Substrates, definition

A LARGE NUMBER OF tests exist for establishing the reliability of nonmetallic protective coatings on metal substrates. Definitions, fundamentals, methodology, and practical examples are offered for a better understanding of tests for protective coatings and to demonstrate that well defined tests alone are not adequate without rational application and interpretation. 

A third definition of surface mobility is essentially a rheological one it represents the extension to films of the criteria we use for bulk phases and, of course, it is the basis for distinguishing states of films on liquid substrates. Thus as discussed in Chapter IV, solid films should be ordered and should show elastic and yield point behavior liquid films should be coherent and show viscous flow gaseous films should be in rapid equilibrium with all parts of the surface. 

It is useful to define the tenns coverage and monolayer for adsorbed layers, since different conventions are used in the literature. The surface coverage measures the two-dimensional density of adsorbates. The most connnon definition of coverage sets it to be equal to one monolayer (1 ML) when each two-dimensional surface unit cell of the unreconstructed substrate is occupied by one adsorbate (the adsorbate may be an atom or a molecule). Thus, an overlayer with a coverage of 1 ML has as many atoms (or molecules) as does the outennost single atomic layer of the substrate. 

It is thus tempting to define the first saturated layer as being one monolayer, and this often done, causing some confiision. One therefore also often uses tenns like saturated monolayer to indicate such a single adsorbate layer that has reached its maximal two-dimensional density. Sometimes, however, the word saturated is omitted from this definition, resulting m a different notion of monolayer and coverage. One way to reduce possible confiision is to use, for contrast with the saturated monolayer, the tenn fractional monolayer for the tenn that refers to the substrate unit cell rather than the adsorbate size as the criterion for the monolayer density. 

Self-assembled monolayers (SAMs) are molecular layers tliat fonn spontaneously upon adsorjDtion by immersing a substrate into a dilute solution of tire surface-active material in an organic solvent [115]. This is probably tire most comprehensive definition and includes compounds tliat adsorb spontaneously but are neither specifically bonded to tire substrate nor have intennolecular interactions which force tire molecules to organize tliemselves in tire sense tliat a defined orientation is adopted. Some polymers, for example, belong to tliis class. They might be attached to tire substrate via weak van der Waals interactions only. 

Attention should be paid to the fact that the ratio of Pd and phosphine ligand in active catalysts is crucial for determining the reaction paths. It is believed that dba is displaced completely with phosphines when Pd2(dba)3 is mixed with phosphines in solution. However the displacement is not eom-plcte[16]. Also, it should be considered that dba itself is a monodentate alkene ligand, and it may inhibit the coordination of a sterically hindered olefinic bond in substrates. In such a case, no reaction takes place, and it is recommended to prepare Pd(0) catalysts by the reaction of Pd(OAc)2 with a definite amount of phosphinesflO]. In this way a coordinatively unsaturated Pd(0) catalyst can be generated. Preparation of Pd3(tbaa)3 tbaa == tribenzylidene-acetylacetone) was reported[17], but the complex actually obtained was Pd(dba)2[l8],... 

Fn some cases, r-allylpalladium complex formation by retention syn attack) has been observed. The reaction of the cyclic allyiic chloride 33 with Pd(0) affords the 7r-allylpalladium chlorides 34 and 35 by retention or inversion depending on the solvents and Pd species. For example, retention is observed in benzene, THF, or dichloromethane with Pd2(dba)3. However, the complex formation proceeds by inversion in these solvents with Pd(Ph3P)4, whereas in MeCN and DMSO it is always inversion[33]. The syn attack in this case may be due to coordination of Pd to chlorine in 33, because Pd is halophilic. The definite syn attack in complex formation has been observed using stereoche-mically biased substrates. The reaction of the cxoallylic diphenylphosphino-acetate 36 with phenylzinc proceeds smoothly to give 37. The reaction can be explained by complex formation by a syn mechanism[31]. However, these syn attacks are exceptional, and normally anti attack dominates. 

Roll-up. The principal means by which oily soil is removed is probably roU-up. The appHcable theory is simply the theory of wetting. In briefest outline, a droplet of oily soil attached to the substrate forms at equiUbrium a definite contact angle at the oil-sohd-air boundary line. This contact angle (Fig. 4) is the result of the interaction of interfacial forces in the three phase boundaries of the system. These interfacial forces, expressed in mN/m(= dyn/cm), or interfacial free energy values expressed in mj/m (erg/cm s) are conveniently designated 1SA iSlj subscripts relate to the Hquid-air,... 

These definitions are valid only when the concentration of the enzyme is very small compared with that of the substrate. Moreover, they apply only to the initial rate of formation of products in other words, the rate of formation of the first few percent of the product, before the substrate has been depleted and products that can interfere with the catalytic reaction have accumulated. 

All this being said, perhaps the most definitive study of the relative roles of electrostatic and van der Waals forces was performed by Gady et al. [86,101,102]. In their studies, they attached a spherical polystyrene particle, having a radius between 3 and 6 p.m, to the cantilever of an atomic force microscope. They then conducted three distinct measurements that allowed them to distinguish between electrostatic and van der Waals forces that attracted the particle to various conducting, smooth substrates. 

The definition is intended to differentiate these adhesives from merely sticky materials like flypaper or materials that may have only substrate specific adhesion. 

The performance of a product where adhesion plays a role is determined both by its adhesive and cohesive properties. In the case of silicones, the promotion of adhesion and cohesion follows different mechanisms [37]. In this context, adhesion promotion deals with the bonding of a silicone phase to the substrate and reinforcement of the interphase region formed at the silicone-substrate interphase. The thickness and clear definition of this interphase is not well known, and in fact depends on many parameters including the surface physico-chemistry of... 

To illustrate the relationship between the microscopic structure and experimentally accessible information, we compute pseudo-experimental solvation-force curves F h)/R [see Eq. (22)] as they would be determined in SEA experiments from computer-simulation data for T z [see Eqs. (93), (94), (97)]. Numerical values indicated by an asterisk are given in the customary dimensionless (i.e., reduced) units (see [33,75,78] for definitions in various model systems). Results are correlated with the microscopic structure of a thin film confined between plane parallel substrates separated by a distance = h. Here the focus is specifically on a simple fluid in which the interaction between a pair of film molecules is governed by the Lennard-Jones (12,6) potential [33,58,59,77,79-84]. A confined simple fluid serves as a suitable model for approximately spherical OMCTS molecules confined... 

---