Emulsion using ultrasound

From the environmental viewpoint, the solvent used for coating or film-forming materials is important. The macromonomer technique was therefore applied to form a miniemulsion system of PLA-graft copolymers, as a typical example of the use of water as a green solvent. Four MMm macromonomers (m = 4, 6, 8, and 12 Scheme 1) were prepared and used as comonomer. In the copolymerization, BMA or BA was employed as the vinyl monomer (reaction 2, Scheme 1) [41]. Sodium dodecyl sulfate (SDS) and sodium dioctyl sulfosuccinate (PEREX), both anionic, were found to be appropriate surfactants. To form a stable emulsion system, ultrasound sonication was applied to the mixture of comonomers and surfactant in water before the copolymerization. Then, radical copolymerization was carried out (Table 3) [41, 42]. Relevant to the use of water as reaction solvent. Sect. 4 describes the use of green solvents in enzyme-catalyzed polymerizations. 

In the previous section we demonstrated the use of ultrasonic velocity measurements to characterise creaming, and indirectly to characterise flocculation. However, there is more information to be obtained from an emulsion using ultrasonic spectroscopy. This involves measurement of phase velocity and attenuation of ultrasound as a function of frequency after propagation through the emulsion. There are a number of mechanisms by which ultrasound is attenuated by the emulsion, resulting in characteristic ultrasonic properties. Figure 4.15 shows the prineipal mechanisms of absorption. 

Membranes and Osmosis. Membranes based on PEI can be used for the dehydration of organic solvents such as 2-propanol, methyl ethyl ketone, and toluene (451), and for concentrating seawater (452—454). On exposure to ultrasound waves, aqueous PEI salt solutions and brominated poly(2,6-dimethylphenylene oxide) form stable emulsions from which it is possible to cast membranes in which submicrometer capsules of the salt solution ate embedded (455). The rate of release of the salt solution can be altered by surface—active substances. In membranes, PEI can act as a proton source in the generation of a photocurrent (456). The formation of a PEI coating on ion-exchange membranes modifies the transport properties and results in permanent selectivity of the membrane (457). The electrochemical testing of salts (458) is another possible appHcation of PEI. 

Ultrasonically assisted extraction is also widely used for the isolation of effective medical components and bioactive principles from plant material [195]. The most common application of low-intensity ultrasound is as an analytical technique for providing information about the physico-chemical properties of foods, such as in the analysis of edible fats and oils (oil composition, oil content, droplet size of emulsions, and solid fat content) [171,218]. Ultrasonic techniques are also used for fluids characterisation [219]. 

The effect of ultrasound on liquid-liquid interfaces between immiscible fluids is emulsification. This is one of the major industrial uses of ultrasound (74-76) and a variety of apparatus have been devised which will generate micrometer-sized emulsions (9). The mechanism of ultrasonic emulsification lies in the shearing stresses and deformations created by the sound field of larger droplets. When these stresses become greater than the interfacial surface tension, the droplet will burst (77,78). The chemical effects of emulsification lie principally in the greatly increased surface area of contact between the two immiscible liquids. Results not unlike phase transfer catalysis may be expected. 

In organometallic chemistry, the use of ultrasound in liquid-liquid heterogeneous systems has been limited to Hg. The emulsification of Hg with various liquids dates to the very first reports on sonochemistry (3,203,204). The use of such emulsions for chemical purposes, however, was delineated by the extensive investigations of Fry and co-workers (205-212), who have reported the sonochemical reaction of various nucleophiles with a,a -dibromoketones and mercury. The versatility of this reagent is summarized in Eqs. (30)-(36). 

Liposphere formulations are prepared by solvent or melt processes. In the melt method, the active agent is dissolved or dispersed in the melted solid carrier (i.e., tristearin or polycaprolactone) and a hot buffer solution is added at once, along with the phospholipid powder. The hot mixture is homogenized for about 2 to 5 min, using a homogenizer or ultrasound probe, after which a uniform emulsion is obtained. The milky formulation is then rapidly cooled down to about 20°C by immersing the formulation flask in a dry ice-acetone bath, while homogenization is continued to yield a uniform dispersion of lipospheres. 

Ultrasound is known to generate extremely fine emulsions from mixtures of immiscible liquids. Ultrasonic homogenisation has been used for many years in the food industry for the production of tomato sauce, mayormaise and other similar blended items. In chemistry such extremely fine emulsions provide enormous interfacial contact areas between immiscible liquids and thus the potential for greater reaction between the phases. This can be particularly beneficial in phase transfer catalysis. 

It is liquid-liquid reactions involving phase transfer catalysts which generally benefit from the use of ultrasound. Sonication produces homogenisation - i. e. very fine emulsions - which greatly increase the reactive interfacial area and allows faster reaction at lower temperatures. Davidson has reported an example of this with the ultrasonically enhanced saponification of wool waxes by aqueous sodium hydroxide using tetra n-heptyl ammonium bromide as a PTC [124]. 

For ideal mixtures there is a simple relationship between the measurable ultrasonic parameters and the concentration of the component phases. Thus ultrasound can be used to determine their composition once the properties of the component phases are known. Mixtures of triglyceride oils behave approximately as ideal mixtures and their ultrasonic properties can be modeled by the above equations [19]. Emulsions and suspensions where scattering is not appreciable can also be described using this approach [20]. In these systems the adiabatic compressibility of particles suspended in a liquid can be determined by measuring the ultrasonic velocity and the density. This is particularly useful for materials where it is difficult to determine the adiabatic compressibility directly, e.g., powders, biopolymer or granular materials. Deviations from equations 11 - 13 in non-ideal mixtures can be used to provide information about the non-ideality of a system. 

An application of ultrasound that is becoming increasingly popular in the food industry is the determination of creaming and sedimentation profiles in emulsions and suspensions (Basaran et al., 1998). Acoustic techniques can also assess nondestructively the texture of aerated food products such as crackers and wafers. Air cells, which are critical to consumer appreciation of baked product quality, are readily probed due to their inherent compressibility (Elmehdi et al., 2003). Kulmyrzaev et al. (2000) developed an ultrasonic reflectance spectrometer to relate ultrasonic reflectance spectra to bubble characteristics of aerated foods. Experiments were carried out using foams with different bubble concentration and the results showed that ultrasonic reflectance spectrometry is sensitive to changes in bubble size and concentration of aerated foods. 

Ultrasound is by far the most sensitive technique for detecting the initial stages of crystallization. Ultrasound velocity is very sensitive to the state of fat in a dairy emulsion (Figure 21.2) and can be used to follow changes in the amount of solid fat which occurs as the temperature changes. 

The term ME is often incorrectly used in the literature to describe oil and water dispersions of small droplet size produced by prolonged ultrasound mixing, high-shear homogenization, and microfluidisation, that is, submicrometer emulsions. The major differences between a microemulsion and a coarse emulsion are shown in Table 1. 

Emulsions can be made in different ways. The most common class of processes applies strong flow fields, usually a combination of simple shear flow and of exten-sional flow. Extensional flow is more effective than shear flow in breaking up droplets into smaller ones. Industrial equipment usually operates with turbulent flow, in which inertial forces can be important as well. In addition, for some applications ultrasound is used, which creates, through cavitation, strong local turbulence. 

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