Viscosity of dispersed systems

The introduction forms Chapter 1 of this survey. Chapter 2 deals briefly with various approaches to the description of the concentration dependence of the viscosity of disperse systems, including the transition region from fluid to solid-like systems. Chapter 3 describes viscosity from the standpoint of the free volume theory and the specific features of the transition from mobile to glasslike systems. Chapter 4 presents the concept of the free volume of disperse systems developed by us as well as the results of experiments illustrating it Chapter 5 contains the pertinent generalizations and conclusions. 

The Dependence of the Viscosity of Disperse Systems on Concentration and Their Flow Theories... 

It is interesting that Eq. (79) obtained in describing the dependence of viscosity of liquids whose molecules are modelled by solid spheres or their assemblies is very similar in its form to Eq. (69) and to equations describing the dependence of viscosity of disperse systems on concentration also modelled by assemblies of solid spheres. 

Ostwald W (1925) About the rate function of the viscosity of dispersed systems. Kolloid Z 36 99-117... 

The viscosity of dispersed systems is different from the dispersion medium viscosity (pure liquid). To establish these deviations in Newtonian liquids, the following relations are used the relative viscosity r/ = rj/rj (rj = viscosity of dispersed system, = viscosity of pure dispersion medium), the specific viscosity = (jj-jJq)/)Jq = or viscosity number t/jp/c (c = dispersed phase concentration) and limiting viscosity number [t ] = limj. Q r/splx- In dispersed systems, where the dispersed phase particle sizes are comparable to the molecular dimensions of the dispersion medium, the following equation can be used Imj =. ln jj + X2.bit)2, where t , and t/j = viscosities of components, X[ and X2 = their mole fractions. 

Additives. Because of their versatility, imparted via chemical modification, the appHcations of ethyleneimine encompass the entire additive sector. The addition of PEI to PVC plastisols increases the adhesion of the coatings by selective adsorption at the substrate surface (410). PEI derivatives are also used as adhesion promoters in paper coating (411). The adducts formed from fatty alcohol epoxides and PEI are used as dispersants and emulsifiers (412). They are able to control the viscosity of dispersions, and thus faciHtate transport in pipe systems (413). Eatty acid derivatives of PEI are even able to control the viscosity of pigment dispersions (414). The high nitrogen content of PEIs has a flame-retardant effect. This property is used, in combination with phosphoms compounds, for providing wood panels (415), ceUulose (416), or polymer blends (417,418) with a flame-retardant finish. 

This is because the effect of the dispersed soHd, rather than the dispersing medium, is usually more significant. However, the latter should not be ignored. Many industrial problems involving unacceptably high viscosities in dispersed systems are solved by substituting solvents of lower viscosity. 

Concrete, Mortar, and Plaster. Citric acid and citrate salts are used as admixtures in concrete, mortar, and plaster formulations to retard setting times and reduce the amount of water requited to make a workable mixture (172—180). The citrate ion slows the hydration of Portland cement and acts as a dispersant, reducing the viscosity of the system (181). At levels below 0.1%, citrates accelerate the setting rate while at 0.2—0.4% the set rate is retarded. High early strength and improved frost resistance have been reported when adding citrate to concrete, mortar, and plaster. 

If there is particle—particle interaction, as is the case for flocculated systems, the viscosity is higher than in the absence of flocculation. Furthermore, a flocculated dispersion is shear thinning and possibly thixotropic because the floccules break down to the individual particles when shear stress is appHed. Considered in terms of the Mooney equation, at low shear rates in a flocculated system some continuous phase is trapped between the particles in the floccules. This effectively increases the internal phase volume and hence the viscosity of the system. Under sufficiently high stress, the floccules break up, reducing the effective internal phase volume and the viscosity. If, as is commonly the case, the extent of floccule separation increases with shearing time, the system is thixotropic as well as shear thinning. 

Kandyrin, L. B. and Kuleznev, V. N. The Dependence of Viscosity on the Composition of Concentrated Dispersions and the Free Volume Concept of Disperse Systems. Vol. 103, pp. 103-148. 

As established in [214], in roller-mixed PVC-based composites one observes a much better uniformity of filler distribution over the matrix volume the relative viscosity is thereby considerably reduced. That is, for a fixed filler content, the viscosity of a system with agglomerates is always higher than that of the well-dispersed sample. 

At least, in absolute majority of cases, where the concentration dependence of viscosity is discussed, the case at hand is a shear flow. At the same time, it is by no means obvious (to be more exact the reverse is valid) that the values of the viscosity of dispersions determined during shear, will correlate with the values of the viscosity measured at other types of stressed state, for example at extension. Then a concept on the viscosity of suspensions (except ultimately diluted) loses its unambiguousness, and correspondingly the coefficients cn cease to be characteristics of the system, because they become dependent on the type of flow. 

Porous inkjet papers are in general created from colloidal dispersions. The eventual random packing of the colloid particles in the coated and dried film creates an open porous structure. It is this open structure that gives photographic-quality inkjet paper its apparently dr/ quality as it comes off the printer. Both the pore structure and pore wettability control the liquid invasion of the coated layer and therefore the final destination of dyes. Dispersion and stability of the colloidal system may require dispersant chemistries specific to the particle and solution composition. In many colloidal systems particle-particle interactions lead to flocculation which in turn leads to an increase in viscosity of the system. The viscosity directly influences the coating process, through the inverse relation between viscosity and maximum coating speed. 

The concept of interfacial mesophases promoting spontaneous emulsification (21.22) can be applied to the Tagat TO - Miglyol 812 system, where stable liquid crystalline dispersion phases are adequate to promote the process of self-emulsification. The stability of the resulting emulsion systems can also be accounted for by liquid crystalline interface stabilisation (23.24). Phase separation of material as observed above 55f surfactant, in conjuction with the increased viscosities of such systems, will inhibit the dynamics of the self-emulsification process and hence the quality of self-emulsified systems declines when the surfactant concentration is increased above 55. ... 

Mixing processes involved in the manufacture of disperse systems, whether suspensions or emulsions, are far more problematic than those employed in the blending of low-viscosity miscible liquids due to the multi-phasic character of the systems and deviations from Newtonian flow behavior. It is not uncommon for both laminar and turbulent flow to occur simultaneously in different regions of the system. In some regions, the flow regime may be in transition, i.e., neither laminar nor turbulent but somewhere in between. The implications of these flow regime variations for scale-up are considerable. Nonetheless, it should be noted that the mixing process is only completed when Brownian motion occurs sufficiently to achieve uniformity on a molecular scale. 

Mixing processes involved in the manufacture of disperse systems, whether suspensions or emulsions, are far more problematic than those employed in the blending of low-viscosity miscible liquids, due to the multiphasic character of the... 

The type of chosen polymer and additives most strongly influences the rheological and processing properties of plastisols. Plastisols are normally prepared from emulsion and suspension PVC which differ by their molecular masses (by the Fickentcher constant), dimensions and porosity of particles. Dimensions and shape of particles are important not only due to the well-known properties of dispersed systems (given by the formulas of Einstein, Mooney, Kronecker, etc.), but also due to the fact that these factors (in view of the small viscosity of plasticizer as a composite matrix ) influence strongly the sedimental stability of the system. The joint solution of the equations of sedimentation (precipitation) of particles by the action of gravity and of thermal motion according to Einstein and Smoluchowski leads 37,39) to the expression for the radius of the particles, r, which can not be precipitated in the dispersed system of an ideal plastisol. This expression has the form ... 

The apparent viscosity of a system which thins on shearing is most susceptible to changes in the shear rate in the intermediate range where there is a balance between randomness and alignment, and between aggregation and dispersion. 

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