Subscribe to the gold package and get unlimited access to Shamra Academy
Register a new userEffects of Confinement on Critical Adsorption: Absence of Critical Depletion for Fluids in Slit Pores
78
0
0.0
(
0
)
Ask ChatGPT about the research
No Arabic abstract
The adsorption of a near-critical fluid confined in a slit pore is investigated by means of density functional theory and by Monte Carlo simulation for a Lennard-Jones fluid. Our work was stimulated by recent experiments for SF_6 adsorbed in a mesoporous glass which showed the striking phenomenon of critical depletion, i.e. the adsorption excess Gamma first increases but then decreases very rapidly to negative values as the bulk critical temperature T_c is approached from above along near-critical isochores. By contrast, our density functional and simulation results, for a range of strongly attractive wall-fluid potentials, show Gamma monotonically increasing and eventually saturating as the temperature is lowered towards T_c along both the critical (rho=rho_c) and sub-critical isochores (rho<rho_c). Such behaviour results from the increasingly slow decay of the density profile away from the walls, into the middle of the slit, as T->T_c. For rho < rho_c we find that in the fluid the effective bulk field, which is negative and which favours desorption, is insufficient to dominate the effects of the surface fields which favour adsorption. We compare this situation with earlier results for the lattice gas model with a constant (negative) bulk field where critical depletion was found. Qualitatively different behaviour of the density profiles and adsorption is found in simulations for intermediate and weakly attractive wall-fluid potentials but in no case do we observe the critical depletion found in experiments. We conclude that the latter cannot be accounted for by a single pore model.
rate research
Read More
Fluids in porous media are commonly studied with analytical or simulation methods, usually assuming that the host medium is rigid. By evaluating the substrates response (relaxation) to the presence of the fluid we assess the error inherent in that assumption. One application is a determination of the ground state of 3He in slit and cylindrical pores. With the relaxation, there results a much stronger cohesion than would be found for a rigid host. Similar increased binding effects of relaxation are found for classical fluids confined within slit pores or nanotube bundles.
The paramagnetic-to-ferromagnetic phase transition is believed to proceed through a critical point, at which power laws and scaling invariance, associated with the existence of one diverging characteristic length scale -- the so called correlation length -- appear. We indeed observe power laws and scaling behavior over extraordinarily many decades of the suitable scaling variables at the paramagnetic-to-ferromagnetic phase transition in ultrathin Fe films. However, we find that, when the putative critical point is approached, the singular behavior of thermodynamic quantities transforms into an analytic one: the critical point does not exist, it is replaced by a more complex phase involving domains of opposite magnetization, below as well as $above$ the putative critical temperature. All essential experimental results are reproduced by Monte-Carlo simulations in which, alongside the familiar exchange coupling, the competing dipole-dipole interaction is taken into account. Our results imply that a scaling behavior of macroscopic thermodynamic quantities is not necessarily a signature for an underlying second-order phase transition and that the paramagnetic-to-ferromagnetic phase transition proceeds, very likely, in the presence of at least two long spatial scales: the correlation length and the size of magnetic domains.
The excess adsorption $Gamma $ in two-dimensional Ising strips $(infty times L)$ subject to identical boundary fields, at both one-dimensional surfaces decaying in the orthogonal direction $j$ as $-h_1j^{-p}$, is studied for various values of $p$ and along various thermodynamic paths below the critical point by means of the density-matrix renormalization-group method. The crossover behavior between the complete wetting and critical adsorption regimes, occurring in semi-infinite systems, are strongly influenced by confinement effects. Along isotherms $T=const$ the asymptotic power law dependences on the external bulk field, which characterize these two regimes, are undercut by capillary condensation. Along the pseudo first-order phase coexistence line of the strips, which varies with temperature, we find a broad crossover regime where both the thickness of the wetting film and $Gamma$ increase as function of the reduced temperature $tau$ but do not follow any power law. Above the wetting temperature the order parameter profiles are not slab-like but exhibit wide interfacial variations and pronounced tails. Inter alia, our explicit calculations demonstrate that, contrary to opposite claims by Kroll and Lipowsky [Phys. Rev. B {bf 28}, 5273 (1983)], for $p=2$ critical wetting transitions do exist and we determine the corresponding wetting phase diagram in the $(h_1,T)$ plane.
The Boltzmann factor comes from the linear change in entropy of an infinite heat bath during a local fluctuation; small systems have significant nonlinear terms. We present theoretical arguments, experimental data, and Monte-Carlo simulations indicating that nonlinear terms may also occur when a particle interacts directly with a finite number of neighboring particles, forming a local region that fluctuates independent of the infinite bath. A possible mechanism comes from the net force necessary to change the state of a particle while conserving local momentum. These finite-sized local regions yield nonlinear fluctuation constraints, beyond the Boltzmann factor. One such fluctuation constraint applied to simulations of the Ising model lowers the energy, makes the entropy extensive, and greatly improves agreement with the corrections to scaling measured in ferromagnetic materials and critical fluids.
The theory of phase transitions is based on the consideration of idealized models, such as the Ising model: a system of magnetic moments living on a cubic lattice and having only two accessible states. For simplicity the interaction is supposed to be restricted to nearest--neighbour sites only. For these models, statistical physics gives a detailed description of the behaviour of various thermodynamic quantities in the vicinity of the transition temperature. These findings are confirmed by the most precise experiments. On the other hand, there exist other cases, where one must account for additional features, such as anisotropy, defects, dilution or any effect that may affect the nature and/or the range of the interaction. These features may have impact on the order of the phase transition in the ideal model or smear it out. Here we address two classes of models where the nature of the transition is altered by the presence of anisotropy or dilution.
Log in to be able to interact and post comments
comments
Fetching comments
Sign in to be able to follow your search criteria
