A. E IOFFE PHYSICAL-TECHNICAL INSTITUTE OF THE RUSSIAN ACADEMY OF SCIENCES, ST. PETERSBURG, 194021, RUSSIA DSC was used to study the influence of fast electron irradiation on the molecular mobility and melting of semicrystalline polymers and copolymers of ethylene and of fluorocopolymer. The heat eapacity-temporature dependences obtained in the range from 100 K to 500 K revealed the specific features of the irradiation effect on four relaxational transitions associated with the appearance of segmental motion in different molecular elements of the disordered regions in the polymer. The pronounced dependence of the radiation stability of crystallites on the thermal prehistory of the object under study was found. The results were interpreted on the basis of the decisive role of the molecular mobility and free volume for the predominance of the radiation cross-linking of the molecules. Correlations were established between the characteristics of the thermal transitions and the mechanical properties of the irradiated polymers.
Molecular motion and thermal stability in two series of nanophase‐separated polyimide‐silica (PI‐SiO2) hybrid networks with chemically bound components were studied. The hybrids were prepared via a sol‐gel process and differed in PI structure and chain length, and in SiO2 content ranging from 10 to 50 wt.%. Differential scanning calorimetry, laser‐interferometric creep rate spectroscopy, dielectric relaxation spectroscopy, thermally stimulated depolarization current techniques, and thermogravimetry were used covering, on the whole, the ranges of 100–900 K and 10−3‐109 Hz. Silica domains influenced PI dynamics in two opposite directions. Loosened segmental packing in chains confined to nanovolumes resulted mainly in rise of small‐scale motion below β‐relaxation region, while anchoring of chain ends to ‘rigid walls’ caused, contrarily, a partial or total suppression of segmental motion above Tβ, especially drastically at the temperatures close to and within glass transition. The latter resulted in a large change in thermal stability, e.g., 2.5‐fold increasing of the apparent activation energy of thermooxidative degradation, and more than 100° rise of predicted long‐term thermal stability for the hybrids as compared to that for PI.
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