4) translational and rotational diffusion coefficients, (5) zero-shear viscosity, and (6) rheological behavior in the liquid crystal state. Among the related theories, the scaled particle theory is chosen to compare with experimental results for properties (1H3), the fuzzy cylinder model theory for properties (4) and (5), and Doi s theory for property (6). In most cases the agreement between experiment and theory is satisfactory, enabling one to predict solution properties from basic molecular parameters. Procedures for data analysis are described in detail. 

Rubber-based nanocomposites were also prepared from different nanofillers (other than nanoclays) like nanosilica etc. Bandyopadhyay et al. investigated the melt rheological behavior of ACM/silica and ENR/silica hybrid nanocomposites in a capillary rheometer [104]. TEOS was used as the precursor for silica. Both the rubbers were filled with 10, 30 and 50 wt% of tetraethoxysilane (TEOS). The shear viscosity showed marginal increment, even at higher nanosilica loading, for the rubber/silica nanocomposites. All the compositions displayed pseudoplastic behavior and obeyed the power law model within the experimental conditions. The... 

Thermodynamically unfavourable interactions between two biopolymers may produce a significant increase in the surface shear viscosity (rf) of the adsorbed protein layer. This change in surface rheological behaviour is a consequence of the greater surface concentration of adsorbed protein. For instance, with p-casein + pectin at pH = 5.5 and ionic strength = 0.01 M (Ay = 2.6 x 10 m3 mol kg-2), the surface shear viscosity at the oil-water interface was found to increase by 20-30%, i.e., rp = 750 75 and 590 60 mN s m-1 in the presence and absence of polysaccharide. These values of rp refer to data taken some 24 hours following initial protein layer formation (Dickinson et al., 1998 Semenova et al., 1999a). 

---