Homogeneous nucleation in polyamide 66, a two-stage process as revealed by combined nanocalorimetry and IR spectroscopy

Abstract

AbstractNanocalorimetry and Fourier transform infrared (FTIR) spectroscopy are combined to measure the calorimetric properties and molecular spectra of the same sample (sample amount about 5 ng) of polyamide 66 (PA66). By determining IR difference absorption spectra between a quenched and a sample annealed at varying temperatures (Ta) and annealing time (ta), the initial steps of homogeneous nucleation is for the first time revealed on a molecular scale, long before crystallization takes place. As starting point (i), isolated H-bonds are formed between (N–H) and (C = O) moieties of adjacent (neighboring) polymer segments promoted by far-reaching dipole–dipole interactions. In the second step (ii), the H-bonds realign, which in part requires the opening of already established H-bonds. In stage (i), the FTIR absorption intensity of the free (C = O)f moieties decreases while that of the H-bonded (C = O)b ones increases as a function of Ta at constant ta. This implies an increase in the H-bonding network in amorphous domains. The second stage of nucleation in the studied PA66 is characterized by an increase in the number of (C = O)f and a corresponding decrease in (C = O)b moieties as the sample transitions to the ordered crystalline structure. This is attributed to a change from γ to α polymorphs in PA66. The non-polar methylene units in PA66 are largely unaffected during the nucleation steps, where no changes in the overall heat capacity are detectable, proving that these changes occur prior to the onset of crystal growth. Graphical abstract