1. Structural and mechanical properties of the dispersed systems Plan 1.Rheology of dispersion system. Sol’s viscosity. 2.Liquid dispersed systems: suspensions, emulsions, foams. 3.Gas dispersed systems: aerosols, powders. Assistant Kozachok S.S. prepared

2. Rheology is the science of the deformation and flow of matter It is a subject of tremendous and increasing technological importance - in many industries, such as rubber, plastics, food, paint and textiles, the suitability of the products involved is to a large extent judged in terms of their mechanical properties. In biology and medicine (particularly haematology) rheological behaviour is also of major importance. The most straightforward rheological behaviour is exhibited on the one hand by Newtonian viscous fluids and on the other by Hookean elastic solids. However, most materials, particularly those of a colloidal nature, exhibit mechanical behaviour which is intermediate between these two extremes, with both viscous and elastic characteristics in evidence. Such materials are termed viscoelastic.

3. The rheological behaviour of colloidal dispersions depends mainly on the following factors: 1. Viscosity of the dispersion medium. 2. Particle concentration. 3. Particle size and shape. 4. Particle-particle and particle-dispersion medium nteractions.

4. Newtonian viscosity The viscosity of a liquid is a measure of the internal resistance offered to the relative motion of different parts of the liquid. Viscosity is described as Newtonian when the shearing force per unit area σ between two parallel planes of liquid in relative motion is proportional to the velocity gradient D between the planes - i.e. where η is the coefficient of viscosity. The dimension of η is, therefore, (mass) (length) -1 (time) -1. For most pure liquids and for many solutions and dispersions, η is a well-defined quantity for a given temperature and pressure which is independent of σ and D, provided that the flow is streamlined (i.e. laminar). For many other solutions and dispersions, especially if concentrated and if the particles are asymmetric and/or aggregated deviations from Newtonian flow are observed. The main causes of non-Newtonian flow are the formation of a structure throughout the system and orientation of asymmetric particles caused by the velocity gradient.

5. Measurement of viscosity Capillary flow methods The most frequently employed methods for measuring viscosities are based on flow through a capillary tube. The pressure under which the liquid flows furnishes the shearing stress. The relative viscosities of two liquids can be determined by using a simple Ostwald viscometer (Figure). Sufficient liquid is introduced into the viscometer for the levels to be at B and C. Liquid is then drawn up into the left- hand limb until the liquid levels are above A and at the bottom of the right-hand bulb. The liquid is then released and the time for the left-hand meniscus to pass between the marks A and B is measured.

7. Since the pressure at any instant driving the liquid through the capillary is proportional to its density, where k is the viscometer constant, p is the density of the liquid and t is the flow time. Therefore, for two different liquids,

8. Ostwald’s capillary flow methods where η – viscosity ρ – the density of the liquid К – the viscometer constant, t – the flow time [η] = Pa·s

9. Stock’s viscometer wher d – density of the globule’s material, ρ о – liquid density,  - translational velocity of the uniform motion of the globule g - acceleration of gravity

10. Viscosities of dilute colloidal solutions and dispersions Functions of viscosity When colloidal particles are dispersed in a liquid, the flow of the liquid is disturbed and the viscosity is higher than that of the pure liquid. The problem of relating the viscosities of colloidal dispersions (especially when dilute) with the nature of the dispersed particles has been the subject of much experimental investigation and theoretical consideration. In this respect, viscosity increments are of greater significance than absolute viscosities, and the following functions of viscosity are defined:

12. Spherical particles Einstein (1906) made a hydrodynamic calculation (under assumptions similar to those of Stokes;) relating to the disturbance of the flow lines when identical, non-interacting, rigid, spherical particles are dispersed in a liquid medium, and arrived at the expression: The effect of such particles on the viscosity of a dispersion depends, therefore, only on the total volume which they occupy and is independent of their size.

13. For dispersions of non-rigid spheres (e.g. emulsions) the flow lines may be partially transmitted through the suspended particles, making k in Einstein's equation less than 2.5.

14. Structural and mechanical behavior of the dispersion systems ElasticityPlasticity StrengthViscosity Relative viscosity (it’s true when the spherical particles don’t react with each other): Reduced viscosity (or viscosity number): 1/η - fluidity

15. Scheme formation of the dimensional structure Aggregates which close a fixed fluid inside temselves

16. Non-Newtonian flow Shear-thinning Shear-thinning, as the term suggests, is characterised by a gradual (time-independent) decrease in apparent viscosity with increasing rate of shear, and can arise from a number of causes. If particle aggregation occurs in a colloidal system, then an increase in the shear rate will tend to break down the aggregates, which will result, among other things, in a reduction of the amount of solvent immobilised by the particles, thus lowering the apparent viscosity of the system.

17. Shear thinning is an effect where viscosity decreases with increasing rate of shear stress. Materials that exhibit shear thinning are called pseudoplastic. This property is found in certain complex solutions, such as lava, ketchup, whipped cream, blood, paint, and nail polish. It is also a common property of polymer solutions and molten polymers.viscosityshear stresslavaketchupwhipped creambloodpaintnail polishpolymer A shear stress, denoted (tau), is defined as a stress which is applied parallel or tangential to a face of a material, as opposed to a normal stress which is applied perpendicularly.taustressparalleltangentialnormal stressperpendicularly

18. Shear-thinning is particularly common to systems containing asymmetric particles. Asymmetric particles disturb the flow lines to a greater extent when they are randomly orientated at low-velocity gradients than when they have been aligned at high-velocity gradients. In addition, particle interaction and solvent immobilisation are favoured when conditions of random orientation prevail. 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.

19. Plasticity and yield value Plasticity is similar to shear-thinning, except that the system does not flow noticeably until the shearing stress exceeds a certain minimum value. The applied stress corresponding to a small but arbitrarily chosen rate of deformation is termed the yield value. Plasticity is due to a continuous structural network which imparts rigidity to the sample and which must be broken before flow can occur. It is often difficult to distinguish between plastic and ordinary shear-thinning behaviour. Modelling clay, drilling muds and certain pigment dispersions are examples of plastic dispersions.

21. Time-dependent phenomena Thixotropy 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. Solutions of high polymers are, in general, thixotropic to a certain extent; intermolecular attractions and entanglements are overcome and the extent of solvent immobilisation is reduced on shearing, while Brownian motion restores the system to its original condition when left to stand. The classical examples of thixotropic behaviour are given by the weak gel systems, such as flocculated sols of iron(III) oxide, alumina and many clays (particularly bentonite clays), which can be liquefied' on shaking and 'solidify' on standing. Thixotropy is particularly important in the paint industry, as it is desirable that the paint should flow only when being brushed on to the appropriate surface (high rate of shear) and immediately after brushing.

22. Rheopexy Rheopexy is time-dependent shear-thickening, and is sometimes observed as an acceleration of thixotropic recovery - for example, bentonite clay suspensions often set only slowly on standing but quite rapidly when gently disturbed, Shear-thickening Shear-thickening is characterised by an increase in apparent viscosity with increasing rate of deformation.

25. Emulsion (liquid/liquid)

26. Emulsifying agents and emulsion stability Probably the most important physical property of an emulsion is its stability. The term 'emulsion stability' can be used with reference to three essentially different phenomena - creaming (or sedimentation), coagulation and a breaking of the emulsion due to droplet coalescence. If an emulsion is prepared by homogenising two pure liquid components, phase separation will usually be rapid, especially if the concentration of the dispersed phase is at all high. To prepare reasonably stable emulsions, a third component - an emulsifying agent (or emulsifier) - must be present. The materials which are most effective as emulsifying (and foaming) agents can be broadly classified as: 1. Surface-active materials. 2. Naturally occurring materials. 3. Finely divided solids.

27. The functions of the emulsifying agent are to facilitate emulsification and promote emulsion stability. The emulsifying agent forms an adsorbed film around the dispersed droplets which helps to prevent coagulation and coalescence. The stabilising mechanism is usually complex and may vary from system to system. In general, however, the factors which control droplet coagulation are the same as those which control the stability of sols. The following factors (which depend on the nature of the emulsifying agent and/or on a suitable choice of formulation and manufacturing conditions) favour emulsion stability: 1, Low interfacial tension The adsorption of surfactant at oil-water interfaces causes a lowering of interfacial energy, thus facilitating the development and enhancing the stability of the large interfacial areas associated with emulsions. 2. A mechanically strong and elastic interfacial film This is particularly important when the volume fraction of the dispersed phase is high

28. 3. Electrical double layer repulsions (see page 212) Interparticle repulsion due to the overlap of similarly charged electric double layers is an important stabilising mechanism in O/W emulsions. When ionic emulsifying agents are used, lateral electric double layer repulsion may prevent the formation of a close-packed film. This film-expanding effect can be minimised by using a mixed ionic plus non-ionic film and/or by increasing the electrolyte concentration in the aqueous phase. 4. Relatively small volume of dispersed phase (see below). 5. Narrow droplet size distribution Larger droplets are less unstable than smaller droplets on account of their smaller area-to-volume ratio, and so will tend to grow at the expense of the smaller droplets. 6. High viscosity A high Newtonian viscosity simply retards the rates of creaming, coalescence, etc. If a weak gel network is formed by, for example, dissolving sodium carboxymethyl cellulose in an O/W emulsion, genuine stability might ensue. However, the overall Theological properties of such an emulsion may not be acceptable.

29. Emulsifying agents and emulsion type The type of emulsion which is formed when a given pair of immiscible liquids is homogenised depends on (1) the relative volumes of the two phases, and (2) the nature of the emulsifying agent. 1. Phase volume The higher its phase volume, the more likely a* liquid is to become the dispersion medium. However, the liquid with the greater phase volume need not necessarily be the dispersion medium. If the emulsion consisted of an assembly of closely packed uniform spherical droplets, the dispersed phase would occupy 0.74 of the total volume. Stable emulsions can, however, be prepared in which the volume fraction of the dispersed phase exceeds 0.74, because (a) the droplets are not of uniform size and can, therefore, be packed more densely, and (b) the droplets may be deformed into polyhedra, the interfacial film preventing coalescence.

30. Types of emulsion: diluted concentrated jelly emulsion 74 %

31. 2. Nature of the emulsifying agent Alkali-metal soaps favour the formation of O/W emulsions, whereas heavy-metal soaps favour the formation of W/O emulsions. O/W emulsions in the middle concentration region stabilised by alkali-metal soaps can often be broken, and even inverted into W/O emulsions, by the addition of heavy-metal ions. The most satisfactory general theory of emulsion type is that originally proposed for emulsions stabilised by finely divided solids (see Figure). If the solid is preferentially wetted by one of the phases, then more particles can be accommodated at the interface if the interface is convex towards that phase

33. The amphiphilic nature of many emulsifying agents (particularly non-ionic surfactants) can be expressed in terms of an empirical scale of so-called HLB (hydrophile-lipophile balance) numbers222 (see Table 10.1). The least hydrophilic surfactants are assigned the lowest HLB values.

34. Suspension (solid/liquid)

35. Foams (gas/liquid)

36. Aerosol (liquid/gas, solid /gas)

37. Powder (solid with high concentration / gas) flour

38. Characteristics of powder: Bulk density(It is defined as the mass of many particles of the material divided by the total volume they occupy).massvolume The clumping behavior (of a powder arises because of the molecular Van der Waals force that causes individual grains to cling to one another).Van der Waals force