Dispersions of silica nanoparticles in ionic liquids investigated with advanced rheology

The colloidal stabilities of dispersions of unmodified and surface-functionalized SiO₂ nanoparticles in hydrophobic and hydrophilic imidazolium-based ionic liquids were studied with advanced rheology at three temperatures (25, 100, and 200 °C). The rheological behavior of the dispersions was strongly affected by the ionic liquids hydrophilicity, by the nanoparticles surface, by the concentration of the nanoparticles in the dispersion as well as by the temperature. The unmodified hydrophilic nanoparticles showed a better compatibility with the hydrophilic ionic liquid. The SiO₂ surface functionalization with hydrophobic groups clearly improved the colloidal stability of the dispersions in the hydrophobic ionic liquid. The temperature increase was found to lead to a destabilization in all studied systems, especially at higher concentrations. The results of this study imply that ionic liquids with tailored properties could be used in absorbers directly after reactors for gas-phase synthesis of nanoparticles or/and as solvents for their further surface functionalization without agglomeration or aggregation.     

Collapse transitions of a periodic hydrophilic hydrophobic chain

We study a single self avoiding hydrophilic hydrophobic polymer chain, through Monte-Carlo lattice simulations. The affinity of monomer i for water is characterized by a (scalar) charge , and the monomer-water interaction is short-ranged. Assuming incompressibility yields an effective short ranged interaction between monomer pairs (i,j), proportional to . In this article, we take (resp. ()) for hydrophilic (resp. hydrophobic) monomers and consider a chain with (i) an equal number of hydro-philic and -phobic monomers (ii) a periodic distribution of the along the chain, with periodicity 2p. The simulations are done for various chain lengths N, in d=2 (square lattice) and d=3 (cubic lattice). There is a critical value p _c (d,N) of the periodicity, which distinguishes between different low temperature structures. For p >p _c , the ground state corresponds to a macroscopic phase separation between a dense hydrophobic core and hydrophilic loops. For p <p _c (but not too small), one gets a microscopic (finite scale) phase separation, and the ground state corresponds to a chain or network of hydrophobic droplets, coated by hydrophilic monomers. We restrict our study to two extreme cases, and to illustrate the physics of the various phase transitions. A tentative variational approach is also presented. Received: 10 March 1998 / Received in final form: 25 June 1998 / Accepted: 1st July 1998     

Transport and Coulomb drag for two interacting carbon nanotubes

We study nonlinear transport for two coupled one-dimensional quantum wires or carbon nanotubes described by Luttinger liquid theory. Transport properties are shown to crucially depend on the contact length L _c. For a special interaction strength, the problem can be solved analytically for arbitrary L _c. For point-like contacts and strong interactions, a qualitatively different picture compared to a Fermi liquid emerges, characterized by zero-bias anomalies and strong dependence on the applied cross voltage. In addition, pronounced Coulomb drag phenomena are important for extended contacts. Received 28 July 2000     

Superconductivity,lattice transformations,and electronic instabilities in CuxMo3S4

The variations of the superconducting transition temperature (T_c) and of the lattice transformation temperature (T_L) with composition are reported for the Chevrel-phase system Cu_xMo₃S₄ (1 ≤ × ≤ 2). A complex low temperature phase diagram was found, containing at least three distinct low temperature phases, each exhibiting its own characteristic T_c (11 K, 6.5 K, 4.5 K), T_L (280 K - 125 K), and electronic transport behavior. Pressure-induced transformations between these three phases were observed at pressures below 25 kbar. Temperature-induced lattice distortion for compositions near Cu₂Mo₃S₄ was found to increase the T_c above that (< 1.1 K) of the high temperature, higher symmetry rhombohedral phase. This is apparently the first time the latter behavior has been observed: in all previous studies of other materials, the opposite behavior was reported.     

Dextran‐Coated Antiferromagnetic MnO Nanoparticles for a T1‐MRI Contrast Agent with High Colloidal Stability

A simple approach to synthesize carboxymethyl dextran‐coated MnO nanoparticles (CMDex‐MnONPs) with high colloidal stability in physiological saline solutions is described here for potential applications as a magnetic resonance imaging (MRI) T₁ contrast agent. The thermal decomposition methodology is used to produce uniform MnONPs with an average size of around 20 nm, and its hydrophobic surface is modified with CMDex molecules, conferring hydrophilic properties. After CMDex coating, the nanoparticle presents high colloidal stability in concentrations ranging from 10 to 50 μg mL^?1, average hydrodynamic size (Z‐average) of 130 nm, polydispersity degree of ≈12%, and negative surface charge in both simulated body fluid solutions and pure water with zeta‐potential of –20 and –40 mV, respectively. The CMDex‐MnONPs with 20 nm show antiferromagnetic behavior at room temperature, and the magnetic properties are found to be strongly dependent of the nanoparticle size, increasing the contribution of the ferromagnetic Mn₃O₄ phase with decreasing size for nanoparticles about 3 nm. Cytotoxicity evaluation in cancerous and noncancerous cells in the range of 5.0–50.0 μg mL^?1 shows low toxicity for cancerous cells and lack of the same for healthy cells lines. Related to the magnetic properties, CMDex‐MnONP presents significant r₁ relaxivity and low r₂/r₁ relaxivity ratio. The results suggest that these nanoparticles display characteristics for potential applications as an MRI T₁ contrast agent.     

Statistical thermodynamics of the liquid surface

The current theoretical situation regarding the structure of the liquid-vapour transition zone and the associated thermodynamic surface properties of simple liquids is reviewed. The thermodynamic and statistical mechanical treatments of the surface structure are assessed, and it is concluded that the former approach has limiting validity only as T→T _crit. Liquid metal systems are discussed, together with the recent experimental evidence supporting the existence of stable density oscillations at the surfaces of certain liquid metals. The liquid inert gas systems, argon in particular, are considered in some detail, and a discussion of the statistical thermodynamics of the liquid ⁴He surface is given.     

A Light and X‐Ray Scattering Study of Aqueous Micellar Solutions of a Diblock Copolymer of Propylene Oxide and Ethylene Oxide with Solubilized Alkylcyanobiphenyl Liquid Crystals

Abstract

The temperature and concentration dependences of the physicochemical properties of aqueous solutions of the diblock copolymer P₄₃E₃₁₂ (P = oxypropylene, E = oxyethylene) with solubilized liquid crystal (LC) have been studied using static and dynamic light scattering (SLS and DLS), small‐angle x‐ray scattering (SAXS), and ultraviolet (UV) spectroscopy. Relaxation time distributions from DLS obtained from inverse Laplace transformation of intensity correlation functions are multimodal, where the two fastest modes are attributed to diblock copolymer unimers and micelles, respectively. The remaining modes at longer decay times reflect the presence of free LC with hydrodynamic radii (R _h) of hundreds of nm. The R _h of both unimers and micelles were independent of temperature (T), while the hydrodynamic virial coefficient k _D and the second virial coefficient, A ₂, decreased with increasing T. The UV spectroscopy measurements showed that there is a reduction in the amount of solubilized LC per gram of copolymer (c _s) as the copolymer concentration (c _p) is increased. The SAXS results agree well with a model of a homogeneous system of polydisperse interacting hard spheres. In solution, both the effective micellar radius of interaction (R _eff) and the hard‐sphere micellar radius (R¯_s) increase in the presence of LC due to solubilization of the latter in the hydrophobic micellar core. Both SAXS and SLS results show that intermicellar interactions become important at c _p > 1% (w/w) at high temperatures [T > the critical micelle temperature (cmt)].     

掺Ba对Bi系2212相超导电性的影响

研究了掺Ｂａ对Bi₂Sr_2-xBa_xCaCu₂O_y（０≤ｘ≤０．１５，０．３）单晶和多晶样品超导电性的影响，结果表明，有少量Ｂａ^２＋离子进入了超导相，且有固溶度极限．对于２２１２相单晶，ｃ轴参数和Ｔ_c均随Ｂａ含量增加而增加；对于慢冷多晶样品，掺Ｂａ可明显提高Ｔ_c；然而对于淬大多晶样品，Ｔ_c没有明显变化，用掺Ｂａ 关键词：     

Liquids in equilibrium: Beyond the hypernetted chain

Density functional techniques are used to derive a charging expression for the non-uniform density of a molecular liquid. In the atomic limit the equation reduces to an exact form due to Fixman. The theory is simplified greatly via a physical approximation that accounts for three-body correlations beyond those included in the hypernetted chain (HNC) closure of the Ornstein-Zernike (OZ) equation. The radial distribution function is obtained as a special case. The theory is tested by examining the phase behavior of two fundamental complex fluids: the homopolymer blend and diblock copolymer melts. For the former it is found, contrary to HNC theory and its molecular generalizations, that a critical temperature T_c is predicted from the structure route. This T_c scales linearly with degree of polymerization N in agreement with Flory theory. The simplest form of the theory can be considered as a way to incorporate attractive interactions within a formalism that is very similar to that of the OZ or reference interaction site model (RISM). The relevance of the theory to charged liquids is also discussed.     

Statistical mechanics of flux lines in high-T c superconductors

A theory of the entangled flux liquids which arise in the new high-T _c superconductors is reviewed. New physics appears because of the weak interplanar couplings and high critical temperatures in these materials. Flux line wandering melts the conventional Abrikosov flux lattice, and leads to an entangled vortex state whose statistical mechanics is closely related to the physics of interacting bosons in two dimensions. The phase diagram as a function of magnetic field and temperature is discussed, and it is argued that an entangled vortex liquid appears just aboveH _c1 at all nonzero temperatures. The decay of vortex line correlations in the entangled liquid state is controlled by the superfluid excitation spectrum of the bosons. Line wandering produces drastic changes in theB(H) constitutive relation nearH _c1.     

Application of a radioactive tracer method for diffusion study in some liquids

In this paper a radioactive tracer technique based on sliding cell method developed in our laboratory for the study of diffusion in liquids is presented in detail. This method consists of radioactive and non-radioactive liquid columns of equal length and the radiation detector is placed in a vertical geometry over the diffusion column. Some liquid metals and aqueous electrolyte solutions were studied by this method. The data of liquid metals like mercury and gallium have been analyzed from the point of view of hard sphere model and those of electrolyte solutions from phenomenological theories. Onsager’s coefficientsL ₁₁,L ₁₂,L ₂₂ have been calculated from the experimental data and the variation of diffusion with solute concentration has been explained from ion-ion interaction.     

Phase diagram and transport properties of Sb-doped Ca0.88La0.12Fe2As2 single crystals

The effects of isovalent Sb substitution on the superconducting properties of the Ca_0.88La_0.12Fe₂(As_1-ySb_y)₂ system have been studied through electrical resistivity measurements. It is seen that the antiferromagnetic or structural transition is suppressed with Sb content, and a high-T_c superconducting phase, accompanied by a low-T_c phase, emerges at 0.02 ≤ y ≤ 0.06. In this intermediate-doping regime, normal-state transport shows non-Fermi-liquid-like behaviors with nearly T-linear resistivity above the high-T_c phase. With further Sb doping, this high-T_c phase abruptly vanishes for y > 0.06 and the conventional Fermi liquid is restored, while the low-T_c phase remains robust against Sb impurities. The coincidence of the high-T_c phase and non-Fermi liquid transport behaviors in the intermediate Sb-doping regime suggests that AFM fluctuations play an important role in the observed non-Fermi liquid behaviors, which may be intimately related to the unusual nonbulk high-T_c phase in this system.     

Temperature dependence of the effective anchoring energy for a nematic-ferroelectric interface

Specific features of the anisotropic interaction between a nematic mixture and a polar surface of a ferroelectric triglycine sulfate crystal have been studied over a wide temperature range including the substrate's Curie point T_c. The mixture was composed of two nematic liquid crystals, 60% of p-methoxybenzylidene-p-n-butylaniline (MBBA) and 40% of p-ethoxybenzylidene-p-n-butylaniline (EBBA), and doped with a small amount of a dichroic dye. The temperature dependence of the polarized components of optical density D_j of the dye absorption band for the nematic and isotropic phases of the MBBA+EBBA mixture has been obtained using polarization optic techniques. The temperature-induced structural changes in the nematic layer near T_c were found to be related to the changes in the orientational part of the tensor order parameter Q_ik. The experimental data have been interpreted using the model, in which the dispersive van der Waals forces of the substrate stabilize the planar orientation of the nematic in the bulk competing with the short-range anchoring forces in the vicinity of T_c. At the same time, the anisotropic part of the surface energy has two terms with the orthogonal easy axes. The nature of the surface electric field and its effect on the director alignment at the interface have been clarified. Taking into account the known relation between anchoring strength and the nematic order parameter, the effective anchoring energy w_eff for the studied system has been determined as a function of temperature.     

Synthesis,X-ray,magnetic and electrical studies of substituted (Pr,Sr)MnO3 perovskites

A systematic study of the structural, magnetic and electrical properties of the manganites Pr_1-x Sr _x MnO₃(0≤ x ≤ 0.5) has been carried out. X-ray diffraction investigation shows a structural change with composition, from orthorhombic (0 ≤ x ≤ 0.2) to rhombohedral (0.25 ≤ x ≤ 0.5). The magnetic properties of Pr_1-x Sr _x MnO₃ samples could be explained on the basis of a double exchange mechanism between pairs of Mn³⁺ and Mn⁴⁺ ions. These properties are strongly dependent on the ratio of Mn³⁺/Mn⁴⁺. The maximum of the ferromagnetic transition temperature T_c is reached at x ≈ 0.35 corresponding to a value 1.85 of this ratio. The investigation of the electrical properties shows a semiconductor to metal transition as a function of temperature (0.25≤x≤0.4) with a metallic-like behaviour above a critical temperature T_p . A semiconducting-like one is observed for all the range of temperature (50–300 K) for (0 ≤ x ≤ 0.2 and x = 0.5). The evolution of activated energies with the carrier concentration has been investigated.     

Pressure Ionization in Nonideal Alkali Plasmas

A system of electrons (e) and ions (i) is considered in which beside the Coulomb interaction short range forces are taken into account, i.e. for the e-i interaction a pseudopotential is used, and for the (classical) ions crystallographic radii are used. For a Cesium plasma the thermodynamic properties are calculated quantumstatistically in a wide temperature-density region. Degeneration effects are taken into account approximately. In the region with bound states the ionization equilibrium is discussed, and the Mott-Transition is investigated critically. A phase transition occurs in the framework of the model chosen at T_c ≈ 4500 K and n^c ≈ 4.10²⁰ cm^?3.     

Giant magneto-optical response of ferromagnetic EuB<Subscript><Emphasis Type="Bold">6</Emphasis></Subscript>

Intercalation of polyatomic molecules into a superconductor can drastically affect the properties of the compound. A mechanism responsible for a large increase in T _c for such systems is proposed. It explains the recent remarkable observation of high T _c superconductivity in the hole-doped C₆₀/CHX₃ (X≡Cl, Br) compounds and the large shift in their T _c upon Cl↦Br substitution. The increase in T _c is due to contribution to the pairing arising from the interaction of electrons with the vibrational manifold of the molecule. The proposed mechanism opens up the possibility to observe a site-selective isotope effect. We also suggest that intercalating CHI₃ would further increase the critical temperature to T _c≃ 140 K. Received 23 January 2002     

Survival of Virus Particles in Water Droplets: Hydrophobic Forces and Landauer’s Principle

Many small biological objects, such as viruses, survive in a water environment and cannot remain active in dry air without condensation of water vapor. From a physical point of view, these objects belong to the mesoscale, where small thermal fluctuations with the characteristic kinetic energy of k_BT (where k_B is the Boltzmann’s constant and T is the absolute temperature) play a significant role. The self-assembly of viruses, including protein folding and the formation of a protein capsid and lipid bilayer membrane, is controlled by hydrophobic forces (i.e., the repulsing forces between hydrophobic particles and regions of molecules) in a water environment. Hydrophobic forces are entropic, and they are driven by a system’s tendency to attain the maximum disordered state. On the other hand, in information systems, entropic forces are responsible for erasing information, if the energy barrier between two states of a switch is on the order of k_BT, which is referred to as Landauer’s principle. We treated hydrophobic interactions responsible for the self-assembly of viruses as an information-processing mechanism. We further showed a similarity of these submicron-scale processes with the self-assembly in colloidal crystals, droplet clusters, and liquid marbles.     

Swelling Parameters and Mechanical Properties of Functional Fibers Based on Butyl Methacrylate-Hydroxyethyl Methacrylate Copolymer

Butyl methacrylate-hydroxyethyl methacrylate (BMA-HEMA) copolymers were synthesized by the method of suspension polymerization. The copolymer fibers were prepared for absorbing liquid organic matter by gelation-spinning in a twin screw extrusion machine. The swelling parameters and mechanical properties were investigated, and the morphology was observed by scanning electron microscope (SEM). The results show that the degree of equilibrium swelling for the fibers increased with increasing the mass fraction of HEMA in the monomer feed when toluene, trichloroethylene, or chloroform were selected as organic absorbates. All of the interaction parameters, χ ₁, for the fibers and organic liquids were less than 0.5, with the order of the interaction parameters χ ₁ being as follows: toluene > trichloroethylene > chloroform. Average molecular weights between crosslink points, M _c, and effective crosslink density, V _e, were dependent on the selected organic liquids; for the different organic liquids, M _c and V _e were different. The breaking tenacity, initial modulus, and yield stress of the fibers increased with an increase in the mass fraction of HEMA. However, elongation at break and elongation at yield decreased with increasing the mass fraction of HEMA; in particular, for the mass fraction of HEMA equal to 15 wt%, the fiber did not yield, and underwent a brittle fracture.     

Superconducting Properties of Indium Nanostructured in Pores of Thin Films of SiO<Subscript>2</Subscript> Microspheres

Samples of a superconducting indium nanocomposite based on a thin-film porous dielectric matrix prepared by the Langmuir–Blodgett method are obtained for the first time, and their low-temperature electrophysical and magnetic properties are studied. Films with thickness b ≤ 5 μm were made from silicon dioxide spheres with diameter D = 200 and 250 nm; indium was introduced into the pores of the films from the melt at a pressure of P ≤ 5 kbar. Thus, a three-dimensional weakly ordered structure of indium nanogranules was created in the pores, forming a continuous current-conducting grid. Measurements of the temperature and magnetic field dependences of the resistance and magnetic moment of the samples showed an increase in the critical parameters of the superconductivity state of nanostructured indium (critical temperature T_c ≤ 3.62 K and critical magnetic field H_c at T = 0 K H_c(0) ≤ 1700 Oe) with respect to the massive material (T_c = 3.41 K, H_c(0) = 280 Oe). In the dependence of the resistance on temperature and the magnetic field, a step transition to the superconductivity state associated with the nanocomposite structure was observed. A pronounced hysteresis M(H) is observed in the dependence of the magnetic moment M of the nanocomposite on the magnetic field at T < T_c, caused by the multiply connected structure of the current-conducting indium grid. The results obtained are interpreted taking into account the dimensional dependence of the superconducting characteristics of the nanocomposite.