Adsorbed polymer loop 2026-10-20
A nonadsorbed chain section whose two ends connect to surface-bound portions of the same adsorbed polymer. Loops extend into the solvent and contribute to the thickness, steric repulsion and conformational entropy of an adsorbed layer.
For , the given model predicts attraction proportional to in force, independent of the ion's charge sign; the energy is proportional to and vanishes at large separation. A larger electric polarizability gives a stronger interaction.
This is induction by a charged object. Ordinary nonretarded London interaction between two small neutral polarizable objects instead has an energy dependence; geometry-integrated colloidal dispersion laws can have other powers. Calling the specified law a generic dispersion force would conceal its charge-dependent origin.
Attraction can favor association or adsorption. A stable suspension normally requires an opposing free-energy barrier, such as double-layer or steric repulsion, relative to Brownian motion. Salt, surface coatings and solvent quality alter that balance. However, one ion–particle pair potential alone does not establish the phase behavior or aggregation rate of a many-particle suspension; concentrations, diffusion, surface chemistry and the remaining interactions also matter.
polymers at interfaces balance favorable surface contacts against lost conformational entropy and interactions among neighboring chains. At an attractive solid–liquid interface, an adsorbed polymer train consists of consecutive bound segments. An adsorbed polymer loop leaves the surface and returns to it, while an adsorbed polymer tail extends to a free chain end. A chain can contain all three, so adsorption does not imply a completely flattened molecule. Surface affinity, solvent quality, persistence length, chain length and concentration control the balance and the resulting segment-density profile.
Figure 1.
Original schematic of adsorbed trains, loops and tails, and the crossover from isolated grafted mushrooms to an overlapping polymer brush
. Details.
adsorption gains energy of order per bound segment but reduces the number of accessible chain configurations. Weak adsorption can be described through adsorption blobs whose thickness exceeds the statistical segment length; each blob loses an energy of order through confinement. Stronger attraction generally creates more contacts and a more compact layer, while loops and tails can still dominate its outer extent. A measurement of adsorbed mass alone therefore does not determine layer thickness or conformation.
End-grafted chains are different: their attachment is fixed at one end. At grafting density , the mean lateral spacing is . At low coverage the chains behave as isolated polymer mushrooms. The polymer mushroom-to-brush crossover occurs when . At higher coverage in a good solvent, crowding makes chains extend away from the surface. A free-energy balance per chain,
combines stretching entropy with repulsive excluded volume . Minimization gives , or
This is a scaling result with an undetermined order-one coefficient, valid for overlapping chains stretched below their contour length. In a compact poor-solvent layer, a roughly fixed internal polymer volume fraction instead gives .
Small-angle neutron scattering on end-grafted polydimethylsiloxane layers on porous silica has distinguished the good- and poor-solvent density exponents. The chemical system and scattering contrast matter: changing solvent quality should be separated from changing graft coverage, chain molar mass or adsorption strength.[ref]
An interface can also localize chains of a block copolymer when its blocks prefer different media. Such layers change interfacial tension and can stabilize dispersed droplets or particles through steric repulsion. Overlapping layers in a good solvent cost osmotic and conformational free energy; incomplete adsorption can instead produce polymer bridging between particles. Nonadsorbing chains can cause depletion attraction. Thus the presence of a polymer does not by itself guarantee stabilization.
In a regular solution, ideal combinatorial entropy competes with a nonzero unlike-contact energy. For equal molecular volumes and mole fraction of species A, write mixing free energy per site as
where
Here is the coordination number and a pair-contact energy counted consistently in the lattice model. A positive penalizes unlike contacts; a negative value favors them. The logarithmic terms lower free energy on mixing. The sign of the enthalpy of mixing alone therefore does not determine miscibility.
At fixed temperature and composition, a homogeneous phase is globally stable only if no division into two compositions lowers its free energy. The common-tangent construction selects coexisting compositions , equivalent to equality of both species' chemical potentials. Local stability to infinitesimal fluctuations instead requires
Zero curvature gives the spinodal, while the coexistence boundary is the binodal. Between them a homogeneous state can be metastable and require nucleation; inside the spinodal its small composition fluctuations grow. The symmetric regular solution has
Below this contact penalty, the free energy is convex at every composition. Above it a miscibility gap is possible around the central composition. If with , heating promotes mixing, but specific interactions or temperature-dependent noncombinatorial terms can produce other trends.
For two polymers, let count equal-volume segments per chain, and now let be the segment volume fraction of A. Connecting segments into chains reduces their independent translational entropy. The binary Flory-Huggins polymer blend has
The energetic contact term remains extensive in the number of segments, while the favorable entropy per segment is reduced by and . This is the key long-chain limit of polymer-blend miscibility: a small positive incompatibility can overcome the mixing entropy. The lattice treatment is a controlled model for this argument, rather than a claim that every real blend has composition-independent .[ref]
The local stability condition and critical interaction parameter become
For equal chain lengths, . Similar segment chemistry and matched cohesive interactions can reduce the unlike-contact penalty; favorable specific interactions, such as complementary hydrogen bonding, can make mixing favorable even for long chains. Lower molar mass increases mixing entropy. temperature can help when it lowers the effective , but heating is not universally sufficient. A suitable common solvent can facilitate processing or ternary mixing, and a block-copolymer compatibilizer can stabilize fine domains; neither guarantees that the final solvent-free binary material is one equilibrium molecular phase.
An oil–water emulsion illustrates emulsion stability versus molecular miscibility. A surfactant adsorbs with its water-affine head toward water and its oil-affine tail toward oil, lowering interfacial tension and the work needed to make additional interface. Breaking a fixed oil volume into spherical droplets of radius gives total area , so creating small droplets still requires substantial area and usually mechanical work.
Adsorbed surfactants can oppose droplet coalescence through charged double-layer repulsion, hydrated-head interactions or steric repulsion from sufficiently extended groups. Adequate coverage, adsorption time, ionic conditions and film drainage affect the lifetime. A lower interfacial tension does not itself remove the bulk miscibility gap, and a protected emulsion is commonly kinetically stabilized. A thermodynamically stable microemulsion is a distinct situation requiring an appropriate composition and free-energy balance. The two liquids must not be called molecularly miscible simply because droplets disperse visibly.
For the capillary, balance upward contact-line force against hydrostatic column weight, neglecting meniscus volume and gas density. For inner radius ,
The contact angle is measured through the liquid. complete wetting means , so the contact-angle change of capillary rise gives
This follows from the stipulated wetting change, holding radius, bulk liquid surface tension and density fixed. One should not replace that premise with a general claim that grease always improves glass wetting; if contamination also changes the liquid surface tension, the original height and new angle alone would not determine the new height.
For two wide vertical plates separated by gap , use unit width. There are two upward contact-line contributions and liquid cross-sectional area , giving the capillary rise between parallel plates:
Only one principal meniscus curvature contributes between wide plates, whereas a circular tube has two. For the same fluid and angle,
If the plate gap equals the tube diameter, , the rise is half as large: the initial and completely wetting heights would be cm and cm. If instead , the heights are equal. In either geometry, changing only the angle from to zero multiplies the height by . Since the question specifies no plate spacing, the general gap-dependent relation is the unambiguous result; the half-height answer requires the equal-gap-to-diameter convention.