Effect of thickness on the thermal properties of hydrogen-bonded LbL assemblies. Academic Article uri icon


  • Layer-by-layer (LbL) assemblies have attracted much attention for their functional versatility and ease of fabrication. However, characterizing their thermal properties in relation to the film thickness has remained a challenging topic. We have investigated the role of film thickness on the glass transition temperature (T(g)) and coeffecient of thermal expansion for poly(ethylene oxide)/poly(acrylic acid) (PEO/PAA) and PEO/poly(methacrylic acid) (PEO/PMAA) hydrogen-bonded LbL assemblies in both bulk and ultrathin films using modulated differential scanning calorimetry (modulated DSC) and temperature-controlled ellipsometry. In PEO/PAA LbL films, a single, well-defined T(g) was observed regardless of film thickness. The T(g) increased by 9 C relative to the bulk T(g) as film thickness decreased to 30 nm because of interactions between the film and its substrate. In contrast, PEO/PMAA LbL films show a single glass transition only after a thermal cross-linking step, which results in anhydride bonds between PMAA groups. The T(g), within error, was unaffected by film thickness, but PEO/PMAA LbL films of thicknesses below ~2.7 m exhibited a small amount of PEO crystallization and phase separation for the thermally cross-linked films. The coefficients of thermal expansion of both types of film increased with decreasing film thickness.

published proceedings

  • Langmuir

author list (cited authors)

  • Sung, C., Vidyasagar, A., Hearn, K., & Lutkenhaus, J. L.

citation count

  • 30

complete list of authors

  • Sung, Choonghyun||Vidyasagar, Ajay||Hearn, Katelin||Lutkenhaus, Jodie L

publication date

  • May 2012