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Dynamic surface tensions are extensively studied to gain properties of liquid adsorption layers . The drop profile analysis tensiometry (PAT) is superior over other methods for the following advantages : PAT is a contactless method and therefore has a higher accuracy as compared to contact methods, for example ring or plate tensiometry.
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... carried out by the program included in PAT-2, using the Fourier transform and the model described in . Dilatational module E is presented in  as a complex indicator that includes real and imaginary components: ...
... It can be noted that the results using the drop shape method may differ from rheological parameters for a flat surface. For a flat surface with the diffusion mechanism of adsorption of a surfactant, both components of the module are given by the equations [15,16]: ...
The progress in recent years in characterising the properties of the interface between air and water in the presence of commonly used surfactants in mineral flotation (termed frothers) is summarized. The focus of this review is on techniques that provide access to dynamic aspects of frother interactions at the interface between air and water, and those techniques that provide a unique perspective of equilibrium adsorbed layer properties. Profile analysis tensiometry (PAT) and other forms of interfacial tension measurement are described, and recent work highlighted. In addition, the methods of dilational interfacial rheology, which probes the viscoelastic properties of the air-water interface and the influence of dynamic adsorption processes, is discussed in relation to published work on flotation frother, as is work on measurement of rising bubble velocities, which allows probing of the dynamic adsorption layer (DAL). In addition to these more traditional measures of interfacial activity and effect, the study of the air-water interface with vibrational spectroscopy, and its relevance to flotation (with reference to recent published work), is described.
The dependence of the dynamic surface tension of water at the interface with saturated hexane and cyclohexane vapours was measured by the drop profile analysis method. The surface tension for the adsorption layers of cyclohexane at different temperatures was compared with the results reported earlier for the adsorption of hexane and other alkanes from the vapour phase on water drops. It is shown that cyclohexane is adsorbed significantly slower than the adsorption of hexane occurs, and is characterised by a much larger induction time. The error in the drop radius measurements at 40 ºC attains 45 m. The experimental rheologic characteristics of the adsorbed layers are studied and the results are compared with the model developed to describe an adsorption process governed by a kinetic mechanism.
Dynamic surface tensions and dilational visco-elasticity are easy accessible parameters of liquids. For human body liquids, such as urine, blood serum, amniotic fluid, gastric juice, saliva and others, these parameters are very characteristic for the health status of people. In case of a disease the composition of certain liquids specifically changes and the measured characteristics of dynamic surface tension of the dilational surface elasticity and viscosity reflect these changes in a clear way. Thus, this kind of physico-chemical measurements represent sensitive tools for evaluating the severity of a disease and can serve as control tool for the efficiency of applied therapies. The overview summarises the results of a successful work over about 25years on this subject and gives specific insight into a number of diseases for which the diagnostics as well as the therapy control have been significantly improved by the application of physico-chemical experimental techniques.
The influence of temperature on the dynamic surface tension of water in heptane vapour is studied using drop profile analysis tensiometry. The water drops are formed in air saturated by heptane and water vapours. For long life times a new phenomenon is found: a sharp decrease of surface tension from about 60 mN/m down to 30 mN/m. The time until this sharp surface tension sets in decreases with increasing temperature. This phenomenon is attributed to the formation of heptane adsorption layers with a significant thickness.
To ensure that the sharp surface tension decrease is not an artefact, the experimental error (deviation of drop profiles from the Young-Gauss-Laplace equation) was determined using harmonic oscillations imposed to the surface of pure heptane drops. It was shown that fitting errors below 10 μm in the determination of the drop radius do not affect the calculated surface tension value. The sharp surface tension decrease was observed with fitting errors below 5 μm, so that this phenomenon was explained to be caused by the formation of multilayers. The surface tensions and adsorbed amounts are described by a model developed earlier.
The experimental results depend essentially on the experimental method used. In another experiment the atmosphere in the measuring cell was pre-saturated only by water vapour, and heptane (pentane) was added onto the cell bottom just immediately before the water drop was formed. The increase of temperature results in a slower adsorption process which is opposite to the case where the composition of the mixed atmosphere inside the cell was established prior to the experiments.
The dynamic and equilibrium surface tension for drops of aqueous C14EO8 solutions at the interface to pure air or pentane, hexane, heptane and toluene saturated air, and the dynamic surface tension of pure water at these interfaces are presented. Two theoretical models were employed: both assuming a diffusion controlled adsorption of the surfactant, and either a diffusion or kinetic barrier governed adsorption of the alkanes. The experimental results are best described by the model which implies a diffusion control for the C14EO8 molecules and the existence of a kinetic barrier for the alkane molecules. The desorption of alkanes from the surface layer after equilibration and their subsequent removal from the measuring cell was studied as well. The desorption process was shown to be slow for heptane and hexane. However, for the pentane vapor the desorption is quite rapid, and after the desorption commences the surface tension becomes equal to that at the interface with pure air.
The dynamics of surfactant interfacial layers was first discussed more than a century ago. In 1946 the most important work by Ward and Tordai was published which is still the theoretical basis of all new models to describe the time dependence of interfacial properties. In addition to the diffusion controlled adsorption mechanism, many other models have been postulated in literature, however, well performed experiments with well defined surfactant systems have shown that the diffusional transport is the main process governing the entire formation of surfactant adsorption layers. The main prerequisite, in addition to the diffusional transport, is the consideration of the right boundary condition at the interface, given by a respective equation of state. In addition to the classical models of Langmuir and Frumkin, also the so-called reorientation or interfacial aggregation models are to be assumed to reach a quantitative description of respective experimental data. Moreover, the adsorption of surfactants at the interface between water and a gas phase different from air can be strongly influenced by the type of molecules within the gas phase, such as alkane vapours. These oil molecules co-adsorb from the gas phase and change the adsorption kinetics strongly.
Besides the discussion of how to apply theoretical adsorption kinetics models correctly, a large number of experimental data are presented and the way of a quantitative analysis of the adsorption mechanism and the main characteristic parameters is presented. This includes micellar solutions as well as mixtures of surfactants of ionic and non-ionic nature.
The adsorption of proteins (β-lactoglobulin, β-casein) and the oxyethylated non-ionic surfactants C10EO8 and C14EO8 at the aqueous solution/air interface is strongly enhanced and accelerated by the presence of hexane vapour in the air phase caused by the co-adsorption of hexane molecules. Due to this hexane co-adsorption, the dependence of dilational visco-elasticity modulus on surface pressure is shifted towards larger surface pressure values. The adsorption kinetics of the studied non-ionic surfactants shows the same picture as that observed for the two proteins. In contrast, the desorption process of the hexane molecules from a pre-adsorbed mixed adsorption layer is very slow. This decelerated desorption is explained by a rather large desorption energy required by the hexane molecules. The experimental data are compared with several theoretical models developed earlier. The results allow estimating the activation energy for the hexane desorption from adsorption layers of the two studied non-ionic surfactants.
The surface tension and dilational surface visco-elasticity of the individual solutions of the biopolymer DNA and the azobenzene-containing cationic surfactant AzoTAB, as well as their mixtures were measured using the drop profile analysis tensiometry. The negatively charged DNA molecules form complexes with the cationic surfactant AzoTAB. Mixed DNA + AzoTAB solutions exhibit high surface activity and surface layer elasticity. Extremes in the dependence of these characteristics on the AzoTAB concentration exist within the concentration range of 3 × 10−6–5 × 10−5 M. The surface tension of the mixture shows a minimum with a subsequent maximum. In the same concentration range the elasticity shows first a maximum and then a subsequent minimum. A recently developed thermodynamic model was modified to account for the dependence of the adsorption equilibrium constant of the adsorbed complex on the cationic surfactant concentration. This modified theory shows good agreement with the experimental data both for the surface tension and the elasticity values over the entire range of studied AzoTAB concentrations.
The adsorption of surfactants from aqueous solution at the water/air interface is changed when the air phase contains hexane vapor. This co-adsorption of surfactant and hexane depends on the hexane vapor pressure. A thermodynamic model developed for the adsorption of surfactant mixtures can be adapted to the present situation. The surfactants studied were SDS, C12TAB and C12DMPO, and the dependence of their adsorption characteristics on the partial hexane vapor pressure was determined. The co-adsorption of hexane from the vapor phase increases the surface activity of the adsorbing surfactants.
Liquid interfaces are met everywhere in our daily life. The corresponding interfacial properties and their modification play an important role in many modern technologies. Most prominent examples are all processes involved in the formation of foams and emulsions, as they are based on a fast creation of new surfaces, often of an immense extension. During the formation of an emulsion, for example, all freshly created and already existing interfaces are permanently subject to all types of deformation. This clearly entails the need of a quantitative knowledge on relevant dynamic interfacial properties and their changes under conditions pertinent to the technological processes. We report on the state of the art of interfacial layer characterization, including the determination of thermodynamic quantities as base line for a further quantitative analysis of the more important dynamic interfacial characteristics. Main focus of the presented work is on the experimental possibilities available at present to gain dynamic interfacial parameters, such as interfacial tensions, adsorbed amounts, interfacial composition, visco-elastic parameters, at shortest available surface ages and fastest possible interfacial perturbations. The experimental opportunities are presented along with examples for selected systems and theoretical models for a best data analysis. We also report on simulation results and concepts of necessary refinements and developments in this important field of interfacial dynamics.
Alkanes, although not amphiphilic molecules, adsorb at the surface of water drops from the vapour phase. At the drop surface of the surfactant solution formed in hexane saturated air, a competitive adsorption of surfactant and hexane is observed. Experiments with drop profile analysis tensiometry are performed to quantify the adsorption of the non-ionic surfactantC10EO8 at the water/hexane vapour interface. The equilibrium surface tension isotherm shows a remarkable shift towards much lower tensions, even much below those values reached by micellar C10EO8 solutions. A thermodynamic model allows the description of the mixed hexane/C10EO8 adsorption layer at the water/vapour interface quite well. The incorporation of hexane molecules also significantly increases the dilation elasticity values, although the layers of hexane alone show only very low dilational elasticities and high viscosities. While a diffusional exchange of matter theory describes the visco-elasticity of the surfactant very well, it fails for the mixed adsorption layer.
Recent application of the methods of surface dilational rheology to solutions of the complexes between synthetic polyelectrolytes and oppositely charged surfactants (PSC) gave a possibility to determine some steps of the adsorption layer formation and to discover an abrupt transition connected with the formation of microaggregates at the liquid surface. The kinetic dependencies of the dynamic surface elasticity are always monotonous at low surfactant concentrations but can have one or two local maxima in the range beyond the critical aggregation concentration. The first maximum is accompanied by the generation of higher harmonics of induced surface tension oscillations and caused by heterogeneities in the adsorption layer. The formation of a multilayered structure at the surface for some systems leads to the second maximum in the dynamic surface elasticity. The hydrophobicity and charge density of a polymer chain influence strongly the surface structure, resulting in a variety of dynamic surface properties of PSC solutions. Optical methods and atomic force microscopy give additional information for the systems under consideration. Experimental results and existing theoretical frameworks are reviewed with emphasis on the general features of all studied PSC systems.
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