We examined the liquid-solid transition for polyamides (PA) 6, 66, and 610 by the Chambon-Winter method under cooling. The polyamides exhibited the transition via the critical gel, for which the critical exponent and the stiffness were consistent with those reported under the isothermal measurements for the other polymers. The DSC measurements showed that, for a few materials, the crystallinity at the gelation φgel was very small. This result implies that the hydrogen bonding partially stabilizes the critical gel of such polyamides. The FT-IR measurements demonstrated that the hydrogen bonding was formed cooperatively around the gelation temperature. However, we also found that with increasing the molecular weight, the gelation temperature decreased and φgel increased for PA6. Besides, φgel was smaller for PA66 and PA610 than that for PA6. The mechanism is unknown for these results that locate in the opposite side to the suggested role of hydrogen bonding.
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The authors appreciate the supports from Dr. Yoshifumi Amamoto, Prof. Atsushi Noro, Prof. Atsuhiko Yamanaka, and Prof. Tetsuya Yamamoto.
This study is partly supported in part by Grant-in-Aid for Scientific Research (A) (17H01152) from JSPS and by Council for Science, Technology, and Innovation, Cross-ministerial Strategic Innovation Promotion Program, Structural Materials for Innovation from JST.
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Skrovanek et al. (1985) showed that the peak position of N-H stretching mode, which is located around 3300 cm−1, shifts to lower wavenumber with decreasing the temperature, reflecting the fact that the number of hydrogen bonding increases with decreasing the temperature. Namely, the shift of the peak position results from the fact that the peak is two (or more) overlapping broad absorption peaks at close positions (the absorption peaks of the hydrogen-bonded and free amide groups are at 3355 cm−1 and 3300 cm−1, respectively) and the relative magnitudes of the two peaks change with decreasing the temperature. Nevertheless, we observed the peak-shift as shown in the left panel of Fig 12. The wavenumber at the peak is extracted and plotted as a function of temperature in the right panel. The peak-wavenumber decreased with decreasing the temperature, and the magnitude of the decrease is significant across the critical gel temperature, although data points were somewhat scattered.
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Hirayama, T., Uneyama, T. & Masubuchi, Y. Characterization of critical gel state of polyamides by viscoelastic, thermal, and IR measurements. Rheol Acta 58, 281–290 (2019). https://doi.org/10.1007/s00397-019-01136-0
- Semi-crystalline polymers