Anomalous elasticity of an ordered lamellar liquid foam

We investigate experimentally the linear viscoelastic properties of a lamellar liquid foam as a function of the cell size and spatial organisation. The system consists of multilamellar vesicles generated by a simple shear flow on a lyotropic lamellar phase. The vesicles can be prepared either in an amorphous or a spatially ordered state. Their size is easily tunable in the range R = 0.5-15 μm. Whereas the shear modulus of the amorphous lamellar foam is alike that of usual liquid foams or concentrated emulsions and scales linearly with 1/R, the elastic modulus of the ordered foam is almost independent of the cell size. This result --probably the first describing the elasticity of an ordered foam-like system-- remains unexplained. Received 7 August 2000     

Rheological behaviour of polyoxometalate-doped lyotropic lamellar phases

We study the influence of nanoparticle doping on the lyotropic liquid crystalline phase of the industrial surfactant Brij30 ( C₁₂E₄ and water, doped with spherical polyoxometalate nanoparticles smaller than the characteristic dimensions of the host lamellar phase. We present viscometry and in situ rheology coupled with small-angle X-ray scattering data that show that, with increasing doping concentration, the nanoparticles act to decrease the shear viscosity of the lamellar phase, and that a shear-induced transition to a multilamellar vesicle “onion” phase is pushed to higher shear rates, and in some cases completely suppressed. X-ray data reveal that the nanoparticles remain encapsulated within the membranes of the vesicles, thus indicating a viable method for the fabrication of nanoparticle incorporating organic vesicles.     

Surfactant fluorescence in the study of aggregation and clouding

The intrinsic fluorescence of Triton X-114 and Igepal CO-630 was used to monitor the aggregation behavior of micellar solutions of these surfactants. The response to changes in surfactant concentration, increases in temperature up to and beyond the cloud point, and addition of an ionic surfactant (SDS) was monitored. The intrinsic fluorescence was used to measure aggregate anisotropy as a function of SDS concentration and temperature. Relative aggregate abundance showed a minimum at the CMC, confirming the existence of premicellar assemblies. Structural differences in the hydrophobic portions of the two nonionic surfactants led to vastly different packing in their aggregates. The addition of SDS produced smaller, more closely packed micelles.     

Elasticity and polarization of Ga<Subscript>x</Subscript>Al<Subscript>1-x</Subscript>N alloys subjected to uniaxial and biaxial compression

Elasticity and polarization of Ga_xAl_1-xN alloys subjected to uniaxial and homogeneous biaxial compression are calculated using first-principles methods. The uniaxial compression along the c-axis reduces Young’s modulus along the c-axis, and enhances bulk modulus and total polarization, whereas the biaxial compression in the plane perpendicular to the c-axis enhances bulk and Young’s moduli. It is also found that when the in-plane biaxial compression is applied by constraining the a-axis lattice constant to that of AlN, the bulk and Young’s moduli dramatically increase with increasing Ga concentration, and the total polarization could be suppressed, even annihilated, and finally enhanced by controlling Ga concentration.     

The effect of excess surfactants on the adsorption of iron oxide nanoparticles during a dip-coating process

The effect of excess surfactants (oleic acids) in a colloidal solution on the adsorption behavior of 9.5-nm-sized, sterically stabilized iron oxide (γ-Fe₂O₃) nanoparticles on hydrogen terminated Si (Si:H) substrates during a dip-coating process is examined. While the particle coverage follows a type of Langmuir adsorption isotherm as initially increasing and subsequently saturating with increasing particle concentration, it also critically depends on the excess surfactant concentration in the solution. For instance, it is noted that by adding the oleic acids from 0.06 to 2.80 × 10¹⁸ ml⁻¹ in the solution with 4.65 × 10¹³ ml⁻¹ particle concentration, the coverage is gradually reduced from 0.42 to 0.25. In addition, increasing surfactant concentration distinctly changes the morphology of a self-assembled particle layer from densely distributed smaller clusters to sparsely connected, larger ones with enlarged space. The reduced coverage and enlarged cluster size with increasing oleic acid concentration are explained by the reduced interaction energy between particle and substrate and the increased capillary force between particles.     

Electrical properties and electromechanical responses of acrylic elastomers and styrene copolymers: effect of temperature

The electrical properties and electromechanical responses of acrylic elastomers and styrene copolymers were investigated towards electroactive applications such as artificial muscle and/or MEMS (micro-electro-mechanical systems) devices. The effect of temperature, between 300 and 370 K, on electrical conductivity, dielectric constant, storage and loss moduli (G’ and G”), storage modulus response (ΔG’_2 kV/mm), and the storage modulus sensitivity (ΔG’_2 kV/mm/G’₀) of acrylic elastomers and styrene copolymers were investigated under applied electric field strengths varying from 0 to 2 kV/mm. The acrylic elastomers (AR70, AR71, and AR72) possess linearly positive storage modulus responses or sensitivities with increasing temperature and dielectric constant. On the other hand, the styrene copolymers (SAR, SBS, and SIS) attain the maximum storage modulus responses or sensitivities at the glass-transition temperature of the hard segments. PACS  77.22.-d; 82.35.Lr; 83.60.Np; 83.80.Va; 91.60.Ki     

Cellular solid behaviour of liquid crystal colloids 2. Mechanical properties

This paper presents the results of a rheological study of thermotropic nematic colloids aggregated into cellular structures. Small sterically stabilised PMMA particles dispersed in a liquid crystal matrix densely pack on cell interfaces, but reversibly mix with the matrix when the system is heated above . We obtain a remarkably high elastic modulus, , which is a nearly linear function of particle concentration. A characteristic yield stress is required to disrupt the continuity of cellular structure and liquify the response. The colloid aggregation in a “poor nematic” MBBA has the same cellular morphology as in the “good nematic” 5CB, but the elastic strength is at least an order of magnitude lower. These findings are supported by theoretical arguments based on the high surface tension interfaces of a foam-like cellular system, taking into account the local melting of nematic liquid and the depletion locking of packed particles on interfaces. Received 13 March 2000 and Received in final form 6 June 2000     

Elastic properties and spectroscopic studies of lithium lead borate glasses

Elastic properties of xLi₂O — 20PbO — (80-x)B₂O₃ glasses have been measured at a frequency of 10 MHz using X-cut and Y-cut quartz transducers. The trends in the variation of elastic moduli, Poisson’s ratio and Debye temperature have been studied. The elastic moduli namely longitudinal and young’s modulus show strong linear dependence while bulk and shear modulus vary marginally as a function of Li₂O concentration. The Poisson’s ratio is found to be almost constant and Debye temperature increases with the increase of Li₂O concentration. IR, MAS-NMR and glass transition temperature studies have been also carried out. Glass transition temperature is found to increase with increase of Li₂O concentration. IR and MAS-NMR spectra show characteristic features of borate network and systematic change as a function of Li₂O concentration. The variation in the elastic properties and structural features of IR and MAS-NMR indicate that Pb²⁺ ions are likely to occupy network forming positions in this glass system. Paper presented at the 2nd International Conference on Ionic Devices, Anna University, Chennai, India, Nov. 28–30, 2003.     

Swelling kinetics of the onion phase

A theory is presented for the behavior of an array of multi-lamellar vesicles (the onion phase) upon addition of solvent. A unique feature of this system is the possibility to sustain pressure gradients by tension in the lamellae. Tension enables the onions to remain stable beyond the unbinding point of a flat lamellar stack. The model accounts for various concentration profiles and interfaces developing in the onion as it swells. In particular, densely packed “onion cores” are shown to appear, as observed in experiments. The formation of interfaces and onion cores may represent an unusual example of stabilization of curved interfaces in confined geometry. Received 6 September 2000     

Effect of melt compounding temperature on dielectric relaxation and ionic conduction in PEO–NaClO<Subscript>4</Subscript>–MMT nanocomposite electrolytes

Polymer nanocomposite electrolytes (PNCEs) of poly(ethylene oxide) and sodium perchlorate monohydrate complexes with montmorillonite (MMT) clay up to 20 wt.% MMT concentration of poly(ethylene oxide) (PEO) are synthesized by melt compounding technique at melting temperature of PEO (∼70 °C) and NaClO₄ monohydrate (∼140 °C). Complex dielectric function, electric modulus, alternating current (ac) electrical conductivity, and impedance properties of these PNCEs films are investigated in the frequency range 20 Hz to 1 MHz at ambient temperature. The direct current conductivity of these materials was determined by fitting the frequency-dependent ac conductivity spectra to the Jonscher power law. The PNCEs films synthesized at melting temperature of NaClO₄ monohydrate have conductivity values lower than that of synthesized at PEO melting temperature. The complex impedance plane plots of these PNCEs films have a semicircular arc in upper frequency region corresponding to the bulk material properties and are followed by a spike in the lower frequency range owing to the electrode polarization phenomena. Relaxation times of electrode polarization and ionic conduction relaxation processes are determined from the frequency values corresponding to peaks in loss tangent and electric modulus loss spectra, respectively. A correlation is observed between the ionic conductivity and dielectric relaxation processes in the investigated PNCEs materials of varying MMT clay concentration. The scaled ac conductivity spectra of these PNCEs materials also obey the ac universality law.     

Small angle neutron scattering study of temperature-independent formulation of mixed micellar structures

SANS measurements have been performed on mixed systems of ionic surfactant sodium dodecyl sulphate (SDS) and nonionic surfactant polyoxyethylene 10 lauryl ether (C12E10). The total concentration of the mixed system was kept fixed (10 wt%) and the ionic to nonionic surfactant ratio varied in the range 0 to 1. The temperature effect on the structures of mixed micelles has been studied for temperatures between 30 and 75°C. Micelles of pure ionic and nonionic surfactants show opposite trends when the temperature is increased. Sizes of pure ionic micelles decrease and those of nonionic micelles increase with increase in temperature. We show a formulation balancing these two effects which is temperature-independent and consists of about 25% of ionic surfactants in the mixed system. Contrast variation SANS measurements by contrast matching one of the surfactant components to the solvent suggest homogeneous single mixed micelles of the two components in the mixed systems.      

Ultrasound response of viscoelastic changes of cellulose hydrogels triggered with Sono-deviced rheometer

Sono-deviced rheometer,which enabled viscoelastic properties under ultrasound operation, was used to investigate for cellulosic hydrogels. The viscoelastic behavior was compared in cellulosic hydrogels prepared at 0.5, 1 and 2 wt% concentration in the DMAc/LiCl solution. The sono-deviced equipment could measure the effect of changes in storage modulus G’ and loss modulus G” under 43 kHz ultrasound exposure. It was noted that the 43 kHz ultrasound significantly changed the values of the G′, meaning that the hydrogel was soften under the exposure within few seconds. When the ultrasound exposed 50 W of the out-put power at 1% strain, the G′ value of 4.2x10⁴ Pa was reduced to 4.0x10³ Pa during 5 min of the US interval. The declined lowering value of G’ then returned to the original moduli value when ultrasound was stopped. The values of both G’ and G” values were measured at applied strain % during viscoelastic measurements of the cellulosic hydrogels without and with ultrasound exposure. The comparison indicated that the ultrasound has reinforced the effect of the mechanical deformation of the hydrogel structure at the smaller mechanical strain values applied during the ultrasound operation. The ultrasound soften effect on the viscoelastic change efficiently occurred in the 0.5 wt% sample and easily induced the structural deformation probably due to the breakage of hydrogen bonds in the cellulose hydrogels.     

Some structural and dynamical properties of multilamellar vesicles incorporated with propranolol

Summary Spin labelling ESR, calorimetry and³¹P NMR have been used to investigate dipalmitoyl phosphatidylcholine dispersions incorporated with propranolol which is a β-adrenoceptor blocking drug, widely used in the treatment of arrhythmy. The drug appears to enter the lipid bilayer also at the lowest concentrations and to induce a progressive fluidification of multilamellar vesicles. In fact, the presence of drug reduces the temperature of chain melting transition and the corresponding cooperation number. Furthermore the phase transitionL _β′ −P _β′ is not observable also at the lowest drug concentrations. Work presented at the First USSR-Italy Bilateral Meeting on Liquid Crystals held in Portonovo, Ancona (Italy), September 30–October 2, 1987.     

Elastic moduli of nc-TiN/a-Si3N4 nanocomposites: Compressible, yet superhard

Earlier measurements of elastic moduli of nc-TiN/a-Si₃N₄ nanocomposites of different composition and hardness by means of vibrating reed and surface Brillouing scattering, that yield Young’s and shear modulus, as well as the Poisson’s ratio, have been confirmed by high-pressure X-ray diffraction measurements, that yield bulk modulus. It is found that elastic moduli of all measured samples are essentially the same within relatively small error of measurements, and only slightly lower than that of pure TiN. The nanocomposites are superhard thanks to their unique nanostructure with strengthened SiN_x interface.     

Response of thin polymer layers confined between solid surfaces and submitted to normal oscillatory deformations

Summary The viscoelastic properties of liquids close to solid surfaces differ from the bulk. Nanorheology has been performed by using a surface force apparatus adapted to operate as a rheometer in a sphere-plane geometry. Axial oscillatory measurements have been carried out with high polymer solutions filling the gap. The deformations were kept sufficiently small not to perturb the film structure and were applied in a large range of frequency (10⁻³ to 10² s⁻¹). It is shown that the complex modulus characterizing the confined medium can be split into two components: a shear modulus (it accounts for the viscous dissipation due to the flow of solvent molecules through the mesh created by the long polymer chains which connect the two solid surfaces) and a compression modulus which is related to the normal stress response of the chains confined between the solid surfaces. The hydrodynamic screening lengthξ _h and the correlation length ξ deduced from the two moduli are compared and are found to scale in the same way as a function of the distance between the two surfaces. Paper presented at the I International Conference on Scaling Concepts and Complex Fluids, Copanello, Italy, July 4–8, 1994.     

Elastic properties of ultrahard fullerites

The elastic properties of C₆₀ fullerite samples synthesized under pressure P=13.0 GPa at high temperatures were investigated using acoustic microscopy. The velocities of longitudinal (c _L=17–26 km/s) and transverse (c _T=7.2–9.6 km/s) elastic waves in the samples were measured. It was established that the longitudinal sound velocity of ultrahard fullerites is higher than that of any other known solid. The bulk modulus of these ultrahard samples is higher than that of diamond and reaches a value greater than 1 TPa. The high bulk modulus, the relatively large shear moduli, and the substantial Poisson ratio indicate that the structure of the ultrahard fullerites is fundamentally different from that of diamond. Zh. éksp. Teor. Fiz. 114, 1365–1374 (October 1998)     

Slow nonlinearity kinetics of the viscoelastic properties of oil during shear vibrations

Earlier we discovered the slow evolution of viscoelastic moduli of heavy crude oil. The shear modulus was measured at frequencies of 0.5, 5, and 50 Hz at different temperatures over 72 h. New studies of the dependence of the complex shear modulus on the strain amplitude revealed a logarithmic increase in the nonlinearity parameter as a function of time for this oil sample. It was experimentally established that the complex shear modulus is a linear function of the amplitude of shear perturbations. This is possible in the case of a linear dependence of values of the viscoelastic characteristics on the medium modulus of deformation.     

The effect of shear flow on the Helfrich interaction in lyotropic lamellar systems

We study the effect of shear flow on the entropic Helfrich interaction in lyotropic surfactant smectic fluids. Arguing that flow induces an effective anisotropic surface tension in bilayers due to a combination of intermonolayer friction, bilayer collisions and convection, we calculate the reduction in fluctuations and hence the renormalised change in effective compression modulus and steady-state layer spacing. We demonstrate that non-permeable or slowly permeating membranes can be susceptible to an undulatory instability of the Helfrich-Hurault type, and speculate that such an instability could be one source of a transition to multilamellar vesicles.     

Premicellar and micelle formation behavior of aqueous anionic surfactants in the presence of triphenylmethane dyes: protonation of dye in ion pair micelles

The premicellar and micelle formation behaviors of four cationic triphenylmethane dyes, viz, Pararosaniline (RN), Crystal violet (CV), Ethyl violet (EV), and Malachite green (MG), in aqueous anionic surfactant solutions of sodium dodecyl sulfate (SDS), sodium dodecyl benzene sulfonate (SDBS), and sodium dodecyl sulfonate (SDSN) have been studied by spectral and surface tension measurements. The study was carried out within a pH range where the dyes are stable in their quinoid forms. The dyes have been found to form dye–surfactant ion pairs (DSIPs) with the surfactants, at the surfactant concentrations well below their critical micelle concentration, CMC*. The DSIPs behave like nonionic surfactants and form an air–water interfacial monolayer. The DSIPs have a lower critical micelle concentration (CMC_IP), greater efficiency, and lower effectiveness than the corresponding pure surfactants. As the surfactant concentration is increased below the CMC*, the DSIPs start forming micelles of their own where the dye gets protonated and exists as a protonated dye–surfactant ion pair (PDSIP) in the ion pair micelles. As the concentration of the surfactant exceeds the CMC* of the pure surfactant, the protonation reverses gradually with the dye remaining in the micelles in solubilized form and the DSIPs in the air–water interfacial monolayer are replaced by pure surfactants. The distorted helical isomeric form (isomer B) of the dyes is favored in the PDSIPs. Copyright © 2009 John Wiley & Sons, Ltd.