For a long ideal chain of independent statistical steps of length , . With fixed chain chemistry and , the molar mass is proportional to . Thus multiplying molar mass by multiplies the radius of gyration by ; solvent quality can change both the statistical segment length and the size exponent.
Gel permeation chromatography separates by solution hydrodynamic volume, rather than molar mass alone. At equal molar mass, a more extended chain accesses fewer pores and elutes earlier. The relatively rigid, conjugated poly(3-hexylthiophene) is the natural first-eluting candidate, compared with the more flexible chains, provided all samples are molecularly dissolved.
This is a structural prediction, not an unconditional ordering: solvent quality, polymer aggregation and column interactions affect retention, and the hydrogen-bonding polyamide may not dissolve adequately in tetrahydrofuran. An insoluble sample cannot be assigned an ordinary solution gel permeation chromatography elution time.
A differential refractive index detector can detect all four polymers when their refractive-index contrasts are nonzero. Light scattering with an appropriate concentration detector can additionally provide molar mass. A single ultraviolet detector is unsuitable as the universal detector because polypropylene lacks the strong chromophores present in the aromatic and conjugated products.
This is the second printed “(vi)”, concerning solvent temperature. The coil is expected to expand, so its radius of gyration increases. For the usual upper-critical-solution-temperature behavior of polystyrene in cyclohexane, heating above the stated theta condition improves solvent quality. Effective repulsion between segments favors more expanded conformations than the ideal coil.
In a Flory–Huggins solution theory description, the theta condition corresponds approximately to interaction parameter , whereas a good solvent has a positive effective excluded volume. The asymptotic size dependence crosses toward with near for a flexible chain in three dimensions. These scaling ideas establish the expected direction, not a numerical expansion factor for a ten-degree temperature change. Its value would require measured solvent-interaction data or a calibrated crossover model.
The coil-globule transition is the contraction of an isolated flexible polymer as solvent quality worsens. A swollen chain in a good solvent has size in the Flory approximation. At the theta temperature the effective two-segment excluded volume vanishes and . A poor solvent favors a dense polymer globule, with at fixed internal density.
The competition is visible in the scaling free energyFor , elastic cost balances two-segment repulsion to give the swollen-coil law. At , three-segment repulsion stabilizes ideal-chain scaling; for , attraction balanced by the positive three-segment term gives . The dense polymer globule also has an interfacial free energy. The scaling expression explains regimes, not all fluctuation corrections or a detailed finite-chain transition curve. A finite chain crosses over smoothly; the sharp theta-point limit refers to indefinitely long chains.
A dilute-solution light-scattering experiment can follow radius of gyration while changing temperature or solvent composition. Measure at several concentrations and extrapolate toward isolated chains; check molecular-weight distribution, reversibility and the absence of growing multi-chain aggregates. dynamic light scattering measures hydrodynamic size, which is related to but distinct from radius of gyration. A falling scattering-derived size accompanied by a rising aggregate population cannot by itself establish single-chain collapse. solvent quality controls conformation through the balance of segment interactions and conformational entropy.
For a long ideal chain of statistical segments of length , . At fixed repeat chemistry and statistical segment length, molar mass is proportional to . The molecular-weight scaling of an ideal-chain gyration radius thus givesThe supplied size and ideal statistics are used as stipulated; an independently tabulated coil size would not replace the given baseline.
solvent quality changes the balance of segment–segment and segment–solvent contacts. In a good solvent, excluded-volume repulsion swells a sufficiently long isolated chain, with , in three dimensions; the Flory approximation gives . At theta conditions the effective two-segment excluded volume vanishes and the ideal exponent is recovered for long chains. A poor solvent favors a compact polymer globule, whose large-chain size scales approximately as at fixed internal density. solvent and temperature can also change local persistence length and hence the prefactor. These different conformations need not have the same radius at the same molar mass.
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.
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 , orThis 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]
Characterization of the brush regime for grafted polymer layers at the solid-liquid interface by P. Auroy and others. Physical Review Letters 66, 719–722 (1991), abstract: actual polymer/substrate system, neutron-scattering method and the two thickness scalings
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.
