Cold Crystallization of Glassy Polylactide during Solvent Crazing.

Uniaxial tension accompanied by the orientation and crystallization of polymer chains is one of the powerful methods for the improvement of mechanical properties. Crystallization of amorphous isotropic polylactide (PLA) at room temperature is studied for the first time during the drawing of films in the presence of liquid adsorption-active media (ethanol, water-ethanol mixtures, and n-heptane) by the solvent crazing mechanism. The crystalline structure arises only under simultaneous actions of a liquid medium and a tensile stress and does not depend on the nature of the environment. The degree of polymer crystallinity increases nearly linearly with the growth in the fraction of the fibrillar material and reaches a maximum value of 42-45%. It has been stated that polymer crystallization happens in crazes involving nanofibrils with a diameter of about 10-20 nm without affecting the bulk polymer parts. Wide-angle X-ray scattering has been used to confirm that the crazing-induced crystallization is accompanied by the formation of the α'-crystalline phase with crystallite sizes (X-ray coherent scattering region) of 3-5 nm, depending on the nature of the liquid medium. After stretching in liquid media to a high tensile strain, the strength of a PLA film has increased to 200 MPa.

Phosphorescent Oxygen and Mechanosensitive Nanostructured Materials Based on Hard Elastic Polypropylene Films.

It is well known that sensitivity of quenched-phosphorescence O2 sensors can be tuned by changing the nature of indicator dye and host polymer acting as encapsulation and quenching mediums. Here, we describe a new type of sensor materials based on nanostructured hard elastic polymeric substrates. With the example of hard elastic polypropylene films impregnated with Pt-benzoporphyrin dye, we show that such substrates enable simple one-step fabrication of O2 sensors by standard and scalable polymer processing technologies. In addition, the resulting sensor materials show prominent response to tensile drawing via changes in phosphorescence intensity and lifetime and O2 quenching constant, Kq. The mechanosensitive response shows reversibility and hysteresis, which are related to macroscopic changes in the nanoporous structure of the polymer. Such multifunctional materials can find use as mechanically tunable O2 sensors, as well as strain/deformation sensors operating in a phosphorescence-lifetime-based detection mode.

Oxygen-sensitive phosphorescent nanomaterials produced from high-density polyethylene films by local solvent-crazing.

Discrete solid-state phosphorescent oxygen sensors produced by local solvent-crazing of high density polyethylene films are described. The simple spotting of dye solution followed by tensile drawing of the polymer substrate provides uniform nanostructures with good spatial control, effective encapsulation of dye molecules, and quenchability by O2. The dye-polymer composite sensors prepared using toluene as a solvent and stabilized by annealing at high temperature, show moderate optical signals, near-optimal sensitivity to O2 (RSD at 21 KPa 1.9%), and reproducible phosphorescence lifetime readings. Calibration experiments performed over 0-25 kPa O2 and 10-30 °C temperatures ranges reveal linear Stern-Volmer plots and temperature dependences and minimal effect of humidity on sensor calibration. The high degree of lateral and in-depth homogeneity of these O2-sensitive materials was confirmed by high-resolution atomic force and wide-field optical microscopy, including 2D and 3D phosphorescence lifetime imaging.