The rheology of lupin seed (Lupinus albus ssp. graecus) protein isolate films at the corn oil–water interface

Lupin seed protein isolates adsorbed at the corn oil–water interface formed, after long ageing times, interfacial films with viscoelastic properties. The viscoelastic parameters of the films, derived by analysis of creep compliance–time curves, were markedly influenced by the aqueous phase protein concentrations, pH, ageing time and isolate preparation methods. Instantaneous elastic modulus, E₀(s), showed maxima at a certain concentration which probably corresponded to monolayer saturation coverage and at pH 5.5, i.e. near to its isoelectric point, where the protein molecules are in a more compact form than at other pH values. The full fat lupin seed protein fractions gave the highest viscoelasticity values under all conditions and this in turn have an effect on the corresponding emulsion/foam stability.     

The interaction of modified 7S soy protein with mono- and di-glycerides at the oil-water interface and its effect on the stability of concentrated corn oil-in-water emulsions

The influence of chemically modified 7S fraction of soybean protein (7MSPF), and its partial replacement by mono- and di-glycerides in various ratios, on the rate of drop coalescence in concentrated corn oil-in-water emulsions has been investigated. A total emulsifier concentration of 2.0 % (wt/wt) was used. The minimum drop coalescence rate was achieved when using 1.0% (wt/wt) 7MSPF in conjunction with 0.5% (wt/wt) monoglyceride and 0.5 % (wt/wt) di-glyceride at pH 5.5. At other mono-/di-glycerides and protein/glycerides ratios, and at other pHs, the rate of drop coalescence was higher than when 2.0% (wt/wt) 7MSPF was used. The reduction in drop coalescence rate under these conditions is attributed to association of 7MSPF with the glycerides at the oil-water interface. The influence of protein/glycerides ratio on the viscoelastic properties of mixed interfacial films supports this view.     

Effects of surfactants on wave-induced drainage of foam and emulsion films

It is well established that the plane-parallel models of foam and emulsion films underestimate the velocity of film thinning by up to several orders of magnitude and show an incorrect dependence of thinning velocity on film radius. A new theory of film thinning has been previously formulated for tangentially immobile films [12, 13], and shows that the reason for this discrepancy is the neglect of experimentally observed finite amplitude surface waves. For thin films of relatively large radii (> 1o^–2 cm), the pumping of the fluid generated by oscillations of the surface waves, provides the dominant contribution to film thinning velocity. The present hydrodynamic model includes the effects of surfactants (Marangoni-Gibbs-effect, surface viscosity and surface diffusion) and surface waves on thinning velocity. As in the case of a tangentially immobile film, it is concluded that the thinning velocity varies inversely with less than the first power of the film radius, and not with the square of the film radius, as predicted by the plane-parallel models of thin film. Also, the velocity of thinning is found to be up to several orders of magnitudes larger than that evaluated from the plane-parallel models. The influence of waves in enhancing the thinning velocity is found to be most significant for a tangentially immobile film and this effect decreases by a factor of up to 3, with a decrease in surface elasticity and surface viscosity.     

Spontaneous film formation from a polymer solution

An unusual continuous film formation process of lateral pentyloxy substituted poly(p-phenylene terephthalate)s (s-PPPT) and poly(carbonate) (PC) is observed. A liquid film of polymer solution creeps over the surface of water dropped into the polymer solution. By vaporization of the solvent a solid polymer film is formed on the water surface and can be removed. The driving force for the film formation mechanism is assumed by the reduction of the surface tension of water. Experiments verify this mechanism by increasing the film formation speed using a gas stream, by reducing the formation speed through lowering the surface tension by rinsing agents, and by lowering the solubility of the polymer. As expected, no effects are found by variation of the pH-value of water. Necessary conditions for the film formation process are: good solubility of the polar polymers in organic solvents having a high vapor pressure, complete phase separation, solution density higher than water density, and a surrounding gas phase unsaturated with solvent vapor.The thickness of the mechanically stable films is less than 0.5 m. The films are amorphous by microscopical, FT-IR, x-ray, and DTA investigations.     

Overall crystallization kinetics of thin polymer films. General theoretical approach. I. Volume nucleation

A general theoretical approach of the overall crystallization kinetics of thin polymer films is developed. This new model makes it possible to calculate the evolution of the transformed volume fraction anywhere in the film, whatever the cooling conditions are. In its isothermal limit this model is equivalent to previous approaches which have been well verified by a computer simulation. In conclusion, it is pointed out that both isothermal and anisothermal determinations of crystallization kinetic parameters are greatly dependent on the sample thickness.     

Effect of polymerized silicic acid on mixed lipid-protein monolayers used as cell-membrane models II. Pepsin-sphingomyelin films

Mixed pepsin-sphingomyelin films exhibit behavior typical of bidimensional systems whose components are miscible in all proportions. The non-polar chains of their components are believed to establish weak hydrophobic interactions. The dynamic compression-expansion II-A curves obtained in the presence of polysilicic acid differ from those recorded in its absence, which may arise from an ionic interaction whereby silicate ions accommodate themselves among the film molecules and bind strongly to the sphingomyelin molecules to form a rigid surface network in which the protein molecules are trapped.     

Permeability of Newtonian black foam films to gas

The gas permeability of Newtonian black foam films, formed on the top of a small bubble at the solution surface, was studied experimentally. The aqueous solutions contained sodium dodecylsulphate with concentrations in the range 1.5×10^–4 to 3×10^–3 mol/dm³ and sodium chloride (constant concentration of 0.5 mol/dm³). A dependence of the gas permeability coefficient on the surfactant concentration was obtained. The experimental results are discussed on the basis of a theory assuming the presence of clusters of molecule vacancies (holes) in the bilayer foam film, their number and size depending on the surfactant concentration. The experimental results are in agreement with this film structure and confirm the existence of flow through both the hole-free bilayer film and the holes. It was found that the holes of three molecule vacancies make the main contribution to gas permeability at low surfactant concentration. The diffusion coefficients through the hole-free film and through the three-vacancy holes are calculated.Dedicated to Professor Dr. Armin Weiss on the occassion of his 60th birthday.     

Dynamics of hydrogen bond complexes in polymer melts

The dynamics of hydrogen bond complex formation between functional groups which are attached to a polymer chain, is studied in the molten state. The concentration of complexes in the thermodynamic equilibrium is distorted by the application of a large oscillatory strain in the nonlinear viscoelastic regime. The relaxation back to the thermodynamic equilibrium is studied as a function of the temperature in the linear viscoelastic regime. From the mechanical response the kinetic analysis can be performed using a modified Doi-Edwards theory. Using the equilibrium constants obtained from IR-spectroscopy, the rate constants for complex formation and decomplexation are obtained. The temperature dependence is equivalent to the temperature dependence of the zero shear viscosity which implies that complex formation is a diffusion-controlled process.     

Preparations and properties of polyurethane aqueous dispersion from uncatalyzed systems of H12MDI,PTAd/bisphenol A polyol,and DMPA

Aqueous dispersions of polyrethane (PU) containing ionic and nonionic hydrophilic segments were prepared in a prepolymer mixing process using substantial amount of solvent. The acid groups were neutralized with tertiary amine, and chain extension in aqueous media was carried out with triethylene tetramine. Average particle size and particle size distribution of the dispersion, and mechanical and viscoelastic properties of the emulsion cast films were determined.     

Behavior of pure and mixed DPPC liposomes spread or adsorbed at the air-water interface

Liposomes from pure dipalmitoylphosphatidylcholine (DPPC) and mixed DPPC: distearoylphosphatidylcholine (DSPC): soybean lecithin (SL) prepared by the Bangham method with sonication were dispersed into solution or spread at the interface and the kinetics of the surface film formation was studied by measuring and recording the evolution of superficial tension, surface potential, and superficial (¹⁴C labeled) DPPC density.A simple theoretical approach can describe these kinetics by two processes: irreversible diffusion of closed vesicles into or from the bulk phase, and irrevers ible transformation of closed spherical vesicles into destroyed ones which form the surface film. Diffusion controls the phenomenon for small initial amounts of liposomes.Transformation controls the phenomenon for important initial amounts of liposomes. The kinetic constant of the transformation,K, does not depend on the technique used to form the surface film (spreading or adsorption).The equilibrium and rheological properties of surface films formed after liposome spreading are compared to those of monolayers     

Crsslinking effect of ultrahigh molecular weight polyethylene-low molecular weight polyethylene blend films produced by gelation/crystallization from solutions

Polyethylene-polyethylene blend films were prepared by gelation/crystallization from semidilute solution by using ultrahigh molecular-weight (mw) polyethylene (UHMWPE) (mw=6×10⁶) and low molecular weight polyethylene (LMWPE) (mw=4×10⁴). The UHMWPE/LMWPE compositions chosen were 50/50, 67/33, and 91/9. Elongation was carried out in a hot oven at 115–130°C. The drawn films were exposed to an electron beam under nitrogen flow. Radiation doses chosen were 10, 20, 40, and 100 Mrad. crosslinking caused a significant effect in improving high temperature resistance for the blend film with draw ratio of 20 in the case of irradiation doses less than 20 Mrad. The elongation beyond 20 times and high doses beyond 20 Mrad hampered the crosslinking effect and the specimens were easily torn manually. This is thought to be due to the fact that the excess irradiation dose causes main chain scission apart from crosslinking.     

Monolayers of methacrylic polymers containing aromatic groups

Monolayers of poly-methacrylates containing either aromatic or linear side groups were studied at the air-water interface. The aim of the work is to define the role of the aromatic group in determining the interfacial distribution and orientation of these polymers. Surface pressure measurements show that all the polymers give stable expanded monomolecular films between 288 K and 308 K temperature range.Surface potential and ellipsometric measurements show that both aromatic and aliphatic polymers are in an almost horizontal conformation at the liquid-air interface. From a comparison of the experimental isotherms with Huggins' theory, it was deduced that no preferential interactions exist between benzene rings in the film. In contrast, preferential attractive energies are observed for n-alkylmethacrylates.Further information on the state of the collapsed film was obtained from electron scanning micrographs.     

The influence of surfactants on the structure of transparent gelatin films

The interference image of cold-dried transparent gelatin films containing different surfactants was determined in the conoscopic ray of monochromatic light. From the results obtained the order of the structure of gelatin in the film was characterized. Unlike the ionic surfactants (sodium dodecyl sulfate and hexadecyltrimethyl ammonium bromide), which lead to a reduction of the ordered structure, the addition of nonionic and amphoteric surfactants [ethoxylized octylphenole and a technical C₁₂/C₁₄-dipoly(oxyethylene)ammoniopropane sulfonate] causes an increase of the ordered structure of gelatin. The results quantitatively agree with those found for the influence of surfactants on the secondary structure of gelatin in diluted gelatin solutions. The influence is independent of the gelatin/surfactant ratio and has been explained by gelatin/gelatin interaction competing with the gelatin/surfactant interaction if the gelatin concentration becomes sufficiently high.     

Electron microscope study of viscoelastic cationic surfactant systems

Some cationic surfactants such as cetyltrimethylammonium bromide (CTAB) show a very spectacular viscoelasticity in solution, in even very diluted states, with some aromatic substances added, such as salicylic acid. Formerly, the authors established that the remarkable solution behaviour was the result of the entanglement of such enormously elongated giant micelles, based on recognition of the existence of large aggregates, through direct observation of them as substantial images under the electron microscope.In this report, we further confirm the relation between micelle length and solution viscoelasticity after arbitrarily obtaining different size aggregates by altering the media pH, or by admixing shorter chain length surfactants than CTAB, which alone did not induce viscoelasticity.     

Spreading and compression of n-hexadecyl acrylate at liquid-air interface

Usingn-hexadecyl acrylate, surface pressure-area (F-A) curves and equilibrium spreading pressuresF ^e were measured at various temperatures (5.7°–46°C) by the Langmuir balance (F-A) and the Wilhelmy-plate method (F ^e). At low temperatures (T<13 °C) condensed films and the liquid-condensed/solid condensed transition can be observed. At high temperatures (T>30 °C) liquid-expanded films occur. In the intermediate range the compression curves have two transition points. The transition pressureF ₁ between liquid-expanded and condensed film has a marked temperature dependence. The transition enthalpiesH ₁ decrease with increasing temperature and become zero at 29.2 °C. The second transition is related to a transition between the condensed films (F ₂). The slight temperature dependence of this transition is accompanied by an increasing change of area as well as by increasing transition enthalpiesH ₂.TheF ^e-T curve has two distinct breaks, at the melting pointT _m and atT=30 °C. The break atT _m is due to the melting process and the break atT=30 °C is caused by a phase transition between a liquid-expanded film and a condensed film.The phase diagram was constructed from the transition pressures. It can be demonstrated that the highest pressures of the thermodynamic stable film occurs atT _m. At temperaturesT>T _m equilibrium spreading pressure and equilibrium collapse pressure are identical whereas atT _m supercompression of the monolayer occurs. The film in this state behaves like a supercooled liquid. Obviously, rupture and collapse of such a film lead to a thermodynamically metastable bulk phase.     

Viscoelastic properties of polyacrylonitrile particles stabilised by a poly-2-vinylpyridine/polytert butylstyrene block copolymer

The viscoelastic properties of a dispersion of polyacrylonitrile particles stabilised by a block copolymer poly-2-vinylpyridine/polytert butylstyrene dispersed in solvesso have been measured as a function of particle concentration and frequency at ambient temperatures. At low volume fraction of particles it was found that the loss modulus of the dispersions was larger than the storage modulus, whilst at volume fractions > 0.40 the storage modulus dominates the rheology. This is attributable to there being a steric repulsion between the particles as a result of an increasing concentration of particles and the resultant reduction in interparticle separation in the dispersion. In addition the observed exponential increase of the storage modulus with increasing particle volume fraction mirrors the exponential increase in force with decreasing surface separation of the same type of polymers adsorbed to mica.     

The spinnability of viscoelastic solutions of tetradecyl- and hexadecyl-trimethylammonium salicylates

The spinnability was measured for aqueous viscoelastic solutions of tetradecyl- and hexadecyltrimethylammonium salicylates (C₁₄TASal, C₁₆TASal) in the absence and presence of sodium salicylate (NaSal) and sodium bromide (NaBr). The spinnability is classified into two types, D and C. While the intrinsic drawing length in type D is proportional to the drawing velocity, the drawing intrinsic length in type C decreases with the drawing velocity or is independent of it. The spinnability changes from type D to C, as the drawing velocity and the surfactant concentration increase, and the temperature lowers. The effect of salt is different between NaSal and NaBr. It can be assumed that a pseudo-network structure composed of rod-like micelles is formed in viscoelastic and spinnable surfactant solutions. Then, the spinnability depends on the balance between the elasticity and the viscosity in which the structure results.     

Surfactant-free emulsion polymerization of styrene using crosslinked seed particles

The aim of this research was to prepare a monodisperse polystyrene latex without surfactants adsorbed at the particle surface. Conventional polymerization formulations usually lead to large amounts of oligomers. Furthermore, they are characterized by a low reproducibility with respect to particle size. This was overcome by using a seed latex that was crosslinked in order to overcome dissolution in the monomer phase. By adjusting the seed concentration, any desired particle size in the range 0.5–1.2 m could be obtained. The monodispersity was very good.     

Aqueous dispersion of polyurethane ionomers from hexamethylene diisocyanate and trimellitic anhydride

Polyurethane (PU) ionomers were prepared from trimellitic anhydride (TMA), poly(tetramethylene adipate) glycol (PTAd), and hexamethylene diisocyanate (HDI) in acetone. Upon neutralizing the carboxylic groups with a tertiary amine (TEA), and adding water to PU ionomer solution, followed by removing the acetone, stable aqueous PU dispersions were obtained.Effects of interionic molecular weight and nonionic hydrophilic segment, viz. monofunctional ethylene-propylene oxide ether on particle, size, emulsion viscosity, mechanical, and viscoelastic properties of the emulsion cast films were examined.     

Lipolysis of didecanoyl-lecithin/triolein mixed monolayers by phospholipaseA 2

A study of enzyme lipolysis by pancreatic phospholipaseA ₂ and by vipera berus phospholipaseA ₂ on monomolecular mixed films of didecanoyl-lecithin and triolein on an aqueous subphase of pH 8 has been carried out. The influence of the composition of the mixed film, the surface pressure of the film and the amount and type of the injected enzyme on the lipolysis rate were studied.In order to relate the lipolytic activity with the monolayer state, the compression isotherms of the didecanoyl-lecithin/triolein mixed monolayers have also been obtained.The resuls are compared to observations on lipolytic activity of phospholipaseA ₂ on the didecanoyl-lecithin/cholesterol mixed monolayers. Triolein improves the kinetic conditions of the lipolysis of lecithin films in a higher degree than cholesterol. Probably it increases the enzyme penetration by the fluidifying effect exerted on the lecithin monolayers.