Neue schnelle Ionenleiter vom Typ MMIIICl6 (MI = Li,Na, Ag; MIII = In,Y)

Novel Fast Ion Conductors of the Type M M^IIICl₆ (M^I = Li, Na, Ag; M^III = In, Y) The ternary chlorides Li₃InCl₆, Na₃InCl₆, Ag₃InCl₆, and Li₃YCl₆ have been studied by difference scanning calorimetry, high-temperature X-ray, infrared, and high-temperature Raman methods. Impedance spectroscopic measurements exhibit fast ionic conductivity increasing in the sequence Na₃InCl₆ < Li₃YCl₆ < Ag₃InCl₆ < Li₃InCl₆. In the range of 300°C, Li₃InCl₆ is the best lithium ion conductor known so far (σ = 0,2 Ω^?1 cm^?1 at 300°C). With the exception of Na₃InCl₆, the chlorides exhibit complicated order-disorder phase transitions.     

Volumes,heat capacities and solubilities of amyl compounds in decyltrimethylammonium bromide aqueous solutions

Apparent molar heat capacities and volumes of amylamine (PentNH₂) 0.02m, capronitrile (PentCN) 0.02m and nitropentane (PentNO₂) 0.009m in decyltrimethylammonium bromide (DeTAB) micellar solutions, in water and in octane were measured at 25°C. By assuming that their concentration approaches the standard infinite dilution state, heat capacities and volumes were rationalized by means of previously reported equations following which the distribution constant between the aqueous and the micellar phase and heat capacity and volume of the additives in both phases are simultaneously derived. The present results are compared to those we have previously obtained for pentanol (PentOH). The thermodynamic properties of PentNH₂ in water and in micellar phase are substantially identical to those of PentOH but different from those of PentCN and PentNO₂ whereas the opposite behavior was observed in their pure liquid state and in octane. The nature of the solvent medium seems to affect the thermodynamic behavior of PentNH₂. Also, the study of the apparent molar heat capacities of the amyl compounds investigated here in micellar solutions as a function of surfactant concentration shows evidence of a maximum at about 0.4m DeTAB, which can be attributed to a micellar structural transition. Accordingly, the solubilities of PentCN and PentNO₂ as a function of the DeTAB concentration drop in the neighborhood of the concentration where heat capacities display the maximum.     

Hierarchical Structure‐Within‐Structure Morphologies in A2‐star‐(B‐alt‐C) Molecules

We employ dissipative particle dynamics (DPD) to examine the self‐assembly behavior of A₂‐star‐(B‐alt‐C) molecules. We successfully observe various types of hierarchical structure‐within‐structures, such as A‐formed spheres in the matrix formed by B and C alternating layers, hexagonally packed A‐formed cylinders in the matrix with B and C segregated layers, B and C alternating layers‐within‐lamellae, coaxial B and C alternating domains within hexagonally packed BC‐formed cylinders in the A‐matrix, and co‐centric BC‐alternating domains within BC‐formed spheres in the A‐matrix, by increasing the A composition. Generally speaking, the small length‐scale B and C segregated domains are in parallel to the large length‐scale structures. This hierarchical periodicity along the same axis as well as the various characteristic structures, that the A₂‐star‐(B‐alt‐C) copolymers display, are quite different from those in A‐block‐(B‐graft‐C) coil‐comb copolymers. Moreover, it is interesting to find that when the copolymer chain length increases, though the hierarchical structure type is maintained, the number of small length‐scale lamellae that can form within the large length‐scale structure increases. These hierarchical structures under various compositions are reported theoretically for the first time in the copolymer systems consisting of the alternating blocks, and are in good agreement with the most recent experimental work by Matsushita and co‐workers (Macromolecules 2007 , 40, 4023).     

Two-color photoionization spectroscopy of jet-cooled nickelocene

Two-photon ionization of the nickelocene molecules cooled in a supersonic jet was performed for the first time by simultaneous excitation of (⁵–C₅H₅)2Ni with two tunable nano- second dye lasers. The one-photon transition from the HOMO to the Rydberg R4p level was used as the initial step of the multiphoton excitation. In a one-color experiment, the conditions were found for generation of the intact molecular ion, (⁵–C₅H₅)2Ni⁺, as the only ionic product of the multiphoton ionization. The use of an intense pulse of the second dye laser lead to an increase in the yield of the molecular ion.Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1604–1606, August, 2004.     

Texture of zirconia obtained by forced hydrolysis of ZrOCl2 solutions

The structure and surface properties of ZrO₂ strongly depend on its preparation. In the present work the impact of prolonged aging at basic conditions (pH = 9, T = 100°C, t = 48 h), on the phase composition and textural properties, obtained by calcination of the precipitate, was investigated using several techniques conjointly (DTA/TG, DSC, XRD, porosimetry). The thermal effects accompanying the ZrO₂·xH₂O gel formation, the coalescence of the particles and crystallization were evaluated and discussed in terms of the structural differences between the aged and non-aged samples. This revised version was published online in July 2006 with corrections to the Cover Date.     

Structural evolution of (Ca0.35Sr0.65)TiO3 perovskite at high pressures

Lattice parameters of a synthetic powder sample of Ca_0.35Sr_0.65TiO₃ perovskite have been determined by the method of Le Bail refinement, using synchrotron X-ray diffraction patterns collected at pressures up to 15.5 GPa with a membrane-driven diamond anvil cell. At ambient conditions, diffraction data were consistent with the I4/mcm structure reported previously in the literature for the same composition. Diffraction data collected at high pressures were consistent with tetragonal (or, at least, pseudo-tetragonal) lattice geometry, and no evidence was found for the development of any of the orthorhombic structures identified in other studies of (Ca, Sr)TiO₃ perovskites. Additional weak reflections, which could not be accounted for by the normal I4/mcm perovskite structure, were detected in diffraction patterns collected at pressures of 0.9-2.5 GPa, and above ∼13.5 GPa, however. Small anomalies in the evolution of unit cell volume and tetragonal strain were observed near 3 GPa, coinciding approximately with breaks in slope with increasing pressure of bulk and shear moduli for a sample with the same composition which had previously been reported. The anomalies could be due either to new tetragonal↔tetragonal/pseudo-tetragonal phase transitions or to subtle changes in compression mechanism of the tetragonal perovskite structure.     

Damage spreading in a single-component irreversible reaction process: Dependence of the system's immunity on the Euclidean dimension

The spreading of a globally distributed damage, created in the stationary regime, is studied in a single-component irreversible reaction process, i.e., the BK model [Browne and Kleban,Phys. Rev. A 40, 1615 (1989)]. The BK model describes one variant of the A+AA₂ reaction process on a lattice in contact with a reservoir of A species. The BK model has a single parameter, namely the rate of arrival of A species to the lattice (Y). The model, exhibits an irreversible phase transition between a stationary reactive state with production of A₂ species and a poisoned state with the lattice fully covered by A species. The transition takes place at critical points (Y _C ) which solely depend on the Euclidean dimensiond. It is found that the system is immune ford=1 andd=2, in the sense that even 100% of initial damage is healed within a finite healing period (T _H ). Within the reactive regime,T _H diverges when approachingY _C according toT _H (Y _C –Y)^–, with 1.62 and 1.08 ford=1 andd=2, respectively. Ford=3 a frozen-chaotic transition is found close toY _s 0.4125, i.e., well inside the reactive regime 0YY _C 0.4985. Just atY _S the damageD(t) heals according toD(t) t ^–, with 0.71. For the frozen-chaotic transition atd=3 the order parameter critical exponent 0.997 is determined.     

Criticality and phase transitions in ionic fluids

Recent experimental investigations of criticality and phase separation in ionic fluids have revealed behavior of great theoretical interest. In seeking to understand the experiments, some of which appear to exhibit argonlike criticality and some of which exhibit classical (mean-field) criticality, a convenient starting point is the restricted primitive model (RPM) of symmetrically charged hard spheres, all of equal diameter , each sphere bearing a positive or negative charge of magnitudeq. There is overall charge neutrality, so that the expected number densities of the anions and cations are equal, ₊= _-. Studies of RPM charge-charge and density-density correlation functions indicate that the fluctuation-suppressing mechanism that yields mean-field critical behavior in nonionic systems with long-range interparticle potentials is not operative in the RPM. On the basis of plausible assumptions, Ising-like behavior is instead expected. The above work is summarized. New work of Zhang and the author is outlined, showing that when one loses the RPM symmetry (through, e.g., different valence, diameter, or dipole moment of anions and cations) a strong coupling between charge-charge and density-density correlation ensues. The way in which this can be expected to give rise to mean-field or mean-field-like behavior is noted. Other new observations concern the mean-field analogy found by Høye and the author between the parameter 2/(d–2) (d is the dimensionality) in that model and the monomer number in high polymers, with respect to the coexistence-curve shape dependence on those parameters.     

Cluster description of water-in-oil microemulsions near the critical and percolation points

The three-component ionic microemulsion system consisting of AOT/water/decane shows an unusual phase behavior in the vicinity of room temperature. The phase diagram in the temperature-volume fraction (of the dispersed phase) plane exhibits a lower consolute critical point at about 40 degrees centigrades and 10% volume fraction. A percolation line, starting from the vicinity of the critical point, cuts across the plane, extending to high volume fraction side at progressively lower temperatures. In this paper we review the evidence that allows to interpret the phase behavior of our system in terms of interacting spherical droplets. We also investigate the dynamics of droplets, below and approaching the critical point by dynamic light scattering. The first cumulant and time evolution of the droplet density correlation function can be quantitatively calculated by assuming the existence of polydispersed fractal clusters formed by the microemulsion droplets due to attraction. The relaxation phenomena observed in an extensive set of measurements of electrical conductivity and permittivity close to percolation is also reviewed and interpreted through the same cluster-forming mechanism, which reproduces the most relevant features of the frequency-dependent complex dielectric constant of this system. Paper presented at the I International Conference on Scaling Concepts and Complex Fluids, Copanello, Italy, July 4–8, 1994.     

Phase transitions and hysteresis in a cellular automata-based model of opinion formation

A particular case of a cellular automata-based model of two-state opinion formation in social groups with a strong leader is studied. We consider a 2D Euclidian geometry of social space and mutual interactions 1/r ⁿ . The model shows an interesting dynamics which can be analytically calculated. There are two stable states of the system: a cluster around the leader and unification. Unstable clusters may also appear. A variation in parameters such as the leader's strength or the social temperature can change the size of a cluster or, when they reach some critical values, make the system jump into another state. For a certain range of parameters the system exhibits bistability and hysteresis phenomena. We obtained explicit formulas for the cluster size, critical leader's strength, and critical social temperature. These analytical results are verified by computer simulations.