Small angle neutron scattering studies on micellar systems part 2. Mixed systems of ammonium decanoate and ammonium perfluoro-octanoate

Mixtures of ammonium decanoate (AmDec) and ammonium perfluoro-octanoate (APFO), in ammonium chloride: ammonium hydroxide buffer at pH 8.8 and an ionic strength of 0.1, were examined by small angle neutron scattering with varying proportions of the two surface active agents. The results indicated that mixed micelles were formed and it is suggested from analysis of the data that these were cylindrical in shape at APFO: AmDec ratios of 21, 11 and 12. At 21 and 11 the micelles were found to contain more APFO than expected on the basis of ideal mixing of the surface active agents in the micelle. At a ratio of 19 the micelles were found to be spherical but larger than those formed from AmDec alone. A speculative model is proposed for the mixed micelle which still, however, allows for segregation between hydrocarbon and fluorocarbon chains within the micelle.     

Small-angle neutron scattering on shear-induced micellar structures

Small-angle neutron scattering (SANS) experiments on sheared aqueous surfactant solutions of tetradecyltrimethylammoniumsalicylate (TTMA-Sal) are reported. A5-mM-solution without shear shows a weak correlation peak at a momentum transfer of 0.09 nm^–1 which has its origin in the micellar interaction. For shear rates above a threshold value of =40 s^–1 the scattering pattern shows an irregular increase in anisotropy. The analysis of the anisotropic pattern reveals the existence of two types of micelles: Small rodlike micelles which are weakly aligned and very large rodlike aggregates which are strongly aligned and which are present above the threshold value of. The two micelles are in equilibrium with each other and the equilibrium shifts with increasing shear rate to the side of the large oriented micelles.     

Structure of casein micelles I. Small angle neutron scattering and light scattering fromβ- andχ-casein

Casein is the main protein component of milk and is of remarkable colloidal stability. Under the influence of milk clotting enzymes casein shows the striking behaviour of coagulation. This clotting process has already been studied by other groups, neglecting the fact that casein is not a homogeneous protein. The purpose of the present study is focused, in this first stage, on the determination of the structure of the various casein components. In cooperation with other laboratories we have been able to obtain the well separated individual proteins. Studies have been performed so far with- and-casein. For detailed structural information we carried out small angle neutron scattering and combined static and dynamic light scattering measurements and determined the molecular weight,M _w, the radius of gyration, S ² the hydrodynamic radius,R _H, the-value and the particle scattering factor, P_z(q). The two caseins show a strikingly different behaviour. For the-casein we found a star-like structure, i. e. an aggregation pattern that is expected for a common micelle. The micelle consists of about 38 monomer chains. The aggregates of-casein appear to be composed of star-like submicelles, where each submicelle contains nine-casein chains and the total degree of aggregation is about 140.     

Physical gels from PVC: molecular structure of pregels and gels by low-angle neutron scattering

In this paper we report on investigations into the short-range molecular structure of pregels (aggregates formed in dilute solutions) and gels as a function of ageing time, temperature and solvent type. In some solvents (diethyl oxalate and bromobenzene) it is found that the structure of the pregels is cylinder-like or ellipsoid-like. The structure is seen to be the same for the gels and the pregels in the investigated range of transfer momentum which leads us to conclude that the gels are probably fiber-like, a statement in agreement with the morphology observed by Yang and Geil. The fiber section is also about the same order of magnitude as that reported by these authors. Also, further evidence is given for the existence of a second type of physical knot, different from those formed by the more syndiotactic sequences. The validity of the molecular structures deduced from these experiments is discussed in the light of macroscopic properties such as compression modulus and swelling.     

Small-angle neutron scattering of colloidal silica dispersions in a non-polar solvent

Small-angle neutron scattering studies were performed on dilute dispersions of colloidal silica spheres in mixtures of h₁₂- and d₁₂-cyclohexane. The particles consisted of a SiO₂-core and a layer of stearyl alcohol molecules terminally attached with a chemical bond (Si-O) to the particle surface. The contrast variation method was applied to reveal the internal structure of the particles. The matchpoints determined with this method were in accordance with those calculated from the mass density of the particles and the atomic composition, as determined with elemental analysis.For a detailed interpretation of the scattering curves, we assumed that the particles were spherosymmetrical and consisted of two concentric layers. With the relation we derived between the radius of gyration and the reciprocal contrast for such a model, it was possible to determine all the parameters characterizing the particle in terms of this model. The model calculations performed using these parameters fitted very well to the experimental intensities for high contrasts. For lower contrasts, the fit was somewhat less good. This is probably due to random fluctuations in the scattering length density within the particle core.The different radii as found by neutron scattering, agreed very well with those determined using other techniques, such as light scattering (static and dynamic) and electron microscopy.     

Counter ion condensation on mixed cationic/nonionic micellar systems: Bjerrum's electrostatic condition

The association of counter-ions with mixed ionic/nonionic micelles has been investigated in the case of dodecyl/tetradecyl/ and hexadecyl-trimethylammonium bromide with two nonionic surfactants: dodecylpolyoxyethylene 23 and Triton X-100. The degree of association has been measured by potentiometry using a Bromide ion-selective electrode. Previous results with sodium and copper dodecylsulfate suggesting that in the nonionic-rich composition domain, bare mixed micelles are formed without associated counter-ions have been confirmed. These results are in agreement with the prediction of Bjerrum's condition for ion association. The effect of copper dodecylsulfate on the cloud point of Triton X-100 has also been determined as a means of investigating mixed micelles with multivalent counter-ions. The dramatic cloud point increase observed, even larger than with sodium dodecylsulfate, has been discussed as evidence of the solvation of divalent ions by ether groups, a factor which complicates the analysis of multivalent counterion condensation on mixed micelles.     

Shear-induced deformation of polystyrene coils in dilute solution from small angle neutron scattering 2. Variation of shear gradient,molecular mass and solvent viscosity

The technique of small angle neutron scattering (SANS) has been used to study the conformation of polystyrene chains in dilute solution under a constant shear gradient. The experiments reveal a distinct anisotropy of the molecular dimensions with regard to the directions parallel and perpendicular to the flow direction on the 2D-multidetector. The deformation ratio of the single polymer chain (R ²/R _iso ² )–1 as a function of the reduced shear gradient=([] · · M _w G)/RT shows a transition from the ideal ²-behaviour for dynamic infinitely flexible coils found at small gradients, to a behaviour with smaller increase at larger. These results are qualitatively consistent with the theory of Cerf for a polymer with finite internal viscosity in a shear gradient. At low(<1), a better agreement with the model of a free-draining coil (Rouse behaviour) than with the Zimm model is observed.     

Solutions of alkali soaps and water in fatty acids XI. Correlation between the acid sodium octanoate in the most water-rich part of the L2-phase and the acid soaps in two adjacent phases

The special nature of the outer-most water-rich region of theL ₂-phase in the ternary system sodium octanoate-octanoic acid-water is evidenced by its somewhat turbid appearance and by the character of its equilibria with adjacent phases. The phase contains aggregated acid sodium octanoate which is dispersed in a very dilute aqueous solution of sodium octanoate. The acid octanoate has the composition 1 NaC₈2 HC₈x H₂O and is composed of closely packed amphiphilic units, all with the polar groups in the same direction. This acid soap obviously forms double-layered aggregates with the lipophilic hydrocarbon chains pointing inwards and the polar groups pointing outwards towards the surrounding bulk-water. The phase is formed when octanoic acid is added to theL ₁-phase of the system just above the l.a.c.; in this aqueous solution, the acid reacts with dissolved acid octanoate 1 NaC₈1 HC₈x H₂O and that results in the formation of the slightly soluble acid soap 1 NaC₈ 2 HC₈x H₂O that separates as a new phase, the turbidL ₂ phase. On further addition of octanoic acid, the content of the mentioned acid soap increases until the solution phase is transformed into a liquid crystalline lamellarD-phase with the same acid soap composition. This formation of acid soap 1 NaA2 HA on addition of fatty acid to the dilute soap solution just above the l.a.c., has been known for a long time to occur in various systems containing a long-chain sodium soap. However, at suitably low temperatures, the reaction in these systems does not result in separation of the acid soap in the liquid crystalline, but in the solid crystalline state.     

Small angle X-ray scattering study of an extremely elongated micelle system of CTAB-p-toluidine solution

Whenp-toluidine is added to an aqueous solution of CTAB, a remarkable increase of viscosity is accompanied by a spectacular elasticity. We detected the existence of extremely elongated rod-like micelles in electron micrographs. SAXS measurements indicate a closely packed array of cylindrical rod-like micelles, brought about when solutions flow through a thin capillary. A scattering maximum ofd=160 Å almost corresponds to the distance between the nearest neighbours of the cylindrical rod-like micelles. This value agrees with the diameter measured on electron micrographs. The second broad peak (d=75 Å) is assigned to a subsidiary maximum of the shape function of the cylinder with infinite length.     

Spinodal decomposition of the polymer blend deutereous polystyrene (d-PS) and polyvinylmethylether (PVME) studied with high resolution neutron small angle scattering

Decomposition of a polymer blend in the miscibility gap has been studied by small angle scattering of neutrons, using a double crystal diffractometer. It covers a range of 10^–5 to 10^–3 Å^–1, which connects the region of elastic light scattering and, at the upper end, the region of conventional neutron small angle scattering instruments. The decomposed structure in the miscibility gap can be described by a characteristic lengthR which increases with time,t ^1/3 between 7 and 25 min. At longer times, the growth follows a more linear power law. This behaviour is consistent with predictions of the domain growth for liquid mixtures and is estimated by using the self diffusion constant, viscosity, and the surface energy of the polymer.on leave ESFM-IPN Mexico     

Steric fitting of the spherical micelle size

A model was developed to explain the size of spherical micelles on the basis of steric effects. Here the electrostatic repulsion within polar heads is considered as a steric effect. The predictions of this model concerning micelle size; water penetration into the hydrocarbon micelle core; and the dependence of the aggregation number on temperature, electrolyte addition, hydrocarbon chain length, head group size, and counterion size agreed quite well with literature data.     

Small angle neutron scattering studies on non-aqueous dispersions of calcium carbonate. Part III. Concentrated dispersions

Small angle neutron scattering has been used to examine calcium carbonate dispersions in toluene over the w/w concentration range 5 to 40 %. The particles were stabilised by a combination of a surface active agent and a linear polymeric molecule. Analysis of the experimental data gave results for the structure factorS(Q) and the pair correlation functiong(r).Theoretical computations of the structure factor were made using a hard sphere model and the mean spherical approximation approach. These analyses indicated that the interaction was essentially soft at low volume fractions but became hard at the higher volume fractions.     

The dynamik contact angle II. Investigation of the adsorption mechanism based on the measurement of the preceding contact angles

The structure of the adsorption layer at the solid/gas interface is characterized, as a function of conditioning concentration, by the measurement of preceding contact angles. The contact angles were determined tensiometrically (plate method) and cinema tographically (capillary rise method) in the system glass or mercury/n-dodecyl ammonium chloride solution/air, respectively. In the dependence of contact angle on concentration, four regions are provable. These regions correlate with the surfactants, which are bound to adsorption in a heteropolar mode or by van der Waals forces of interaction, with the formation of layer-like coverage and with bilayers. Special attention was given to the fact that loosely bound surfactants are transferred from the solid/gas interface to the liquid/gas interface and cause a reduction of the preceding contact angle.Publication No. 1077 from the Research Institut of Mineral Processing, Academy of Sciences of the GDR, Freiberg, G.D.R.     

Formamide,a water substitute XIV (1) waterless microemulsions 8. Structural analysis by X-ray scattering of CTAB aggregates in formamide and in the microemulsion system (formamide,CTAB, isooctane, 1-butanol)

X-ray scattering was used to analyse the structures of aggregates of CTAB in various formamide-containing media.Firstly, CTAB micelles were detected in formamide solutions. A spherical micelle model was proposed; at values close to the CMC, smaller micelles were observed in formamide than in water.Secondly, the structure of microemulsions in the isooctane-rich zone of the system (formamide/CTAB=2, isooctane, 1-butanol) was studied by X-ray scattering. The structure was found to be quite different in this zone from that normally observed in aqueous microemulsions. Structures compatible with small filaments of formamide were detected. The results were related to previous measurements of electrical conductivity.     

Thermodynamics of mixed micellar systems of sodium octanoate and ethoxylated alcohols in water at 25°C

Thermodynamic volume and compressibility properties of binary aqueous systems of sodium octanoate (C₈Na) and polyoxyethylene butyl ether compounds (ethoxylated alcohols), with one to three oxyethylene groups (C₄EO_X), and ternary systems of these compounds, have been determined as a function of surfactant and alcohol concentrations at 25°C from density and ultrasonic velocity measurements. Values of standard state apparent molar volume and apparent molar adiabatic compressibility properties of transfer of ethoxylated alcohols from water to aqueous C₈Na solutions were obtained. The observed trends in the properties of the aqueous binary C₈Na systems and of the transfer functions for C₄EO_x, at a given low concentration of 0.05m, were analyzed using theoretical models. Good agreement between the simulated results and the experimental data was achieved. The results obtained for the distribution coefficients of the alcohols and the thermodynamic properties of both components of the mixed micelle show that the hydrophobicity of the ethoxylated alcohols is enhanced by introducing more oxyethylene groups into the alcohol. The distribution behavior of these compounds between the C₈Na micelles and the aqueous phase also depends on the difference between the hydrophobicity of the surfactant and the alcohols.     

Mass,size and shape of micelles formed in aqueous solutions of ethoxylated nonyl-phenols

The study was extended to analysis of mass, size and conformation of micelles formed in aqueous solutions of ethoxylated nonyl phenols. The results obtained by ultracentrifugal technique between 293 and 323 K have proved that the slightly ethoxylated nonyl phenols form micelles with high molecular mass and larger size at constant temperature, while the increasing length of the ethylene oxide chain favours formation of micelles of smaller molecular mass and size. The transformation of conformation from oblate to spherical shapes ensues with increasing temperature at constant ethoxy number or with ethoxylation at constant temperature. The second virial coefficient decreases with increasing temperature and decreasing ethoxy number. In accordance with the earlier conclucions, the change of the second virial coefficient relates to enhanced variation of monomer solubility, stabilization of micelle structure and increased deviation from ideal behaviour of a given micellar system.Symbols a major axis of micelle, Å - a _m attractivity factor, cm³ erg molecule² - b minor axis of micelle, Å - c concentration, g dm^–3 - c _b equilibrium concentration at the bottom of the cell, g dm^–3 - c _m equilibrium concentration at the meniscus of the cell, g dm^–3 - c _o initial concentration in the cell, g dm^–3 - c _M critical micellization concentration, mol dm^–3 - e eccentricity - f _IS Isihara-constant - f/f _o frictional ratio of micelle - amount of water in micelle per ethoxy group, mol H₂O/mol EO - n aggregation number, monomer micelle^–1 - n _EO number of ethoxy groups - r distance of Schlieren peak from the axis, cm - r _b distance of cell bottom from the axis, cm - r _m distance of cell meniscus from the axis, cm - R _h equivalent hydrodynamic radius of micelle, Å - s _t sedimentation coefficient, s - reduced sedimentation coefficient, s - reduced limiting sedimentation coefficient, s - ¯v _t volume of micelle, cm³ micelle^–1 - partial specific volume of solute, cm³g^–1 - partial specific volume of solute reduced to 293 K, cm³ g^–1 - B _a, B_e constants, cm³ mol g^–2 - B ₂ second virial coefficient, cm³ mol g^–2 - M _m ^a mass average apparent molecular mass of micelle, g mol^–1 - M _m mass average molecular mass of micelle corrected withB ₂, g mol^–1 - M _m ^cM mass average molecular mass of micelle belonging toc _M, g mol^–1 - M ¹ mass average molecular mass of monomer, gmol^–1 - N _A the Avogadro's number, molecule mol^–1 - R universal gas constant, erg mol^–1 K^–1 - T temperature, K - _t ^o dynamic viscosity of solvent atT temperature, g cm^–1 s^–1 - dynamic viscosity of solvent at 293 K, g cm^–1 s^–1 - _t density of solution atT temperature, g cm^–3 - _t ^o density of solvent atT temperature, g cm^–3 - density of solvent at 293 K, g cm^–3 - angular velocity, rad s^–1 - time, s     

Effect of polymerized silicic acid on mixed lipid-protein monolayers used as cell membrane models. I. Hemoglobin-stearoyl erythroceramide films

The effect of polysilicic acid on mixed monolayers of hemoglobin and stearoyl erythroceramide used as cell membrane models has been studied. The presence of the sphingolipid at the interface stabilizes the hemoglobin monolayer, hindering expulsion of its residues from the surface when the collapse pressure (ca. 23 mN/m) is reached. The interaction between the components of the mixed film results in non-additivity of their molecular areas to a degree depending on film composition and substrate pH. The presence of polysilicic acid in the substrate increases the miscibility of the components in the mixed monolayer as a result of ionic interaction between the silicic acid and the protein.     

Small angle neutron scattering studies on nonaqueous dispersions of calcium carbonate Part 2. Determination of the form factor for concentric spheres

Colloidal dispersions of calcium carbonate, stabilised primarily by a surface active agent, in both toluene and dodecane have been examined by small angle neutron scattering. A model has been developed to simulate the scattering behaviour of the particles and is based on the idea of a concentric sphere with a homogeneous layer of adsorbed material surrounding a core particle. Computations based on the model show a wide variation of scattering behaviour with variation of the coherent scattering length of the dispersion medium. These predictions were confirmed by experiment. A method is described for analysis of the experimental data which leads to a determination of the thickness of the adsorbed layer, the radius of the core particle and the standard deviation of core particle radius.     

X-ray diffraction studies on homologous thallium soaps below the temperature range of the neat phase 1. Calculation and comparison of the structure parameters of unit cells

The results of X-ray diffraction patterns of homologous thallium soaps TlC _n (n-8, 9, 10, 11, 12, 14, 15, 16, 17, 18, 20 and 22) in dependence on the temperature showed that the structures of the phases below the temperature range of the liquid-crystalline neat phase (so called phase C₁, phase C₂, phase I, phase II) are crystalline-like, not liquid-crystalline.As function of the chain length of the fatty acid group, we found the following phase sequences to be a function of temperature: TlC₈: phase Ineat phase: TlC₉–Tl₁₄: phase C₂phase IIphase Ineat phase; TlC₁₅, TlC₁₆: phase C₁phase IIphase Ineat phase; TlC₁₇–TlC₂₂: phase C₁phase IIneat phase.From the X-ray patterns of the thallium soaps were calculated the lattice parameters and the unit cells of these homologues at various temperatures. The comparison between the lattice parameters of the homologues showed, surprisingly, that these parameters were independent of chain length and temperature. This X-ray data are the basis for the following development of structure models of the phase C₁, phase C₂, phase I, and phase II, including the neat phase (see Part 2).     

Free radical copolymerization of 1-vinyl naphthalene with styrene,methyl methacrylate,and acrylonitrile

Investigations on free radical copolymerization of 1-vinyl naphthalene (1-VNph, monomerM ₂) with styrene (St), methyl methacrylate (MMA) and acrylonitrile (AN) (monomersm ₁) in bulk at 60°C with AIBN as initiator are presented. Relative reactivity ratios were calculated by the Kelen-Tüdös method yielding:r _st=0.70 ±0.23 andr _1–VNph=2.02 ±0.40 for system St/1-VNph;r _MMA=0.32 ±0.10 andr _1–VNph=0.57 ±0.07 for system MMA/1-VNph andr _AN=0.11 ±0.03 andr _1–VNph=0.45 ±0.09 for system AN/1-VNph.Q, e values for 1-VNph according to Alfrey, Price scheme were calculated toQ _1–VNph=1.02,e ₁–VNph=–0.62.