Rounding of phase transitions in cylindrical pores.

Phase transitions of systems confined in long cylindrical pores (capillary condensation, wetting, crystallization, etc.) are intrinsically not sharply defined but rounded. The finite size of the cross section causes destruction of long range order along the pore axis by spontaneous nucleation of domain walls. This rounding is analyzed for two models (Ising or lattice gas and Asakura-Oosawa model for colloid-polymer mixtures) by Monte Carlo simulations and interpreted by a phenomenological theory. We show that characteristic differences between the behavior of pores of finite length and infinitely long pores occur. In pores of finite length a rounded transition occurs first, from phase coexistence between two states towards a multidomain configuration. A second transition to the axially homogeneous phase follows near pore criticality.

[1]  G. G. Stokes.  "J." , 1890, The New Yale Book of Quotations.

[2]  L. Onsager.  Crystal statistics. I. A two-dimensional model with an order-disorder transition , 1944 .

[3]  Chen Ning Yang,et al.  The Spontaneous Magnetization of a Two-Dimensional Ising Model , 1952 .

[4]  Fumio Oosawa,et al.  On Interaction between Two Bodies Immersed in a Solution of Macromolecules , 1954 .

[5]  E. M. Lifshitz,et al.  Statistical physics. Pt.1 , 1969 .

[6]  Kurt Binder,et al.  Monte Carlo calculation of the surface tension for two- and three-dimensional lattice-gas models , 1982 .

[7]  M. Fisher,et al.  Phase Transitions and Critical Phenomena , 2021, Statistical and Thermal Physics.

[8]  Vladimir Privman,et al.  Finite-size effects at first-order transitions , 1983 .

[9]  P. Tarazona,et al.  Capillary condensation and adsorption in cylindrical and slit-like pores , 1986 .

[10]  K. Gubbins,et al.  Liquid-vapour coexistence in a cylindrical pore , 1987 .

[11]  K. Binder,et al.  The Ising square lattice in aL×M geometry: A model for the effect of surface steps on phase transitions in adsorbed monolayers , 1989 .

[12]  Wiltzius,et al.  Wetting and random-field transition of binary liquids in a porous medium. , 1989, Physical review letters.

[13]  Wolff,et al.  Collective Monte Carlo updating for spin systems. , 1989, Physical review letters.

[14]  R. Evans.  REVIEW ARTICLE: Fluids adsorbed in narrow pores: phase equilibria and structure , 1990 .

[15]  Liu,et al.  Wetting transitions in a cylindrical pore. , 1990, Physical review letters.

[16]  Drake,et al.  Study of phase separation of a binary fluid mixture in confined geometry. , 1994, Physical review letters.

[17]  K. Gubbins,et al.  Liquid-liquid phase separation in cylindrical pores: Quench molecular dynamics and Monte Carlo simulations , 1997 .

[18]  K. Morishige,et al.  Capillary Critical Point of Argon, Nitrogen, Oxygen, Ethylene, and Carbon Dioxide in MCM-41 , 1997 .

[19]  A. Neimark,et al.  Evaluation of Pore Structure Parameters of MCM-41 Catalyst Supports and Catalysts by Means of Nitrogen and Argon Adsorption , 1997 .

[20]  A. Neimark,et al.  Pore Size Analysis of MCM-41 Type Adsorbents by Means of Nitrogen and Argon Adsorption. , 1998, Journal of colloid and interface science.

[21]  K. Morishige,et al.  Adsorption hysteresis and pore critical temperature in a single cylindrical pore , 1998 .

[22]  K. Kaneko,et al.  Capillary Condensation of N2 on Multiwall Carbon Nanotubes , 1998 .

[23]  W. D. Machin.  Properties of Three Capillary Fluids in the Critical Region , 1999 .

[24]  David P. Landau,et al.  Phase transitions and critical phenomena , 1989, Computing in Science & Engineering.

[25]  K. Gubbins,et al.  Phase separation in confined systems , 1999 .

[26]  H. Christenson.  Confinement effects on freezing and melting , 2001 .

[27]  Aleksey Vishnyakov and,et al.  Studies of Liquid−Vapor Equilibria, Criticality, and Spinodal Transitions in Nanopores by the Gauge Cell Monte Carlo Simulation Method , 2001 .

[28]  A. Schreiber,et al.  Effect of surface modification on the pore condensation of fluids: experimental results and density functional theory , 2002 .

[29]  A. Neimark,et al.  Capillary condensation as a morphological transition. , 2002, Advances in colloid and interface science.

[30]  P. Nielaba,et al.  Phase transitions and quantum effects in pore condensates: a path integral Monte Carlo study. , 2003, Physical review. E, Statistical, nonlinear, and soft matter physics.

[31]  Zhaoning Yu,et al.  Fabrication of large area subwavelength antireflection structures on Si using trilayer resist nanoimprint lithography and liftoff , 2003 .

[32]  J. Horbach,et al.  Grand canonical Monte Carlo simulation of a model colloid-polymer mixture: coexistence line, critical behavior, and interfacial tension. , 2004, The Journal of chemical physics.

[33]  A. Geiger,et al.  Water in nanopores: II. The liquid–vapour phase transition near hydrophobic surfaces , 2004 .

[34]  K. Gubbins,et al.  Effects of confinement on freezing and melting , 2006, Journal of physics. Condensed matter : an Institute of Physics journal.

[35]  Meyya Meyyappan,et al.  Carbon Nanotubes: Science and Applications , 2007 .

[36]  Kurt Binder,et al.  Confinement effects on phase behavior of soft matter systems. , 2008, Soft matter.

[37]  D. Bonn,et al.  Fluctuation forces and wetting layers in colloid-polymer mixtures. , 2008, Physical review letters.

[38]  Kurt Binder,et al.  A Guide to Monte Carlo Simulations in Statistical Physics: Frontmatter , 2009 .

[39]  P. Nowakowski,et al.  Properties of the solvation force of a two-dimensional Ising strip in scaling regimes , 2009, 0908.1775.

[40]  Kurt Binder,et al.  A Guide to Monte Carlo Simulations in Statistical Physics: More on importance sampling Monte Carlo methods for lattice systems , 2009 .