Bubble methods dynamic surface tension

Hsu and Berger [43] used the maximum bubble pressure method (MBP) to study the dynamic surface tension and surface dilational viscosity of various surfactants including AOS and have correlated their findings to time-related applications such as penetration and wetting. A recent discussion of the MBP method is given by Henderson et al. [44 and references cited therein]. 

On-line Determination of Dynamic Surface Tension by the Bubble-pressure Method... 

Bendure, R.L. 1971. Dynamic surface tension determination with maximum bubble pressure method. J. Colloid Interface Sci. 37 228-238. 

A number of methods are available for the measurement of surface and interfacial tension of liquid systems. Surface tension of liquids is determined by static and dynamic surface tension methods. Static surface tension characterises the surface tension of the liquid in equilibrium and the commonly used measurement methods are Du Notiy ring, Wilhelmy plate, spinning drop and pendant drop. Dynamic surface tension determines the surface tension as a function of time and the bubble pressure method is the most common method used for its determination. 

Dynamic surface tension is the time trajectory of surface tension before equilibrium is reached. Dynamic surface tension tracks the changes during surface formation when surfactants are added. The bubble pressure method is the one most commonly used for the determination of dynamic surface tension. The details of this method are described in ASTM D3825-90 (2000) [ 19]. In this method a capillary tube is immersed in a sample liquid and a constant flow of gas is maintained through the tube forming bubbles in the sample liquids. The surface tension of the sample is calculated from the pressure difference inside and outside the bubble and the radius of the bubble. 

ASTM D3825-90(2000). Standard test method for dynamic surface tension by the fast-bubble technique. 

The most suitable technique for studying adsorption kinetics and dynamic surface tension is the maximum bubble pressure method, which allows measurements to be obtained in the millisecond range, particularly if correction for the so-called dead time, t. The dead time is simply the time required to detach the bubble after it has reached its hemispherical shape. A schematic representation of the principle of maximum bubble pressure is shown in Figure 18.14, which describes the evolution of a bubble at the tip of a capillary. The figure also shows the variation of pressure p in the bubble with time. 

Various experimental methods for dynamic surface tension measurements are available. Their operational timescales cover different time intervals. - Methods with a shorter characteristic operational time are the oscillating jet method, the oscillating bubble method, the fast-formed drop technique,the surface wave techniques, and the maximum bubble pressure method. Methods of longer characteristic operational time are the inclined plate method, the drop-weight/volume techniques, the funnel and overflowing cylinder methods, and the axisym-metric drop shape analysis (ADSA) " see References 54, 55, and 85 for a more detailed review. 

The maximum bubble pressure technique is a classical method in interfacial science. Due to the fast development of new technique and the great interest in experiments at very small adsorption times in recent years, commercial set-ups were built to make the method available for a large number of researchers. Rehbinder (1924, 1927) was apparently the first who applied the maximum bubble pressure method for measurement of dynamic surface tension of surfactant solutions. Further developments of this method were described by several authors (Sugden 1924, Adam Shute 1935, 1938, Kuffiier 1961, Austin et al. 1967, Bendure 1971,... 

Fig. 5.28 Dynamic surface tension of two TRITON X-100 solutions measured using the maximum bubble pressure (n- ) and inclined plate ( ) methods Cq= 0.2 ( ) 0.5 ( ) g/1 according to Fainerman et al. (1994a)...

Fig. 5.30 Dynamic surface tension of a 0.025 mol/l pt-BPh-EOlO solution measured using the maximum bubble pressure ( ) and drop volume ( ) methods original data ( - ), corrected data ( ) according to Miller et al. (1994d)...

The Marangoni elasticity can be determined experimentally from dynamic surface tension measurements that involve known surface area changes. One such technique is the maximum bubble-pressure method (MBPM), which has been used to determine elasticities in this manner (24, 26). In the MBPM, the rates of bubble formation at submerged capillaries are varied. This amounts to changing A/A because approximately equal bubble areas are produced at the maximum bubble pressure condition at all rates. Although such measurements include some contribution from surface dilational viscosity (23, 27), the result will be referred to simply as surface elasticity in this work. 

Let us first look into the dynamic surface tensions for CjoEOg at the water/air interface, as it was measured by Chang et al. [228] using the pendent bubble method. The experimental data given in Fig. 4.29 are compared with calculations for two models, based on the Langmuir and the reorientation isotherm (two-state model). 

The graphs shown in Fig. 4.35 are the dynamic surface tensions of three mixtures of CioDMPO and CmDMPO measured with the maximum bubble pressure method MPT2 (O) and ring tensiometer TE2 (O). Although there is a general theoretical model to describe the adsorption kinetics of a surfactant mixture, model calculations are not trivial and a suitable software does not exists. 

It has been already indicated (Fig. 7) that micelles can lead to an essential acceleration of the adsorption process. Therefore, special experimental techniques are necessary for its investigation, allowing measurements of the dynamic surface tension in a time interval of milliseconds. The maximum bubble pressure method [78, 81, 83, 89,90,93] and the oscillating jet method [77, 82, 86, 87, 88, 90, 92, 93, 156] are most frequently used for these purposes. The inclined plate method [83, 89, 90, 93], the method of constant surface dilation [85] and the drop volume method [84] have been used also for slow adsorbing surfactants. 

A method based on the comparison of experimental and calculated kinetic dependencies of the dynamic surface tension can be more precise in comparison with the use of Eq. (5.253) [77, 85, 89, 92, 93]. Mitrancheva et al. presented the most detailed data and compared calculated dynamic surface tension with results obtained for solutions of TRITON X-100 using three different experimental methods the inclined plate, the oscillating jet and the maximum bubble pressure methods [93]. The inclined plate method yielded values of i2 different from the results of the two other techniques. This discrepancy is probably connected with the differences in the attainable surface age. Thus the inclined plate method can be used only at relatively high surface life times when the surface tension tends asymptotically to equilibrium, and when the accuracy of determination of i2 decreases. In addition the insufficiently investigated peculiarities of the liquid flow along the inclined plane can be another source of experimental errors [93]. 

Fig. 5.14. Dependence ot T2 on the relative amount ot Triton X-100 aggregated in micelles obtained by different methods of the dynamic surface tension oscillating jet [93] ( ), maximum bubble pressure [93] (A), [89] ( ), [90] (T), inclined plate [83] ( ) open symbols refer to results of relaxation methods for the bulk phase [166, 167] according to [93].

One of the reasons of the insufficient reliability of micellisation kinetics data determined from dynamic surface tensions, consists in the insufficient precision of the calculation methods for the adsorption kinetics from micellar solutions. It has been already noted that the assumption of a small deviation from equilibrium used at the derivation of Eq. (5.248) is not fulfilled by experiments. The assumptions of aggregation equilibrium or equal diffusion rates of micelles and monomers allow to obtain only rough estimates of the dynamic surface tension. An additional cause of these difficulties consists in the lack of reliable methods for surface tension measurements at small surface ages. The recent hydrodynamic analysis of the theoretical foundations of the oscillating jet and maximum bubble pressure methods has shown that using these techniques for measurements in the millisecond time scale requires to account for numerous hydrodynamic effects [105, 158, 159]. These effects are usually not taken into account by experimentalists, in particular in studies of micellar solutions. A detailed analysis of... 

Fainerman, V. B., Makievski, A. V., and Miller, R., The measurement of dynamic surface tensions of highly viscous liquids by the maximum bubble pressure method, Colloid Surf A, 75, 229-235 (1993). 

The two methods maximum bubble pressure and profile analysis tensiometry complement each other experimentally and cover a total time range of nine orders of magnitude from about lO" seconds up to 10 seconds (many hours). The example given in Fig. 33 shows the dynamic surface tension of two Triton X-100 solutions measured with the instruments BPA and PAT (SINTERFACE Technologies) over the time interval of 7 orders of magnitude. As one can see, the experiments cover the beginning of the adsorption process and the establishment of the equilibrium state. 

The graph in Fig. 41 shows the dynamic surface tensions of a mixtured solution of CioDMPO and C14DMPO measured with the maximum bubble pressure method BPAl (O) and profile analysis tensiometer PATl ( ). The theoretical curves shown were calculated due to the adsorption kinetics model for surfactant mixtures discussed above (Miller et al. 2003). 

Our results also proved the correlation between foamability and surface tension gradient for aqueous nonionic surfactant solutions. Foam formation was estimated from a dynamic surface tension using the maximum bubble pressure method, and foam stability was estimated from a transfer distance of lamella using a laminometer. Laminometer measurements were made using the Du Noiiy ring method [1,78,96]. Force profile during the expansion of lamella was monitored using an electronic-balance with... 

Fig. 12 Dynamic surface tension during the adsorption of C10E5 at water/air interface. From top, the bulk concentrations are 6 10", and lO mol/cm the empty symbols refer to data acquired by the dynamic maximum bubble pressure method, while the filled ones to data acquired by the drop shape method the solid lines are the theoretical prediction by the diffusion controlled adsorption with the two-state isotherm...

The dynamic surface tension of [3-casein solutions at three concentrations 5 10, 10 and 10 mol/1 are shown in Fig. 14. As one can see the results from the two methods differ significantly. For the bubble the surface tension decrease starts much earlier. The surface tensions at long times, and hence the equilibrium surface tension from the bubble experiment are lower than those from the drop. However, the establishment of a quasi-equilibrium for the drop method is more rapid at low (3-casein concentrations while at higher P-casein concentrations this process is more rapid for the bubble method. This essential difference between solutions of proteins and surfactants was discussed in detail elsewhere [50]. In brief, it is caused by simultaneous effects of differences in the concentration loss, and the adsorption rate, which both lead to a strong difference in the conformational changes of the adsorbed protein molecules. 

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