Surfactant adsorption hydrophobization

The colloid probe technique was first applied to the investigation of surfactant adsorption by Rutland and Senden [83]. They investigated the effect of a nonionic surfactant petakis(oxyethylene) dodecyl ether at various concentrations for a silica-silica system. In the absence of surfactant they observed a repulsive interaction at small separation, which inhibited adhesive contact. For a concentration of 2 X 10 M they found a normalized adhesive force of 19 mN/m, which is small compared to similar measurements with SEA and is probably caused by sufactant adsorption s disrupting the hydration force. The adhesive force decreased with time, suggesting that the hydrophobic attraction was being screened by further surfactant adsorption. Thus the authors concluded that adsorption occurs through... 

In many cases, the adsorption of surfactants on hydrophobic surfaces may follow a Langmuir-type isotherm,... 

The increase in the hydrophilic head group size reduces the amount of adsorbed surfactant at surface saturation. On the other hand, increasing the hydrophobic tail length may increase, decrease or maintain the surfactant adsorption. If the surfactant molecules are not closely packed, the increase in the chain length of the tail increases surfactant adsorption on solid surfaces. If the adsorption of surfactant on the solid surface is due to polarisation of tc electrons, the amount of surfactant adsorbed on the surface reduces at surface saturation. If the adsorbed surfactants are closely packed on the solid surface, increasing the chain length of the surfactant tail will have no effect on the surfactant adsorption. 

To find out whether a hydrophobizing effect can be obtained by surfactant adsorption, photoresist layers processed with exposure doses between 50% and 120% of the threshold dose have been investigated by the captive bubble method. Their receding contact angle was first... 

The experiment described above does surely not yield the contact angles that determine the capillary forces since the surfactant layer is desorbed partially in water. It proves, however, that a noticeable hydrophobizing effect after surfactant adsorption can be found for the rather hydrophilic photoresist surfaces processed with the threshold dose. 

The scope of the chapter will include an introduction to the technique of neutron reflectometry, and how it is applied to the study of surfactant adsorption at the planar solid-solution interface, to obtain adsorbed amounts and details of the structure of the adsorbed layer. The advantages and limitations of the technique will be put in the context of other complementary surface techniques. Recent results on the adsorption of a range of anionic, cationic and nonionic surfactants, and surfactant mixtures onto hydrophilic, hydrophobic surfaces, and surfaces with specifically tailored functionality will be described. Where applicable, direct comparison with the results from complementary techniques will be made and discussed. 

The more recent neutron reflectivity studies have established that flattened surface micelle or fragmented bilayer structure in more detail and with more certainty, using contrast variation in the surfactant and the solvent [24, 31]. However, the extent of the lateral dimension (in the plane of the surface) and the detailed structure in that direction is less certain. From those neutron reflectivity measurements [24, 31] and related SANS data on the adsorption of surfactants onto colloidal particles [5], it is known that the lateral dimension is small compared with the neutron coherence length, such that averaging in the plane is adequate to describe the data. The advent of the AFM technique and its application to surfactant adsorption [15] has provided data that suggest that there is more structure and ordering in the lateral direction than implied from other measurements. This will be discussed in more detail in a later section of the chapter. At the hydrophobic interface, although the thickness of the adsorbed layer is now consistent with a monolayer, the same uncertainties about lateral structure exist. 

Toluene, an apolar solute, seems to have a higher affinity for the CTAB covered phases than for the SDS covered phases. If we consider the two processes of surfactant adsorption (Figure 1), the silanophilic process is important in CTAB adsorption given the great affinity of quaternary ammonium for surface-sllanols (11). As a result, the stationary phase becomes more hydrophobic with CTAB than with SDS, which could explain the magnitude of the Kg values for toluene. Caffeine is a polar solute, its Kg values on the more hydrophobic stationary phases (MOS and ODS Hypersil) were weak and much lower than the respective toluene-Kg values. The caffeine Kg values were greater on SDS covered stationary phases than on CTAB covered ones. The explanation in the case of toluene holds true, that is to say caffeine has more affinity for the more polar SDS covered stationary phases (9.6 on C8, for example) than for the same phase but CTAB covered (1.8 on C8 with CTAB) (Table VI). 

In this Section instability of asymmetric films is explained by decrease in the surfactant adsorption. Another reason for this instability can be the presence of solid particles at the water-oil interface. Such a heterogeneous defoaming is created when a foam is broken down by the antifoam drops that contain solid hydrophobic particles. The mechanism of action of such types of antifoams will be discussed in Section 9.4. 

Thus it is possible to estimate the time for surfactant adsorption required for the formation of black spots. Table 11.2 presents the clinical and threshold concentrations for total phospholipids (PL) and for disaturated phosphatidylcholine (DSPC) in each preparation. The most abundant PL of the lung surfactant system is DSPC, principally the DPPC species, which is believed the essential determinant of surfactant function in vivo [2], While DPPC is the only PL in EX, both IN and SU contain other PLs and small quantities of hydrophobic surfactant-associated proteins that may add to the desired functional properties of the material in situ. 

Surfactant adsorption can change the wettability of the porous medium from hydrophilic to hydrophobic and even back again. 

Correlation equations relating surfactant chemical structure to performance characteristics and physical properties have been established. One atmosphere foaming properties of alcohol ethoxyl-ates and alcohol ethoxylate derivatives have been related to surfactant hydrophobe carbon chain length, ethylene oxide content, aqueous phase salinity, and temperature. Similar correlations have been established for critical micelle concentration, surfactant cloud point, and surfactant adsorption. 

Surfactant surface activity is most completely presented in the form of the Gibbs adsorption isotherm, the plot of solution surface tension versus the logarithm of surfactant concentration. For many pure surfactants, the critical micelle concentration (CMC) defines the limit above which surface tension does not change with concentration, because at this stage, the surface is saturated with surfactant molecules. The CMC is a measure of surfactant efficiency, and the surface tension at or above the CMC (the low-surface-tension plateau) is an index of surfactant effectiveness (Table XIII). A surfactant concentration of 1% was chosen where possible from these various dissimilar studies to ensure a surface tension value above the CMC. Surfactants with hydrophobes based on methylsiloxanes can achieve a low surface tension plateau for aqueous solutions of —21-22 mN/m. There is ample confirmation of this fact in the literature (86, 87). 

The nonpolar portion of surfactant ions has an important role in promoting the adsorption process because it increases the affinity of these organic ions to the interfacial region. The effect derives from mutual attraction between the hydrophobic tails as well as their tendency to escape from an aqueous environment. That mechanism is precisely the same one which causes the spontaneous formation of micelles in aqueous solution and is known as the hydrophobic effect [78]. In the case of surfactant adsorption, it is responsible for the formation of surface aggregates. However, it is not easy to accurately predict the shape and the size of such molecular associations in the same way that the structure of bulk aggregates can be determined from the geometry of the molecule. This is because the surface imposes different restrictions on the organization of the adsorbed layer. 

In another recent study, Chen and coworkers [11] also investigated the effect of surfece oxygen complexes, introduced by air and ozone treatments, on the adsorption of the commercial surfactants SDS, Darex II (anionics), and Tergitol (nonionic). Results revealed that the surfactant adsorption was strongly suppressed by surface oxidation. These authors proposed that surfactant adsorption primarily occurs on nonpolar carbon surface patches by hydrophobic interactions. Therefore, the oxidative suppression of surfactant adsorption was... 

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