Adsorption of polymers at the solution‐solid interface. VIII. Competitive effects in the adsorption of polystyrenes on silica

Howard, G. J.; Woods, S. J.

doi:10.1002/pol.1972.160100606

Cited by 28 publications

(7 citation statements)

References 5 publications

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“…This is the first competitive study of molecular mass preference, but preferential intercalation of high-molecular-mass polymer in clay is supported by noncompetitive intercalation isotherms ,− that show higher-molecular-mass PEG produces a greater uptake and has a higher affinity for clay surfaces than low-molecular-mass material. Preferential surface adsorption of high-molecular-mass polymer from solution on high energy surfaces is usually found − and the specific adsorption A is related to molecular mass M by where K is a constant and the index is 0 < α < 0.3. It is interesting to see if eq 3 can be applied to intercalation as well as to adsorption data.…”

Section: Resultsmentioning

confidence: 99%

Preferential Intercalation in Polymer-Clay Nanocomposites

Chen

Evans

2004

J. Phys. Chem. B

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When polymer-clay nanocomposites are prepared from a polymer of broad molecular mass distribution, the question arises whether the clay scavenges the low molecular mass fractions or prefers to receive the larger molecules which might provide bridges between nanoparticles. This is the first report of competitive sorption experiments for molecular mass in polymer-clay nanocomposites and shows that high molecular mass fractions of polymer intercalate preferentially into a smectite clay during solution preparation. Poly(ethylene glycol)s (PEGs) with different monomodal molecular mass distributions were mixed and added to montmorillonite in aqueous suspension. After centrifuging, excess PEG in the supernatant was analyzed gravimetrically and by gel permeation chromatography (GPC). The montmorillonite preferentially absorbed the higher mass fractions. X-ray diffraction confirmed intercalation. Sodium-treated montmorillonite also showed this preference. A heat-treated montmorillonite with collapsed layers was used as an experimental control to distinguish surface adsorption and gallery intercalation.

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Section: Resultsmentioning

confidence: 99%

Preferential Intercalation in Polymer-Clay Nanocomposites

Chen

Evans

2004

J. Phys. Chem. B

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“…55 Systems that ad-sorb weakly with nonspecific van der Waals type interactions, are more freely removable from the surface. For instance, polystyrene in cyclohexane at 35 °C, a Θ-solvent, adsorbs reversibly to the solid/liquid interface and may be displaced by polystyrene with higher molecular weight 56 (a phenomenon governed by entropy considerations 41,53 ). Polymers with multiple strong adsorbers, such as those bearing (chemisorbing) thiol groups, stick to the surface irreversibly.…”

Section: Resultsmentioning

confidence: 99%

Adsorption of a Radiolabeled Random Hydrophilic/Hydrophobic Copolymer at the Liquid/Liquid Interface: Kinetics, Isotherms, and Self-Exchange

Wang

Schlenoff

1998

Macromolecules

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The synthesis and labeling (with 35S) of a water-soluble random copolymer of styrenesulfonate and tert-butylstyrene (20 mol %) is described. Adsorption of this copolymer to the toluene/water interface is followed in situ using a proximity radiometric detection scheme, where the organic phase also serves as a scintillator. Adsorption isotherms, determined with the aqueous phase either salt-free or containing 1 M NaCl, are of the high-affinity type, with respective pseudolimiting adsorbed amounts of 0.24 and 1.4 mg m-2. Adsorption is fairly rapid, occurring with a time constant of a few minutes. Self-exchange of radiolabeled polymer at the interface, performed with a solution excess of unlabeled polymer, is complete within a few hours, providing evidence that the surface excess is under thermodynamic, rather than kinetic, control. Preliminary comparisons of the liquid/liquid interface and a chemically similar polystyrene/water interface reveal that the adsorption isotherms are similar despite the additional mobility afforded to adsorbed segments at the fluid interface. The free energy of adsorption for tert-butylstyrene units is estimated to be ca. 13 kT from solubility and partitioning measurements of the corresponding monomer.

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“…Thus the strong adsorption enthalpy may be responsible for the experimental result that the ellipsometric thickness of PEO adsorbed on solid surface is less than 20 A. 21 The fraction p0H, defined by eq 2, represents the relation = (Cs -C0h)/Ca (2) of the number of silanol groups occupied by adsorbed polymer to the total number of polymer segments in the adsorbed layer. CA is the quantity of adsorbed polymer expressed as (C0 -Cp).…”

Section: Resultsmentioning

confidence: 99%

Competitive and displacement adsorption of polystyrene and poly(ethylene oxide)

Kawaguchi¹,

Sakai²,

Takahashi³

1986

Macromolecules

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Competitive and displacement adsorption of polystyrene (PS) and polyethylene oxide) (PEO) with narrow molecular weight distributions onto a nonporous silica (Aerosil 130) from carbon tetrachloride solutions at 35 °C was studied by IR and UV spectroscopy. The fraction of silanol groups occupied by styrene or ethylene oxide units was determined from the shift in the IR frequency of the silanol groups. In competitive adsorption, PEO absorbs preferentially over PS, and the preferential adsorption of large molecules over small molecules occurs even in the presence of different species. PS molecules are completely desorbed from the silica surface by addition of PEO (displacer). The degree of displacement of PS by PEO depends on the fraction of styrene units directly attached to the silanol groups as well as on the molecular weights of PS and PEO.

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Adsorption of polymers at the solution‐solid interface. VIII. Competitive effects in the adsorption of polystyrenes on silica

Cited by 28 publications

References 5 publications

Preferential Intercalation in Polymer-Clay Nanocomposites

Preferential Intercalation in Polymer-Clay Nanocomposites

Adsorption of a Radiolabeled Random Hydrophilic/Hydrophobic Copolymer at the Liquid/Liquid Interface: Kinetics, Isotherms, and Self-Exchange

Competitive and displacement adsorption of polystyrene and poly(ethylene oxide)

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