TY - JOUR
T1 - Nylon-6/Ti3C2Tz MXene Nanocomposites Synthesized by in Situ Ring Opening Polymerization of ϵ-Caprolactam and Their Water Transport Properties
AU - Carey, Michael
AU - Hinton, Zachary
AU - Sokol, Maxim
AU - Alvarez, Nicolas J.
AU - Barsoum, Michel W.
N1 - Publisher Copyright:
© 2019 American Chemical Society.
PY - 2019/6/5
Y1 - 2019/6/5
N2 - Clay-reinforced nylon-6 nanocomposites (NCs)-characterized by the full exfoliation of the nanoreinforcement-were introduced in the marketplace in the 1990s. Herein, we demonstrate, for the first time, that Ti3C2Tz MXene can be incorporated into nylon-6 to synthesize melt-processable nanocomposites with excellent water barrier properties (94% reduction in water vapor permeation). To intercalate the ϵ-caprolactam monomer between the MXene multilayers, the latter were first treated with 12-aminolauric acid, a low-cost, nontoxic, biodegradable, and long shelf life compound. Upon heating to 250 °C, in the presence of 6-aminocaproic acid, in situ polymerization occurred, yielding melt-processable nylon-6/MXene NCs that were, in turn, studied by thermogravimetric analysis, differential scanning calorimetry, X-ray diffraction, scanning and transmission electron microscopy, infrared spectroscopy, and dynamic vapor sorption analysis. Using the latter, moisture-sorption isotherms of a neat and a 1.9 vol % NC, at 60 °C, were fit to the Guggenheim, Anderson, and de Boer equation. Solubility, permeation, and diffusion coefficients of water through the NCs were measured as a function of temperature and found to be the lowest ever reported for nylon-6, despite the fact that, at 1.9 and 5.0 vol %, the MXene loads were relatively low. This record low diffusivity is ascribed to the very large aspect ratios-500 to 1000-of Ti3C2Tz flakes and their dispersion. The water permeation rate is a factor of 5 lower than the best reported in the much more mature nylon/clay field, suggesting lower values can be achieved with further optimization. Lastly infrared spectroscopy spectra of neat and NC samples suggest the surface terminations of the 12-Ti3C2Tz flakes bind with nylon-6, limiting water adsorption sites, resulting in reduced solubility in the NC films.
AB - Clay-reinforced nylon-6 nanocomposites (NCs)-characterized by the full exfoliation of the nanoreinforcement-were introduced in the marketplace in the 1990s. Herein, we demonstrate, for the first time, that Ti3C2Tz MXene can be incorporated into nylon-6 to synthesize melt-processable nanocomposites with excellent water barrier properties (94% reduction in water vapor permeation). To intercalate the ϵ-caprolactam monomer between the MXene multilayers, the latter were first treated with 12-aminolauric acid, a low-cost, nontoxic, biodegradable, and long shelf life compound. Upon heating to 250 °C, in the presence of 6-aminocaproic acid, in situ polymerization occurred, yielding melt-processable nylon-6/MXene NCs that were, in turn, studied by thermogravimetric analysis, differential scanning calorimetry, X-ray diffraction, scanning and transmission electron microscopy, infrared spectroscopy, and dynamic vapor sorption analysis. Using the latter, moisture-sorption isotherms of a neat and a 1.9 vol % NC, at 60 °C, were fit to the Guggenheim, Anderson, and de Boer equation. Solubility, permeation, and diffusion coefficients of water through the NCs were measured as a function of temperature and found to be the lowest ever reported for nylon-6, despite the fact that, at 1.9 and 5.0 vol %, the MXene loads were relatively low. This record low diffusivity is ascribed to the very large aspect ratios-500 to 1000-of Ti3C2Tz flakes and their dispersion. The water permeation rate is a factor of 5 lower than the best reported in the much more mature nylon/clay field, suggesting lower values can be achieved with further optimization. Lastly infrared spectroscopy spectra of neat and NC samples suggest the surface terminations of the 12-Ti3C2Tz flakes bind with nylon-6, limiting water adsorption sites, resulting in reduced solubility in the NC films.
KW - MXene
KW - polyamides
KW - polymer nanocomposites
KW - water diffusion coefficients
KW - water permeation
UR - http://www.scopus.com/inward/record.url?scp=85066485390&partnerID=8YFLogxK
U2 - 10.1021/acsami.9b05027
DO - 10.1021/acsami.9b05027
M3 - Article
C2 - 31071257
AN - SCOPUS:85066485390
SN - 1944-8244
VL - 11
SP - 20425
EP - 20436
JO - ACS Applied Materials and Interfaces
JF - ACS Applied Materials and Interfaces
IS - 22
ER -