Drop tensiometers

Tests were performed at 75°C using a University of Texas Model 500 spinning drop tensiometer. Active surfactant concentration in the aqueous phase prior to oil addition was 0.50% wt. The Kem River crude oil was from the Patricia Lease. The pH of the deionized water surfactant solutions was 8. The pH of the aqueous NaCl surfactant solutions was 9.5 unless otherwise noted. values represent the average deviation of two or three measurements at different times (0.75-1 h apart). D.I., deionized. 

Tests were performed at 75°C using a University of Texas Model 500 spinning drop tensiometer. Active surfactant concentration in the aqueous phase prior to addition of the oil phase was 0.5% wt. Interfacial tension values are the average of duplicate or triplicate determinations. 

The dynamic interfacial tension behavior of reacting acidic oil-alkaline solutions has been studied for both an artificially acidified synthetic oil and a real crude oil at various concentrations [131,132] with either a drop volume tensiometer or a spinning drop tensiometer. 

S. D. Ball. Comparison of transient interfacial tension behaviours of oiUalkaline systems as measured by the drop volume and spinning drop tensiometers. PhD thesis, Ottawa Univ, 1995. 

Equipaent and Procedures. Crude o iI/aqueous i nterfac ia I tens i ons were measured using a spinning drop tensiometer built at the Alberta Research Council and designed for operation at elevated temperatures [211. The main difficulty in operating at elevated temperatures was the wear on the bearing improved operation was... 

Modifications of the conventional spinning drop tensiometer were required for operating at temperatures up to 200°C. Measurements carried out with heavy oil samples required the use of D20 instead of H20 to maintain a sufficient density difference between oil and water. For accurate measurements, considerable care must be used to ensure that heavy oil drops do not lag behind the rotation of the capillary tube in the tensiometer. Also, repeatability of measurements conducted with chemically ill-defined substances may be hampered by the inhomogeneity of the oil drops. 

Surface and interfacial tension measurements were made at 40° C with a Model 300 Spinning Drop Tensiometer obtained from the University of Texas at Austin, Chemistry Department. 

We can distinguish between two types of stresses on an interface a shear stress and a dilatational stress. In a shear stress experiment, the interfacial area is kept constant and a shear is imposed on the interface. The resistance is characterized by a shear viscosity, similar to the Newtonian viscosity of fluids. In a dilatational stress experiment, an interface is expanded (dilated) without shear. This resistance is characterized by a dilatational viscosity. In an actual dynamic situation, the total stress is a sum of these stresses, and both these viscosities represent the total flow resistance afforded by the interface to an applied stress. There are a number of instruments to study interfacial rheology and most of them are described in Ref. [1]. The most recent instrumentation is the controlled drop tensiometer. 

The controlled drop tensiometer is a simple and very flexible method for measuring interfacial tension (IFI) in equilibrium as well as in various dynamic conditions. In this technique (Fig. 1), the capillary pressure, p of a drop, which is formed at the tip of a capillary and immersed into another immiscible phase (liquid or gas), is measured by a sensitive pressure transducer. The capillary pressure is related to the IFT and drop radius, R, through the Young-Laplace equation [2,3] ... 

When two fluid interfaces have a high radius of curvature, such as in the pseudoemulsion film, the distance between the interference patterns is too small to be measured by common reflected light interferometry. In this case, differential interferometry can be used for imaging the interface profile [40-45]. (Another technique for studying curved films is the controlled drop tensiometer, as was shown in section 2.)... 

Figure 11. Photograph of bitumen drop in aqueous NaOH showing low- and high-tension sites due to periodic diffusion of natural surf actants from the oil-water interface to the aqueous phase in a spinning drop tensiometer.

Dynamic Interfacial Tension. Crude-oil-alkali systems are unusual in that they exhibit dynamic interfacial tension (Figure 11). A solution of 0.05 wt% sodium hydroxide in contact with David Lloydminster crude oil initially produces ultralow values of IFT. A minimum value is reached, after which IFT increases with time by nearly 3 orders of magnitude, measured in the spinning drop tensiometer. Taylor et al. (57) showed that dynamic inter-facial tension can also occur in crude-oil-alkali-surfactant systems. Figure 11 shows interfacial tension versus time for a solution containing 1 wt% sodium carbonate, and the same solution containing 0.02 wt% of Neodol 25-... 

For instance. G. Faour et al. (J. Colloid Interface Set 181 (1996) 385) developed an automated pendent drop tensiometer allowing 3-5 measurements per second, so dynamic processes slower than that could be studied. 

Figure 3.72 shows a dynamic drop tensiometer in which the volume of a... 

Figure 3.72. Measuring principle of a dynamic drop tensiometer. Controlled level changes in the syringe lead to concomitant changes in the drop volume. (Redrawn from Benjamins et al., (1996).)...

The results of spinning drop experiments with the equilibrated oil (styrene) and aqueous (1 1 SLS/LA) phases are shown in Figure 5. No "tails" were formed on droplets of the pre-equilibrated styrene when injected into the capillary tube containing the pre-equilibrated aqueous phase. Thus, the formation of an interfacial layer in the spinning drop tensiometer is a non-equilibrium affect. 

The kinetics of hydrolysis of purified soybean oil (PSO) by the lipase were monitored by recording the interfacial tension decrease with time, using the oil drop tensiometer (ITConcept, France) as described by Nury et al. [58]. The interfacial tension was measured by automatically analysing the drop profile on-line, using the Laplace equation [59]. The accumulation with time of tensio-active components, i.e., lipolytic products, at the surface of an oil drop results in a decrease in the interfacial tension, which in turn is correlated with changes in the oil drop... 

Labourdenne, S., Gaudry-Rolland, N., Letellier, S., Lin, M., Cagna, A., Esposito, G., Verger, R. and Riviere, C. (1994) The oil-drop tensiometer potential applications for studying the kinetics of (phospho)lipase action. Chem. Phys. Lipids 71, 163-173... 

In the present work we have studied the dynamics of formation and structure of the air-water interface in the presence of (3-lg - - PS at 20°C and at pH 7 in a drop tensiometer. As PS with interfacial activity we have used propylene glycol alginates (PGA). To evaluate the effect of the degree of PGA esterification and viscosity, different commercial samples were studied. Xanthan gum (X) and X-carrageenan (X-c) were studied as nonsurface active polysaccharides. 

The d)mamics of adsorption and the development of film structure were monitored simultaneously using an automatic drop tensiometer, as described elsewhere (Rodriguez, 1999). 

Figure 6.7 Liquid surface tension determination by the spinning drop tensiometer method. A liquid drop (7) is suspended in an immiscible denser liquid (2) in a horizontal transparent tube which can be spun about its longitudinal axis, and the drop (7) elongates from a spherical shape to a prolate ellipsoid with increasing speed of revolution. Later, the drop becomes approximately cylindrical, at very high rotational velocities. A camera with a frame grabber captures the images of the drop inside the transparent tube.

Equation (515) is known as Vonnegut s equation and it is valid on the assumption that the drop is in equilibrium and its length is larger than four times its diameter (/ > 4r ). The spinning drop tensiometer method is widely used for measuring liquid-liquid interfacial tension, and is especially successful for examination of ultra-low interfacial tensions down to l(T6mNnr1. In addition, it can also be used to measure interfacial tensions of high viscosity liquids when precise temperature control is maintained. 

The spinning drop tensiometer method is particularly suitable for measuring the interfacial tension of melted polymers and is generally used in polymer compatibility, blend and composites research. In this case, a spinning polymer drop (smaller density) is rotated inside another immiscible polymer (higher density). Measurement of drop diameter versus time allows the determination of relaxational and extensional properties of polymeric systems. 

When the value of the interfacial tension is significantly less than 1 mN m 1, then we consider the measurement of ultra-low interfacial tension, which is common in liquid-liquid emulsification processes when effective surfactant solutions are used. The dynamic spinning drop tensiometer method is especially suitable for this purpose. Ultra-low interfacial tension measurement is important in the chemical industry because the cleaning of solid surfaces of dirt, grease, and oil the formulation of stable emulsions the recovery of petroleum, and other applications often rely on lowering the interfacial tension between immiscible liquids to ultra-low values by the use of surfactants. 

Dynamic properties of interfaces have attracted attention for many years because they help in understanding the behaviour of polymer, surfactant or mixed adsorption layers.6 In particular, interfacial rheology (dilational properties) is crucial for many technological processes (emulsions, flotation, foaming, etc).1 The present work deals with the adsorption of MeC at the air-water interface. Because of its amphiphilic character MeC is able to adsorb at the liquid interface thus lowering the surface tension. Our aim is to quantify how surface active this polymer is, and to determine the rheological properties of the layer. A qualitative and quantitative evaluation of the adsorption process and the dilata-tional surface properties have been realised by dynamic interface tension measurements using a drop tensiometer and an axisymmetric drop shape analysis. 

The adsorption of a surfactant at an interface between CO2 and a second fluid, such as water, may be determined directly from measurement of the interfacial tension (change in Gibbs free energy with surface area), y, versus surfactant concentration. A novel tandem variable-volume pendant drop tensiometer has been developed to measure equilibrium and dynamic values of y as a function ofT.p and time (Figure 2.4-1) [21]. An organic [21] or aqueous phase [18] is preequilibrated with CO2 in the first variable-volume cell (drop-phase cell). A droplet of this liquid is injected into the second variable-volume cell, with two windows at 180° mounted on a diameter, containing either pure CO2 or CO2 and surfactant. 

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]. 

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