Viscosity hysteresis

Food-grade CMC is a cellulose carboxylic acid ether with an optimum DS = 0.4-0.7. The higher the DS within this range, the more hydrophilic is the polyanion. Uniformity of substitution makes CMC more compatible with dissolved salts and less inclined to thixotropy than uneven distribution (Feddersen and Thorp, 1993). This gum does not precipitate from a 50% ethanol solution. Below approximately pH 4 in water, the polyanions revert to the un-ionized, water-insoluble acid. CMC viscosity-hysteresis has already been described (Fig. 2 in Chapter 3). CMC dispersions and films have the extra advantage of transparency relative to many other polysaccharide dispersions. The films are resistant to oils, grease, and organic solvents (Hercules, Inc., 1980). 

The analysis of solutions (2.73) and (2.74) has shown that with the increase of T, depending on the inerease or decrease of the ratio kiq)i +RIP), the value of can both increase or decrease. In the first case, when, with the growth of the temperature, the fraction kiq)l - RJP) increases, and the amplitude of the k constant change during the increase of Fj is sufficiently high, three stationary states are possible in the system two stable and one imstable. This situation can be called bistable. This non-trivial conseqnence of this model allowed us to give an adeqnate explanation of the viscosity hysteresis phenomenon whieh has been first found for the oligomer systems in paper [121]. 

Thixotropy and Other Time Effects. In addition to the nonideal behavior described, many fluids exhibit time-dependent effects. Some fluids increase in viscosity (rheopexy) or decrease in viscosity (thixotropy) with time when sheared at a constant shear rate. These effects can occur in fluids with or without yield values. Rheopexy is a rare phenomenon, but thixotropic fluids are common. Examples of thixotropic materials are starch pastes, gelatin, mayoimaise, drilling muds, and latex paints. The thixotropic effect is shown in Figure 5, where the curves are for a specimen exposed first to increasing and then to decreasing shear rates. Because of the decrease in viscosity with time as weU as shear rate, the up-and-down flow curves do not superimpose. Instead, they form a hysteresis loop, often called a thixotropic loop. Because flow curves for thixotropic or rheopectic Hquids depend on the shear history of the sample, different curves for the same material can be obtained, depending on the experimental procedure. 

A rotational viscometer connected to a recorder is used. After the sample is loaded and allowed to come to mechanical and thermal equiUbtium, the viscometer is turned on and the rotational speed is increased in steps, starting from the lowest speed. The resultant shear stress is recorded with time. On each speed change the shear stress reaches a maximum value and then decreases exponentially toward an equiUbrium level. The peak shear stress, which is obtained by extrapolating the curve to zero time, and the equiUbrium shear stress are indicative of the viscosity—shear behavior of unsheared and sheared material, respectively. The stress-decay curves are indicative of the time-dependent behavior. A rate constant for the relaxation process can be deterrnined at each shear rate. In addition, zero-time and equiUbrium shear stress values can be used to constmct a hysteresis loop that is similar to that shown in Figure 5, but unlike that plot, is independent of acceleration and time of shear. 

As substituent uniformity is increased, either by choosing appropriate reaction conditions or by reaction to high degrees of substitution, thixotropic behavior decreases. CMCs of DS >1.0 generally exhibit pseudoplastic rather than thixotropic rheology. Pseudoplastic solutions also decrease in viscosity under shear but recover instantaneously after the shear stress is removed. A plot of shear rate versus shear stress does not show a hysteresis loop. 

Figure 3 gives an example of a typical force profile. The force is increased continuously and reaches the point - at the end of the first part of the force profile - where the pectin preparations start to flow. The so-called yield point is reached. The further increase leads to the continuous destruction of the internal structure and the proceeding shear thinning. The applied stress in part 3 of the stress profile destroys the structure of the fruit preparations completely. Now the stress is reduced linearly, see part 4 and 5, down to zero stress. The resulting flow curves 2, 3 and 4 and the enclosed calculated area from the hysteresis loop give important evidence about the time-dependent decrease of viscosity and a relative measure of its thixotropy. 

An unusually extensive battery of experimental techniques was brought to bear on these comparisons of enantiomers with their racemic mixtures and of diastereomers with each other. A very sensitive Langmuir trough was constructed for the project, with temperature control from 15 to 40°C. In addition to the familiar force/area isotherms, which were used to compare all systems, measurements of surface potentials, surface shear viscosities, and dynamic suface tensions (for hysteresis only) were made on several systems with specially designed apparatus. Several microscopic techniques, epi-fluorescence optical microscopy, scanning tunneling microscopy, and electron microscopy, were applied to films of stearoylserine methyl ester, the most extensively investigated surfactant. 

The second category, time-dependent behaviour, is common but difficult to deal with. The best known type is the thixotropic fluid, the characteristic of which is that when sheared at a constant rate (or at a constant shear stress) the apparent viscosity decreases with the duration of shearing. Figure 1.21 shows the type of flow curve that is found. The apparent viscosity continues to fall during shearing so that if measurements are made for a series of increasing shear rates and then the series is reversed, a hysteresis loop is observed. On repeating the measurements, similar behaviour is seen but at lower values of shear stress because the apparent viscosity continues to fall. 

When we compared the viscosities of solutions of natural rubber and of guttapercha and of other elastomers and later of polyethylene vs.(poly)cis-butadiene, with such bulk properties as moduli, densities, X-ray structures, and adhesiveness, we were greatly helped in understanding these behavioral differences by the studies of Wood (6) on the temperature and stress dependent, melting and freezing,hysteresis of natural rubber, and by the work of Treloar (7) and of Flory (8) on the elasticity and crystallinity of elastomers on stretching. Molecular symmetry and stiffness among closely similar chemical structures, as they affect the enthalpy, the entropy, and phase transitions (perhaps best expressed by AHm and by Clapeyron s... 

Consistent with the Newtonian flow of concentrated PAMAM solutions, it was found that all three types of dendrimers [40, 41, 50] under steady-shear conditions, and both PAMAMs [40] and PPIs [50] under creep [16,50] showed typical viscous behavior at all applied stress levels and testing temperatures. For example, as illustrated in Figure 14.9 [40], all of the first seven generations of PAMAMs showed constant viscosities over the entire ranges of shear rates investigated, and in addition to this, there was no hysteresis between the forward and the reverse stress sweeps in steady shearing, indicating the absence of thixotropy. 

Another test of film stability is shown in Figure 13, where compressed films were expanded and recompressed. The hysteresis pattern was observed for both enantiomer films and racemate films at 15°C but not at25°C(101). This indicates again the relatively high viscosity of surface films and the sensitivity of molegular reorganization to changes in structure and conditions. 

The solvent composition affects not only the hysteresis or history dependence of the viscosity, but also its magnitude and temperature dependence. The viscosity was 10% higher using pure MeOH as the solvent than when a 1 1 MIBK/MeOH mixture was used. However, the 9 1 solvent mixture produces the highest solution viscosity by more than a factor of four. (A solution using a 19 1 MIBK/MeOH solvent mixture was so viscous it would barely flow in the flask in which it was prepared.) The apparent activation energy for flow... 

Figure 6.2. Relations between shear stress, deformation rate, and viscosity of several classes of fluids, (a) Distribution of velocities of a fluid between two layers of areas A which are moving relatively to each other at a distance x wider influence of a force F. In the simplest case, F/A = fi(du/dx) with ju constant, (b) Linear plot of shear stress against deformation, (c) Logarithmic plot of shear stress against deformation rate, (d) Viscosity as a function of shear stress, (e) Time-dependent viscosity behavior of a rheopectic fluid (thixotropic behavior is shown by the dashed line). (1) Hysteresis loops of time-dependent fluids (arrows show the chronology of imposed shear stress).

Rheopectic fluids have apparent viscosities that increase with time, particularly at high rates of shear as shown on Figure 6.3. Figure 6.2(f) indicates typical hysteresis effects for such materials. Some examples are suspensions of gypsum in water, bentonite sols, vanadium pentoxide sols, and the polyester of Figure 6.3. 

Numerous investigations have noted the instability of the physicochemical characteristics of Al(OR)3—the first members of the homologous series, which can display varied physical states, m.p., density, vapor pressure (hysteresis on measurement), viscosity, refraction coefficient, solubility in alcohols, and so... 

Unstable branches on the P(Q) curve and the appearance of hysteresis loops can occur for various reasons usually connected with an increase in viscosity. Thus, a non-monotonic P(Q) curve was first encountered in an analysis of the flow of a hot inert (non-reactive) liquid in a cold tube when the viscosity of the liquid was strongly dependent on temperature.190 The intense dissipative heat output may have been the reason for the instability in the flow of an inert liquid.191 In both cases, the reason for the nonmonotonic in P(Q) dependence was the strong dependence of viscosity on temperature, which is equivalent here to time dependence for viscosity. Detailed investigations of the hysteresis transitions shown in Fig. 4.24 proved that they have a wave character 192 in this case, the transition occurs at a constant flow rate. 

Amongst different channels of the energy dissipation, the most relevant are the sample viscosity, the contact friction, and the adhesion hysteresis. When the drive frequency is chosen to be CQ0, the power that is dissipated when the tip periodically interacts with the sample can be written as... 

Thixotropy is the time-dependent analogue of shear-thinning and plastic behaviour, and arises from somewhat similar causes. If a thixotropic system is allowed to stand and is then sheared at a constant rate, the apparent viscosity decreases with time until a balance between structural breakdown and structure re-formation is reached. If the sheared system is then allowed to stand, it eventually regains its original structure. A thixotropic hysteresis loop (Figure... 

According to the change of strain rate versus stress the response of the material can be categorized as linear, non-linear, or plastic. When linear response take place the material is categorized as a Newtonian. When the material is considered as Newtonian, the stress is linearly proportional to the strain rate. Then the material exhibits a non-linear response to the strain rate, it is categorized as Non Newtonian material. There is also an interesting case where the viscosity decreases as the shear/strain rate remains constant. This kind of materials are known as thixotropic deformation is observed when the stress is independent of the strain rate [2,3], In some cases viscoelastic materials behave as rubbers. In fact, in the case of many polymers specially those with crosslinking, rubber elasticity is observed. In these systems hysteresis, stress relaxation and creep take place. 

---