Adsorption kinetics measurements of some nonionic surfactants

Dynamic surface tension values of aqueous surfactant solutions were measured by using the ring and plate method. The mean diffusion coefficients calculated on the basis of the purely diffusion controlled adsorption model vary between 2 · 10^–6 to 7 · 10^–6 cm²/s for all surfactants studied:n-alkanols,n-alkanoic acids, dimethyl and diethyln-alkyl phosphine oxides. That means the surfactants investigated adsorb with a purely diffusion controlled adsorption mechanism and no barriers excist to hinder sorption processes.Nomenclature c ₀ surfactant bulk concentration - D diffusion coefficient - surface concentration - ₀ equilibrium surface concentration - ¯ (t)/ ₀ reduced surface concentration - maximum surface concentration - K ₀/c₀ - surface tension - t time - Dt/K ² reduced time - a _L coefficient of the Langmuir isotherm     

Forces between silica surfaces with adsorbed cationic surfactants: influence of salt and added nonionic surfactants

Forces have been measured between silica surfaces with adsorbed surfactants by means of a bimorph surface force apparatus. The surfactants used are the cationic surfactant tetradecyltrimethylammonium bromide (TTAB) and the nonionic surfactant hexakis(ethylene glycol) mono-n-tetradecyl ether (C(14)E(6)) as well as mixtures of these two surfactants. The measurements were made at elevated pH, and the effect of salt was studied. At high pH the glass surface is highly charged, which increases the adsorption of TTAB. Despite the low adsorption generally seen for nonionic surfactants on silica at high pH, addition of C(14)E(6) has a considerable effect on the surface forces between two glass surfaces in a TTAB solution. The barrier force is hardly affected, but the adhesion is reduced remarkably. Also, addition of salt decreases the adhesion, but increases the barrier force. In the presence of salt, addition of C(14)E(6) also increases the thickness of the adsorbed layer. The force barrier height is also shown to be related to literature values for surface pressure data in these systems.     

Adsorption kinetics of nonionic surfactants using the drop volume method

The kinetic results obtained for the nonionic surfactantsn-octyl,n-decyl, andn-dodecyl dimethyl andn-octyl, andn-decyl diethyl phosphine oxide show purely diffusion controlled adsorption. The drop volume technique applied in a static and dynamic version proves to be useful to measure the adsorption kinetics in the form of surface tensions in function of time. Comparisons of the results obtained from both the static and the dynamic measuring procedure confirm the validity of a theory applied to interpret the kinetic data.Nomenclature a Langmuir parameter - c ₀ surfactant bulk concentration - D diffusion coefficient - surface concentration - ₀ equilibrium surface concentration - ¯ (t)/ ₀ reduced surface concentration - maximum value of - R gas law constant - surface tension - ₀ surface tension of pure water - t time - T absolute temperature     

Adsorption of ionic surfactants on polar surfaces with a low content of chemically adsorbed alkyl chains

Colloidal silica and titanium dioxide were surface-modified by chemisorption of octadecyl dimethylmethoxy silane. The surface density of these alkyl silane groups was adjusted to less than 7% of the available surface hydroxyls, leaving the adsorbents hydrophilic and electrically charged in aqueous solution.Ionic surfactants (tetradecylpyridinium chloride and sodium lauryl sulfate) are adsorbed onto the surface-modified silica and titanium dioxide from aqueous solution, even in the case where the surface of the adsorbents exhibits the same sign of electrical charge as the surfactant ionic head groups. According to the adsorption model of Gu the chemiadsorbed alkyl chains are supposed to serve as anchors for small surface aggregates of the ionic surfactants.     

Orientation of nonionic surfactants on solid surfaces: n-alkyl polyglycol ethers on montmorillonite

Summary Complexes of nonionic surfactantsR-(OCH₂CH₂)x OH with montmorillonite have been studied (R =n-hexadecyl,n-octadecyl and oleyl ;x=2, 10 and 20).On internal surfaces the surfactant molecules are arranged in bilayers. Withx=2 the alkyl chain and about one half of the polar group, (-R OCH₂CH₂O-) stand perpendicularly whereas the terminal —CH₂CH₂OH group is attached to the silicate surface (₁-phase). The bilayer thickness decreases stepwise with rising temperature due to the formation of kinks (i-phases). At higher temperature (52 °C withR=C₁₈H₃₇-, 43°C withR=n-C₁₆H₃₃-, and 12 °C withR = oleyl-) surfactant molecules are squeezed out of the interlayer space reversibly, the packing density decreases, the whole polar head group gets attached to the silicate surface and the alkyl chains rearrange into a gauche-block structure. This structure undergoes further structural changes at still higher temperatures ( _i -phases).The complexes withx =10 and 20 form -phases even at room temperature. These -phases take up long chain alkanol molecules under formation of -structures which rearrange at higher temperatures into -phases. Long-chain impurities of the surfactants can be intercalated in a similar way.Previous data indicating mono- or bilayers of flatly lying surfactant molecules refer to metastable phases due to steric hindrances of lattice expansion.It is proposed that the surfactant molecules build up similar films on the external surfaces, which can adopt - or -structures depending upon number of ethylene oxide groups and temperature. The films of hexadecyl polyglycol ethers for instance are about 27 Å thick in the -phases and about 17 Å in the a-phases.

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Zusammenfassung Es wurden Montmorillonitkomplexe mit nichtionogenen TensidenR(-OCH₂CH₂) _x ,OH (R =n-hexadecyl-,n-octadecyl- und oleyl-;x = 2, 10 and 20) hergestellt. Die Tensidmoleküle bilden zwischen den Silicatschichten bimolekulare Filme.Mitx=2 sind die hydrophoben Reste und die anschließende -OCH₂CH₂-Äthergruppe bei niedriger Temperatur gestreckt und senkrecht zu den Silicatschichten orientiert ( _i -Phase); nur die endständige HOCH₂CH₂-Gruppe sitzt direkt auf der Silicatschicht auf. Beim Erwärmen erniedrigt sich die Dicke der bimolekularen Tensidschicht stufenweise durch den Einbau von Kinken ( _i -Phasen). Bei höheren Temperaturen (52°C mitR =C₁₈H₃₇-, 43 °C mitR =C₁₆H_33- und 12 °C mitR = oleyl) werden Tensidmoleküle reversibel aus den Schichtzwischenräumen verdrängt, die Packungsdichte erniedrigt sich, die gesamte polare Gruppe kommt in direkten Kontakt mit der Silicatschicht und die Alkylketten ordnen sich in eine Gaucheblockstruktur ( _i -Phase). Diese kann bei noch höheren Temperaturen weitere Phasenumwandlungen erleiden.Mitx =10 undx = 20 werden auch bei Zimmertemperatur nur -Phasen gebildet. Diese -Phasen können zusätzlich langkettige Alkanolmoleküle aufnehmen und ternäre Komplexe mit -Struktur bilden, die sich beim Erhitzen reversibel in -Formen umwandeln. Langkettige polare Verunreinigungen in den Tensiden wirken ähnlich wie die Alkanolmoleküle.An den äußeren Oberflächen werden die Tensidmoleküle gleichartige Filme mit - oder -Struktur bilden, je nach der Zahl der -CH₂CH₂O-Gruppen und der Temperatur. Ein Film aus Hexadecylpolyglykoläthern wird etwa 27 Å dick sein in der -Phase und etwa 17 Å in der -Form.

     

Adsorption and heterocoagulation of nonionic surfactants and latex particles on cement hydrates

The adsorption of nonionic surfactants of the alkyl-phenol-poly(ethylene oxide) family and of acrylic latex particles on several anhydrous (but hydrating) or fully hydrated mineral phases of Portland cement was studied. No or negligible adsorption of the surfactant was observed. This was assigned to the ionized character of the surface silanol groups in calcium-silicate-hydrates and to the strongly ionic character of the OH groups in calcium hydroxide and in the calcium-sulfoaluminate-hydrates, which prevents the formation of surface-ethoxy hydrogen bonds. In contrast, provided they are properly stabilized by the surfactant, the latex particles form a loose monolayer on the surface of hydrating tricalcium silicate particles. The attractive interaction between the positive mineral surface and the negative latex surface appears to be the driving force for adsorption. In line with this, adsorption is reduced by sulfate anions, which adsorb specifically onto the silicate surface. Compared to tricalcium silicate, portlandite and gypsum interact only marginally with the latex particles. Our results show that the stability of the nonionic surfactant/latex/cement systems is essentially controlled by the latex colloidal stability and the latex-cement interactions, the surfactant having little direct interaction, if any, with the mineral surfaces.     

吸附与润湿I非离子表面活性剂在SiO2/水和SiO2/环己烷界面的吸附层结构

根据Triton X-100在硅胶/水和硅胶/环己烷界面以及Triton x-305在硅胶/水界面的吸附结果,提出了两种简单的吸附模型,在硅胶/环己烷界面上形成的是单分子吸附层,吸附质分子以乙氧基链躺在硅胶表面上而以碳氢链伸入环己烷的方式取向.在硅胶/水界面上形成的是双分子吸附层,第一层中的分子以乙氧基链躺在硅胶表面上而以碳氢链朝外;第二层中的分子取向相反,即以碳氢链朝向第一层分子形成的碳氢链层,而以乙氧基链伸进水中,对石英玻璃-水-环己烷的接触角(θ水)的测定结果表明,θ水随水相中表面活性剂浓度的增加先升后降,进一步支持了上述吸附模型。     

Adsorption of four non-ionic cellulose derivatives on cellulose model surfaces

The adsorption of four commercial non-ionic cellulose derivatives onto two different model surfaces of cellulose fibres has been studied with surface plasmon reflectance. The model surfaces of cellulose were ultrathin films of either nano fibrillated cellulose or regenerated cellulose on Au(s). Partial least squares models were used in the analysis of the data and it was found that the type of cellulose model surface seems to be most important for both the total adsorption and the initial adsorption rate of the studied cellulose derivatives. It is believed that this can be explained by morphological differences between the surfaces, and it was found that the properties of the cellulose derivatives that affect the adsorption of the two types of cellulose surface differ. For adsorption onto a NFC-based model surface, the type of cellulose derivative and the polydispersity index (PDI) of the cellulose derivative seem to be the two most important variables for the observed adsorption of these cellulose derivatives. For the regenerated cellulose surface the three most important variables are the M _n of the cellulose derivatives, the DS _NMR of the methyl celluloses, and PDI of the cellulose derivatives. Thus the adsorption of cellulose derivatives on the NFC-based cellulose model surface is strongly affected by the type of substituent, while the same cannot be said for a surface regenerated from N-methylmorpholine-N-oxide. Additionally, the DS _NMR of methyl celluloses affects their adsorption differently on the investigated cellulose model surfaces.     

Surface enhanced Raman scattering of surfactants adsorbed on silver mirror surfaces

The surface enhanced Raman scattering (SERS) spectra of two surfactants: Triton X-100 and n-hexadecylpyridinium bromide adsorbed on the interfaces between chemically reduced silver mirrors and water are obtained. By comparing and analyzing their bulk and SERS spectra, we have studied the adsorption configurations of the two surfactants on the silver/water interfaces.     

Adsorption relaxation for nonionic surfactants under mixed barrier-diffusion and micellization-diffusion control

Relaxation processes of surfactant adsorption and surface tension, which are characterized by two specific relaxation times, are theoretically investigated. We are dealing with fluid interfaces and small initial deviations from equilibrium. For surfactant concentrations below the critical micellization concentration (CMC), we consider adsorption under mixed barrier-diffusion control. General analytical expressions are derived, which are convenient for both numerical computations and asymptotic analysis. Series expansions for the short- and long-time limit are derived. The results imply that the short-time asymptotics is controlled by the adsorption barrier, whereas the long-time asymptotics is always dominated by diffusion. Furthermore, for surfactant concentrations above the CMC, adsorption under mixed micellization-diffusion control is considered. Again, a general analytical expression is derived for the relaxation of surfactant adsorption and surface tension, whose long- and short-time asymptotics are deduced. The derived equations show that at the short times the relaxation is completely controlled by the diffusion, whereas the long-time asymptotics is affected by both demicellization and diffusion. The micellar effect is manifested as an exponential (rather than square-root) decay of the perturbation. The derived expressions are applied to process available experimental data for the nonionic surfactant Triton X-100 and to determine the respective demicellization rate constant.     

Characterization of the adsorbed layer of a mixture of nonionic and cationic hydrocarbon surfactants on silica

The adsorption of hexadecyl trimethylammonium bromide (HDTAB) and nonylphenyl polyglycol ether (NP20) from mixed aqueous solutions on silica has been investigated. The adsorption from mixed solutions is enhanced at low concentration, but is decreased at high concentration compared with those of the single surfactants. Further, measurements of fluorescence spectra of pyrene-3-carboxaldehyde and of ESR spectra of 2,2,6,6-tetramethylpiperidinyl-1-oxy in the surfactant adsorbed layer indicate that the micropolarity of the adsorbed layer is affected by feed mole fraction of HDTAB, in particular over the range of 0.3–0.7, while the microviscosity of the adsorbed layer is almost constant in the same range at a high feed concentration. This suggests that over the same range, the ratio of HDTAB/NP20 at the second layer is almost the same.     

Interactions between nonpolar surfaces in mixed solutions of cationic and nonionic surfactants

The interaction energy between hydrophobic SiO₂ particles in aqueous solutions of a cationic surfactant (dodecylpyridinium bromide, DDPB), a nonionic surfactant (Triton X-100, TX-100), and their mixed solutions was measured as a function of concentration. Synergism has been observed in mixed surfactant solutions: the surfactant concentration required for achieving the set interaction energy in the mixed solutions was lower than in the solutions of the individual surfactants. The molecular interaction parameters in surfactant mixtures were calculated using the Rosen model. Chain-chain interactions between nonionic and cationic surfactants were suggested as the main reason for the synergism.     

Adsorption of carboxymethyl cellulose on polymer surfaces: evidence of a specific interaction with cellulose

The adsorption of carboxymethyl cellulose (CMC), one of the most important cellulose derivatives, is crucial for many scientific investigations and industrial applications. Especially for surface modifications and functionalization of materials, the polymer is of interest. The adsorption properties of CMC are dependent not only on the solutions state, which can be influenced by the pH, temperature, and electrolyte concentration, but also on the chemical composition of the adsorbents. We therefore performed basic investigation studies on the interaction of CMC with a variety of polymer films. Thin films of cellulose, cellulose acetate, deacetylated cellulose acetate, polyethylene terephthalate, and cyclo olefin polymer were therefore prepared on sensors of a QCM-D (quartz crystal microbalance) and on silicon substrates. The films were characterized with respect to the thickness, wettability, and chemical composition. Subsequently, the interaction and deposition of CMC in a range of pH values without additional electrolyte were measured with the QCM-D method. A comparison of the QCM-D results showed that CMC is favorably deposited on pure cellulose films and deacetylated cellulose acetate at low pH values. Other hydrophilic surfaces such as silicon dioxide or polyvinyl alcohol coated surfaces did not adsorb CMC to a significant extent. Atomic force microcopy confirmed that the morphology of the adsorbed CMC layers differed depending on the substrate. On hydrophobic polymer films, CMC was deposited in the form of larger particles in lower amounts whereas hydrophilic cellulose substrates were to a high extent uniformly covered by adsorbed CMC. The chemical similarity of the CMC backbone seems to favor the irreversible adsorption of CMC when the molecule is almost uncharged at low pH values. A selectivity of the cellulose CMC interaction can therefore be assumed. All CMC treated polymer films exhibited an increased hydrophilicity, which confirmed their modification with the functional molecule.     

Clouding and phase behavior of nonionic surfactants in hydrophobically modified hydroxyethyl cellulose solutions

Clouding phenomena and phase behaviors of two nonionic surfactants, Triton X-114 and Triton X-100, in the presence of either hydroxyethyl cellulose (HEC) or its hydrophobically modified counterpart (HMHEC) were experimentally studied. Compared with HEC, HMHEC was found to have a stronger effect on lowering the cloud point temperature of a nonionic surfactant at low concentrations. The difference in clouding behavior can be attributed to different kinds of molecular interactions. Depletion flocculation is the underlying mechanism in the case of HEC, while the chain-bridging effect is responsible for the large decrease of cloud point for HMHEC. Composition analyses for the formed macroscopic phases were carried out to provide support for associative phase separation for the case of HMHEC, in contrast to segregative phase separation for HEC. An interesting three-phase-separation phenomenon was reported in some HMHEC/Triton X-100 mixtures at high surfactant concentrations.     

Adsorption of mixtures of nonionic sugar-based surfactants with other surfactants at solid/liquid interfaces II. Adsorption of n-dodecyl-beta-D-maltoside with a cationic surfactant and a nonionic ethoxylated surfactant on solids

Synergy and antagonism between sugar-based surfactants, a group of environmentally benign surfactants, and cationic surfactants and nonionic ethoxylated surfactants have been investigated in this study with solids which adsorbs only one or other when presented alone. Sugar-based n-dodecyl-beta-D-maltoside (DM) does not adsorb on silica by itself. However, in mixtures with cationic dodecyltrimethylammonium bromide (DTAB) and nonionic nonylphenol ethoxylated decyl ether (NP-10), DM adsorbs on silica through hydrophobic interactions. In contrast, although DM does adsorb on alumina, the presence of NP-10 reduces the adsorption of DM as well as that of the total surfactant adsorption. Such synergistic/antagonistic effects of sugar-based n-dodecyl-beta-D-maltoside (DM) in mixtures with other surfactants at solid/liquid interfaces were systematically investigated and some general rules on synergy/antagonism in mixed surfactant systems are identified. These results have implications for designing surfactant combinations for controlled adsorption or prevention of adsorption.     

Computer simulation of adsorption kinetics of surfactants on solid surfaces

Adsorption kinetics of surfactants on solid surfaces has been studied by using computer simulation. Both bulk surfactant concentration and diffusion region are explicitly integrated in our model. Depending on the head-surface interaction, our simulation results indicate that there exist two different kinetic modes in adsorption process of surfactants on solid surfaces. One is the four-regime mode and the other is step-wise mode. For the strongly attractive head-surface interaction, four distinct regimes of surfactant adsorption are found: a diffusion-controlled regime, a self-assembly controlled regime, an intermediate coverage regime and a saturated regime. In particular, the adsorption in second regime displays a power-law time dependence with an exponent unrelated to bulk concentrations and diffusion coefficients. While for the weaker adsorption surfaces, the step-wise mode is found. The mode includes a low-coverage nucleation regime and the saturated regime after a sudden aggregation of surfactants on the substrates which occurs stochastically. Besides the head-surface interaction, in this work, the effects of surfactant diffusivity, bulk concentration, the length of diffusion zone and surfactant architecture on the adsorption kinetics are also considered. The simulated adsorption kinetics is compared qualitatively with experimental results.     

AFM of adsorbed polyelectrolytes on cellulose I surfaces spin-coated on silicon wafers

Thin layers of cellulose I nanocrystals were spin-coated onto silicon wafers to give a flat model cellulose surface. A mild heat treatment was required to stabilize the cellulose layer. Interactions of this surface with polyelectrolyte layers and multilayers were probed by atomic force microscopy in water and dilute salt solutions. Deflection–distance curves for standard silicon nitride tips were measured for silicon, cellulose-coated silicon, and for polyelectrolytes adsorbed on the cellulose surface. Transfer of polymer to the tip was checked by running deflection–distance curves against clean silicon. Deflection–distance curves were relatively insensitive to adsorbed polyelectrolyte, but salt addition caused transfer of cationic polyelectrolyte to the tip, and swelling of the polyelectrolyte multilayers.     

Adsorption and spectral studies of 3,6-diaminoacridine adsorbed on montmorillonite clay and cellulose

Montmorillonite-and cellulose-adsorbed 3,6-diaminoacridine are prepared. The adsorption isotherm studies show that while 3,6-diaminoacridine molecules are adsorbed in the interlayer spaces of the montmorillonite clay, the dye molecules are adsorbed on the surface of cellulose. Quenching studies reveal that the Al³⁺ ions of the aluminosilicate layers of the clay also quench the excited state emission of the adsorbed 3,6-diaminoacridine.