Uniaxial Negative Thermal Expansion of Polyvinyl Acetate Thin Film

The present paper reports some experimental observations of reproducible uniaxial negative thermal expansion (u-NTE) in an amorphous polyvinyl acetate (PVAc) ultrathin film. It has been found that the mechanism of the phenomena is different from latest reports on so-called NTE in crystal or other topological materials. It is known that PVAc exhibits glass transition at around 31 °C. During cooling from the high-temperature side, one can observe the decrease of the thickness by monitoring interference fringes in the X-ray reflectivity curve as a function of temperature. Across the glass transition, however, the thickness starts to increase, instead of reducing. In the heating process, the thickness decreases as long as the temperature is lower than that for glass transition ( T_g). In the present research, such changes in thickness during repeated heating/cooling cycles have been studied systematically. To discuss the mechanism, dependence on film thickness has been investigated as well. It has been found that the present phenomena are well explained as u-NTE, which induces reduction and increase of thickness ( z-direction) just by thermal expansion and shrinking in x- y directions, respectively. This would be caused and enhanced by the growth of a mechanically hard, high-density layer near the interface to the surface of hydrophilic silicon dioxide. The structural change during heating/cooling cycles is discussed in detail.