For a clean liquid interface at fixed temperature and composition, surface tension is the reversible free-energy cost per added area, , so . Its units are both and . Molecules at an interface have a different environment from those in the bulk; creating more interface changes their interactions and entropy. For constant , the interfacial free energy is up to a reference constant. This is not generally identical to the internal surface energy: the interfacial entropy density is , giving internal-energy density .
A line of length in one interface transmits a tangential force , perpendicular to the line. A soap film has two interfaces, giving force on a sliding rim. Quasistatic extension by creates total area , recovering that force from . Uniform positive surface tension favors minimum area at fixed volume, hence an isolated spherical droplet when gravity is negligible. curvature gives the Young–Laplace equation, with outward normal chosen consistently:A spherical liquid drop has ; a thin soap bubble with two similar interfaces has approximately . The capillary length compares gravity with capillarity. surface tension also restores capillary waves, rather than providing a bulk static shear modulus.
Interfacial contamination and added surfactants can change substantially; a nonuniform value produces tangential Marangoni stress. A rim-force measurement should therefore control temperature, cleanliness and the number of interfaces. Capillary-rise methods additionally need the contact angle, because the vertical component is proportional to . An independent frame-force measurement can distinguish a contact-angle change from a true change of surface tension.
A moving or externally forced colloid disturbs the surrounding fluid, changing the velocity of other colloids even without direct contact. These hydrodynamic interactions are long-ranged at small Reynolds number. In an unbounded incompressible Newtonian liquid, the Stokes flow response to a point force is the Stokeslet:Its Oseen tensor isThis is a mobility tensor, with units velocity per force, rather than a stress tensor. At separation the response parallel to the line of centres is ; the perpendicular response is . Flow is not isotropic even though the solvent is. The disturbance decays as , so treating all drag forces as independent can miss correlated motion.
For well-separated equal spheres of radius , the leading hydrodynamic mobility matrix givesThe first term is the isolated-sphere self mobility; the remaining terms couple distinct particles. At thermal equilibrium the fluctuation-dissipation theorem also predicts correlated short-time increments, with the configuration locally fixed. Thus correlated Brownian displacements can reveal hydrodynamic coupling without an applied force.
The point-force approximation requires and negligible inertia. It diverges at the origin and cannot replace the finite self mobility. Near-contact lubrication, walls, many-body corrections, and a viscoelastic solvent require more complete mobility laws. A force-free particle can instead have a faster-decaying leading disturbance, so the claim specifically concerns a net-force-driven object.
Use polymer volume fraction horizontally and the Flory interaction parameter vertically. Lower gives better solvent quality. The simplest Flory–Huggins solution theory assigns the dimensionless mixing free energy per lattice siteThus gives positive excluded volume and a good-solvent coil, is the long-chain theta condition, and is the poor-solvent side. It is the net two-segment interaction that vanishes at theta, not every molecular force.
At fixed good-solvent quality, the polymer overlap volume fraction separates isolated coils from a semidilute polymer solution. Above overlap, many chains interpenetrate, but there is still solvent on the segment scale. As approaches order unity the solution is concentrated; these concentration-regime boundaries are crossovers, not first-order phase transitions. The overlap fraction increases from order in a strong good solvent toward order at theta. The crossover can be expressed as while ; it saturates at the theta scaling when that condition fails.
On the poor-solvent side there can instead be coexistence of polymer-poor and polymer-rich phases. The binodal follows a common tangent of ; the spinodal followsThe critical point of a Flory–Huggins polymer solution isFor finite , lies above . Therefore poor solvent does not automatically mean demixing at every concentration, and an overlap line must not be mistaken for a coexistence boundary. The original figure uses the stated ideal model for an illustrative chain length; it does not assert a measured phase boundary. A vertical temperature axis would additionally require a material-specific relation .
Polymer solution regimes
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