Case studies analyzing films

Up to this point the essential equations have been presented. Now, it is possible to analyze the work carried out in connection with the classical thermodynamic approach. The first systematic study of a thermodynamic adsorption quantity was perhaps the work done by de Boer and coworkers [10] on the determination, interpretation and significance of the enthalpy and entropy of adsorption. Their papers analyzed almost all aspects of the experimental determination of the entropy and how to interpret the values obtained in terms of two extreme models, i.e., those of mobile and locahzed adsorption, which today have lost much of their usefulness. To catalog the behavior of the adsorbed film as localized or mobile is a very simplistic solution and it has been demonstrated [9] that in most cases the adsorbed film is neither completely localized nor completely mobile. This approach also is somehow outdated because numerical simulations provide a better microscopic interpretation of the system s behavior. 

In 1988 a modified surface forces apparatus (SFA) was introduced [470,471] to analyze friction. The principle of operation of the SFA has already been introduced in Section 6.4. The modified version allowed a relative shearing of the two mica surfaces. In the SFA, the substrate has to have an atomically flat, transparent surface. In most cases mica is used to fulfill these requirements. Although there is a strong limitation in the choice of materials, due to the high resolution in the vertical direction, the SFA has become an important tool to study the friction and lubrication properties of molecularly thin films. 

Discrete and continuum models of transfer of molecules over various sorption sites of a microheterogeneous membrane were considered for systems with weak intermolecular interactions and membranes with constant composition and structure. An equation for estimating size effects on permeability coefficient II of microheterogeneous membranes was derived [188], and the possibility of applying the continuum model to calculate the n value in thin films of thickness L is numerically analyzed. The effect of the composition and structure of a uniformly microheterogeneous membrane on the permeability coefficients II was studied. The dependence of n on the composition is a convex function if the migration between different sorption sites proceeds more quickly than between identical sites and a concave one in the opposite case [189],... 

Cross-linked polystyrene porous particles (with 21 mol% DVB) have been prepared by the concentrated emulsion polymerization method, using either toluene or decane as the porogen and an aqueous solution of SDS as the continuous phase. Since toluene is a good solvent for polystyrene while decane is a nonsolvent , the morphologies obtained in the two cases were different. The particles based on toluene (with a volume fraction of dispersed phase of 78%) have very small pores which could not be detected in the SEM pictures. The pore size distribution, which has sizes between 20 and 50 A and was determined with an adsorption analyzer, almost coincides with that in a previous study [49] in which porous polystyrene beads have been prepared by suspension polymerization. In contrast, the porous particles based on decane have pore sizes as large as 0.1-0.3 pm, which could be detected in the SEM pictures [44a], and also larger surface areas (47 m2 g ) than those based on toluene (25 m2 g ). The main difference between the concentrated emulsion polymerization and the suspension polymerization consists of the much smaller volume fraction of continuous phase used in the former procedure. The gel-like emulsion that constitutes the precursor in the former case contains polyhedral cells separated by thin films of continuous phase. The polymerization of the cells does not... 

Mechanical Properties. To reveal the reinforcing effect of liquid crystalline polymer microfibrils on the mechanical properties of the films both their dynamic torsional moduli and dynamic tensile moduli have been studied as a function of temperature using a Rheometrics Mechanical Spectrometer (RMS 800) and a Rheometrics Solids Analyzer (RSA II), respectively. For comparison purpose the modulus of neat matrix polymers and, in some cases, the modulus of carbon fiber and Kevelar fiber reinforced composites has also been measured. 

As we saw previously, the system designed at the beginning of the century by Seemann and Bohlin to study powdery samples is one of the three traditional diffraction systems for polycrystalline samples. We saw in section 12.12 that this diffractometer enables the user to study the sample either in transmission or in reflection. When the sample is analyzed in reflection, it is possible to arrange the elements of the system in a way, so as to have a low incidence angle between the beam and the sample. In this case, the system will make it possible to characterize thin films [HAA 85, VAL 90, FIS 96, LIG 94]. This configuration is shown in Figure 2.63. 

The first studies of polyferrocenylsilane block copolymer films were reported in 1996 and utilized DSC and TEM to analyze the phase separation in the materials (83j. In the case of PS-b-PFS (3.54) and PFS-b-PDMS (3.52), it was demonstrated that the electron-rich Fe atoms of the polyferrocenylsilane block cause sufficient electron scattering to provide contrast with the organic or inorganic coblocks, so that selective staining of one of the blocks, which is generally required for all-or-... 

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