Adsorbate anchoring

The efficiency of steric stabilisation depends on both architecture and the physical properties of the stabilising molecule. Steric stabilisers should have an adsorbing anchor with a high affinity for the particles and/or be insoluble in the medium. The stabiliser should be soluble in the medium and highly solvated by its molecules. For aqueous or highly polar oil systems, the stabiliser block can be ionic or hydrophilic... 

The use of a strongly adsorbed ( anchored ) dispersant, for example by multipoint attachment of a block or graft copolymer. 

The first case concerns particles with polymer chains attached to their surfaces. This can be done using chemically (end-)grafted chains, as is often done in the study of model colloids. Alternatively, a block copolymer can be used, of which one of the blocks (the anchor group) adsorbs strongly to the particles. The polymer chains may vary from short alkane chains to high molecular weight polymers (see also section C2.6.2). The interactions between such... 

If an adsorbed chemical group (anchor) is more strongly bound to the surface than a solvent molecule would be at that site, an equiHbrium expression may be written for the displacement of solvent by adsorbate. Adsorption is particularly strong if the chemical nature of the adsorbed group is similar to that of the particle surface for example, in aqueous systems perfluoroalkane groups adsorb weU on polytetrafluoroethene particles and aromatic polyethene oxides adsorb weU on polystyrene. 

Apart from the mentioned advantages, the polymeric reagents covalently adsorbed by silica also diminish its inherent non-specific adsorptivity. One of the ways to synthesize a polymeric modifier of this type is a copolymerization of a vinylsilane with a compound of the desired functionality. The segments carrying silyl groups will condense with the surface silanols forming anchors or trains . 

Fig. 3 a-c. Summary of data from different laboratories, obtained by surface force measurement, on the average layer thickness L as a function of tethered chain length for flat, tethered layers constructed by adsorption of amphiphilic polymers on mica. Adapted from Ref. 21. (a) Data of reference 20 on poly-tert-butylstyrene chains anchored by adsorbing blocks of poly-2-vinylpyridine. (b) Data of references 11 and 12 on polystyrene chains anchored by adsorbing blocks of poly-2-vinylpyridine. (c) Data of references 13 and 14 on polystyrene chains anchored by adsorbing zwitterionic groups [13] or by small adsorbing blocks of polyethyleneoxide [14]... 

AB diblock copolymers in the presence of a selective surface can form an adsorbed layer, which is a planar form of aggregation or self-assembly. This is very useful in the manipulation of the surface properties of solid surfaces, especially those that are employed in liquid media. Several situations have been studied both theoretically and experimentally, among them the case of a selective surface but a nonselective solvent [75] which results in swelling of both the anchor and the buoy layers. However, we concentrate on the situation most closely related to the micelle conditions just discussed, namely, adsorption from a selective solvent. Our theoretical discussion is adapted and abbreviated from that of Marques et al. [76], who considered many features not discussed here. They began their analysis from the grand canonical free energy of a block copolymer layer in equilibrium with a reservoir containing soluble block copolymer at chemical potential peK. They also considered the possible effects of micellization in solution on the adsorption process [61]. We assume in this presentation that the anchor layer is in a solvent-free, melt state above Tg. The anchor layer is assumed to be thin and smooth, with a sharp interface between it and the solvent swollen buoy layer. 

Figure 7 shows the results of measurements of adsorption density by Parsonage, etal. [77] on a series of eighteen block copolymers, with poly(2-vinylpyridine) [PVP] anchors and polystyrene [PS] buoys, adsorbed from toluene (selective for PS) of variable molecular weight in each block. The results are presented as the reciprocal square of Eq. 28, that is, as a dimensionless number density of chains ct (d/Rg A)-2. For all but the copolymers of highest asymmetry, Eq. 28 is in good agreement with the data of Fig. 7. The high asymmetry copolymers are in the regime of the data of curves (a) and (c) of Fig. 3 where the large relative size...

Clearly Fig. 7 must actually have a maximum at high asymmetry since this corresponds to negligible anchor block size and therefore to no adsorption (ct = 0). The lattice theory of Evers et al. predicts this quantitatively [78] and is, on preliminary examination, also able to explain some aspects of these data. From these data, the deviation from power law behavior occurs at a number density of chains where the number of segments in the PVP blocks are insufficient to cover the surface completely, making the idea of a continuous wetting anchor layer untenable. Discontinuous adsorbed layers and surface micelles have been studied theoretically but to date have not been directly observed experimentally [79]. 

As early as 1848, it had been suggested that sensory receptors transduce only one sensation, independent of the manner of stimulation. Behavioral experiments tend to support this theory. In 1919, Renqvist proposed that the initial reaction of taste stimulation takes place on the surface of the taste-cell membrane. The taste surfaces were regarded as colloidal dispersions in which the protoplasmic, sensory particles and their components were suspended in the liquor or solution to be tested. The taste sensation would then be due to adsorption of the substances in the solution, and equal degrees of sensation would correspond to adsorption of equal amounts. Therefore, the rate of adsorption of taste stimulants would be proportional to the total substances adsorbed. The phenomenon of taste differences between isomers was partly explained by the assumption that the mechanism of taste involves a three-dimensional arrangement for example, a layer of fatty acid floating on water would have its carboxylic groups anchored in the water whereas the long, hydrocarbon ends would project upwards. 

During the last two decades a variety of transition metal macrocycles have been shown to exhibit activity for O2 reduction In alkaline and acid media when adsorbed, chemically anchored or physically dispersed on electrode surface (Jf5). This class of compounds provides a unique opportunity to examine In detail some of the factors Involved In the activation and further reduction of 02 These would Include the effects associated with axial, peripheral... 

Thermal reduction at 623 K by means of CO is a common method of producing reduced and catalytically active chromium centers. In this case the induction period in the successive ethylene polymerization is replaced by a very short delay consistent with initial adsorption of ethylene on reduce chromium centers and formation of active precursors. In the CO-reduced catalyst, CO2 in the gas phase is the only product and chromium is found to have an average oxidation number just above 2 [4,7,44,65,66], comprised of mainly Cr(II) and very small amount of Cr(III) species (presumably as Q -Cr203 [66]). Fubini et al. [47] reported that reduction in CO at 623 K of a diluted Cr(VI)/Si02 sample (1 wt. % Cr) yields 98% of the silica-supported chromium in the +2 oxidation state, as determined from oxygen uptake measurements. The remaining 2 wt. % of the metal was proposed to be clustered in a-chromia-like particles. As the oxidation product (CO2) is not adsorbed on the surface and CO is fully desorbed from Cr(II) at 623 K (reduction temperature), the resulting catalyst acquires a model character in fact, the siliceous part of the surface is the same of pure silica treated at the same temperature and the anchored chromium is all in the divalent state. 

When a supported metal on an oxide is prepared from an adsorbed precursor incorporating a noble metal bonded to an oxophilic metal, the result may be small noble metal clusters, each more-or-less nested in a cluster of atoms of the oxophilic metal, which is cationic and anchored to the support through metal-oxygen bonds [44,45]. The simplest such structure is modeled on the basis of EXAFS data as Re4Pt2, made from Re2Pt(CO)i2 (Fig. 6) [45]. 

Sulfiir-anchored SAMs and thin films, mostly from organosulfiir precursors, have been discussed at length by a number of authors [10, 181]. SAMs of organosulfiir compounds (thiols, disulfides, sulfides) form on gold substrates by spontaneous adsorption from either the liquid or the vapor phase. A number of experimental factors can affect the formation and structure of SAMs such as choice of solvent, temperature, concentration, immersion time, purity of adsorbate, oxygen concentration in solution, cleanliness, and structure of the adsorbate. Interestingly, the... 

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