Statistical description of glass-forming alloys with chemical interaction: Application to Al-R systems

The statistical model for describing network-forming systems, developed in our previous works, is applied to study of metallic alloys with chemical bonding. The model is based on the representation of the sum of statistical weights over all possible configurations for a thermoreversible network in the form of a functional integral over a scalar field. The mean-field solution of the model is derived, and for particular case of a binary alloy having single element of chemical short-range order A₂B-type, thermodynamic and structural properties have been analyzed. This analysis allows to plot the temperature-concentration phase diagram of the model representing two immiscibility gap meeting in the distectic point. It is shown that at some temperatures and concentrations, geometry percolation of the network of chemical bonds and thus a sol-gel transition may take place. The critical percolation line was plotted in common with phase diagram. Then, the structural transitions, glass-forming ability and magnetic properties of Al-R alloys are discussed in the frames of this conception. It is proposed that the range of easy glass formation is confined on the left by the minimal concentration for the sol-gel transition and on the right by the concentration corresponding to the fractal-to-Euclidian crossover in the structure of percolation cluster. Finally, the abnormal growth of Al-REM magnetic susceptibility occurring above melting point of Al₂R compound is also explained.     

Variable reactivity and phase separation in patchy particle systems

ABSTRACT

Using statistical model, we study mechanisms of phase separation in a solution consisting of patchy particles, which are capable to form directed and saturated thermoreversible bonds. We focus on the impact of variable reactivity of patchy particles on the form of miscibility gap. We show that the variation of model parameters determining features of interparticle interaction makes it possible to obtain miscibility gaps of different types within the unified formalism. In particular, we uncover two different mechanisms of the formation of phase separation curves with lower critical solution temperature. The first mechanism is realised in the case of positive bonding energy; the second one can takes place when the energy of formation of two-bonded particles is lower than that for all other m-bonded ones. We conclude that the most interesting and non-trivial phase behavior is observed in the case of patchy particles with variable reactivity. Using rigorous statistical model, we uncover new mechanisms of phase separation in a solution consisting of patchy particles, which are capable to form directed and saturated thermoreversible bonds. This topic corresponds to state of the art in modern chemical physics. The results obtained shed light on interplay between features of non-isotropic interactions and phase behavior in both molecular and nanoparticle systems. We conclude that the most interesting and non-trivial phase behavior is observed in the case of patchy particles with variable reactivity.     

Photophysical Properties of Luminescent Quaternary Lanthanide Molecular Hybrid Systems with Chemical Bonds from the Cooperative Design and Assembly of Structure and Function

Two long chain aliphatic acyl chlorides (dodecanoyl chloride (C₁₀H₁₉OCl, abbreviated as DC) and stearoyl chloride (C₁₈H₃₅Ocl, abbreviated as SC)) were modified by means of the amidation reaction with crosslinking molecules (N-aminopropyl-triethoxylsiliane, (APES, H₂N(CH₂)₃Si(OC₂H₅)₃)) and afford two kinds of structural molecular bridge DC (SC)− APES with double reactivity. Subsequently, according to the principle of coordination chemistry, ternary lanthanide (terbium and europium) molecular complex systems with two molecular bridges DC (SC)− APES and 1,10-phenanthroline (phen) of were successfully assembled. Then the modified molecular bridges behave as structural ligands to form the covalent bond Si− O network with matrix precursor (tetraethoxysilane, TEOS) through a sol-gel process (cohydrolysis and copolycondensation process), resulting in a novel quaternary molecular hybrid material (so called as phen-Tb(Eu)−DC(SC)− APES) with strong chemical bonds (N− Tb(Eu)− O coordination bonds and Si− O covalent bonds). And phen behaves as functional ligand to sensitize the luminescence of terbium or europium ions through the effective intramolecular energy transfer process, which gives rise to the characteristic emission of metal ion.     

Separation and gelation in associated systems with thermoreversible chemical bonds

Possible types of separation curves for a binary solution of chemically interacting molecules in a neutral solvent have been analyzed within the statistical model. It has been shown that the variation of the model parameters characterizing the energy and entropy of chemical bonds makes it possible to describe most of the possible types of solubility curves within the unified formalism. It has been demonstrated that the sol-gel transition for the case where the reactivity of molecules depends on the number of bonds can occur as a first-order phase transition; in the opposite case, gelation is a purely geometrical percolation transition.     

Grain Boundary Phase Transitions and their Influence on Properties of Polycrystals

Grain boundary (GB) phase transitions can change drastically the properties of polycrystals. The GB wetting phase transition can occur in the two-phase area of the bulk phase diagram where the liquid (L) and solid (S) phases are in equlibrium. Above the temperature of the GB wetting phase transition a GB cannot exist in equlibrium contact with the liquid phase. The experimental data on GB wetting phase transitions in numerous systems are analysed. The GB wetting tie-line can continue in the one-phase area of the bulk phase diagram as a GB solidus line. This line represents the GB premelting or prewetting phase transitions. The GB properties change drastically when GB solidus line is crossed by a change in the temperature or concentration. The experimental data on GB segregation, energy, mobility and diffusivity obtained in various systems both in polycrystals and bicrystals are analysed. In case if two solid phases are in equilibrium, the GB “solid state wetting” can occur. In this case the layer of the solid phase 2 has to substitute GBs in the solid phase 1. Such GB phase transition occurs if the energy of two interphase boundaries is lower than the GB energy in the phase 1.     

First-order depinning transition in two-dimensional abraham model: RG approach

Using a position-space renormalization group (RG) we analyse the competition for an interface between the boundary defect and an additional line of defect bonds in the two-dimensional Abraham model. The RG phase diagram, obtained over the whole range of temperatures and pinning parameters, indicate that beside the continuous wetting transition this model exhibits a finite-temperature interface depinning transition of the first order in agreement with recently obtained exact results.     

Structural phase diagram of rare-earth-cadmium equiatomic compounds

A structural phase diagram is proposed for rare-earth-cadmium equiatomic compounds essentially established by means of magnetic susceptibility in a SQUID susceptometer. A structural transition occurs at about 210 K throughout the series; for light rare-earth compounds, a second transition line delimits an intermediate phase between 210 K and low temperatures. Both phases are unknown.     

Monte Carlo study of the triangular XY vector Blume-Emery-Griffiths model

The vectorial generalization of the Blume-Emery-Griffiths model, proposed by Berker and Nelson to describe the behavior of films of ³He-⁴He mixtures, is studied by Monte Carlo simulations on the triangular lattice. The temperature versus chemical potential plane phase diagram, for a biquadratic coupling constant equal to the bilinear coupling constant, presents a Berezinzkii-Kosterlitz-Thouless transition line that ends in a first-order transition line at a critical end point. This first-order transition line, on the other hand, terminates at a single critical point. No tricritical point has been detected. The critical exponent η as a function of temperature is independent of the chemical potential.     

Dynamical arrest transition in nanoparticle dispersions with short-range interactions

We measure the dynamical arrest transition in a model, thermoreversible, adhesive hard sphere dispersion. At low volume fractions ?, below the critical point, gelation occurs within the gas-liquid phase boundary. For ? slightly below and above the critical concentration, the phase boundary follows the predicted percolation transition. At high ?, it melds into the predicted attractive-driven glass transition. Our results demonstrate that for ? above ～20% physical gelation is an extension of the attractive-driven glass line and occurs without competition for macroscopic phase separation.     

Multiple intermediate valence in plutonium

On the basis of the concepts of an intermediate-valence (IV) regime, an empirical model is proposed that quantitatively describes the magnetic susceptibility, specific heat, and effective atomic volume of the low-temperature α phase and the gallium or aluminum-stabilized face-centered cubic (fcc) δ phase of plutonium metal. The results of the paper allow one to estimate the entropy change associated with the α → δ structural phase transition, the value of this change being very close to the experimental value. According to the model, both phases of plutonium are systems with multiple intermediate valence, whose ground state is a many-particle Kondo singlet, and fluctuations occur between 5f electron configurations with integer valences of 3+, 4+, and 2+.     

Universal incommensurate structures

Certain phase transitions in quasiperiodic systems are characterized byuniversal structures. In these cases the functional form of the order parameter corresponding to the modulated phase,P(r), is determined by the symmetry properties of the system and is independent of the details of the associated Landau-Ginzburg model. Here we consider a simple one-dimensionalXY-like model corresponding to this type of phase transition. The universal modulated structure of this model is calculated numerically at various points along the critical line.     

Equation of state of hadron resonance gas and the phase diagram of strongly interacting matter

The equation of state of hadron resonance gas at finite temperature and baryon density is calculated taking into account finite-size effects within the excluded-volume model. Contributions of known hadrons with masses up to 2 GeV are included in the zero-width approximation. Special attention is paid to the role of strange hadrons in the system with zero total strangeness. A density-dependent mean field is added to guarantee that the nuclear matter has a saturation point and a liquid-gas phase transition. The deconfined phase is described by the bag model with lowest order perturbative corrections. The phasetransition boundaries are found by using the Gibbs conditions with the strangeness neutrality constraint. The sensitivity of the phase diagram to the hadronic excluded volume and to the parametrization of the mean-field is investigated. The possibility of strangeness-antistrangeness separation in the mixed phase is analyzed. It is demonstrated that the peaks in the K/π and Λ/π excitation functions observed at low SPS energies can be explained by a nonmonotonous behavior of the strangeness fugacity along the chemical freeze-out line. The text was submitted by the authors in English.     

Quantitative theory of thermal fluctuations and disorder in the vortex matter

A metastable supercooled homogeneous vortex liquid state exists down to zero fluctuation temperature in systems of mutually repelling objects. The zero temperature liquid state therefore serves as a (pseudo) ‘fixed point’ controlling the properties of vortex liquid below and even around the melting point. Based on this picture, a quantitative theory of vortex melting and glass transition in Type II superconductors in the framework of Ginzburg-Landau approach is presented. The melting line location is determined and magnetization and specific heat jumps are calculated. The point-like disorder shifts the line downwards and joins the order-disorder transition line. On the other hand, the disorder induces irreversible effects via replica symmetry breaking. The irreversibility line can be calculated within the Gaussian variational method. Therefore, the generic phase diagram contains four phases divided by the irreversibility line and melting line: liquid, solid, vortex glass and Bragg glass. We compare various experimental results with the theoretical formula.     

Statistical thermodynamics of the formation of an infinite cluster of thermally reversible chemical bonds

A systematic “mean-field” treatment of the thermodynamic equilibrium formation of an infinite cluster of bonds in a system of identical monomers capable of forming from n=0 to n>2 reversible chemical bonds with one another is proposed within the Cayley-tree approximation. For this purpose the difference between the symmetry of the monomers appearing in “point-to-point” and closed bond paths, respectively, is taken into account on the basis of an analysis of the structure of the infinite cluster. Minimization with respect to the distribution of such monomers yields a nontrivial solution corresponding to a lower free energy than the classical solution, which does not allow for the symmetry difference indicated. In addition, it is shown that the classical solution corresponds to the free-energy maximum when the infinite cluster is formed and that the formation of the infinite cluster is a first-order phase transition. The possible form of the phase diagrams of the systems considered is analyzed. Zh. éksp. Teor. Fiz. 115, 979–990 (March 1999)     

Low-temperature structural phase transition in a monoclinic KDy(WO4)2 crystal

The low-temperature thermal and magnetic-resonance properties of a monoclinic KDy(WO₄)₂ single crystal are investigated. It is established that a structural phase transition takes place at T _c=6.38 K. The field dependence of the critical temperature is determined for a magnetic field oriented along the crystallographic a and c axes. The initial part of the H-T phase diagram is plotted for H∥a. The prominent features of the structural phase transition are typical of a second-order Jahn-Teller transition, which is not accompanied by any change in the symmetry of the crystal lattice in the low-temperature phase. The behavior of C(T) in a magnetic field shows that the transition goes to an antiferrodistortion phase. An anomalous increase in the relaxation time (by almost an order of magnitude) following a thermal pulse is observed at T>T _c(H), owing to the structural instability of the lattice. A theoretical model is proposed for the structural phase transition in a magnetic field, and the magnetic-field dependence of T _c is investigated for various directions of the field. Fiz. Tverd. Tela (St. Petersburg) 40, 750–758 (April 1998)     

Small-angle light scattering studies of dense AOT-water-decane microemulsions

Summary We have performed extensive studies of a three-component microemulsion system composed of AOT-water-decane (AOT=sodium-bis-ethylhexyl-sulfosuccinate is an ionic surfactant) using small-angle light scattering (SALS). The small-angle scattering intensities are measured in the angular interval 0.001–0.1 radians, corresponding to a Bragg wave number range of 0.14 μm⁻¹<Q<<1.4 μm⁻¹. The measurements were made by changing temperature and volume fraction ϕ of the dispersed phase (water + AOT) in the range 0.05<ϕ<0.75. All samples have a fixed water-to-AOT molar ratio,w=[water]/[AOT]=40.8, in order to keep the same average droplet size in the stable one-phase region. With the SALS technique, we have been able to observe all the phase boundaries of a very complex phase diagram with a percolation line and many structural organizations within it. We observe at the percolation transition threshold, a scaling behavior of the intensity data. This behavior is a consequence of a clustering among microemulsion droplets near the percolation threshold. In addition, we describe in detail a structural transition from a droplet microemulsion to a bicontinuous one as suggested by a recent small-angle neutron scattering experiment. The loci of this transition are located several degrees above the percolation temperatures and are coincident with the maxima previously observed in shear viscosity. From the data analysis, we show that both the percolation phenomenon and this novel structural transition are derived from a large-scale aggregation between microemulsion droplets.     

The Gibbs equilibrium conditions applied to the QGP–hadron transition curve

A method is developed to consistently satisfy the Gibbs equilibrium conditions between the quark–gluon and hadronic phase, although each phase has been formulated in separate grand canonical partition functions containing three quark flavours. The sector in the space of thermodynamic variables where the transition takes place is restricted to a curve, according to the phase diagram of QCD. The conservation laws of quantum numbers are also imposed on the transition curve. The effect of the inclusion of the pentaquark states is considered. The data from S+S, S+Ag (SPS) and Au+Au (RHIC) are found to be compatible with the formation of a QGP phase and the occurrence of the chemical freeze-out immediately after crossing the transition line, but the data from Pb+Pb (SPS) are not. PACS 12.40.Ee; 05.70.Fh; 12.38.Mh; 24.10.Pa     

Specific features of temperature dependences of energy parameters of interfacial interactions in crystalline quartz-pb and (NaCl,KCl)-Pb systems

Temperature dependences of energy parameters, namely, interfacial interaction energy, interfacial tension, work of adhesion, and energy of adhesive bonds in crystalline quartz-(AT-cut)-Pb and (NaCl,KCl)-Pb systems in the presence of a structural phase transition in a quartz substrate (α ? β) and a solid phase-liquid phase transition in Pb, have been studied. The influence of the type of chemical bond of the substrate on the parameters of interfacial interaction has been analyzed.     

New Universality Class Associated with Jahn–Teller Distortion and Double Exchange

The scaling of the magnetic heat capacity in the two manganites La0.85Ag0.15MnO3 and Sm0.55Sr0.45MnO has given the critical exponents α = –0.23 and ν = 0.7433 of the heat capacity and correlation radius of the magnetic order parameter, respectively, which do not belong to any known universality class. These results cannot be attributed to chemical inhomogeneities and/or structural imperfections because the samples are of a high quality. Thus, unusual critical exponents can be associated not only with the chemical disorder and/or structural defects but also with the collective behavior of the lattice. An analogy has been revealed between the effects of the magnetic field and doping on ternary oxides of transition metals: the magnetic field affecting lattice distortions through the orientation of t2g orbitals acts as chemical doping. It seems that scaling relations are more stable than critical exponents in them. The synchronism of lattice distortions and ferromagnetism leads to a novel criticality, but their desynchronization induced by magnetostructural disorder results in the violation of scaling relations between isothermal and isomagnetic exponents. Although double-exchange systems demonstrate novel criticality, they satisfy scaling relations until the magnetic behavior is synchronized with the coherent lattice behavior in the form of cooperative Jahn–Teller distortions. Breaking of double exchange bonds leads to the formation of metamagnetic clusters with magnetic dipole–dipole interaction between them, which desynchronizes lattice distortions and ferromagnetism, resulting in the violation of scaling relations. The proposed new universality class includes diverse materials such as manganites, cobaltites, crystalline Fe–Pt and amorphous Fe–Mn alloys, and high-Tc superconductors. Unusual criticality in double-exchange systems is due to an unusual semiclassical nature of double-exchange ferromagnetism caused by real exchange, i.e., electron current through Mn3+–O–Mn4+ chains with the conservation of the spin rather than by virtual exchange as in a usual ferromagnet. Double-exchange ferromagnetism arises only because to freely itinerate, electrons orient the magnetic moments of Mn cations in a single direction.