Conformation of preadsorbed polyelectrolyte layers on silica studied by secondary adsorption of colloidal silica

The conformation of cationic polyelectrolytes preadsorbed on macroscopic silica surfaces was studied before and after addition of colloidal silica (CS) and compared to the fixation capacity of CS. The study included two polyelectrolytes of equal charge density, cationic polyacrylamide and cationic dextran. Adsorbed amounts were determined with stagnation point adsorption reflectometry (SPAR) and quartz crystal microgravimetry (QCM). Unsaturated layers of polyelectrolyte were formed in SPAR by stopping the adsorption at a fractional coverage relative to saturation adsorption. These layers were probed by secondary saturation adsorption of colloidal silica (CS). At low salt concentrations a high fractional coverage of polyelectrolyte was required to attain adsorption of CS, while significant adsorption of CS was found also for low fractional coverages of polyelectrolyte at salt concentrations above 10 mM NaCl. Saturation adsorption of cationic polyacrylamide (CPAM) and cationic dextran (Cdextran) onto the silica surface was found to be similar, while the secondary adsorption of CS was significantly higher onto preadsorbed CPAM compared with Cdextran. The QCM and SPAR data together indicated that the adsorbed layer of Cdextran was thinner than CPAM, and that a loose, expanded layer was formed after adsorption of CS on CPAM but not on Cdextran.     

Forces between two polymer layers adsorbed at a solid-liquid interface in a poor solvent

The forces between mica surfaces a distance D apart immersed in cyclohexane, bearing adsorbed layers of polystyrene, have been measured at temperatures lower than the corresponding critical temperatures. Polymers of two different molecular weights were used. The results show that these forces are attractive for 3R_g > D >. R_g (where R_g is the polymer radius of gyration) and repulsive at lower D, and may be understood in terms of the phase equilibrium of the polystyrene-cyclohexane system. The adsorption of the polymer under these conditions appears to be effectively irreversible over the time of our experiments. The adsorbance of polymer and the thickness of the adsorbed layers are comparable with values measured in other studies using entirely different techniques.     

Short range order of silica particles bound through adsorbed polymer layers

Small angle neutron scattering was used to examine the organization of silica spheres which had been flocculated by various cationic copolymers. When the adsorbed polymers bound the spheres without compensating their surface charge, the resulting aggregates had a liquid-like short range order. When the polymers compensated for the surface charges, we found only tenuous aggregates with self-similar structures.This work used the neutron beams of ILL in Grenoble and LLB in Saclay.     

Conformation of polyesters adsorbed on solid surfaces

The conformation of a polyester, poly(ethylene o-phthalate), of relatively low molecular weight was studied after adsorption. The extension of the adsorbed molecule in a poor solvent on several planar metal surfaces was studied by ellipsometry and the fraction p of attached groups on colloidal silica particles in a good solvent was determined by the shift in the infrared absorption frequency between free and adsorbed carbonyl groups. In contrast to previously reported results for polystyrene, the extension normal to the surface remained constant (～70 A.) while the concentration of polymer in the adsorbed film increased during the adsorption period. The value of p (0.34 for MW = 5400) is relatively high and was independent of surface population for the range of solution concentrations measured. Differences between these results and those for polystyrene are interpreted as resulting from differences in interaction energy and chain stiffness.     

Van der Waals attraction between Stöber silica particles in a binary solvent system

Hydrophilic Stöber silica particles are stable in ethanol, but flocculation may be induced by the addition of sufficient cyclohexane. Low-shear rheological measurements indicated non-Newtonian behaviour beyond the critical cyclohexane concentration. The thickness and composition of the solvation layer around the particles were calculated from the adsorption excess isotherm on the basis of a multilayer adsorption model. The composition dependences of the Hamaker constants of the dispersion medium and the adsorption layer were obtained from optical dispersion measurements. A single-sheet, hard-sphere model predicted a weak van der Waals attraction in the ethanolic regime, but a strong attraction in the cyclohexane-rich region, in good accordance with the rheological properties of the dispersions and visual observations.     

Adsolubilization of 2-naphthol into adsorbed layers of triblock PEO-PPO-PEO copolymers on hydrophobic silica particles

Adsolubilization of 2-naphthol into an adsorbed layer of triblock poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) (PEO-PPO-PEO, Pluronics) copolymers on hydrophobically modified silica particles has been investigated. Four kinds of Pluronics (P103, P105, P123, and F108) were employed in order to understand the effect of the hydrophobicity of the surfactants on the adsolubilization. The amount of the Pluronics adsorbed of the maximum/saturation adsorption level was increased with a decrease in the HLB value, suggesting that the more hydrophobic Pluronics (P103 and P123) adsorb preferentially onto the hydrophobic silica surface over the more hydrophilic Pluronics (P105 and F108). The greater adsorbed amount of the more hydrophobic surfactants resulted in a greater amount of 2-naphthol adsolubilized into the adsorbed Pluronics layers. In the case of simultaneous addition of the Pluronics and 2-naphthol, the amount adsolubilized into the adsorbed P123 and P103 layers increased in their low-surfactant-concentration regime, reached a maximum, and then decreased with a further increase in the Pluronics concentration. On the other hand, for both the P105 and F108 copolymers, a decrease in the adsolubilized amount was not observed over the whole range of copolymer concentration investigated. This difference is attributed to a difference in the hydrophobicity of the micellar aggregates in solution and of the adsorbed layers on the hydrophobic surface. When 2-naphthol was added after replacement of the Pluronics supernatant by a surfactant-free solution, the final decrease in the adsolubilization was insignificant for all the Pluronics. Indeed, the maximum amount of adsolubilization was comparable to the corresponding amount obtained in the case of simultaneous addition.     

Effect of component ratio of binary organic solvent on sorption of phenols by silica

Chromatography is employed to measure the adsorption constants of hydroxybenzenes on SiO₂ in a low-concentration region at varied compositions of a binary organic solvent (n-hexane-ethyl acetate). It is shown that the Henry constants vary depending on the polar-to-nonpolar component ratio in the binary solvent and the number and position of hydroxyl groups in phenol molecules. It is found that the absolute values of changes Δ(ΔG) in the free energy considerably increase as the content of ethyl acetate in the mixtures diminishes, with the ratios between the Δ(ΔG) values of ortho-, meta-, and para-isomers remaining practically unchanged. The data obtained can be used to optimize the processes of the adsorption separation of mixed polyphenols and the isolation of natural phenolic compounds on a preparative scale.     

Spectroscopy of adsorbed layers

Recent developments in surface spectroscopic techniques and their applications to adsorbed films are reviewed. Attention is focused on vibrational spectroscopy, including sum-frequency spectroscopy, Fourier transform infrared spectroscopy and Raman scattering. Systems most relevant to colloid and interface science are emphasised, though related systems of interest are also mentioned.     

Effect of pH on adsolubilization of single and binary organic solutes into a cationic hydrocarbon surfactant adsorbed layer on silica

The adsolubilization behaviors of 2-naphthol, biphenyl, and their binary solutes in the hexadecyltrimethyl ammonium bromide (HTAB) adsorbed layer formed on silica have been studied with solution pH. Two feed concentrations of HTAB are employed: 1.5 and 3.0 mmol dm(-3). At the feed concentration of 1.5 mmol dm(-3) HTAB, most of HTAB are adsorbed on the silica as a monolayer, while a bilayer formation occurs at the feed concentration of 3.0 mmol dm(-3). It is found that the adsolubilized amounts of respective single solutes increase with increasing solution pH except acidic region for biphenyl under a constant feed concentration of 2-naphthol (0.4 mmol dm(-3)) and biphenyl (0.047 mmol dm(-3)). The adsolubilization of binary solutes depends on the feed concentration of HTAB; at the low HTAB feed concentration, competitive adsolubilization between 2-naphthol and biphenyl occurs above pH 4.5, while at the high HTAB feed concentration the adsolubilization of biphenyl is enhanced by the incorporation of 2-naphthol over a whole pH region. These behaviors in the adsolubilization are discussed from the surfactant structure of HTAB adsorbed as well as the admicellar partitioning coefficients.     

Dilational rheology of spread and adsorbed layers of silica nanoparticles at the liquid-gas interface

This short review is devoted to recent achievements in studies of the dilational surface rheological properties of the systems containing complexes of silica nanoparticles with conventional surfactants. It is shown that there is a surfactant concentration range where the dynamic surface elasticity reaches extremely high values up to 1000 mN/m. This result can explain the formation of very stable foams and emulsions containing nanoparticles. In some surfactant concentration ranges the adsorption layer is characterized by a non-linear response to small compressions or expansions of the liquid surface. Possible causes of this behavior and the mechanism of main relaxation processes are briefly discussed.     

Adsorption from binary solvent mixtures onto silica gel by HPLC frontal analysis

Summary The chromatographic technique of frontal analysis is applied to measuring adsorption from binary liquid mixtures by silica gel. The complete adsorption isotherm of a solvent mixture is obtained by measuring the break-through curves for a series of small concentration steps of the mobile phase. This method offers a direct way to determine the composition of the stationary phase in liquid-solid chromatography with mixed mobile phases. The surface excess isotherms of all binary systems formed by benzene, cyclohexane, and 1,2-dichloroethane, at the solution-silica gel interface at 25 °C are presented. The data of the three systems are shown to be thermodynamically mutually consistent.     

Behavior of macromolecules in adsorbed layers

A model for describing the behavior ot macromoiecuies in aosoroea layers is developed by introducing a concept of distribution density of layer thickness U based on stochastic process and probabilistic statistics. The molecular behavior of layers adsorbed on clay particle surfaces is discussed; the random distribution and its statistics of the layer thickness are given by incorporating experimental results with an ionic polyelectrolyte with the molecular weight of 1.08×106and chain charged density of 0.254.     

Influence of a surfactant and electrolytes on adsorbed polymer layers

Solvent relaxation NMR and small-angle neutron scattering have been used to characterize adsorbed poly(ethylene oxide) (PEO) layers on silica at a range of surfactant and electrolyte concentrations. Below the critical aggregation concentration (cac), the results suggest that sodium dodecyl sulfate (SDS) interacts relatively weakly, perhaps analogously to a simple salt reducing the solvency of PEO. This is evidenced by a decrease in the adsorbed layer thickness combined with an increase in the bound fraction, although the total adsorbed amount is not greatly affected. The layer thickness goes through a minimum at the cac, after which further SDS addition results in the formation of PEO/SDS aggregates that repel each other and, hence, tend to desorb. The adsorbed amount therefore decreases, from 0.7 mg m(-2) initially to 0.2 mg m(-2) with 32 mM SDS. The aggregates that remain adsorbed also repel, and hence, there is an increase in the layer thickness and the persistence length, while the bound fraction is reduced. In comparison, the effects of electrolyte at the ionic strength studied are relatively minimal. There is, however, evidence that the repulsions between adsorbed PEO/SDS aggregates are partially screened, allowing them to approach each other more readily. This leads to a contraction of the adsorbed layer when the SDS concentration is sufficiently high.     

Relaxation phenomena of polyethyleneimine molecules within saturated homogeneous and heterogeneous layers adsorbed at a silica/water interface

Surface area exclusion chromatography was used to investigate the adsorption characteristics of the highly branched polyethyleneimine (PEI) molecule and of a related molecule resulting from the grafting of PEI with C12 to C22 alkyl chains. The interfacial relaxation and surface affinity of the two polymers was determined in homogeneous and heterogeneous layers. The presence of hydrophobic moieties within the branched morphology of the grafted PEI molecule was found to modify the adsorption histogram as compared to bare PEI and to lead to greater interfacial stability. The relaxation of the bare and grafted macromolecules proved to be of equal extent but to develop at different rates within homogeneous layers. In heterogeneous layers composed of the two polymers, the slower relaxation of the grafted macromolecules decreased the rate of relaxation of the bare molecules, while the faster relaxation of the bare molecules strongly increased the rate and extent of the relaxation of the grafted macromolecules. The same technique was then used to determine the mode of establishment of the layers. The polymer coating profiles on successive glass fiber filters of the chromatography column were found to depend on the sequence of injection of the two polymers. Simultaneous and sequential adsorption processes were analyzed on the basis of the random sequential adsorption of macromolecules.     

Structure of adsorbed n-dodecyl-beta-D-maltoside layers on hematite

The composition, structure, and thickness of n-dodecyl-beta-D-maltoside self-assembled layers on hematite have been evaluated using infrared external reflection spectroscopy and spectral simulation techniques. From the qualitative and quantitative analysis of the reflection spectra of the same sample recorded at different specific angles of incidence and two polarizations, the orientation of the sugar ring and hydrocarbon chain were obtained. Both of these molecular groups are positioned parallel to hematite surface, the adsorbed molecules being at low (2.2-nm-thick layer) as well as higher (11-nm) coverages. The maltoside is adsorbed through interaction of sugar ring OH groups with hematite surface hydroxyl groups. The adsorption of maltoside is not very strong and desorption takes place easily from acidic and low-basic solutions but with more difficulty from strong-basic solution.     

Photochemistry of ketones adsorbed on porous silica

The Phetochemical reactions of several families of ketones adsorbed on various forms of silica have been investigated. The influence of surface coverage, silica average pore diameter, temperature, applied magnetic fields, and additives on the product distributions have been determined. The results are consistent with a model in which the silica surface consists of two major regions, one consisting of stronger binding sites (active silanol groups) and the other consisting of weaker binding sites (free silanol groups). The relative proportions of these two types of sites are related to the pore size of the silica, smaller pores correlating with a larger fraction of the stronger binding sites and larger pores correlating with a smaller fraction of the stronger binding sites. At low coverage, the initial location of a ketone in one of the two binding sites is an important factor in determining the product distributions. Some preliminary results are reported on the time resolved spectroscopy of ketones adsorbed on silica investigated by diffuse reflectance absorption spectrescopy.     

Conversions of ethanol in thermolysis of dyes adsorbed on a silica surface

Using thermal desorption measurements with mass spectrometric analysis of the gas phase, we have studied the characteristics of the interaction of ethanol molecules with the silica surface under conditions when some of the adsorption centers are occupied by molecules of a heteroaromatic dye. The characteristics of the thermal conversions of ethanol on the surface are described in terms of ideas concerning the nature of the active centers on a surface of dispersed silicon dioxide. We observed occurrence of the reaction of ethoxylation of the surface with an increase in temperature. The interaction between the ethanol molecules and the dye molecules occurs with formation of a complex in an excited state upon UV irradiation, which stimulates adsorption of the solvent in strongly bound forms with decomposition of the complex in the surface layer.Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 28, No. 1, pp. 87–91, January–February, 1992.