Autoadhesion of High‐Molecular‐Weight Monodisperse Glassy Polystyrene at Unexpectedly Low Temperatures

Abstract

Healing of symmetric interfaces of amorphous anionically polymerized high‐ and ultrahigh‐molecular weight (HMW and UHMW, respectively) polystyrene (PS) in a range of the weight‐average molecular weight M _w from 102.5 (M _w/M _n = 1.05) to 1110 kg/mol (M _w/M _n = 1.15) was followed at a constant healing temperature, T _h, well below the glass transition temperature of the polymer bulk [T _g‐bulk = 105–106°C as measured by differential scanning calorimeter (DSC)]. The bonded interfaces were shear fractured in tension on an Instron tester at ambient temperature. Autoadhesion at symmetric HMW PS–HMW PS and UHMW PS–UHMW PS interfaces was detected mechanically after healing at T _h = 38°C for 107 hr, and even at 24°C (for longer healing times). The occurrence of autoadhesion between the surfaces of the UHMW PS with M _w = 1110 kg/mol at 24°C implies that the glass transition temperature at the interface, T _{g‐interface}, of this polymer was a least lower: by 82°C than its DSC T _g‐bulk, by 30–40°C than the Vogel temperature, T _∞—the lowest theoretical value of a kinetic T _g‐bulk at infinite long time—and by 20°C than T ₂ (a “true” thermodynamic T _g‐bulk corresponding to a second‐order phase transition temperature). To our knowledge, this is the first observation of such nature, which gives further evidence of the lowering of the T _g at polymeric surfaces and the persistence of this effect at early stages of healing of polymer–polymer interfaces.

Keywords:

• Polystyrenes
• Interface
• Healing
• Strength

Acknowledgment

The authors express their gratitude to the Danish Technical Research Council of the Danish Research Agency for financial support, including a NATO Senior Science Fellowship granted to Y.M.B.