Dynamic maximum bubble pressure method

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]. 

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

There are static and dynamic methods. The static methods measure the tension of practically stationary surfaces which have been formed for an appreciable time, and depend on one of two principles. The most accurate depend on the pressure difference set up on the two sides of a curved surface possessing surface tension (Chap. I, 10), and are often only devices for the determination of hydrostatic pressure at a prescribed curvature of the liquid these include the capillary height method, with its numerous variants, the maximum bubble pressure method, the drop-weight method, and the method of sessile drops. The second principle, less accurate, but very often convenient because of its rapidity, is the formation of a film of the liquid and its extension by means of a support caused to adhere to the liquid temporarily methods in this class include the detachment of a ring or plate from the surface of any liquid, and the measurement of the tension of soap solutions by extending a film. 

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. 

Figure 3 contains dynamic data for ff-LG received by three methods the maximum bubble pressure method in the time range 0.001 s to 100 s, the drop volume method for times in the range 5 s to 500 s, and the profile analysis tensiometer PAT l in the time range from 10 s up to several hours. 

The aim of this chapter is to present the fundamentals of adsorption at liquid interfaces and a selection of techniques, for their experimental investigation. The chapter will summarise the theoretical models that describe the dynamics of adsorption of surfactants, surfactant mixtures, polymers and polymer/surfactant mixtures. Besides analytical solutions, which are in part very complex and difficult to apply, approximate and asymptotic solutions are given and their range of application is demonstrated. For methods like the dynamic drop volume method, the maximum bubble pressure method, and harmonic or transient relaxation methods, specific initial and boundary conditions have to be considered in the theories. The chapter will end with the description of the background of several experimental technique and the discussion of data obtained with different methods. 

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. 5.32 Dynamic surface tension as a function of the square root of surface age for four pt-BPh-EOlO solutions measured using the maximum bubble pressure method Cg= 0.0001(B) 0.0005 ( ) 0.001 (A) 0.0025 ( ) mol/1 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. 

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]. 

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... 

Wasan and his research group focused on the field of interfacial rheology during the past three decades [15]. They developed novel instruments, such as oscillatory deep-channel interfacial viscometer [20,21,28] and biconical bob oscillatory interfacial rheometer [29] for interfacial shear measurement and the maximum bubble-pressure method [15,29,30] and the controlled drop tensiometer [1,31] for interfacial dilatational measurement, to resolve complex interfacial flow behavior in dynamic stress conditions [1,15,27,32-35]. Their research has clearly demonstrated the importance of interfacial rheology in the coalescence process of emulsions and foams. In connection with the maximum bubble-pressure method, it has been used in the BLM system to access the properties of lipid bilayers formed from a variety of surfactants [17,28,36]. 

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 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 surface tension measurement techniques can be divided into the following three categories (i) Force Methods, which include the truly static methods of the capillary rise and Wilhelmy plate methods, as well as the dynamic detachment methods of the Du Nouy ring and drop weight, (ii) Shape Methods, which include the pendant or sessile drop or bubble, as well as the spinning drop methods, and (iii) Pressure Methods, which are represented by the maximum bubble pressure method. These techniques are summarized in the following sections of this chapter. 

Figure 12.3. Dynamic surface tensions of three aqueous solutions of SDS, as measured by the maximum bubble pressure method (MPT2, Lauda, Germany) , cq = 2 x 10" mol/cm ...

Figure 12.11. Dynamic surface tensions of blood serum samples as measured by the drop shape technique (PATl, SIN-TECH-Berlin, Germany, (0, )) and maximum bubble pressure method (MPT2, LAUDA, Germany, ( , )), samples taken from a 43 years old woman suffering from cervical carcinoma , , before radiotherapy o, at the end of treatment...

Figure Dynamic surface tension, a, versus the surface age, t of submicellar (curves a and b) and micellar (curves c and d) solutions of SDS in the presence of 0.128 M Nad measured by the maximum bubble pressure method at surfactant concentrations (a) 0.2 mM, (b) 0.4 mM, (c) 1.5 mAf, and (d) 2.0 mM. The solid and open symbols correspond to different runs. (After Ref. 84.)...

The dynamic surface activity of the commercial rhamnolipid mixture JBR425 fi om Jeneil was determined as a function of concentration and time with the maximum bubble pressure method using an online bubble tensiometer (Sita T60). Figure 11.14 highlights the good surfactancy properties of rhamnolipids, with low minimum surface tension and moderate dynamics, meaning a relatively fast decrease of surface tension at new surfaces and low bubble lifetimes. 

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