10.1007/s10955-006-9040-z

We derive hydrodynamic equations describing the evolution of a binary fluid segregated into two regions, each rich in one species,which are separated (on the macroscopic scale) by a sharp interface. Our starting point is a Vlasov-Boltzmann (VB) equation describing the evolution of the one particle position and velocity distributions, f_i (x, v, t), i = 1, 2. The solution of the VB equation is developed in a Hilbert expansion appropriate for this system. This yields incompressible Navier-Stokes equations for the velocity field u and a jump boundary condition for the pressure across the interface. The interface, in turn, moves with a velocity given by the normal component of u.     

Pattern formation in diffusion-limited reactions

The conditions for macroscopic segregation ofA andB in a steady-stateA+B 0 reaction are studied in infinite systems. Segregation occurs in one and two dimensions and is marginal ford=3. We note the dependence of these results on the precise experimental conditions assumed in the theory. We also note the difference between these results and our earlier ones for finite systems where the critical dimension isd=2.     

二组分混合物的最小流化特性 Ⅰ.混合/分离状态与最小流化空隙率

分析了二组分混合物的３种混合／分离状态及在完全混合时发生连续相转变的极限组成。提出一个判别非等密度体系混合／分离状态的法则与确定混合物空隙率简易可行的随意松散堆积方法。     

Segregation in zirconia: equilibrium versus non‐equilibrium segregation

The present work considers the differences between the following two phenomena: equilibrium segregation, which is a thermodynamic phenomenon where the driving force is excess interfacial energy; and non‐equilibrium segregation, which can be produced by phenomenological shocks applied to the solid surface. Fully stabilized cubic yttria‐stabilized zirconia (YSZ) is used as the exemplar for these considerations. Equilibrium segregation in YSZ results in enrichment of the surface and near‐surface layers in constituent elements, typically yttria and impurities. This segregation is an intrinsic material property and has an impact on the performance of zirconia at elevated temperatures. On the other hand, non‐equilibrium segregation leads to a complex distribution of properties (structure and concentration gradients) that are determined by the experimental procedures used rather than being a material property. However, such non‐equilibrium segregation can result in localized structural changes. The present paper also considers the effect of the gas phase on surface properties of metal oxides, including YSZ, and the surface dynamics of YSZ at temperatures below that required to reach equilibrium. Copyright © 2005 John Wiley & Sons, Ltd.     

Interfacial segregation in Ag-Au,Au-Pd,and Cu-Ni alloys: I. (100) surfaces

Atomistic simulations of segregation to (100) free surface in Ag–Au, Au–Pd, and Cu–Ni alloy systems have been performed for a wide range of temperatures and compositions within the solid solution region of these alloy phase diagrams. In addition to the surface segregation profiles, surface free energies, enthalpies, and entropies were determined. These simulations were performed within the framework of the free energy simulation method, in which an approximate free energy functional is minimized with respect to atomic coordinates and atomic site occupation. The effects of the relaxation with respect to either the atomic positions or the atomic concentrations are discussed. For all alloy bulk compositions (0.05 C 0.95) and temperatures (400 T(K) 1,100) examined, Ag, Au, and Cu segregates to the surface in the Ag–Au, Au–Pd, and Cu–Ni alloy systems, respectively. The present results are compared with several theories for segregation. The resultant segregation profiles in Au–Pd and Ag–Au alloys are shown to be in good agreement with an empirical segregation theory, while in Cu–Ni alloys the disagreement in Ni-rich alloys is substantial. The width of the segregation profile is limited to approximately three to four atomic planes. The surface thermodynamic properties depend sensitively on the magnitude of the surface segregation, and some of them are shown to vary linearly with the magnitude of the surface segregation.     

Grain boundary segregation diagrams of α-iron

Based on thermodynamic analysis of interfacial segregation, the segregation enthalpy H ^o of a solute I in a given matrix was found to depend linearly on two mutually independent terms reflecting the type of interface and the solid solubility limit X _infI ^sup* at temperature T and can be written as In this equation, the structural dependence of interfacial segregation is contained in H ^*() which corresponds to the extrapolated segregation enthalpy of a solute with unlimited solubility in the matrix. The product [Tln(X _infI ^sup* )] is essentially constant with temperature, and can therefore be obtained from data for maximum solid solubility, [Tln(X _infI ^sup* )]_max. The parameter v>0 represents the relationship between the activity a _infI ^sup* of a solute at the bulk solid solubility limit in a given matrix and X _infI ^sup* , a _infI ^sup* =(X _infI ^sup* ) ^v , and is characteristic for the matrix. Using recent experimental data for silicon, phosphorus, and carbon segregation at well-characterized grain boundaries in oriented bicrystals of -iron, the averaged value was determined. Values of H ^*() range from -8 kJ/mol (general grain boundaries) up to +8 kJ/mol (special grain boundaries). These values are discussed and used for a more precise and generalized construction of grain boundary segregation diagrams of -iron.     

Bond-length fluctuations in transition-metal oxoperovskites

Bond-length fluctuations in transition-metal oxoperovskites may give rise to two-phase fluctuations in what appears to be a single phase to a diffraction experiment. Orbital disorder at Jahn-Teller ions results in bond-length fluctuations that give 3D-ferromagnetic, vibronic Mn(III)-O-Mn(III) superexchange interactions and allow disproportionation into Mn(IV) and Mn(II) in LaMnO₃; where orbitally ordered and disordered phases coexist, an external magnetic field stabilizes the orbitally disordered, ferromagnetic phase relative to the orbitally ordered, antiferromagnetic phase. Spin-lattice interactions in the paramagnetic phase of charge-transfer compounds give bond-length fluctuations arising from the semicovalent component of the superexchange interactions. At the crossover from localized to itinerant electronic behavior, the coexistence of two-phase fluctuations has been demonstrated in both the single-valent RNiO₃ family (R=rare-earth, A=alkaline-earth) and the mixed-valent R_0.5A_0.5MnO₃ perovskites. “Bad-metal” behavior is found to be associated with bond-length fluctuations.     

Binary alloys as a model for the multicultural society

The model of regular solutions, that may be applied to binary alloys (e.g. Au?Pt, Si?Ge) has been compared to binary societies: blacks—non-blacks in the US, catholics—non-catholics, foreigners—German citizen. The excellent agreement of phase diagrams and intermarriage data encourages a calculation of the multicultural society by functions of thermodynamics: Solubility corresponds to integration, miscibility gap to segregation, free enthalpy to happiness and temperature to tolerance of a society. Only a high level of tolerance will integrate ghettos and lead to a peaceful multicultural society.     

Surface properties of ω-perfluorooctyl-alkyl polyacrylates: odd–even effect

A series of ω-perfluorooctyl-alkyl polyacrylates has been prepared and analysed. The odd–even effect, already observed in the case of liquid crystalline polymers has been exhibited for perfluorinated ones. Values of the contact angles to advanced (θ_a), with withdrawal (θ_r), as well as the contact angle hysteresis (Δθ) of various ω-perfluorooctyl-alkyl polyacrylates in water at 20 °C are described. Contrary to the advancing contact angle which is almost independent of spacer length, the receding one varies strongly with it.     

Atom-probe field ion microscopy

The atom probe field ion microscope (AP-FIM) is a combination of a field ion microscope and a time-of-flight mass spectrometer with a single ion detection sensivity. With the field ion microscope topology of a surface, surface reactions and surface modifications can be studied in atomic detail. By time-of-flight measurements surface layers and interface layers can be chemically analyzed atom by atom and atomic layer by atomic layer. Compositional variations according to surface or interface segregation, precipitations, or surface changes in corrosion or in electrochemical layer formation etc. can be studied quantitatively on a subnanometer scale. Some of our studies on related problems will be decribed briefly.