Aggregation behavior and adsorption properties of salt-free catanionic surfactant mixtures containing tetradecyltrimethyl ammonium salts

The aggregation behavior of salt-free catanionic surfactants, tetradecyltrimethyl ammonium hydroxide (TTAOH)/fatty acid (FA) including octanoic acid (OA), decylic acid (DA) and lauric acid (LA) in aqueous solutions were studied. The critical micelle concentration(cmc), surface tension at cmc (γ_cmc), surface excess (Г_max), mean molecular surface area (A_min), adsorption efficiency (pc₂₀) and surface tension reduction effectiveness (π_cmc) were obtained from surface tension isotherms. The influence of temperature on the surface tension of salt-free TTAOH/FA (TTAOF) systems was investigated. Data of adsorption dynamics indicated that at fixed adsorption time, the order of adsorption capacity was TTAOH?相似文献   

Rheology and UV protection properties of suspensions of fine titanium dioxides in a silicone oil

Ultrafine particles of titanium dioxide (TiO2) are very attractive as a UV protection ingredient in cosmetic products. The UV-scattering behavior of TiO2 suspensions in a silicone oil are studied in relation to rheological properties. To control the dispersion stability of suspensions, two types of polyether-modified silicones are used as dispersants. When the suspensions are prepared with branch-type dispersants in which the polyether groups are incorporated as side chains along the backbone, the flow is shear-thinning even at low shear rates. The appearance of plateaus in the frequency-dependence curves of storage modulus implies the solidlike responses. On the other hand, the suspensions prepared with linear conformation dispersants, in which the silicone group and polyether group are alternately repeated in one long chain, are Newtonian at low shear rates. The suspensions are regarded as liquids, because the storage modulus decreases rapidly in the low-frequency region. The suspension rheology is strongly associated with flocculated structures that are primarily controlled by the interparticle attractions. The differences in rheological behavior can be explained by the differences in the adsorbed conformation of dispersant silicones. From optical measurements, it is confirmed that UV scattering increases with decreasing flocculation degree. Therefore, good agreement is established between rheological properties and UV protection ability.     

Self-assembly of fatty acid-alkylboladiamine salts

Long-chain fatty acids are insoluble in aqueous solution and form crystal precipitates. It is then of particular importance to determine the physicochemical parameters allowing their dispersion in water to improve their bioavailability and their utilization as surfactants. Herein, we report a study on salt-free catanionic systems in aqueous solution made of mixtures between palmitic or stearic fatty acids and alkylboladiamines (Abd's) differing by their alkyl chain length. Phase contrast microscopy, solid-state NMR, Fourier transform infrared spectroscopy, and small-angle neutron scattering were used to characterize the phase behavior of these systems at molar ratio of fatty acid to Abd of 1 and 2. Whatever the Abd and the molar ratio, fatty acids were embedded at low temperature in a bilayer gel phase which crystallizes after a period of rest. At an equimolar ratio, the gel phases transited upon raising the temperature to an isotropic phase made of worm-like micelles except in the case of the ethylenediamine chain for which a lamellar fluid phase was observed. At a molar ratio of 2 and high temperature, fatty acids were embedded in a lamellar fluid phase which self-orients with its stacking axis perpendicular to the magnetic field. However, for a long alkylboladiamine such as spermine, worm-like micelles formed. The phase behavior at high temperature is discussed in terms of molecular volume.     

Characterization of a Polydisperse Depletion-Flocculated Emulsion

The addition of nonadsorbing polymer to an alkane-in-water emulsion causes the droplets to flocculate into a space-spanning, stress-bearing network. We report rheological measurements of an emulsion of 1-bromohexadecane-in-water flocculated by hydroxy-ethylcellulose. Small-deformation oscillatory measurements allowed characterization of the structure during formation and an indication of the strength of the resulting network. Emulsions without polymer, and polymer solutions alone, showed essentially viscous behavior, with dominant viscous modulus over the whole frequency range (0.01-10 Hz). However, the emulsion containing polymer demonstrated a significant elastic modulus, dependent on the oil and polymer concentrations, attributable to interdroplet depletion interactions. Power-law relationships were observed between the elastic modulus, elastic strain limit, and oil volume fraction, but the indices were lower than those predicted by fractal models, giving unrealistic fractal dimensionalities. The modulus increased exponentially with polymer concentration, but the elastic strain limit was independent of added polymer. The rate of formation of the network was not consistent with diffusion-controlled aggregation. Copyright 2000 Academic Press.     

超细改性碳酸钙浓悬浮体的正负触变性

以超细改性碳酸钙、氧化钙、邻苯二甲酸二辛脂组成的浓悬浮体为对象,用触变性和屈服应力来探测悬浮体的内部结构,结合悬浮体的分散稳定性能,讨论了正负触变性的形成、稳定性和可逆转变及触变性结构的强度,并考察了游离脂肪酸对悬浮体正负触变性转化的影响.     

酸性模拟油的油水界面扩张粘弹性研究

考察了不同链长脂肪酸模拟油的扩张模量随扩张频率的变化规律,研究了碱和十二烷基磺酸钠对酸性模拟油界面扩张性质的影响.结果表明,不同脂肪酸模拟油的扩张模量随扩张频率和碳链长度的增加而增大.水相中加入十二烷基磺酸钠对酸性模拟油的扩张模量影响不大,对低工作频率下相角影响较大.无论有无十二烷基磺酸钠,水相中加入NaOH的浓度较低时酸性模拟油的扩张模量变化不大;NaOH浓度较高时,酸性模拟油的界面扩张模量增加,慢弛豫过程在界面上起主要作用,此时界面上可能形成了特殊结构.     

Effect of water on foaming properties of diglycerol fatty acid ester-oil systems

We have studied the effect of added water on the nonaqueous foaming properties of diglycerol fatty acid ester nonionic surfactant systems. Diglycerol monomyristate (designated as DGM) could not foam in nonpolar oils squalane and hexadecane at normal room temperature. Nevertheless, addition of a small amount of water induces a dramatic change in foaming properties. Both the foamability and foam stability increases with the amount of added water within the studied concentration range. Phase behavior study showed that in the dilute regions there is dispersion of solid surfactant in the aforementioned oils in the DGM systems. The particle size of the dispersed solid phase was found to be several tens of microns in the water free system, and hence it tends to coagulate and precipitate. In the case of shorter alkyl chain length, diglycerol monolaurate (DGL) surfactant-oil systems, dispersion of lamellar liquid crystal (Lalpha) is observed at room temperature, and the poor foaming properties were attributed to the large particle size of the liquid crystal. In both the DGL and DGM-oil systems, we observed a tendency of the particle size to decrease with the increasing concentration of added water. At higher temperature, the solid surfactant transforms to lamellar liquid crystal phase, and foaming is improved in the DGM/squalane system. Foams are stable for several minutes. Judging from the foaming test and particle size distribution data it can be concluded that the poor foaming in the diglycerol fatty acid esters-oil systems may possibly be due to bigger particle size, which causes precipitation. Addition of water results in the dispersion of smaller particles and improves the foaming behavior.     

Linear viscoelastic behavior of chitosan films as influenced by changes in the biopolymer structure

Films were prepared via solvent casting from different deacetylated and depolymerized chitosans obtained from β‐chitin. The linear viscoelastic behavior of the chitosan films was studied with uniaxial tensile stress–relaxation tests. All stress–relaxation profiles exhibited an asymptotically decaying trend, with a residual value different from zero, thus pointing out a solid‐like, viscoelastic behavior. The decay of the tensile modulus with time was phenomenologically described by a generalized Maxwell model consisting of three exponential functions and an equilibrium elastic modulus. Films prepared from chitosans with higher molecular weights showed higher residual elastic moduli and longer relaxation times. Within the range of the degrees of acetylation analyzed (0–27%), chitosans with the lowest and highest degrees of acetylation exhibited more pronounced solid‐like character. This behavior is explained on the basis of a complex balance between steric effects, types of intermolecular interactions, and aggregation of the chitosan samples. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 1907–1915, 2007     

Rheological properties and structures of cationic surfactants and fatty alcohol emulsions: effect of surfactant chain length and concentration

 Rheological and optical properties of cetyltrimethylammonium chloride (CTAC)/fatty alcohol (FA), behenyltrimethylammonium chloride (BTAC)/FA and CTAC/FA/hydroxyethyl cellulose (HEC) emulsions have been studied with particular emphases on the effects of FA content, the difference in the chain length of the hydrophobic groups between CTAC and BTAC, and the addition of a water soluble polymer, HEC. The effects of the FA content are to accelerate the structure development during the aging period and to increase the storage modulus, the yield stress, and the zero-shear-rate viscosity in the three emulsion systems investigated. At a low FA content of 2% w/w, lamellar and vesicular aggregates and isolated multilamellar vesicles can be observed in the CTAC/FA and BTAC/FA emulsions, respectively. At a high FA content of 6% w/w or with an excess of FA present, networklike structures and sunflower-like structures form, respectively, instead, inducing a higher entanglement storage modulus and a higher yield stress relative to those emulsions with a low FA content. The effect of adding HEC to the CTAC/FA emulsion is to reduce the entanglement storage modulus and the yield stress, consistent with the optical observation that the presence of the polymer disrupts the formations of lamella and vesicular aggregates and network structures. Received: 27 July 2000 Accepted: 28 November 2000     

Viscoelastic properties of sterically stabilized nonaqueous dispersions

The viscoelastic properties of a dispersion of poly(vinyl acetate) particles sterically stabilized by poly(2-ethyl hexyl methacrylate) and dispersed in Isopar G have been measured as a function of particle concentration and frequency at ambient temperature.At low particle concentrations, it was found that the loss modulus was larger than the storage modulus, while at high particle concentrations, i.e.,w>0.40, the storage modulus was found to be larger than the loss modulus. This inversion from a viscous to an elastic response as a function of particle concentration is attributable to the change in the configurational entropy of the steric barrier as a result of increasing the concentration of particles in the dispersion.     

Effects of steric and hydrophobic forces on the rheological properties of ZrO2 suspensions

 The effect of pH on the flow behavior of ZrO₂ suspensions containing polyacrylic and octanoic acids was evaluated. In the flocculated pH regime, the flow behavior is highly shearthinning and can be described by a power-law model. The shear-thinning behavior increases with increasing degree of flocculation. Maximum shearthinning was observed at the zero zeta potential condition. Hydrophobic interaction arising from adsorbed octanoic acid was found to enhance the shear-thinning behavior. No such enhancement was observed for adsorbed polyacrylic acid. It was also illustrated that the viscosity–pH behavior is a mirror image of the yield stress–pH behavior. A quantitative particle-pair interactions model incorporating steric and hydrophobic interactions was proposed to explain the effects of polyacrylic and octanoic acids on the maximum yield stress. Received: 23 May 1997 Accepted: 4 June 1997     

PAA/PEO comb polymer effects on rheological properties and inter-particle forces in aqueous silica suspensions

The effects of a poly(acrylic acid) (PAA)-poly(ethylene) (PEO) comb polymer dispersant on the rheological properties and inter-particle forces in aqueous silica suspensions have been studied under varying pH conditions. The comb polymer was found to adsorb more strongly under acidic than basic conditions, indicating that the PAA backbone of the copolymer preferentially adsorbs onto silica surfaces with the PEO "teeth" extending out from the surface into the solution. In the presence of low concentrations of copolymer, the silica suspensions were stable due to electrostatic repulsions between the silica surfaces. At higher copolymer concentrations and under neutral and basic conditions, where the copolymer interacted only weakly with silica, the suspensions showed a transition from a dispersed to weakly flocculated state and attractive forces were measured between silica surfaces. Under acidic conditions, the silica dispersion also destabilized at intermediate copolymer adsorbed density and then was re-stabilized at higher adsorbed coverage. The silica suspensions were stable at high copolymer coverage due to steric repulsions between the particles. The destabilization at intermediate coverage is thought to be due to polymer bridging between particles or possibly depletion forces.     

Vapor-liquid equilibria for binary mixtures of carbon dioxide and fatty acid ethyl esters

Vapor-liquid equilibria were measured and correlated using the Peng-Robinson equation of state for five binary systems of carbon dioxide and fatty acid ethyl esters (ethyl stearate, ethyl oleate, ethyl linoleate, ethyl eicosapentanoate, ethyl docosahexanoate) at 313.15 K, 323.15 K and 333.15 K. Solubility in CO₂ of fatty acid ethyl esters of equal chain length but of various degrees of unsaturation was compared. Although there was no distinct difference in solubility at lower pressures, at higher pressures (more than 15 MPa), those with a higher degree of unsaturation showed a slightly higher solubility. When the solubility in CO₂ of methyl esters and the corresponding ethyl esters were compared, it was noted that the former showed a slightly higher solubility at all system pressures measured in this work.     

Interparticle interactions in concentrated suspensions and their bulk (rheological) properties

The interparticle interactions in concentrated suspensions are described. Four main types of interactions can be distinguished: (i) "Hard-sphere" interactions whereby repulsive and attractive forces are screened. (ii) "Soft" or electrostatic interactions determined by double layer repulsion. (iii) Steric repulsion produced by interaction between adsorbed or grafted surfactant and polymer layers. (iv)and van der Waals attraction mainly due to London dispersion forces. Combination of these interaction energies results in three main energy-distance curves: (i) A DLVO type energy-distance curves produced by combination of double layer repulsion and van der Waals attraction. For a stable suspension the energy-distance curve shows a "barrier" (energy maximum) whose height must exceed 25kT (where k is the Boltzmann constant and T is the absolute temperature). (ii) An energy-distance curve characterized by a shallow attractive minimum at twice the adsorbed layer thickness 2δ and when the interparticle-distance h becomes smaller than 2δ the energy shows a sharp increase with further decrease of h and this is the origin of steric stabilization. (iii) an energy-distance curve characterized by a shallow attractive minimum, an energy maximum of the DLVO type and a sharp increase in energy with further decrease of h due to steric repulsion. This is referred to as electrosteric repulsion. The flocculation of electrostatically and sterically stabilized suspensions is briefly described. A section is devoted to charge neutralization by polyelectrolytes and bridging flocculation by polymers. A distinction could be made between "dilute", "concentrated" and "solid suspensions" in terms of the balance between the Brownian motion and interparticle interaction. The states of suspension on standing are described in terms of interaction forces and the effect of gravity. The bulk properties (rheology) of concentrated suspensions are described starting with the case of very dilute suspensions (the Einstein limit with volume fraction Φ≤0.01), moderately concentrated suspensions (0.2>Φ≥0.1) taking into account the hydrodynamic interaction and concentrated suspensions (Φ>0.2) where semi-empirical theories are available. The rheological behavior of the above four main types of interactions is described starting with "hard-sphere" systems where the relative viscosity-volume fraction relationship could be described. The rheology of electrostatically stabilized suspensions was described with particular reference to the effect of electrolyte that controls the double layer extension. The rheology of sterically stabilized systems is described using model polystyrene suspensions with grafter poly(ethylene oxide) layers. Finally the rheology of flocculated suspensions was described and a distinction could be made between weakly and strongly flocculated systems.     

Elastic modulus of poly(isobutylene oxide) crystals parallel to the chain axis

The elastic tensile modulus of the crystalline regions parallel to the chain axis E₁ for poly(isobutylene oxide) (PIBO) was determined by an x-ray diffraction method. The stress-strain (σ—ε) curve calculated from the meridional reflection of (002) shows an inflection point at about 75 MN/m² or an extension of 0.25%. The observed moduli below and above this point are 29 and 47 GN/m², respectively, at room temperature. The initial lower modulus agrees well with the value, 29.7 GN/m², calculated on the basis of the double zigzag structure of PIBO chain determined by Kaji and Sakurada. The higher modulus may be due to an intrachain steric hindrance between the hydrogen atoms of the methylenic group in the main chain and those of the two side methyl groups.     

Rheology and gelation kinetics in laponite dispersions containing poly(ethylene oxide)

We report results on the rheology of a model polymer/clay system, laponite clay particles with added poly(ethylene oxide) (PEO), focusing on the kinetics of gel formation and on molecular weight effects. We examined solutions at both pH = 7, where interparticle attractions are present and a networked gel is formed; and at pH = 10, where repulsive forces dominate and laponite forms a colloidal glass. We found that PEO of low to moderate molecular weight significantly slows down gelation and decreases the complex viscosity and elastic modulus of the dispersion by several orders of magnitude for both pH = 7 and 10. In the former case, adsorbed PEO likely forms a steric barrier to the formation of an attractive gel. In the latter case, we propose that free PEO chains in solution induce a depletion attraction between particles, preventing or slowing the formation of a colloidal glass. At higher molecular weights, PEO chains are long enough to bridge between particles and form an associative network, enhancing the viscosity and elastic modulus for both pH = 7 and 10. Finally, we have shown the critical molecular weight for transitioning between these two types of behavior scales with the interparticle distance. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 233–240, 2005     

Mesoscopic dynamics of inhomogeneous polymers based on variable cell shape dynamic self-consistent field theory

In this paper, we combine variable cell shape method with dynamic self-consistent field theory and extend to study structure and dynamics under shear for triblock copolymer melts. Due to shear, the calculation cell shape is variable and no longer orthogonal. Pseudospectral method is employed to solve the diffusion equation for chain propagator on the nonorthogonal coordinate and the shear periodical condition can be easily designed in terms of the variable cell shape method. By using this strategy, the shear induced morphology evolution is investigated for topologically complex polymeric systems such as linear and star triblock copolymers; the morphology of linear ABC triblock copolymers is more shear sensitive than that of star triblocks. In particular, once the chain propagator is obtained, the microscopic elastic stress and spatial stress distribution can be derived and thus the dynamic mechanical property can be calculated under shear. By imitating the dynamic storage modulus G' corresponding to any given morphology in the oscillatory shear measurements, we explore the relationship between the morphology and the storage modulus G' and extend to study the mechanism of phase separation dynamics as well as order-disorder transition (ODT) for linear and star triblock copolymers. The results show that the chain architecture can be easily distinguished by investigating the ODT, though the systems such as AB symmetric diblock and ABA triblock copolymers by coupling AB precursors almost exhibit similar microstructures. In addition, the storage modulus G' and loss modulus G" can be simultaneously determined in frequency sweeps of oscillatory shear measurements and the dependence of the moduli on phase separated patterns and the chain topology is investigated. The simulation findings are in qualitatively agreement with the experimental results.     

Phase Behavior and Polymorphism of Saturated and Unsaturated Phytosterol Esters

This study investigated how the physicochemical characteristics of phytosterol esters are influenced by the chain length and degree of unsaturation of the fatty acid ester moiety. Saturated and unsaturated phytosterol esters (PEs) were synthesized by the esterification of different types of fatty acids (stearic, palmitic, lauric, oleic, and linoleic acid) to β-sitosterol. The non-isothermal crystallization and melting behavior of the pure PEs were analyzed. It was proven by X-ray diffraction that saturated β-sitosteryl esters and β-sitosteryl oleate formed a bilayer crystal structure. The lamellar spacings of the bilayer structure decreased with decreasing fatty acid chain length and with an increasing degree in unsaturation. The degree of unsaturation of the fatty acid chain of the β-sitosteryl esters also influenced the type of subcell packing of the fatty acid moieties in the bilayer structure, whether or not a metastable or stable liquid crystalline phase was formed during cooling. Furthermore, it was found that the melting temperature and enthalpy of the β-sitosteryl esters increased with an increasing fatty acid chain length while they decreased with an increasing degree of unsaturation. The microscopic analyses demonstrated that β-sitosteryl oleate formed much smaller spherulites than their saturated β-sitosteryl analogues.     

Effect of chain length distribution on the phase behavior of polyglycerol fatty acid ester in water

The effect of the chain length distribution on the phase behavior, the structure of liquid crystals, and physicochemical properties was investigated in water/ polyglycerol fatty acid ester. Polyglycerol fatty acid esters with sharply distributed polyglycerol (10G*0.7L) and with broadly distributed polyglycerol (10G0.7L) were used. Unreacted polyglycerol in both surfactants was removed. 10G*0.7L forms hexagonal liquid crystals at a higher concentration than 10G0.7L. The effective cross-sectional area of the lipophilic parts in the hexagonal phase of 10G0.7L is smaller than that of 10G*0.7L owing to the difference in the chain length distribution. Evidently, 10G0.7L molecules are tightly packed in aggregates; therefore, 10G0.7L decreased the surface tension more strongly and promoted emulsification. Received: 11 January 2000 Accepted: 8 March 2000     

Structure formation and fractionation in systems of polydisperse attractive rods

Fractionation effects and the formation of structured domains are investigated in polydisperse systems of attractive spherocylinders with the help of Monte Carlo simulations. For sufficiently high attractive interaction strength and pressure, the large rods in the system aggregate and form a highly ordered hexatic monolayer that coexists with an isotropic fluid of smaller rods. Fractionation diminishes with decreasing interaction strength but is still observed for hard rod systems, in which the large rods form a nematic droplet rather than a monolayer. Results for polydisperse systems are accompanied by phase diagrams for monodisperse systems of attractive spherocylinders. Here, the phase behavior is shown as a function of rod length and pressure.