Compression of films

Upon the compression of films formed by globular proteins (such as albumine, globuline, hemoglobin, trypsine, and others) up to a pressure of 20 mN m"1 the two-dimensional pressure isotherms are quite reversible. At somewhat higher compression, such that the area per amino-group reaches... 

Let us now turn our attention to a more detailed discussion of transitions that occur between different types of films, and in particular to the way in which these transitions are influenced by the temperature, the structure of surfactant molecules and the composition of the medium. The direct transition from gaseous and vapor films to liquid and solid condensed ones is a two-dimensional first-order phase transition that is quite similar to a three-dimensional vapor condensation. A decrease in the area per molecule in the adsorption layer in the region of gaseous films causes a gradual increase in pressure up to the level that corresponds to the condensation pressure of a saturated two-dimensional vapor, 7rc, at an area per molecule equal to sc (see Fig. 11-21). The subsequent compression of film is not accompanied by an increase in the two-dimensional pressure the two-dimensional vapor transforms into the two-dimensional condensed state, which can be either liquid expanded, liquid condensed, or solid, depending on the nature of the... 

In the case of solids, there is no doubt that a lateral tension (which may be anisotropic) can exist between molecules on the surface and can be related to actual stretching or compression of the surface region. This is possible because of the immobility of solid surfaces. Similarly, with thin soap films, whose thickness can be as little as 100 A, stretching or extension of the film may involve a corresponding variation in intermolecular distances and an actual tension between molecules. 

There appear to be two stages in the collapse of emulsions flocculation, in which some clustering of emulsion droplets takes place, and coalescence, in which the number of distinct droplets decreases (see Refs. 31-33). Coalescence rates very likely depend primarily on the film-film surface chemical repulsion and on the degree of irreversibility of film desorption, as discussed. However, if emulsions are centrifuged, a compressed polyhedral structure similar to that of foams results [32-34]—see Section XIV-8—and coalescence may now take on mechanisms more related to those operative in the thinning of foams. 

Sample 250-pm compression-molded films of Teflon PFA 340 from G.E. resonance transformer 2 MeV capacity, at a current of 1 m A. 

Figure 4.29. Sample assembly for optical shock temperature measurements. The sample consists of a metal film deposited on a transparent substrate which serves as both an anvil and a transparent window through which thermal radiation is emitted. Rapid compression of gases and surface irregularities at the interface between the sample film and the driver produce very high temperatures in this region. The bottom portion of the figure illustrates the thermal distribution across through the assembly. (After Bass et al. (1987).)...

Amine-terminated siloxane oligomers have also been utilized in the synthesis of various siloxane-amide and siloxane-imide copolymers, High molecular weight siloxane-amide copolymers have been synthesized by the solution or interfacial co-polymerization of siloxane oligomers with sebacoyl chloride or terephthaloyl chloride respectively 1S5,165). In some reactions diamine chain extenders have also been utilized. Thermal and dynamic mechanical characterization of these copolymers have shown the formation of multiphase systems160). Compression molded films displayed very good elastomeric properties. 

The terminology of L-B films originates from the names of two scientists who invented the technique of film preparation, which transfers the monolayer or multilayers from the water-air interface onto a solid substrate. The key of the L-B technique is to use the amphiphih molecule insoluble in water, with one end hydrophilic and the other hydrophobic. When a drop of a dilute solution containing the amphiphilic molecules is spread on the water-air interface, the hydrophilic end of the amphiphile is preferentially immersed in the water and the hydrophobic end remains in the air. After the evaporation of solvent, the solution leaves a monolayer of amphiphilic molecules in the form of two-dimensional gas due to relatively large spacing between the molecules (see Fig. 15 (a)). At this stage, a barrier moves and compresses the molecules on the water-air interface, and as a result the intermolecular distance decreases and the surface pressure increases. As the compression from the barrier proceeds, two successive phase transitions of the monolayer can be observed. First a transition from the gas" to the liquid state. 

The release of steroids such as progesterone from films of PCL and its copolymers with lactic acid has been shown to be rapid (Fig. 10) and to exhibit the expected (time)l/2 kinetics when corrected for the contribution of an aqueous boundary layer (68). The kinetics were consistent with phase separation of the steroid in the polymer and a Fickian diffusion process. The release rates, reflecting the permeability coefficient, depended on the method of film preparation and were greater with compression molded films than solution cast films. In vivo release rates from films implanted in rabbits was very rapid, being essentially identical to the rate of excretion of a bolus injection of progesterone, i. e., the rate of excretion rather than the rate of release from the polymer was rate determining. 

The deposition procedure described earlier allows one to obtain protein films chemically bound to the activated surface of spherical glass particles. Subsequent compression of preformed protein monolayer with these particles permitted to coverage of the particle area that initially has not come in contact with the monolayer, as schematically shown in Figure 14. Even if such a procedure does not initially result in deposition of strictly one monolayer, this fact does not seem to be critical, because only the monolayer chemically attached to the surface remains after washing. 

Another observation should be made with respect to the term elastic in describing interfacial capacitors. It was originally introduced by Crowley [1] for membranes and reflects the compressibility of lipid layers which behave in some respects like an elastic film. Its relation to electrochemical interfaces is less obvious. Consider an interface between a metal electrode and an electrolyte. As we will see in Section III, the effective gap of the interfacial capacitor is the distance between the centers of mass of the electronic, e, and ionic, i, charge density distributions... 

It should be re-emphasized that although our block copolymers do not display spherulitic morphology when they are compression molded, they are nevertheless crystalline. Hence, this indicates that under this mode of film preparation, aggregation into well developed superstructure is apparently kinetically limited. 

A comparison of the dynamic mechanical properties of our HB at 35 Hz has been made to that of LDPE in Figures 14 A and B. The thermal and sample preparative history affects the mechanical properties of HB films to such an extent that in order to make a meaningful comparison one has to describe the exact history of the samples. Such a thermal history dependence has been examined for LDPE(54,57) and recently for HB.(12) Shown in Figures A and B are the mechanical spectra for HB-PQ, HB-Tol, and LDPE-PQ films. The compression molded films were prepared 1 to 2 days prior to the test. The solution cast film (from toluene), HB-Tol, was annealed at 80°C for 2-3 days and stored at room temperature for 1 week... 

The monolayer stability limit is defined as the maximum pressure attainable in a film spread from solution before the monolayer collapses (Gaines, 1966). This limit may in some cases correspond directly to the ESP, suggesting that the mechanism of film collapse is a return to the bulk crystalline state, or may be at surface pressures higher than the ESP if the film is metastable with respect to the bulk phase. In either case, the monolayer stability limit must be known before such properties as work of compression, isothermal compressibility, or monolayer viscosity can be determined. 

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