Thixotropic, viscosity characteristics

The viscosity of thixotropic materials that exhibit a shear rate dependency is usually determined by the procedure described in ASTM D 2556. The viscosity is determined at different shear rates, and from this plot, apparent viscosity associated with a particular rotational speed and spindle shape can be obtained. Materials with thixotropic characteristics include Vaseline jelly and toothpaste. They are materials that tend to have very high viscosity characteristics and exhibit no flow at low shear rates. However, when pressure is applied (higher shear rates), the material flows easily, exhibiting a characteristic of lower viscosity. Such materials are very common in the adhesive and sealant industries. Thixotropic materials can be pumped through a nozzle, mixed, or applied to a surface with little resistance. However, when applied to a vertical surface, they will not flow under their own weight. 

An understanding of the rheological behaviour is necessary as PVC pastes are classified as non-Newtonian liquids and can be dilatent (shear thickening), pseudoplastic (shear thinning) or thixotropic (viscosity reduces with time under constant shear). Each process requires specific rheological characteristics and this is achieved by formulation of appropriate PVC grades and knowledge of the influence of shear rate and time under constant shear. 

In the temperature range where the carrageenin is normally employed, viscosity characteristics become dependent on temperature, other solutes, and mode of observation. In a system like this it would be more appropriate to speak of consistency, fluidity, or some similar subjective term, and measuring instruments should be selected to reflect the property desired. The texture of a gel is a combination of strength and elasticity, both of which can be measured. The mouth feel of a paste is a combination of yield, viscosity, and melting temperature, the first two of which can be determined by measurements of thixotropic flow. Of particular significance is that measurements assuming Newtonian viscosity do not show the thixotropic characteristics that influence sensory experience. 

An alternative method, often used in conjunction with solvent evaporation, is to include some material in the paint which gives it abnormal viscosity characteristics, so that it is fluid while being agitated, but thickens up over a period when the agitation stops. This type of paint is said to be thixotropic . More detail is given in Chapter 10. 

Anaerobic adhesives, based on the acrylic polyester resins, are produced in viscosities ranging from thin liquids to viscous, thixotropic pastes. Within each viscosity band, individual formulations are available possessing specific strength characteristics. The whole family is unique in being the only one where interrelated strength/viscosity characteristics are provided by manufacturers. 

The polysulfide impression materials can be formulated to have a wide range of physical and chemical characteristics by modifying the base (polysulfide portion), and/or the initiator system. Further changes may be obtained by varying the proportion of the base to the catalyst in the final mix. Characteristics varied by these mechanisms include viscosity control from thin fluid mixes to heavy thixotropic mixes, setting-time control, and control of the set-mbber hardness from a Shore A Durometer scale of 20 to 60. Variations in strength, toughness, and elasticity can also be achieved. 

A study was made of the comparative stabilities at various exposures of an upset stomach remedy suspension. This product consisted of a dispersion of bismuth subsalicylate and phenylsalicylate in an aqueous system. Methyl-cellulose and magnesium aluminum silicate were selected as the suspending agents, because the presence of polyvalent metallic ions precluded the use of hydrocolloids affected by these ions. In addition, it was found that methyl-cellulose contributed a demulcent effect. The viscosity, as well as the suspension characteristics of the combination of protective colloids used, was of a synergistic nature. These colloids formed a thixotropic system. The thixotropy undoubtedly aids in stabilizing this system. In order to make this product palatable and impart elegance, color and flavor were added. Sample 1 (with protective colloids) showed no separation, while sample 2 (without... 

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. 

Among other characteristics, non-Newtonian fluids exhibit an apparent viscosity that varies with shear rate. Consequently, the determination of the shear stress-shear rate curve must be an initial consideration. Although the apparent viscosity of a thixotropic or a rheopectic fluid changes with the duration of shearing, meaningful measurements may be made if the change is relatively slow. Viscoelastic fluids also exhibit behaviour that is a function of time but their apparent viscosities can be measured provided conditions of steady shearing are obtained. 

MCC and carboxymethylcellulose sodium Avicel RC-581, RC-591, CL-611 FMC BioPolymer, Newark, Delaware, U.S.A. Viscosity regulator and modifier, thixotropic characteristics, heat and freeze-thaw stable, long shelf-life stability, lengthy hydration times eliminated, stable at pH range 4-11... 

The thixotropic characteristics provided by fumed sihca are due to its ability to develop a loosely woven, latticelike network by hydrogen bonding between particles. This network raises the apparent viscosity of the system, increases the cohesive forces, and contributes to the suspension of the solid. Because the hydrogen bonds themselves are relatively weak, they are easily disrupted through the action of an apphed stress or shearing force and quickly reform when the stress or shearing force is removed. 

The continuous decrease in A1203 incorporation in copper is also explained by a change in particle surface composition.43 Chloride present as an impurity forms CuCl, which adsorbs on the particles and thereby inhibits the adsorption of copper ions on the particles. This is an effect characteristic for a copper sulfate bath and was not found in nickel or cobalt baths. A different type of aging was reported for the codeposition of aggregated polystyrene particles with zinc.54,76 Polystyrene incorporation increased continuously in successive experiments, where the rotation speed of a cylinder electrode was randomly varied. Thixotropic viscous behavior of the aggregated suspension causes changes in aggregate size and suspension viscosity with rotation speed of the same time-scale as the experiments. 

Solids concentrations can vary from a few percent to well over 50% in a typical stirred tank. Solids concentration, particle shape, and the viscosity of the suspending phase are the main factors affecting the rheology and settling characteristics of the slurry. Cubic- and spherical-shaped solids tend to form Newtonian slurries, while needle-, oblong-, and plate-shaped solids form thixotropic slurries. Such slurries exhibit yield stresses even at quite low solids concentrations. This can lead to the development of caverns, as shown in Section 9.4. Proper design can usually overcome these stagnation problems. 

More recently,thin walled articles have been fabricated by blow-molding composites of liquid crystal polymer (LCP) and expanded porous polydetrafluoroethylene sheetingl l material. Container application examples include food and pharmaceuticals, automotive gas tanks, bottles, and other vessels. Unlike most other thermoplastic polymers, thermotropic LCP forms high-viscosity melts that have thixotropic characteristics. Applying shear force to the melt substantially alters the melt viscosity of LCP and the orientation of its polymer domains. These attributes are useful to... 

This same characteristic explains why carrageenin can be used so effectively in stabilizing suspensions. Perfect suspension requires infinite viscosity at zero rate of shear between particle and liquid under normal gravitational forces. Or, expressed in another way, the yield value of the system is greater than the mass of any of the particles being suspended. This characteristic of thixotropic rheology apparently exists in all effective systems. 

One further feature must be mentioned about pharmaceutical suspensions, namely, their desirable rheolt ical properties (7). In practice, a Bingham plastic" behavior is most used a minimum shear stress yield stress) is needed for the suspension to begin to flow. For tower stresses—and, of course, when the system is left undisturbed—the viscosity is so high that the particles will likely remain homogeneously dispersed. According to Falkiewicz (7). thixotropy is another flow characteristic that can be useful, since in thixotropic fluids a finite lime is needed to rebuild the structure after, for instance, shaking it for administration. For this reason, most formulations contain thixotropic flow regulators intended to confer optima viscous flow propertie.s to the suspensions. The reader is referred to Chapter 5 of this book for details. 

The rheological properties of concentrated suspensions are often time-dependent. If the apparent viscosity continuously decreases with time under shear, with a subsequent recovery of the viscosity when the flow is stopped, the system is said to be thixotropic. The opposite behaviour is called antithixotropy, or sometimes rheopexy. Thixotropy should not be confused with shear-thinning which is a time-independent characteristic of a system. Systems which show an irreversible decrease in viscosity with shear should be termed shear-destructive and not thixotropic. 

The working characteristics of the adhesive relevant to the application conditions must be determined. For instance viscosity is often temperature, shear-rate and time-dependent, and this will influence the choice of dispensing equipment, the method of application, the usable life and the open time. The viscosity should therefore be regulated bearing in mind the adherend rugosity and surface pretreatment, the method and location of application, and the cure temperature and duration of application. A thixotropic material may be required for application to vertical or soffit surfaces. Generally, relatively thick bondlines are encountered so that the adhesive should be able to cure in thick and/or uneven layers. It should also be remembered that for about every 8 C change in... 

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