When scoured nylon 6 filament was exposed to either water vapor or n-alcohol vapor, a portion of the cyclic [NH(CH2)5CO]x, with x = 2 through 7, and the ϵ-caprolactam present migrated to the filament surface and crystallized. A variety of crystal forms were observed. The variations depended partly on the vapor to which the sample had been exposed. During water vapor exposures, the cyclic dimer migrated more easily to the filament surface than the cyclic monomer and the cyclic tetramer migrated more easily than the cyclic trimer. It is postulated that the secondary valence forces acting between the dimer and the nylon 6 polymer are weaker than that between the ϵ-caprolactam and the polymer since the dimer forms intramolecular hydrogen bonds. Consequently, the dimer migrates more easily than the monomer, which can form hydrogen bonds with the polymer. Also the cyclic trimer can form hydrogen bonds with the nylon 6 polymer and thus migrates less easily than the cyclic tetramer, which can form intramolecular hydrogen bonds. In alcohol vapor exposures, the n-alcohol used influenced the concentration of cyclic monomer and oligomer, which migrated to the surface of the nylon 6 filament. The variation of the monomer and oligomer concentration on the fiber surface with the alcohol used in the exposure is discussed.