Layers crosslinking

Other substitution reactions lead to more crystalline phases. Reaction of (4-aminopyridine)i/4FeOCl with methanol at 100 °C, for example, gives crystalline FeOOMe. Reactions with aliphatic and aromatic alkoxides and acids, of the type shown in equations (13) and (14), have also been studied. More rigid and longer molecules, such as 4-hydroxybenzoic acid, can crosslink the iron oxide layers. An initial intercalation step that causes an expansion of the FeOCl interlayer distance is followed by a second substitntion step leading to layer crosslinking. 

In contrast to polygermyne, the layer distance of siloxene decreases slightly with the reaction time (Fig. 3), which can be rationalized by two effects, i.e. by the incorporation of oxygen from the OH ligands into the Si backbone represented by reaction 5c), and by layer crosslinking caused by the condensation reaction 5d). Indeed, it is clear that a further addition of OH to the comparatively... 

Film stability is a primary concern for applications. LB films of photopoly-merizable polymeric amphiphiles can be made to crosslink under UV radiation to greatly enhance their thermal stability while retaining the ordered layered structure [178]. Low-molecular-weight perfluoropolyethers are important industrial lubricants for computer disk heads. These small polymers attached to a polar head form continuous films of uniform thickness on LB deposi-... 

If tire coupling to tire substrate is weak (physisorjDtion), as is tire case for alkylsiloxanes on a SiO surface in tire presence of a water layer, for example, tire packing may also be mainly driven by intennolecular forces. Stability in tliis system is provided by crosslinking between tire molecules (see below). 

In an attempt to determine the applicability of JKR and DMT theories, Lee [91] measured the no-load contact radius of crosslinked silicone rubber spheres in contact with a glass slide as a function of their radii of curvature (R) and elastic moduli (K). In these experiments, Lee found that a thin layer of silicone gel transferred onto the glass slide. From a plot of versus R, using Eq. 13 of the JKR theory, Lee determined that the work of adhesion was about 70 7 mJ/m". a value in clo.se agreement with that determined by Johnson and coworkers 6 using Eqs. 11 and 16. 

Fig. 12. Schematic of a polymer-coated crosslinked PDMS cap in contact with a polymer-coated flat surface. The PDMS cap is oxidized in 02-plasma, and the polymer layer is coated by solvent casting. On flat surface, the polymer layer is spin coated.

Brown [46] continued the contact mechanics work on elastomers and interfacial chains in his studies on the effect of interfacial chains on friction. In these studies. Brown used a crosslinked PDMS spherical cap in contact with a layer of PDMS-PS block copolymer. The thickness, and hence the area density, of the PDMS-PS layer was varied. The thickness was varied from 1.2 nm (X = 0.007 chains per nm-) to 9.2 nm (X = 0.055 chains per nm-). It was found that the PDMS layer thickness was less than about 2.4 nm, the frictional force between the PDMS network and the flat surface layer was high, and it was also higher than the frictional force between the PDMS network and bare PS. When the PDMS layer thicknesses was 5.6 nm and above, the frictional force decreased dramatically well below the friction between PDMS and PS. Based on these data Brown [46] concluded that ... 

The study of acid-base interaction is an important branch of interfacial science. These interactions are widely exploited in several practical applications such as adhesion and adsorption processes. Most of the current studies in this area are based on calorimetric studies or wetting measurements or peel test measurements. While these studies have been instrumental in the understanding of these interfacial interactions, to a certain extent the interpretation of the results of these studies has been largely empirical. The recent advances in the theory and experiments of contact mechanics could be potentially employed to better understand and measure the molecular level acid-base interactions. One of the following two experimental procedures could be utilized (1) Polymers with different levels of acidic and basic chemical constitution can be coated on to elastomeric caps, as described in Section 4.2.1, and the adhesion between these layers can be measured using the JKR technique and Eqs. 11 or 30 as appropriate. For example, poly(p-amino styrene) and poly(p-hydroxy carbonyl styrene) can be coated on to PDMS-ox, and be used as acidic and basic surfaces, respectively, to study the acid-base interactions. (2) Another approach is to graft acidic or basic macromers onto a weakly crosslinked polyisoprene or polybutadiene elastomeric networks, and use these elastomeric networks in the JKR studies as described in Section 4.2.1. 

A WBL can also be formed within the silicone phase but near the surface and caused by insufficiently crosslinked adhesive. This may result from an interference of the cure chemistry by species on the surface of substrate. An example where incompatibility between the substrate and the cure system can exist is the moisture cure condensation system. Acetic acid is released during the cure, and for substrates like concrete, the acid may form water-soluble salts at the interface. These salts create a weak boundary layer that will induce failure on exposure to rain. The CDT of polyolefins illustrates the direct effect of surface pretreatment and subsequent formation of a WBL by degradation of the polymer surface [72,73]. 

Restrained layers—coupling agents develop a highly crosslinked interphase region with a modulus intermediate between that of the substrate and the polymer. 

The activated particles react with polymeric materials so that polymeric radicals are produced on the surface layer of materials. This causes the surface layer to be oxidized, crosslinked, or decomposed. On the other hand, A-s are produced from molecules of the gas and are polymerized, so that the resultant polymers of A coat the surface of the material. 

In the presence of an inert gas, such as He or Ar, crosslinking can be introduced into the surface layer of material by plasma treatment. Hansen and Schon-horn [60] named this Crosslinking by Activated Species of Inert Gases (CASING). As a result, bond strength is enhanced because crosslinking strengthens the surface layer. 

Very thin films may be also obtained through adsorption of a thin layer from solution [11,71,74] or chemical grafting [98] which is achieved by a polymerization reaction at the surface. A polymer film may also be deposited on the surface by plasma polymerization [99]. It is then, however, usually crosslinked and chemically not well-defined. 

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