Adsorption, polymers

Polymers typically exhibit a high-affinity adsorption isotherm as shown in Fig. XI-5 here the adsorbed amount increases very rapidly with bulk concentration and then becomes practically independent of concentration. 

Of particular interest has been the study of the polymer configurations at the solid-liquid interface. Beginning with lattice theories, early models of polymer adsorption captured most of the features of adsorption such as the loop, train, and tail structures and the influence of the surface interaction parameter (see Refs. 57, 58, 62 for reviews of older theories). These lattice models have been expanded on in recent years using modem computational methods [63,64] and have allowed the calculation of equilibrium partitioning between a poly- 

As evident from Fig. XI-6, the mean field produces concentration profiles that decay exponentially with distance from the surface [66]. A useful approximate solution to Eq. XI-18 captures the exponential character of the loop concentration profile [67], Here a chain of length iV at a bulk concentration of (j b has a loop profile that can be estimated by 

An early analytic theory by Hoeve accurately predicts the number of loops ni(s) and trains n,(s) having s segments 

The polymer concentration profile has been measured by small-angle neutron scattering from polymers adsorbed onto colloidal particles [70,71] or porous media [72] and from flat surfaces with neutron reflectivity [73] and optical reflectometry [74]. The fraction of segments bound to the solid surface is nicely revealed in NMR studies [75], infrared spectroscopy [76], and electron spin resonance [77]. An example of the concentration profile obtained by inverting neutron scattering measurements appears in Fig. XI-7, showing a typical surface volume fraction of 0.25 and layer thickness of 10-15 nm. The profile decays rapidly and monotonically but does not exhibit power-law scaling [70]. 

In this section, the above polymer retention mechanisms are surveyed. However, polymer adsorption is treated very briefly since it is discussed in much more detail in Sections 5.4 and 5.6 below. A fuller discussion of mechanical entrapment and hydrodynamic retention is given here since these topics are not discussed again after this section. 

Adsorption refers to the interaction between the polymer molecules and the solid surface—as mediated by the solvent (which is aqueous in all the work presented here). This interaction causes polymer molecules to be bound to the surface of the solid mainly by physical adsorption—van der Waal s and hydrogen bonding—rather than by chemisorption, in which full chemical bonds are formed between the molecule and the surface. Essentially the polymer occupies surface adsorption sites, and the larger the surface area available the higher the levels of adsorption that are observed. Adsorption is the only mechanism that removes polymer from the bulk solution if a free solid powder, such as silica sand or latex beads, is introduced into the bulk 

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A recent design of the maximum bubble pressure instrument for measurement of dynamic surface tension allows resolution in the millisecond time frame [119, 120]. This was accomplished by increasing the system volume relative to that of the bubble and by using electric and acoustic sensors to track the bubble formation frequency. Miller and co-workers also assessed the hydrodynamic effects arising at short bubble formation times with experiments on very viscous liquids [121]. They proposed a correction procedure to improve reliability at short times. This technique is applicable to the study of surfactant and polymer adsorption from solution [101, 120]. 

Smith [113] studied the adsorption of n-pentane on mercury, determining both the surface tension change and the ellipsometric film thickness as a function of the equilibrium pentane pressure. F could then be calculated from the Gibbs equation in the form of Eq. ni-106, and from t. The agreement was excellent. Ellipsometry has also been used to determine the surface compositions of solutions [114,115], as well polymer adsorption at the solution-air interface [116]. 

A logical division is made for the adsorption of nonelectrolytes according to whether they are in dilute or concentrated solution. In dilute solutions, the treatment is very similar to that for gas adsorption, whereas in concentrated binary mixtures the role of the solvent becomes more explicit. An important class of adsorbed materials, self-assembling monolayers, are briefly reviewed along with an overview of the essential features of polymer adsorption. The adsorption of electrolytes is treated briefly, mainly in terms of the exchange of components in an electrical double layer. 

Lab method using porous polymer adsorption tube and thermal desorption with gas chromatography Lab method using porous polymer diffusive samplers with thermal desorption and gas chromatography Lab method using pumped acid-coated filters, desorption and liquid chromatography... 

Lab method using pumped porous polymer adsorption tubes, thermal desorption and gas chromatography 40... 

MDHS 2 Acrylonitrile m air (porous polymer adsorption tubes)... 

Stabilization of Colloidal Dispersions by Polymer Adsorption, Tatsuo Sato and Richard Ruch... 

Because we wanted to suppress the effects of thermodynamic quality of the eluent toward the polymer probes, we therefore looked for liquids that would be thermodynamically good solvents for PMMA. At the same time, one solvent should promote polymer adsorption whereas the others should promote desorption. 

For Yiv > YPv> where y v and Ypv are the surface tensions of liquid and protein, respectively, AFads increases with increasing ysv, predicting decreasing polymer adsorption. An example of this is phosphate buffer saline where y]v = 72.9 mJ/m2 and Ypv is usually between 65 and 70mJ/m2 for most proteins [5]. Therefore, supports for gel-permeation and affinity chromatography should be as hydrophilic as possible in order to minimize undesirable adsorption effects. 

We think, therefore, that the conformation, chain and segment mobilities in the attached macromolecules can play a significant role in the shielding behavior of the polymeric stationary phase as well as in the processes of its formation of complexes with solutes. Obviously, the chromatographic studies relevant to composite supports suffer from a lack of information on the structure of the attached polymer. Nevertheless, we will attempt to point out some relevant data from independent studies on polymer adsorption and/or graft polymerization. 

These predictions are in better agreement with the results of Luckham and Klein [21] who observed an extended force profile between two surfaces coated with polyelectrolyte and supposed the non-equilibrium character of polymer adsorption. 

Another important feature of polymer adsorption is the influence exerted on it by the surface roughness. Ball et al. [22] proposed that if the surface potential is not attractive enough to bind the polymer when flat, then corrugation can aid binding as follows. For a sinusoidal corrugation, one might anticipate that some... 

The drawback of the described adsorbents is the leakage of the bonded phase that may occur after the change of eluent or temperature of operation when the equilibrium of the polymer adsorption is disturbed. In order to prepare a more stable support Dulout et al. [31] introduced the treatment of porous silica with PEO, poly-lV-vinylpyrrolidone or polyvinylalcohol solution followed by a second treatment with an aqueous solution of a protein whose molecular weight was lower than that of the proteins to be separated. Possibly, displacement of the weakly adsorbed coils by the stronger interacting proteins produce an additional shrouding of the polymer-coated supports. After the weakly adsorbed portion was replaced, the stability of the mixed adsorption layer was higher. 

Highly branched polymers, polymer adsorption and the mesophases of block copolymers may seem weakly connected subjects. However, in this review we bring out some important common features related to the tethering experienced by the polymer chains in all of these structures. Tethered polymer chains, in our parlance, are chains attached to a point, a line, a surface or an interface by their ends. In this view, one may think of the arms of a star polymer as chains tethered to a point [1], or of polymerized macromonomers as chains tethered to a line [2-4]. Adsorption or grafting of end-functionalized polymers to a surface exemplifies a tethered surface layer [5] (a polymer brush ), whereas block copolymers straddling phase boundaries give rise to chains tethered to an interface [6],... 

Clay Polymer Adsorption Drag Clay layers separate... 

MDHS 1 Acrylonitrile in air Laboratory method using charcoal adsorption tubes and gas chromatography MDHS 2 Acrylonitrile in air Laboratory method using porous polymer adsorption tubes, and thermal desorption with gas chromatographic analysis... 

T Sato, R Ruch. Stabilization of Colloidal Dispersions by Polymer Adsorption (Surfactant Science Series, No. 9). New York Marcel Dekker, 1980, pp 65-119. 

Emulsions and Emulsion Technology (in three parts), edited by Kenneth J. Lissant Anionic Surfactants (in two parts), edited by Warner M. Linfieid see Volume 56) Anionic Surfactants Chemical Analysis, edited by John Cross Stabilization of Colloidal Dispersions by Polymer Adsorption, Tatsuo Sato and Richard Ruch... 

Protective colloids or polymeric materials can be adsorbed onto the surface of the dispersed phase. Polymer adsorption can be accomplished simply by... 

Cationic polyacrylamide may be used in the initial treatment stages to promote rapid polymer adsorption (201). Adjustment of the pH may allow deeper penetration of the fluids in an aluminate crosslinking system prior to gelation (202). A process involving injection of alternate slugs of stoichiometrically equivalent amounts of partially hydrolyzed polyacrylamide and Al O ) has been evaluated in the laboratory permeability of sana packs were reduced by more than 96% (203). Mixtures of Al(IIl) and Zr(IV) have also been evaluated as partially hydrolyzed polyacrylamide crosslinkers (204). 

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