Instrumentation dynamic surface

A recent design of the maximum bubble pressure instrument for measurement of dynamic surface tension allows resolution in the millisecond time frame [119, 120]. This was accomplished by increasing the system volume relative to that of the bubble and by using electric and acoustic sensors to track the bubble formation frequency. Miller and co-workers also assessed the hydrodynamic effects arising at short bubble formation times with experiments on very viscous liquids [121]. They proposed a correction procedure to improve reliability at short times. This technique is applicable to the study of surfactant and polymer adsorption from solution [101, 120]. 

After the accomplishment of the above mentioned experiment on the nonlinear viscoelasticity of the DPPE thin film, we have tried to construct a new instrument for the measurement of the dynamic surface tension. We have noticed that, the blades used to change the surface area in the commercial instrument, did not show genuine triangle or sinusoidal trajectory but rather mathematically undefined. With our newly designed instrument, the time change of the surface area can be controlled according to a chosen function with the aid of a micro-computer. 

Figure 16 shows the experimental arrangement for the measurement of the surface pressure. The trough (200 mm long, 50 mm wide and 10 mm deep) was coated with Teflon. The subphase temperature was controlled within 0.1 C by means of a jacket connected to a thermostated water circulator, and the environmental air temperature was kept at 18 °C. The surface tension was measured with a Wilhelmy plate of platinum(24.5 x 10.0 x 0.15 mm). The surface pressure monitored by an electronic balance was successively stored in a micro- computer, and then Fourier transformed to a frequency domain. The surface area was changed successively in a sinusoidal manner, between 37.5 A2/molecule and 62.5 A2/molecule. We have chosen an unsaturated phospholipid(l,2-dioleoyl-3-sn-phosphatidyI-choline DOPC) as a curious sample to measure the dynamic surface tension with this novel instrument, as the unsaturated lipids play an important role in biomembranes and, moreover, such a "fluid" lipid was expected to exhibit marked dynamic, nonlinear characteristics. The spreading solution was 0.133 mM chloroform solution of DOPC. The chloroform was purified with three consecutive distillations. 

Figure 4. Automatic dynamic surface tension balance showing Wilhelmy plate suspended in surface. Photograph supplied by Cahn Instruments, Inc.

Water sorption-desorption isotherms can be carried out by using thermobalances. Now specific instruments allow to measure water sorption-desorption isotherms at different constant temperatures (e.g., dynamic vapor sorption instrument (DVS), Surface Measurement Systems Ltd., Monarch Beach, US). 

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. 

Dynamic surface tension was measured with an automatic drop Tracker tensiometer (ITC Concept, France), connected to thermostatic bath to maintain the temperature constant at 25°C during the measurements. The principle of tensiometer is to determine the surface tension of the studied solution from the axis5mmetric shape of a rising bubble analysis [5]. Due to the active control loop, the instrument allows long-time experiments with a constant drop/bubble volume or surface area. 

In this chapter first the theoretical basis of the drop and bubble shape method is described, and then details of its practical use are given. The various functionalities of the instrument are demonstrated then in the form of examples, such as dynamic surface and interfacial tensions of surfactant and protein solutions, and the dilational rheology of some selected systems. 

Figures 19 and 20 illustrate the performance of the profile analysis instrument for atmospheric studies, by displaying the relaxation of dynamic surface tension (at constant surface area) for a cloud water sample and, respectively, the dynamic surface tension response to harmonic surface area disturbances for a marine water sample [74].

The question of time scales has already appeared in this discussion. When a foam is generated, the time scale of surfactant adsorption is very important. If the bubble surfaces are not rapidly covered by surfactant monolayers, bubble rupture is easy, and both foam quantity and stability are poor. The adsorption kinetics can be conveniently studied by dynamic surface tension devices. In these instruments, a fresh surface is created and the surface tension decrease with time due to adsorption can be monitored [6]. Above... 

Since the drop volume method involves creation of surface, it is frequently used as a dynamic technique to study adsorption processes occurring over intervals of seconds to minutes. A commercial instrument delivers computer-controlled drops over intervals from 0.5 sec to several hours [38, 39]. Accurate determination of the surface tension is limited to drop times of a second or greater due to hydrodynamic instabilities on the liquid bridge between the detaching and residing drops [40],... 

In Dynamic Secondary Ion Ma s Spectrometry (SIMS), a focused ion beam is used to sputter material from a specific location on a solid surface in the form of neutral and ionized atoms and molecules. The ions are then accelerated into a mass spectrometer and separated according to their mass-to-charge ratios. Several kinds of mass spectrometers and instrument configurations are used, depending upon the type of materials analyzed and the desired results. 

A final practical note involves instrument intensity measurement calibrations. The intensity measurement is self-calibrating relative to the incident beam from the source. However, measurements typically have a dynamic range of 10 -10 , and care must be taken to insure the detection system is linear. A method of calibrating the scatterometer is to characterize a diffuse reflector having a known scattering characteristic. For example, a surface coated with BaS04 makes a nearly Lambertian scatterer, which has a BRDF of 1/Jt at all angles. 

The measurement range is dependent on the instrument but can cover the range -50 to +500 °C. The accuracy is not as high as the best contact thermometers. One reason for this is that the emissivity of the surface has an effect on the measurement result, and an emissivity correction is necessary for most instruments. The positive features are noncontact measurement and very fast dynamics, which enable a rapid scan of surface temperatures from a distance this is convenient when carrying out, for example, thermal comfort measurements. 

Scleroscope hardness It is a dynamic indentation hardness test using a calibrated instrument that drops a diamond-tipped hammer from a fixed height onto the surface of the material being tested. 

To address these challenges, chemical engineers will need state-of-the-art analytical instruments, particularly those that can provide information about microstmctures for sizes down to atomic dimensions, surface properties in the presence of bulk fluids, and dynamic processes with time constants of less than a nanosecond. It will also be essential that chemical engineers become familiar with modem theoretical concepts of surface physics and chemistry, colloid physical chemistry, and rheology, particrrlarly as it apphes to free surface flow and flow near solid bormdaries. The application of theoretical concepts to rmderstanding the factors controlling surface properties and the evaluation of complex process models will require access to supercomputers. 

For a thermometer to react rapidly to changes in the surrounding temperature, the magnitude of the time constant should be small. This involves a high surface area to liquid mass ratio, a high heat transfer coefficient and a low specific heat capacity for the bulb liquid. With a large time constant, the instrument will respond slowly and may result in a dynamic measurement error. 

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