Complex fluids with a yield value; their microstructures and rheological properties

Summary A general method is presented for the preparation of viscoelastic surfactant phases that consist of densely packed multilamellar vesicles in water. The phases form spontaneously when ionic surfactants are added to L_α-or L₃-phases from uncharged surfactants and cosurfactants. The dimensions and the structure of the vesicles were studied from FF-TEM micrographs for 100 mM surfactant solutions. The average diameter of the vesicles is in the range of 1 μm, the interlamellar spacing is around 800 ?. Under these conditions the vesicles are densely packed and cannot pass each other. The systems are highly viscoelastic and have a yield value. The storage and the loss moduli were determined by oscillating rheological measurements. The storage modulus was about one order of magnitude larger than the loss modulus and independent of frequency. Both parameters were determined as a function of the concentration and the chain length of the surfactant and cosurfactant, the charge density and ionic strength, the solubilization of hydrocarbon and temperature. The yield values and shear moduli increase linearly with the surfactant concentration. For constant surfactant concentration the moduli increase in a S-shaped form with the charge density and reach saturation for a mole fraction of about 7% of ionic surfactant. The storage moduli and yield values decrease with the addition of excess salt. The storage moduli depend strongly on the chain length of the surfactant. The values of the moduli are explained on the basis of a hard-sphere model in which the multilamellar vesicles are considered as hard-sphere particles. Paper presented at the I International Conference on Scaling Concepts and Complex Fluids, Copanello, Italy, July 4–8, 1994.     

Isentropic compressibility behaviour of dilute solutions of ethyl-alcohol in water

Summary The adiabatic compressibility of ethanol-water mixtures was measured as a function of temperature and cosolvent concentration; the measurements were carried out at 5°C intervals over the range (10⋎40) °C, paying particular attention to the water-rich region (mole fraction of cosolventx ₂<0.25). The observed concentration dependencies of the adiabatic compressibility in the low-concentration range were well explained if we consider the existence in the mixture of local structures with a composition that is close to ethanol-17 H₂O like that of solid clathrate hydrate of type II. A simple model, involving the solutesolvent interactions and the molecular aggregation of the solute, is used to explain the observed behaviour. To speed up publication, the author of this paper has agreed to not receive the proofs for correction.     

Mechanical behaviour and fracture mechanism of flux grown holmium orthoferrite single crystals

Results of indentation induced microhardness and fracture studies on (110) and (001) planes of flux grown HoFeO₃ single crystals using a Vicker's hardness tester, in the load range of 10-100 g are presented. The variation of microhardness with load is found to be non-linear and is explained by using Hays and Kendall's law. The hardness results and the indentation-induced cracking yields the values of the yield strength, fracture toughness and brittleness index for (110) and (001) planes of HoFeO₃ crystals. Transition from Palmqvist to median crack systems takes place at higher loads for (110) plane of the crystal whereas (001) plane is characterized by Palmqvist cracks only.     

Stretching DNA: Role of electrostatic interactions

The effect of electrostatic interactions on the stretching of DNA is investigated using a simple worm like chain model. In the limit of small force there are large conformational fluctuations which are treated using a self-consistent variational approach. For small values of the external force f, we find the extension scales as where is the Debye screening length. In the limit of large force the electrostatic effects can be accounted for within the semiflexible chain model of DNA by assuming that only small excursions from rod-like conformations are possible. In this regime the extension approaches the contour length as where f is the magnitude of the external force. The theory is used to analyze experiments that have measured the extension of double-stranded DNA subject to tension at various salt concentrations. The theory reproduces nearly quantitatively the elastic response of DNA at small and large values of f and for all concentration of the monovalent counterions. The limitations of the theory are also pointed out. Received 13 October 1998 and Received in final form 9 June 1999     

The under-pressure behaviour of mechanical,electronic and optical properties of calcium titanate and its ground state thermoelectric response

Abstract

In this study, the elastic, electronic, optical and thermoelectric properties of CaTiO₃ perovskite oxide have been investigated using first-principles calculations. The generalised gradient approximation (GGA) has been employed for evaluating structural and elastic properties, while the modified Becke Johnson functional is used for studying the optical response of this compound. In addition to ground state physical properties, we also investigate the effects of pressure (0, 30, 60, 90 and 120 GPa) on the electronic structure of CaTiO₃. The application of pressure from 0 to 90 GPa shows that the indirect band gap (Γ-M) of CaTiO₃ increases with increasing pressure and at 120 GPa it spontaneously decreases transforming cubic CaTiO₃ to a direct (Γ-Γ) band gap material. The complex dielectric function and some optical parameters are also investigated under the application of pressures. All the calculated optical properties have been found to exhibit a shift to the higher energies with the increase of applied pressure suggesting potential optoelectronic device applications of CaTiO₃. The thermoelectric properties of CaTiO₃ have been computed at 0 GPa in terms of electrical conductivity, thermal conductivity and Seebeck coefficient.     

Indentation behaviour of superelastic hard carbon

Superelastic hard carbon particles widely varying in structure and properties have been studied by instrumented microindentation technique. The carbon particles up to 200 μm in size were produced by fullerene collapse upon high-pressure high-temperature treatment of metal–fullerene powder mixture with simultaneous sintering of metal matrix composite materials (CM) reinforced by the particles. The structure and properties of the carbon particles were controlled by changing synthesis parameters and the state (composition and structure) of the parent fullerite crystals. The specific features of the instrumented indentation behaviour of the particles were studied as a function of their hardness. Mechanical properties of the particles tested at loads of up to 1970 mN exhibit an indentation size effect, which becomes more pronounced with increasing hardness of the carbon particles. Upon holding at a constant load, the fullerene-derived carbon particles undergo unrecoverable deformation, and the indentation creep C_IT increases with increasing particle hardness. An increase in hardness of the reinforcing carbon particles substantially improves the wear resistance of the CM and decreases their friction coefficient.     

Temperature effect on the molecular interactions between two ammonium ionic liquids and dimethylsulfoxide

To understand the molecular interactions between newly synthesized ammonium ionic liquids (ILs) and highly polar solvent dimethylsulfoxide (DMSO), precise measurements such as densities (ρ), ultrasonic sound velocities (u) and viscosities (η) have been performed over the whole composition range at temperature ranging from 298.15 to 308.15 K and at atmospheric pressure. The ILs investigated in the present study included diethyl ammonium acetate ([Et₂NH][CH₃COO], DEAA) and triethyl ammonium acetate ([Et₃NH][CH₃COO], TEAA). Further, to gain some insight into the nature of molecular interactions in these mixed solvents, we predicted the excess molar volume (V^E), the deviation in isentropic compressibilities (ΔK_s) and deviation in viscosity (Δη) as a function of the concentration of IL using the measured properties of ρ, u and η, respectively. Redlich-Kister polynomial was used to correlate the results. The intermolecular interactions and structural effects were analyzed on the basis of the measured and the derived properties. A qualitative analysis of the results is discussed in terms of the ion-dipole, ion-pair interactions, and hydrogen bonding between ILs and DMSO molecules and their structural factors.     

Effect of intercalation on electrical and mechanical properties of C/C composites

The work is concerned with modification of C/C composites by intercalation of copper chloride. The samples of composites were made from graphite fibres and carbon matrix derived from mesophase pitch and from phenol-formaldehyde resin. The samples were prepared by impregnating graphite fibres with a liquid pitch or polymer solution to obtain unidirectional laminates. The laminates were used to prepare the composites which were then subjected to carbonization and graphitization up to 2150 °C. The work discusses the problem relevant to the effect of intercalation on mechanical and electrical properties of composites. The studies indicated that both mesophase pitch-based composites and phenolic-derived carbon-carbon composites changed their electrical and mechanical properties upon intercalation with copper chloride. Electrical conductivity of both types of composites decreased as a result of the damages formed during intercalation.     

Phase transitions in simple models of rod-like and disc-like micelles

The interplay of interactions between micelles, and the aggregation of these micelles into large, highly anisotropic micelles, is studied. Simple, hard-body, models of rod-like and disc-like micelles are used, which allows us to apply fundamental measure theory to determine the free energy. Then we study the phase transition from the fluid phase to a liquid crystalline phase. We find that aggregation induces a strongly first order transition from a fluid phase of small micelles to a close packed liquid crystalline phase of infinitely large micelles. Received: 3 December 1997     

Rheological behaviour of ethylene glycol-titanate nanotube nanofluids

Experimental work has been performed on the rheological behaviour of ethylene glycol based nanofluids containing titanate nanotubes over 20–60 °C and a particle mass concentration of 0–8%. It is found that the nanofluids show shear-thinning behaviour particularly at particle concentrations in excess of ~2%. Temperature imposes a very strong effect on the rheological behaviour of the nanofluids with higher temperatures giving stronger shear thinning. For a given particle concentration, there exists a certain shear rate below which the viscosity increases with increasing temperature, whereas the reverse occurs above such a shear rate. The normalised high-shear viscosity with respect to the base liquid viscosity, however, is independent of temperature. Further analyses suggest that the temperature effects are due to the shear-dependence of the relative contributions to the viscosity of the Brownian diffusion and convection. The analyses also suggest that a combination of particle aggregation and particle shape effects is the mechanism for the observed high-shear rheological behaviour, which is also supported by the thermal conductivity measurements and analyses.     

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.     

Summation of electrostatic interactions in quasi-two-dimensional simulations

An error in our previous paper (Clark, A. T., Madden, T. J. and Warren, P. B., 1996 Molec. Phys., 87, 1063) is corrected. This brings the results into agreement with the recent work of Grønbech-Jensen et al. (Grønbech-Jensen, N., Hummer, G. and Beardmore, K. M., Molec. Phys., 1997, 92, 941).     

Melt fracture of entangled polymers*

We construct a model for a slippage plane in a sheared melt, based on a balance between reptation bridging and shear debonding. The resulting state could show up at rather low shear rates and be locally stable. But it is not easy to nucleate: the conventional entangled state is also locally stable. We propose that slippage occurs on solid walls: either at the container surface, or on dust particles floating in the melt. Slippage at solid/melt interfaces was studied (experimentally and theoretically) long ago. There is a critical stress for slippage: our estimate (for strong adsorption of melt chains on the solid) gives (plateau modulus) for typical cases. Thus, melt fracture is expected at moderate stresses, in agreement with observations by S.Q. Wang and coworkers.     

Strong anisotropic nematic order in liquid crystal polymers: [4] a quasi-elastic neutron scattering study

From quasi-elastic neutron scattering experiments performed in glassy, nematic and isotropic phases, the dynamics of oriented samples of strong anisotropic side-on fixed liquid crystal polymers have been analysed. Using the selective deuteration method, we are able to attribute motions to specific parts of the molecule in the parallel and perpendicular orientations. The motions of the whole macromolecule decrease as soon as the temperature decreases below the isotropic-nematic transition. Nevertheless, the motions of the polymer backbone, compared to the whole polymer dynamics, are systematically reduced, even in the isotropic phase. Moreover, an anisotropy of the motions is revealed, with a reduction in the direction parallel to the orientation. An harmonic character of the vibrational processes is also evidenced. We conclude that the anisotropy of the dynamic corroborates the anisotropy of conformation of the macromolecule (so-called jacketed structure). Received: 29 October 1997 / Revised: 22 January 1998/ Accepted: 11 May 1998     

Monte Carlo simulations of star-branched polyelectrolyte micelles

The concentration profiles of monomers and counterions in star-branched polyelectrolyte micelles are calculated through Monte Carlo simulations, using the freely jointed chain model. We have investigated the onset of different regimes corresponding to the spherical and Manning condensation of counterions as a function of the strength of the Coulomb coupling. The Monte Carlo results are in fair agreement with the predictions of Self-Consistent-Field analytical models. We have simulated a real system of diblock copolymer micelles of (sodium-polystyrene-sulfonate)(NaPSS)-(polyethylene-propylene)(PEP) with f = 54 hydrophilic branches of N = 251 monomers at room temperature in salt-free solution. The calculated form factor compares nicely with our neutron scattering data. Received 18 July 2002 and Received in final form 11 October 2002 RID="a" ID="a"e-mail: roger@drecam.saclay.cea.fr     

Rupture energy of a pendular liquid bridge

We propose a simple expression for the rupture energy of a pendular liquid bridge between two spheres, taking into account capillary and viscous (lubrication) forces. In the case of capillary forces only, the results are in accordance with curve fitting expressions proposed by Simons et al. [2] and Willett et al. [5]. We performed accurate measurements of the force exerted by liquid bridges between two spheres. Experimental results are found to be close to theoretical values. A reasonable agreement is also found in the presence of viscous forces. Finally, for small bridge volumes, the rupture criterion given by Lian et al. [10] is modified, taking into account additional viscous effects. Received 18 September 2000 and Received in final form 10 June 2001     

Effect of flexibility of grafted polymer on the morphology and property of nanosilica/PVC composites

In this study, poly(methyl methacrylate)-grafted-nanosilica (PMMA-g-silica) and a copolymer of styrene (St), n-butyl acrylate (BA) and acrylic acid (AA)-grafted-nanosilica (PSBA-g-silica) hybrid nanoparticles were prepared by using a heterophase polymerization technique in an aqueous system. The grafted polymers made up approximately 50 wt.% of the resulted hybrid nanoparticles which showed a spherical and well-dispersed morphology. The silica hybrid nanoparticles were subsequently used as fillers in a poly(vinyl chloride) (PVC) matrix to fabricate PVC nanocomposite. Morphology study of PVC nanocomposites revealed that both PMMA- and PSBA-grafted-silica had an adhesive interface between the silica and PVC. The tensile strength and elongation to break were found to be improved significantly in comparison with that of untreated nanosilica/PVC composites. Finally our results clearly demonstrated that the properties (e.g. chain flexibility, composition) of the grafted polymer in the hybrid nanoparticles could significantly affect the dispersion behavior of hybrid nanoparticles in PVC matrix, dynamic mechanical thermal properties and mechanical properties of the resulted PVC composites.     

Current fluctuations in nanopores: The effects of electrostatic and hydrodynamic interactions

Using nonequilibrium Langevin dynamics simulations of an electrolyte with explicit solvent particles, we investigate the effect of hydrodynamic interactions on the power spectrum of ionic nanopore currents. At low frequency, we find a power-law dependence of the power spectral density on the frequency, with an exponent depending on the ion density. Surprisingly, however, the exponent is not affected by the presence of the neutral solvent particles. We conclude that hydrodynamic interactions do not affect the shape of the power spectrum in the frequency range studied.     

Magnetic field effects in the presence of electrostatic interactions

Magnetic field effects on ion radical pair (IRP) recombination reactions are considered. In the diffusion approximation simple analytical expressions for the magnitudes of these effects are obtained. They are reduced to those obtained within the simple cage approximation in the case, when the intramolecular spin interactions are strong enough and to those obtained within the free radical approximation in the opposite case. The applicability of both simple approximations are shown to be closely connected with peculiarities of the IRP decay kinetics. Namely, the cage approximation is applicable for the strong spin interactions because the IRP decays exponentially at small times. The free radical approximation is valid in the opposite limit of weak interactions since at large times the IRP decays as a free radical pair.