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Adsorbed film /layer

An interesting question that arises is what happens when a thick adsorbed film (such as reported at for various liquids on glass [144] and for water on pyrolytic carbon [135]) is layered over with bulk liquid. That is, if the solid is immersed in the liquid adsorbate, is the same distinct and relatively thick interfacial film still present, forming some kind of discontinuity or interface with bulk liquid, or is there now a smooth gradation in properties from the surface to the bulk region This type of question seems not to have been studied, although the answer should be of importance in fluid flow problems and in formulating better models for adsorption phenomena from solution (see Section XI-1). [Pg.378]

Brunauer (see Refs. 136-138) defended these defects as deliberate approximations needed to obtain a practical two-constant equation. The assumption of a constant heat of adsorption in the first layer represents a balance between the effects of surface heterogeneity and of lateral interaction, and the assumption of a constant instead of a decreasing heat of adsorption for the succeeding layers balances the overestimate of the entropy of adsorption. These comments do help to explain why the model works as well as it does. However, since these approximations are inherent in the treatment, one can see why the BET model does not lend itself readily to any detailed insight into the real physical nature of multilayers. In summary, the BET equation will undoubtedly maintain its usefulness in surface area determinations, and it does provide some physical information about the nature of the adsorbed film, but only at the level of approximation inherent in the model. Mainly, the c value provides an estimate of the first layer heat of adsorption, averaged over the region of fit. [Pg.653]

Unfortunately none of the various proposed forms of the potential theory satisfy this criterion Equation XVII-78 clearly does not Eq. XVII-79 would, except that / includes the constant A, which contains the dispersion energy Uo, which, in turn, depends on the nature of the adsorbent. Equation XVII-82 fares no better if, according to its derivation, Uo reflects the surface polarity of the adsorbent (note Eq. VI-40). It would seem that after one or at most two layers of coverage, the adsorbate film is effectively insulated from the adsorbent. [Pg.654]

A further complication which not infrequently appears is the occurrence of a phase transition within the adsorbed film. Detailed investigation of a number of step-like isotherms by Rouquerol, Thorny and Duval, and by others has led to the discovery of a kink, or sub-step within the first riser, which has been interpreted in terms of a two-dimensional phase change in the first molecular layer. [Pg.89]

When the film thickens beyond two or three molecular layers, the effect of surface structure is largely smoothed out. It should therefore be possible, as Hill and Halsey have argued, to analyse the isotherm in the multilayer region by reference to surface forces (Chapter 1), the partial molar entropy of the adsorbed film being taken as equal to that of the liquid adsorptive. By application of the 6-12 relation of Chapter 1 (with omission of the r" term as being negligible except at short distances) Hill was able to arrive at the isotherm equation... [Pg.89]

The adsorbed layer at G—L or S—L surfaces ia practical surfactant systems may have a complex composition. The adsorbed molecules or ions may be close-packed forming almost a condensed film with solvent molecules virtually excluded from the surface, or widely spaced and behave somewhat like a two-dimensional gas. The adsorbed film may be multilayer rather than monolayer. Counterions are sometimes present with the surfactant ia the adsorbed layer. Mixed moaolayers are known that iavolve molecular complexes, eg, oae-to-oae complexes of fatty alcohol sulfates with fatty alcohols (10), as well as complexes betweea fatty acids and fatty acid soaps (11). Competitive or preferential adsorption between multiple solutes at G—L and L—L iaterfaces is an important effect ia foaming, foam stabiLizatioa, and defoaming (see Defoamers). [Pg.236]

Lubrication. The slip that readily occurs between layers of graphite planes only partially explains graphite s dry lubricating properties. A suitably adsorbed film such as water must also be present without it graphite ceases to lubricate and may, though rarely does, become abrasive (16). Scrolls (roUed-up layers 1—5 nm) may play a part in the lubricity of graphite by acting as rollers between the planar layers. [Pg.577]

Adsorbed electrolyte layers In this case the water molecules are bound to the metal surface by Van der Waals forces. It is estimated that at 55% r.h. the film on polished iron is about 15 molecular layers thick, increasing to 90 molecular layers at just below 100% r.h.. Such films are capable of... [Pg.342]

The definition of different lubrication regimes is a historic problem [41 ]. In boundary lubrication, molecules will be absorbed on a solid surface of a tribo-pair and form a monomo-lecular absorbed layer as described by Hardy [42] as shown in Fig. 1 (a). If the film thickness of lubricants in the contact region is from a few nanometres to tens of nanometres, different layers will be formed as shown in Fig. 1 (b) proposed by Luo et al. [3,4]. The layer close to the surfaces is the adsorbed film that is a monomolecular layer. The layer in the... [Pg.37]

Unlike traditional textbooks of tribology, in this book we regard boundary lubrication as a limit state of hydrodynamic lubrication when film thickness is down to molecular dimension and independent of the velocity of relative motion. The discussions are based on the existing results, some from literatures but mostly from the authors own work. The topics are mainly focused on the mechanical properties of boundary films, including rheology transitions, molecular ordering, and shear responses. Ordered molecule films, such as L-B films and SAM, are discussed, with emphasis on the frictional performance, energy dissipation and the effects from structural features. Boundary films can be modeled either as a confined substance, or an adsorbed/reacted layer on the... [Pg.94]

This radicals do not escape from the surface (this is indicated by a semiconductor microdetector located near the adsorbent surface) undergoing chemisorption on the same semiconductor adsorbent Him. Thus, they caused a decrease in the electric conductivity of the adsorbent sensor, similarly to the case where free radicals arrived to the film surface from the outside (for example, from the gas phase). Note that in these cases, the role of semiconductor oxide films is twofold. First, they play a part of adsorbents, and photoprocesses occur on their surfaces. Second, they are used as sensors of the active particles produced on the same surface through photolysis of the adsorbed molecular layer. [Pg.232]

At room temperature, unsaturated vapours of the above specified polar and nonpolar liquids do not influence considerably the rate of adsorption and chemical activity of not only adsorbed oxygen layers, but also of acceptors of semiconductor electrons of another type, namely, of alkyl radicals [54]. This is seen from the electric conductivity of ZnO films with adsorbed alkyl radicals or oxygen being invariable in the atmosphere of the saturated vapours of the above specified solvents. In the case of oxygen, this can be also seen from the fact that the oxygen concentration features no decrease. [Pg.263]

The presence of an immobile adsorbed film or layer on the particle surface may lead to the formation of still stronger interparticle van der Waals bonds (R6). First, surface roughness is smoothed out, increasing the apparent particle size and contact area, and second, the separation distance is effectively... [Pg.73]

The ions of the solution are diffused into the surface and react with the adsorbed cations of the inner layer. The first solid thin-film layer has now been formed on the substrate surface. Proceeding in this way, the growth of the thin film occurs only on the surface of the substrate. In a final step, the substrate is rinsed to remove the ions from the diffusion layer. A second growth cycle can now commence. The overall reaction occuring during one SILAR cycle can be presented as follows ... [Pg.241]

Assuming that the adsorbed biomolecular layer thickness T is very small, the electric field within the film can be taken to be a constant and the field distribution in the resonator change is very small, so Et can be approximated by E0, which lead to... [Pg.215]

In order to verify that the adsorbed lipid membrane indeed forms a bilayer film, another experiment is conducted with an aim to detect the formation of a monolayer lipid. It starts with a piranha-cleaned micro-tube treated with silane to render its inner surface hydrophobic. POPC liposome is then injected into the microtube. It is known that POPC lipid will form a monolayer to such a surface by orienting their hydrophobic tails toward the hydrophobic wall. The experimental results using a mode with similar sensitivity as the previous experiment are shown in Fig. 8.39. The resonance shift in this case is 22 pm, which is about half of that observed for the adsorption of a lipid bilayer. These two experiments suggest that the microtube resonator is capable of accurately determining an adsorbed biomolecular layer down to a few nm thicknesses. [Pg.221]

Corn (C7), however, points out that adsorbed films or gas layers may exist between the particles and may alter the nature of the adhesive force. Corn also indicates that various investigators have derived a value of the order of 4na for Kw when adsorbed liquid films are involved. Bradley (Bll) has derived an identical expression where <7 is defined as the surface energy of the solid. All of these forms yield values of Kw of the same general magnitude. There are, however, other reports (Fuchs, F4, pp. 363, 373) that indicate adhesive forces between particles as much as two orders of magnitude smaller than these. [Pg.36]

Fig. 27. Phase diagram of an adsorbed film in- the simple cubic lattice from mean-fleld calculations (full curves - flrst-order transitions, broken curves -second-order transitions) and from a Monte Carlo calculation (dash-dotted curve - only the transition of the first layer is shown). Phases shown are the lattice gas (G), the ordered (2x1) phase in the first layer, lattice fluid in the first layer F(l) and in the bulk F(a>). For the sake of clarity, layering transitions in layers higher than the second layer (which nearly coincide with the layering of the second layer and merge at 7 (2), are not shown. The chemical potential at gas-liquid coexistence is denoted as ttg, and 7 / is the mean-field bulk critical temperature. While the layering transition of the second layer ends in a critical point Tj(2), mean-field theory predicts two tricritical points 7 (1), 7 (1) in the first layer. Parameters of this calculation are R = —0.75, e = 2.5p, 112 = Mi/ = d/2, D = 20, and L varied from 6 to 24. (From Wagner and Binder .)... Fig. 27. Phase diagram of an adsorbed film in- the simple cubic lattice from mean-fleld calculations (full curves - flrst-order transitions, broken curves -second-order transitions) and from a Monte Carlo calculation (dash-dotted curve - only the transition of the first layer is shown). Phases shown are the lattice gas (G), the ordered (2x1) phase in the first layer, lattice fluid in the first layer F(l) and in the bulk F(a>). For the sake of clarity, layering transitions in layers higher than the second layer (which nearly coincide with the layering of the second layer and merge at 7 (2), are not shown. The chemical potential at gas-liquid coexistence is denoted as ttg, and 7 / is the mean-field bulk critical temperature. While the layering transition of the second layer ends in a critical point Tj(2), mean-field theory predicts two tricritical points 7 (1), 7 (1) in the first layer. Parameters of this calculation are R = —0.75, e = 2.5p, 112 = Mi/ = d/2, D = 20, and L varied from 6 to 24. (From Wagner and Binder .)...

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See also in sourсe #XX -- [ Pg.96 , Pg.311 ]




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Adsorbed film

Adsorbed film /layer ageing

Adsorbed film /layer bilayer

Adsorbed film /layer close-packed

Adsorbed film /layer collapsed

Thin films adsorbed layers

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