Determination of the structure factor for concentrated silica dispersions using small angle x-ray scattering. II. Experiment

The structure factor of a number of silica suspensions in cyclohexane, with concentrations ranging from 0.01 to 0.714 gcm^–3, has been determined with small angle x-ray scattering, using a Kratky camera. The experimental structure factor is compared with a theoretical one for which polydispersity effects on the particle scattering factor and on the structure are explicitly taken into account.Analysis of the scattered intensity at a scattering angle=0 shows that the particles in the suspension interact like hard spheres, with a specific hard sphere volume of 0.61 cm³g^–1. A comparison of the experimentally determined structure factor with the structure factor found by a model calculation for a polydisperse system, using the experimental particle size distribution, showed a general agreement. The height of the first maximum agreed well for all concentrations, however its position varied stronger with concentration in the experimental curves. A possible explanation of this effect is given.     

Particle stickiness variations in colloidal dispersions investigated with small-angle x-ray scattering

Small-angle x-ray scattering experiments were performed on concentrated dispersions in benzene, of silica particles coated with octadecyl-chains. Such dispersions are known to exhibit short-ranged attractive particle-interactions which depend on the temperature. At sufficiently low temperature, the attraction gives rise to a reversible phase-separation. In the present study, use was made of this phenomenon to fractionate the system. By analyzing two different fractions, the role of polydispersity in the attractive behavior was investigated.For both original and fractionated material, scattering curves were measured using a Kratky-camera equipped with a stepscanning setup and monitor-detector. The concentrations investigated were 0.033, 0.363, 0.496, and 0.628 g/ml, at temperatures ranging from 25° to 52°C.     

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.     

Morphological changes in SBS block copolymers caused by oil extension as determined by absolute small angle x-ray scattering

A series of SBS block copolymers diluted with different amounts (0–60 wt%) of three different kinds of oil were investigated: 1) lithene PM (a low molecular weight polybutadiene); 2) a paraffinic mineral oil with its electron density close to that of the polybutadiene (PB) phase; 3) a highly aromatic mineral oil with an electron density close to the polystyrene (PS) phase. All the oils seem to go into the polybutadiene matrix. Paraffinic oil and lithene form a homogeneous phase with PB; the aromatic oil at low concentrations mixes with the PB phase with a high level of inhomogeneity, while at higher concentration partial phase separation occurs. In the undiluted polymer, styrene forms cylinders in hexagonal packing. The distance between cylinders (about 43 nm) is not significantly changed upon dilution up to 33 wt%. Previously proposed changes in the morphology of PS domains at larger oil contents can be related to observed changes in the long period, in the segment length distributions, and in the homogeneities of the phase (density fluctuations). The electron density difference obtained for pure SBS is lower than the theoretical one calculated from the densities of pure PS and pure PB. Dilution by paraffinic oil improves the phase separation.     

Reversible flocculation of silica suspensions by water-soluble polymers

The possibility to concentrate, then redisperse colloidal suspensions is not only of great theoretical interest, but is also relevant to the industrial process of solid-liquid separation, which must often be followed by a redispersion stage. Up to now, these consecutive operations were unrealizable in the presence of polymers, since flocculation and adsorption were generally considered irreversible in this case. Previous studies have pointed out the occurrence of two main flocculation mechanisms: charge neutralization and interparticle bridging. The use of copolymers makes it possible to take into account these two different mechanisms together. Using this fact we prepared new copolymers of acrylamide with N-vinylimidazole via radical polymerization and characterized them by light scattering, viscometry, potentiometric titrations, and UV studies. One peculiarity of the chosen system is its dependence on pH: actually the degree of neutralization of such cationic polyelectrolytes does vary with pH, especially near the pK value. This paper shows that these copolymers may induce reversible flocculation of negatively charged suspensions, e.g., silica suspensions, by simple pH adjustment. Performances of the system were followed by various physico-chemical methods. The observed results are explained in terms of flocculation mechanisms as a function of pH.     

Small-angle x-ray scattering by crystalline polymer fibers 2. Investigation of the linear paracrystalline model using various materials

The linear position-sensitive detector is well-suited to measure quantitatively the distribution parallel to the fibre axis of the intensity of small-angle x-ray scattering (SAXS) by polymer fibres, except that in the case of four-point patterns their width is greater than that of the detector window. A method is described which overcomes this problem, and which has high angular resolution. Using this method, the variation of scattered intensity with angles from 0.3° to 2.5° has been measured for fibres of poly(ethylene terephthalate), nylon, and low density poly(ethylene) (LDPE), and compared with that predicted by the linear paracrystalline model. In all cases except LDPE, when the distribution of phase lengths was given by the Reinhold function, there was no significant disagreement between the measured and predicted scattering except for a very small range of angles on the low angle side of the peak intensity. With LDPE small but significant discrepancies were found at other angles as well, and these were worse if the symmetrical Gaussian distribution function was used. The method enabled quantitative parameters describing the morphology to be obtained. It is concluded that the morphology of the linear paracrystalline stack is consistent with the SAXS intensity distribution, and that the Reinhold function is a reasonable approximation to the distribution of phase lengths. A small modification so that this decays more rapidly at long lengths might be necessary to explain the scattering for all materials over the entire angular range and other small changes might be needed with LDPE, although the asymmetrical nature of the distribution must be retained.On leave from Department of Physics, University of Technology Malaysia, 81300 Sekudai, Malaysia.     

Sodium-aluminium-silicates in the washing process Part X. Cobuilders and optical brighteners

This study is concerned with the physico-chemical background to the substitution of phosphates in laundry detergents, with special emphasis on combinations of zeolite A with other detergent ingredients, especially water-soluble cobuilders and optical brighteners. The most important action mechanisms of zeolite A / cobuilder systems were investigated for a variety of washing conditions. It is shown that the builder performance of zeolite A is often reinforced by small amounts of water-soluble substances such as polycarboxylates. These detergents are able to compete, in terms of performance, with products containing a high proportion of phosphate. Further, the interaction of zeolite A with fluorescent whitening agents in detergent powders was studied. It is shown that the photophysical properties of a typical optical brightener are negatively influenced by ionic builders and surfactants. In contrast to sodium triphosphate, zeolite A can enhance the appearance of powders even in the presence of anionic surfactants.Lecture presented at the International Symposium on Zeolites, Zeolites as Catalysts, Sorbents and Detergent Builders, Würzburg, September 4–8, 1988.     

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.     

Swelling and dissolution of latex dispersions of the ethyl acrylate-methacrylic acid copolymers during alkalization

By using non-Newtonian viscometry and the static light-scattering method, changes in the structure of particles of latex dispersions of ethyl acrylate-methacrylic acid copolymer during alkalization with ammonium hydroxide were investigated. It was found that in dispersions with an acid content up to 20 wt% the particles only swell; at acid content between 20 and 40 wt% they decompose to smaller units represented by supermolecular aggregates of macromolecules, and only when approximately starting from 40 wt% of acid does the copolymer become molecularly dissolved. This means that even if dispersions with an acid content from c. 20 wt% are clarified by alkalization, no complete dissolution takes place.     

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.     

SAXS experiments on gel-spun polyethylene fibers

The properties of gel-spun polyethylene fibers hot-drawn to the maximum draw ratio depend on the spinning conditions. Different spinning conditions result in two types of structure in the paraffin oil containing fibers: an isotropic lamellar structure or a shish-kebab structure. Meridional SAXS experiments can identify the structure present. After extraction, these structures are still present but can be detected only in a more indirect way by SAXS experiments because of an excessive contribution of void scattering. During hot-drawing both structures are transformed into a more fibrillar structure. The shish-kebab structures can be drawn only to relatively low hot-draw ratios with an incomplete transformation of the lamellar overgrowth into the fibrils, as demonstrated by the presence of a meridional SAXS maximum/shoulder. This leads to relatively weak fibers. Lamellar structures can be drawn to high draw ratios by chain unfolding. A nearly complete transformation of the lamellae into fibrils is obtained and the fibers have excellent properties. The information about the morphology obtained by SAXS, DSC, WAXS, and SEM can be used to establish a relation between morphology and properties.     

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.     

Film formation with latex particles

The coalescence of latex particles is investigated through small-angle neutron scattering and electron microscopy. The particles are made of a soft polymeric core protected by a hydrophilic membrane, and they are dispersed in water. This dispersion is spread on a substrate, and water is removed to form a dry film. As the membranes of neighboring particles come into contact, they may break up to allow fusion of the particle cores. This is found to occur when the membranes are made of short-chain surfactant molecules; then all hydrophilic material is expelled to the film surface or to large isolated lumps. Alternatively, the membranes may remain until the film is completely dry; this is found to occur when they are made of hydrophilic polymers which are grafted onto the core. Hence, the fusion of particles is controlled by the connectivity of membranes.This work used the neutron beams of ILL in Grenoble and LLB in Saclay     

Changes of mesophase structure of BRIJ 96/water mixtures on addition of liquid paraffin

The influence of the addition of liquid paraffin (LP) on the structure of the lamellar (L ) and hexagonal (H₁) mesophases formed in mixtures of water (W) and BRIJ 96 (B) was studied. Mesophases were identified using polarization microscopy and small angle x-ray diffraction (SAXD). Repeat spacings were also determined with SAXD. Depending on theW/B ratio, addtion ofLP toL gives a large, almost linear one-dimensional swelling or an initial swelling followed by a gradual transition to H₁.L with a highLP-content gives a diffraction pattern showing only the first order diffraction maximum, possibly a result of undulations of the layers. The lamellar structure, however, was confirmed using freeze fracture electron microscopy (FFEM). Addition ofLP to H₁ gives an initial swelling followed by a transition to a transparent, highly viscous, isotropic phase, called the gel-phase (G). The diffraction pattern obtained fromG yields little information on its structure. A large swelling ofG withLP was observed. From the degree of swelling as a function of hydrocarbon content it was inferred that this phase consists of spherical aggregates forming a close-packed structure. Using FFEM, textures were visualized resembling those obtained from the isotropic mesophase (I₁) in water-surfactant mixtures. Finally, geometrical factors are discussed that may play a role in the formation of the gel-phase.     

Further electron microscope observations on polyethylene I. Granule structure of the melt as an artifact

There are still two opinions on the fine structure of polymer melts and glasses: (a) that the structure is similarly homogeneous to that in lower molecular weight materials and (b) that the structure shows larger short-range order regions (2–20 nm), which consist of bundeled segments of the chain molecules. Whereas opinion a relies more on indirect methods of investigation, opinion b is based mainly on fine granular structures which become visible in electron microscope investigations of surfaces of glassy solidified polymers. Such a fine structure can now be observed directly in a polyethylene melt. However, the structure is exposed as an artifact, so opinion a is supported.Dedicated to Prof. Dr. R. Bonart. Presented at the colloquium on 18.1.1985 in Regensburg on the occasion of his 60th birthday.Presented at the 32nd Meeting of the Colloid Society and Berlin Polymer Conference 1985, 2.–4.10.1985 in Berlin.     

The modification of the triple helical structure of gelatin in aqueous solution I. The influence of anionic surfactants,pH-value,and temperature

The modification of the triple helical structure in aqueous gelatin solutions by changing pH and adding alkyl sulphates at 298 K and after rechilling the solution to 283 K was investigated by CD-measurement. At 298 K the triple helical content at the IEP of the gelatin has its maximum value. It is only weakly affected by adding sodium dodecyl sulphate (SDDS) at concentrations <10^–4 M/dm³. The unfolding of the triple helix affected by pH and SDDS is reversible by rechilling the solution. The triple helical content of gelatin solutions decreases at SDDS concentrations higher than 10^–4 M/dm³. In all cases the decrease of the amount of triple helical structure is connected with an increase of the cis-configuration in single chains and leads to chain reversals. At sufficiently high SDDS concentrations-sheets are formed. These changes are thermally irreversible. Sodium decyl sulphate (SDS) has a more minor influence than SDDS except in the range of the c.m.c. of SDS. At sufficiently high SDS concentrations,-turns appear.     

Effects of thermal history on the rigid amorphous phase in poly(phenylene sulfide)

The rigid amorphous phase of semicrystalline poly(phenylene sulfide) (PPS) has been studied as a function of thermal history using scanning calorimetry, dielectric relaxation, density, and small-angle x-ray scattering (SAXS). Based on the new heat of fusion of perfect crystalline PPS, which is 26.7±0.8 cal/gram, the weight fraction of rigid amorphous phase is shown to be nearly twice as large as previously reported [1]. The mass fraction of the rigid amorphous phase ranges from 0.24 to 0.42 and is dependent upon thermal treatment. We have taken the approach of assuming a three-phase model for the morphology of semicrystalline PPS consisting of crystalline lamellae, mobile amorphous, and rigid amorphous components. Using this three-phase model, we determine that the average density of the rigid amorphous fraction is 1.325 g/cc, which is slightly larger than the density of the mobile amorphous phase fraction and was insensitive to thermal history. From the SAXS long period, the layer thicknesses of the mobile amorphous phase, rigid amorphous phase, and crystal lamellae were estimated. Only the lamellar thickness shows a systematic variation with thermal history, increasing with melt or cold crystallization temperature, or with decreasing cooling rate.     

Small-angle-X-ray scattering by crystalline polymer fibres 1. Experimental method and investigation of the linear paracrystalline model

Hosemann's formula for X-ray scattering by a linear paracrystal is investigated using the distribution of intensity parallel to the fibre axis of oriented poly(butylene terephthalate). The formula was put into a form suitable for numerical analysis, and a stepping refinement procedure used to adjust the paracrystalline parameters so that the discrepancy between the calculated and measured intensity was minimised. The measured intensity had been corrected for the spread of scattering transverse to the fibre axis before making this comparison. The pin-hole collimation system was designed so that resolution was limited only by the linear position-sensitive detector, and was good enough not to distort the recorded scattering distribution. Although parasitic scatter could not be measured to the same accuracy, it was so small that negligible error was introduced when it was subtracted. Top-hat, Gaussian and Reinhold distribution functions for the lengths of the two phases all fitted well in the region of the main peak although detailed analysis suggested significant disagreement on the low-angle side. Only the asymmetric Reinhold function fitted around the third-order peak and beyond. The range of parameter values giving a good fit for this distribution were determined.     

A structural study of the mesophases of two oxyethylene alkyl ether-decane-water systems,a comparison between technical grade C12EO〈7〉 and pure C12EO6

As part of a study polyoxyethylene alkyl ethers (C _m EO _n ), water and decane, the phase diagram and the structures of the mesophases of pure C₁₂EO₆ and technical grade C₁₂EO₇ were compared. The constructed phase diagrams of the two systems show a great resemblance except for one difference: the viscous isotropic phase is only present in the C₁₂EO₆ phase diagram.The swelling behavior of the lamellar and hexagonal phases was studied with smallangle x-ray scattering. Both the lamellar and hexagonal phases showed an ideal swelling behavior and no differences between the lamellar and hexagonal phases of the two systems were detected.With freeze-fracture electron microscopy the hexagonal and lamellar phases were visualized. No differences in the textures of the lamellar phases were found, however, the micrographs of the hexagonal phases of the two systems clearly showed different textures. While in the hexagonal phase of the C₁₂EO₆ system only infinite long rods were visualized, short interrupted rods were found in the hexagonal phase of the C₁₂EO₇ system.