Thixotropic behavior

The coefficient Tj is termed the modulus of rigidity. The viscosities of thixotropic fluids fall with time when subjected to a constant rate of strain, but recover upon standing. This behavior is associated with the reversible breakdown of stmctures within the fluid which are gradually reestabflshed upon cessation of shear. The smooth sprea ding of paint following the intense shear of a bmsh or spray is an example of thixotropic behavior. When viscosity rises with time at constant rate of strain, the fluid is termed rheopectic. This behavior is much less common but is found in some clay suspensions, gypsum suspensions, and certain sols. 

The main use of these clays is to control, or adjust, viscosity in nonaqueous systems. Organoclays can be dispersed in nonaqueous fluids to modify the viscosity of the fluid so that the fluid exhibits non-Newtonian thixotropic behavior. Important segments of this area are drilling fluids, greases (79,80), lubricants, and oil-based paints. The most used commercial products in this area are dimethyl di (hydrogen a ted tallow) alkylammonium chloride [61789-80-8] dimethyl (hydrogen a ted tallow)aLkylbenzylammonium chloride [61789-72-8] and methyldi(hydrogenated tallow)aLkylbenzylammonium chloride [68391-01-5]. 

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. 

Time-dependent fluids are those for which structural rearrangements occur during deformation at a rate too slow to maintain equilibrium configurations. As a result, shear stress changes with duration of shear. Thixotropic fluids, such as mayonnaise, clay suspensions used as drilling muds, and some paints and inks, show decreasing shear stress with time at constant shear rate. A detailed description of thixotropic behavior and a list of thixotropic systems is found in Bauer and Colhns (ibid.). 

Nazem [31] has reported that mesophase pitch exhibits shear-thinning behavior at low shear rates and, essentially, Newtonian behavior at higher shear rates. Since isotropic pitch is Newtonian over a wide range of shear rates, one might postulate that the observed pseudoplasticity of mesophase is due to the alignment of liquid crystalline domains with increasing shear rate. Also, it has been reported that mesophase pitch can exhibit thixotropic behavior [32,33]. It is not clear, however, if this could be attributed to chemical changes within the pitch or, perhaps, to experimental factors. 

Fillers (calcium carbonate, calcium sulfate, aluminum oxide, bentonites, wood flour) increase the solid content of the dispersion. They are added up to 50%, based on PVAc. The purpose of the addition is the reduction of the penetration depth, provision of thixotropic behavior of the adhesive, gap filling properties and the reduction of the costs. Disadvantage can be the increase of the white point and a possible higher tool wear. 

Selecting the suitable mechanism largely depends on the release characteristics of the cake from the filter media. Scraper discharge mechanisms generally tend to suit cakes that release readily whereas roller discharge mechanisms are best suited for cakes that exhibit thixotropic behavior. 

Explain what is meant by a sludge displaying thixotropic behavior. 

Muhins L., Thixotropic behavior of carbon black in mbber, J. Phys. Chem., 54, 239, 1950. 

Thixotropic agents, 70 4, 430 Thixotropic behavior, of filled networks, 22 572... 

Since the rheology of many systems depends largely on the temperature, accurate and reproducible measurements require very careful temperature control. A 1°C temperature drop, for instance, increases the apparent viscosity / of an offset printing ink by approximately 15%. To demonstrate the correlation between thixotropy and temperature, Figs. 56 and 57 show the flow curves at different temperatures for two offset printing inks [134], Both materials clearly lose thixotropy-indicated by the area under the thixotropic loop-as the temperature increases. This effect is much more pronounced in the first case (Fig. 56), while the second ink exhibits a very slow decrease thixotropic behavior (Fig. 57). 

Flow and self-leveling characteristics of these products are governed by the rheological behavior of the slurrylike materials. At the low water-cement ratios required to ensure proper suspension of the solids, most selfleveling compositions are characterized by a yield stress and thixotropic behavior [75]. To obtain self-leveling properties, the yield stress has to be reduced and this is achieved by the selection and combination of suitable mix ingredients at... 

Further non-Newtonian types of behavior appear when time is introduced as a variable. Fluids whose viscosity decreases with time when sheared at a constant rate are called thixotropic, whereas fluids whose viscosity increases with time when sheared at a constant rate are termed rheopectic. Thixotropic behavior is represented schematically in Figure 4.6. Note that the two viscosities (slope of shear stress vs. shear rate) rip and r P2 are different, depending upon the time they were sheared at a given rate. 

Figure 4.6 Thixotropic behavior, in which time at constant shear rate affects viscosity. From J. S. Reed, Principles of Ceramics Processing, 2nd ed. Copyright 1995 by John Wiley Sons, Inc. This material is used by permission of John Wiley Sons, Inc.

While rheological literature abounds with examples of thixotropic behavior, several leading authorities (L4, M12, W3) have shown that many of these examples are due to errors in experimental technique and not to the actual presence of thixotropy. In fact, the magnitude of the possible errors in most thixotropy studies to date as indicated by these references throws considerable doubt on the validity of most available quantitative conclusions concerning this phenomenon. 

Thixotropic behavior is responsible for the smooth flow of paints after the intense shear of a paint brush or spray. On standing without shear for a few moments, the fluid recovers" its original viscous nature. The former behavior is desirable to permit the smooth flow necessary for ease of application and for removal of brush marks. The high consistency at rest is needed to prevent flow after application to vertical surfaces (L2). 

Let us see how thixotropic behavior relates to the phenomena of coagulation. The data shown in Figure 4.14a were obtained for a 7% slurry of carbon black in water. Curve 1 shows the results obtained immediately after the dispersion was prepared in a high-speed blender. After additional mild agitation, the results shown in curve 2 are obtained these are independent of further agitation. With shorter periods of mild agitation, a family of curves lying between 1 and 2 would be obtained. 

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).

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