Hydrophilicity of surfactant

Generally speaking, hydrophilic surfactant is used to formulate water continuous microemulsions and lipophilic surfactant is used to formulate oil continuous microemulsions. The hydrophilicity of surfactant can be measured in terms of the HLB (Pasquali et al. 2008). The HLB value of a surfactant is dehned as follows based on Griffin s method ... 

As surfactant composition increases, the water/surfactant ratio decreases. The heat required to destroy the crystal increases as this ratio decreases because the contribution of hydration energy to the process (which is stoichiometry limited) also decreases. Such data could in principle serve to define the intrinsic hydrophilicity of surfactant hydrophilic groups [37], but this analysis has yet to be done. 

The concept of hydrophile-lipophile balance (HLB) was first developed by Griffin [13] to correlate the structure of surfactant molecules with their surface activity. The HLB number (0-20) reflects the hydrophilicity of surfactant, and it increases with increasing hydrophilicity. A general trendi often observed in a family of surfactants is the increased CMC with HLB. Table 2.1 serves as a general guide for the formulator to choose surfactants that are most suited to meet the requirements of end-users. This semiempirical approach has been proved to be quite useful. Davies and Rideal [14] proposed that the HLB value of a particular surfactant could be calculated according to the group contribution approach. 

Soap is one example of a broader class of materials known as surface-active agents, or surfactants (qv). Surfactant molecules contain both a hydrophilic or water-liking portion and a separate hydrophobic or water-repelling portion. The hydrophilic portion of a soap molecule is the carboxylate head group and the hydrophobic portion is the aUphatic chain. This class of materials is simultaneously soluble in both aqueous and organic phases or preferential aggregate at air—water interfaces. It is this special chemical stmcture that leads to the abiUty of surfactants to clean dirt and oil from surfaces and produce lather. 

Polyall lene Oxide Block Copolymers. The higher alkylene oxides derived from propjiene, butylene, styrene (qv), and cyclohexene react with active oxygens in a manner analogous to the reaction of ethylene oxide. Because the hydrophilic oxygen constitutes a smaller proportion of these molecules, the net effect is that the oxides, unlike ethylene oxide, are hydrophobic. The higher oxides are not used commercially as surfactant raw materials except for minor quantities that are employed as chain terminators in polyoxyethylene surfactants to lower the foaming tendency. The hydrophobic nature of propylene oxide units, —CH(CH2)CH20—, has been utilized in several ways in the manufacture of surfactants. Manufacture, properties, and uses of poly(oxyethylene- (9-oxypropylene) have been reviewed (98). 

Cosolvents ana Surfactants Many nonvolatile polar substances cannot be dissolved at moderate temperatures in nonpolar fluids such as CO9. Cosolvents (also called entrainers, modifiers, moderators) such as alcohols and acetone have been added to fluids to raise the solvent strength. The addition of only 2 mol % of the complexing agent tri-/i-butyl phosphate (TBP) to CO9 increases the solubility ofnydro-quinone by a factor of 250 due to Lewis acid-base interactions. Veiy recently, surfac tants have been used to form reverse micelles, microemulsions, and polymeric latexes in SCFs including CO9. These organized molecular assemblies can dissolve hydrophilic solutes and ionic species such as amino acids and even proteins. Examples of surfactant tails which interact favorably with CO9 include fluoroethers, fluoroacrylates, fluoroalkanes, propylene oxides, and siloxanes. 

Internal surfactants, i.e., surfactants that are incorporated into the backbone of the polymer, are commonly used in PUD s. These surfactants can be augmented by external surfactants, especially anionic and nonionic surfactants, which are commonly used in emulsion polymerization. Great attention should be paid to the amount and type of surfactant used to stabilize urethane dispersions. Internal or external surfactants for one-component PUD s are usually added at the minimum levels needed to get good stability of the dispersion. Additional amounts beyond this minimum can cause problems with the end use of the PUD adhesive. At best, additional surfactant can cause moisture sensitivity problems with the PUD adhesive, due to the hydrophilic nature of the surfactant. Problems can be caused by excess (or the wrong type of) surfactants in the interphase region of the adhesive, affecting the ability to bond. 

Figure 20 shows the plot of the surface tension vs. the logarithm of the concentration (or-lg c-isotherms) of sodium alkanesulfonates C,0-C15 at 45°C. In accordance with the general behavior of surfactants, the interfacial activity increases with growing chain length. The critical micelle concentration (cM) is shifted to lower concentration values. The typical surface tension at cM is between 38 and 33 mN/m. The ammonium alkanesulfonates show similar behavior, though their solubility is much better. The impact of the counterions is twofold First, a more polarizable counterion lowers the cM value (Fig. 21), while the aggregation number of the micelles rises. Second, polarizable and hydrophobic counterions, such as n-propyl- or isopropylammonium and n-butylammonium ions, enhance the interfacial activity as well (Fig. 22). Hydrophilic counterions such as 2-hydroxyethylammonium have the opposite effect. Table 14 summarizes some data for the dodecane 1-sulfonates.

A positive value of ME means that the insertion of a hetero atom or group makes the molecule more lipophilic. If ME is negative, the hetero surfactant is more hydrophilic. In general, hetero atom insertion hydrophilizes the surfactant molecule as does the shift of the hetero group to the middle of the carbon chain [71]. ME values are temperature-dependent. / and ME values can also be useful to take into account the influence of various cations on the critical micelle concentration. 

Salts of alkyl phosphates and types of other surfactants used as emulsifiers and dispersing agents in polymer dispersions are discussed with respect to the preparation of polymer dispersions for use in the manufactoring and finishing of textiles. Seven examples are presented to demonstrate the significance of surfactants on the properties, e.g., sedimentation, wetting behavior, hydrophilic characteristics, foaming behavior, metal adhesion, and viscosity, of polymer dispersions used in the textile industry [239]. 

Surfactants have a unique long-chain molecular structure composed of a hydrophilic head and hydrophobic tail. Based on the nature of the hydrophilic part surfactants are generally categorized as anionic, non-ionic, cationic, and zwitter-ionic. They all have a natural tendency to adsorb at surfaces and interfaces when added in low concentration in water. Surfactant absorption/desorption at the vapor-liquid interface alters the surface tension, which decreases continually with increasing concentrations until the critical micelle concentration (CMC), at which micelles (colloid-sized clusters or aggregates of monomers) start to form is reached (Manglik et al. 2001 Hetsroni et al. 2003c). 

The structure of these globular aggregates is characterized by a micellar core formed by the hydrophilic heads of the surfactant molecules and a surrounding hydrophobic layer constituted by their opportunely arranged alkyl chains whereas their dynamics are characterized by conformational motions of heads and alkyl chains, frequent exchange of surfactant monomers between bulk solvent and micelle, and structural collapse of the aggregate leading to its dissolution, and vice versa [2-7]. 

Obviously, water, aqueous solutions of salts, and mixtures of highly hydrophilic solvents have also been found to be solubilized in the micellar core [13,44]. The maximum amount of such solubilizates that can be dissolved in reversed micelles varies widely, strongly depending on the nature of the surfactant and the apolar solvent, on the concentrations of surfactant and of additives, and on temperature [24,45-47]. 

Alkylphenol ethoxylates (APEOs) are a class of surfactants that have been used widely in the drilling fluid industry. The popularity of these surfactants is based on their cost-effectiveness, availability, and range of obtainable hydrophilic-lipophilic balance values [693]. Studies have shown that APEOs exhibit oestrogenic effects and can cause sterility in some male aquatic species. This may have subsequent human consequences, and such problems have led to a banning of their use in some countries and agreements to phase out their use. Alternatives to products containing APEOs are available, and in some cases they show an even better technical performance. 

Aid in the uniform dispersion of additives. Make powdered solids (e.g. particulate fillers with high energy and hydrophilic surface) more compatible with polymers by coating their surfaces with an adsorbed layer of surfactant in the form of a dispersant. Surface coating reduces the surface energy of fillers, reduces polymer/filler interaction and assists dispersion. Filler coatings increase compound cost. Fatty acids, metal soaps, waxes and fatty alcohols are used as dispersants commonly in concentrations from 2 to 5 wt %. 

Rod-like micelles of surfactant molecules with a liquid-crystalline order. The aqueous solution is located between the micelles. Spheres = hydrophilic ends of the surfactant molecules, black zigzag lines = long alkyl groups... 

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