Nonlinear stability and rupture of ultrathin free films

The nonlinear long-wave stability and lifetimes of thin free films subjected to the excess Lifshitz-van der Waals (LW) forces are studied based on numerical solutions, and a weakly nonlinear theory (WNT), which neglects mode interactions. The WNT works best for the fastest growing (dominant) disturbances of small initial amplitudes, and also for relatively thick films. For such cases, the nonlinear viscous effects (stabilizing) and inertia (destabilizing) are usually less significant than the LW force (destabilizing), surface tension force, and the unsteady effects (both stabilizing). For large initial amplitudes, linearly stable disturbances can engender strong subcritical instabilities and film rupture due to the greatly enhanced LW forces, inertia and mode interactions

Comparison of the Behavior of Polymers in Supercritical Fluids and Organic Solvents Via Small Angle Neutron Scattering

Small-angle neutron scattering has been used to study the effect of temperature and pressure on the phase behavior of semidilute solutions of polymers dissolved in organic and supercritical solvents. Above the theta temperature (To), these systems exhibit a ''good solvent'' domain, where the molecules expand beyond the unperturbed dimensions in both organic solvents and in COZ. However, this transition can be made to occur at a critical ''theta pressure'' (PO) in CO2 and this represents a new concept in the physics of polymer-solvent systems. For T < To, and P < Po, the system enters the ''poor solvent'' domain where diverging concentration fluctuations prevent the chains from collapsing and allow them to maintain their unperturbed dimensions

Intramolecular Charge Transfer Reaction, Polarity, and Dielectric Relaxation in AOT/Water/Heptane Reverse Micelles: Pool Size Dependence

Intramol. charge transfer (ICT) reaction in a newly synthesized mol., of 4-(41-morpholinyl) benzonitrile (M6C), in AOT/water/heptane reverse micelles at different pool sizes has been studied by using steady-state and time-resolved fluorescence emission spectroscopy. The pool size dependences of the reaction equil. const. and reaction rate have been explained in terms of the av. polarity of the confined solvent pools estd. from the fluorescence emission Stokes shift of a nonreactive probe, coumarin 153, dissolved in these microemulsions. The complex permittivity measurements in the frequency range 0.01 ≤ ν/GHz ≤ 2 for these microemulsions at different pool sizes (0 ≤ w ≤ 40) and AOT concns. (0.1 ≤ c/M ≤ 0.5) at 298.15 K have also been performed. At sufficient water content, a large dispersion with a relaxation time of ∼600 ps has been obsd. at ∼300 MHz and attributed to the av. reorientation of water mols. residing in the close vicinity of the polar interface of the AOT headgroup and n-heptane. The reorientation of these interfacial water mols. is probably responsible for the nanosecond component obsd. in numerous polar solvation dynamics expts. in these reverse micelles. Subsequently, the estd. polarity and the measured reorientational time scale have been used to explain the dramatic slowing down of the ICT reaction rate and its dependence on pool size in these confined environments

Interfacial phenomena at the compressed co2-water interface

Compressed CO2 is considered to be a viable alternative to toxic volatile organic solvents with potential applications in areas including separation reactions, and materials formation processes. Thus an interest in CO2 stems from the fact that it is very inexpensive, has low toxicity, and is not a regulated. However, compressed CO2 has a zero dipole moment and weak van der Waals forces and thus is a poor solvent for both polar and most high molecular weight solutes, characteristics that severely restrict its applicability. In order to overcome this inherent inability, surfactant-stabilized organic and aqueous dispersions in CO2 have been proposed. This work will discuss fundamentals and recent advances in the design of amphiphiles for the novel CO2-water interface