Foam formation/foaming

Antifoam agents Prevent foam formation. Foaming of lubricants is detrimental for two reasons. First, in an oil-circulation system foaming may lead to a break-down of the lubrication transport. Second, the increased surface area in a foam accelerates oxidation. 

The kinetics of foam collapse, i.e. the process of gas and liquid separation, is characterised by the rate of reduction of foam volume with time or by the rate of decline in its height, if the cross-sectional area is equal along the whole foam column. The stability of the foam as a whole can be characterised quantitatively at any moment by the reciprocal quantity of the rate of foam column destruction. Most often, however, the estimation of the stability of the foam column, is expressed by an integral characteristic time of decay of the whole foam column or a part of it. The relation between the internal foam collapse and the destruction of the foam column is discussed in Section 6.5. Sometimes foam stability is considered in terms of foaming ability of the solution. In general the latter characteristic involves the easiness of foam formation, foam volume and stability. Such an interpretation, however, makes this characteristic rather indefinite. For example, Abramson [12] indicates that for the estimation of the foaming ability of surfactants it is necessary to know the quantity and stability of the foam obtained from a particular surfactant as well as the conditions under which the surfactant acts as a foam stabiliser. That is why it has been repeatedly emphasised that foaming ability... 

Examples of industrial relevance for the first two combinations are the adsorption of pollutants from waste air or water onto activated carbon. Combinations three and four can be observed at the orientation of tensid molecules on water/air interfaces (foam formation, foam stabilization) or at the interface of two immiscible liquids, (e.g. oil and water, emulsion formation). This book deals mainly with the case of liquid molecules adsorbed onto solid surfaces. For this case the following definitions are made ... 

Ideal morphologies are rarely observed. In general, the microstructure of a foam will be a dispersion of the above-noted morphologies, present in varying amounts according to the process used for foam formation. Foams produced by phase separation often exhibit unique microstructures not associated with those mentioned above. Some microstructures have been described as lacy, flaky, spherulitic, and fibril-like. In many polymeric foam materials, several distinctly different morphologies can be observed (5). 

Thus, adding surfactants to minimize the oil-water and solid-water interfacial tensions causes removal to become spontaneous. On the other hand, a mere decrease in the surface tension of the water-air interface, as evidenced, say, by foam formation, is not a direct indication that the surfactant will function well as a detergent. The decrease in yow or ysw implies, through the Gibb s equation (see Section III-5) adsorption of detergent. 

Exerowa and co-workers [201] suggest that surfactant association initiates black film formation the growth of a black film is discussed theoretically by de Gennes [202]. A characteristic of thin films important for foam stability, their permeability to gas, has been studied in some depth by Platikanov and co-workers [203, 204]. A review of the stability and permeability of amphiphile films is available [205]. 

In an interesting medical application, the formation of a stable black foam film from amniotic fluid can be used as an assessment of fetal lung maturity [206]. 

Fig. 2. Aerosol emulsion droplets containing propellant (a) in the internal phase with subsequent formation of aerosol foam and (b) in the external phase...

Antagonism between antimony oxide and phosphoms flame retardants has been reported in several polymer systems, and has been explained on the basis of phosphoms interfering with the formation or volatilization of antimony haUdes, perhaps by forming antimony phosphate (12,13). This phenomenon is also not universal, and depends on the relative amounts of antimony and phosphoms. Some useful commercial poly(vinyl chloride) (PVC) formulations have been described for antimony oxide and triaryl phosphates (42). Combinations of antimony oxide, halogen compounds, and phosphates have also been found useful in commercial flexible urethane foams (43). 

Initiation and Growth of Cells. The initiation or nucleation of cells is the formation of cells of such size that they are capable of growth under the given conditions of foam expansion. The growth of a hole or cell in a fluid medium at equiUbrium is controlled by the pressure difference (AP) between the inside and the outside of the cell, the surface tension of the fluid phase y, and the radius r of the cell ... 

Stabilization of the Cellular State. The increase in surface area corresponding to the formation of many ceUs in the plastic phase is accompanied by an increase in the free energy of the system hence the foamed state is inherently unstable. Methods of stabilizing this foamed state can be classified as chemical, eg, the polymerization of a fluid resin into a three-dimensional thermoset polymer, or physical, eg, the cooling of an expanded thermoplastic polymer to a temperature below its second-order transition temperature or its crystalline melting point to prevent polymer flow. 

Froth flotation (qv) is a significant use of foam for physical separations. It is used to separate the more precious minerals from the waste rock extracted from mines. This method reHes on the different wetting properties typical for the different extracts. Usually, the waste rock is preferentially wet by water, whereas the more valuable minerals are typically hydrophobic. Thus the mixture of the two powders are immersed in water containing foam promoters. Also added are modifiers which help ensure that the surface of the waste rock is hydrophilic. Upon formation of a foam by bubbling air and by agitation, the waste rock remains in the water while the minerals go to the surface of the bubbles, and are entrapped in the foam. The foam rises, bringing... 

Commercially, polymeric MDI is trimerized duting the manufacture of rigid foam to provide improved thermal stabiUty and flammabiUty performance. Numerous catalysts are known to promote the reaction. Tertiary amines and alkaU salts of carboxyUc acids are among the most effective. The common step ia all catalyzed trimerizations is the activatioa of the C=N double boad of the isocyanate group. The example (18) highlights the alkoxide assisted formation of the cycHc dimer and the importance of the subsequent iatermediates. Similar oligomerization steps have beea described previously for other catalysts (61). 

Defoamers. Foam is a common problem in papermaking systems (27). It is caused by surface-active agents which are present in the pulp slurry or in the chemical additives. In addition, partially hydrophobic soHd materials can function as foam stabilizers. Foam can exist as surface foam or as a combination of surface foam and entrained air bubbles. Surface foam usually can be removed by water or steam showers and causes few problems. Entrained air bubbles, however, can slow drainage of the stock and hence reduce machine speed. Another serious effect is the formation of translucent circular spots in the finished sheet caused by permanently entrained air. 

Chemical additives for gas-based drilling fluids are limited to surfactants (qv), certain polymers, and occasionally salts such as sodium or potassium chloride. An aqueous solution of the additives is iajected iato the air or gas flow to generate a mist or foam. No additives are used ia dry air or gas drilling operations. Gas-based fluids are not recirculated and materials are added continuously. As the fluid exits the well, air or water vapor escapes to the atmosphere, gas and oil are burned, and water and formation soflds are collected into a pit for later disposal. Stable foams must be destabili2ed to separate the air from the Hquid phase for disposal. 

The WAG process has been used extensively in the field, particularly in supercritical CO2 injection, with considerable success (22,157,158). However, a method to further reduce the viscosity of injected gas or supercritical fluid is desired. One means of increasing the viscosity of CO2 is through the use of supercritical C02-soluble polymers and other additives (159). The use of surfactants to form low mobihty foams or supercritical CO2 dispersions within the formation has received more attention (160—162). Foam has also been used to reduce mobihty of hydrocarbon gases and nitrogen. The behavior of foam in porous media has been the subject of extensive study (4). X-ray computerized tomographic analysis of core floods indicate that addition of 500 ppm of an alcohol ethoxyglycerylsulfonate increased volumetric sweep efficiency substantially over that obtained in a WAG process (156). 

Alcohol ethoxysulfates have been used in field tests as nitrogen (177) and carbon dioxide (178) foaming agents. Field use of alcohol ethoxysulfates is restricted to low temperature formations owing to its limited hydrolytic stabihty at low pH and elevated temperature (179). It has been reported that some foams can reduce residual oil saturation, not by oil displacement, but by emulsification and imbibition of the oil into the foam (180). 

In some resole appHcations, such as foam and foundry binders, a rapid cure of a Hquid resin is obtained at RT with strong acid. The reactions proceed in the same manner as those of novolak resin formation. Methylol groups react at ortho and para phenoHc hydrogen to give diphenyknethane units (41). 

Ca.ta.lysts, A small amount of quinoline promotes the formation of rigid foams (qv) from diols and unsaturated dicarboxyhc acids (100). Acrolein and methacrolein 1,4-addition polymerisation is catalysed by lithium complexes of quinoline (101). Organic bases, including quinoline, promote the dehydrogenation of unbranched alkanes to unbranched alkenes using platinum on sodium mordenite (102). The peracetic acid epoxidation of a wide range of alkenes is catalysed by 8-hydroxyquinoline (103). Hydroformylation catalysts have been improved using 2-quinolone [59-31-4] (104) (see Catalysis). 

Materials. Supercritical fluids offer many opportunities in materials processing, such as crystallization, recrystallization, comminution, fiber formation, blend formation, and microceUular (foam) formation. 

Urethane network polymers are also formed by trimerization of part of the isocyanate groups. This approach is used in the formation of rigid polyurethane-modified isocyanurate (PUIR) foams (3). 

The steric effects in isocyanates are best demonstrated by the formation of flexible foams from TDI. In the 2,4-isomer (4), the initial reaction occurs at the nonhindered isocyanate group in the 4-position. The unsymmetrically substituted ureas formed in the subsequent reaction with water are more soluble in the developing polymer matrix. Low density flexible foams are not readily produced from MDI or PMDI enrichment of PMDI with the 2,4 -isomer of MDI (5) affords a steric environment similar to the one in TDI, which allows the production of low density flexible foams that have good physical properties. The use of high performance polyols based on a copolymer polyol allows production of high resiHency (HR) slabstock foam from either TDI or MDI (2). 

Hydroxy group containing tertiary amines are also used because they become incorporated into the polymer stmcture, which eliminates odor formation ia the foam (3). Delayed-action or heat-activated catalysts are of particular interest ia molded foam appHcations. These catalysts show low activity at room temperature but become active when the exotherm builds up. In addition to the phenol salt of DBU (4), benzoic acid salts of Dabco are also used (5). 

---