Molecular motion and thermal stability in two series of nanophase‐separated polyimide–silica (PI–SiO2) hybrid materials with chemically bound components were studied. The hybrids were synthesized from p‐aminophenyltrimethoxysilane‐terminated poly(amic acid)s as PI precursors and tetramethoxysilane as a silica precursor via a sol–gel process. The hybrids differed in their PI chemical structure and chain length (number‐average molecular weight = 5.000, 7.500, or 10.000) and in their SiO2 content, which ranged from 0 to 50 wt %. Differential scanning calorimetry, laser‐interferometric creep rate spectroscopy, and thermally stimulated depolarization current techniques were used for studying the dynamics from 100 to 650 K and from 10−3 to 10−2 Hz. Comparative thermogravimetric measurements were also carried out from 300 to 900 K. Silica nano‐ or submicrodomains that formed affected PI dynamics in two opposite directions. Because of the loosening of the molecular packing of PI chains confined to nanometer‐scale spaces between silica constraints, an enhancement of small‐scale motion, mostly at temperatures below the β‐relaxation region, occurred. However, a partial or total suppression of segmental motion could be observed above the β‐relaxation temperature, drastically so for the shortest PI chains at elevated silica contents and within or close to the glass‐transition range, because of the covalent anchoring of chain ends to silica domains. Large changes in thermal stability, including a 2.5‐fold increase in the apparent activation energy of degradation, were observed in the hybrids studied. A greater than 100 °C rise in long‐term thermal stability could be predicted for some hybrids with respect to pure PI. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 1056–1069, 2002

Electrospun polymeric nanofiber materials doped with 5,10,15,20-tetraphenylporphyrin (TPP) photosensitizer were prepared from four different polymers and were characterized with microscopic methods, steady-state, and time-resolved fluorescence and absorption spectroscopy. The polymers used included polyurethane Larithane™ (PUR), polystyrene (PS), polycaprolactone (PCL), and polyamide 6 (PA6). The antibacterial activity of all nanofiber materials against E. coli was activated by visible light and it was dependent on oxygen permeability/diffusion coefficients and the diameter of the polymeric nanofibers. This activity is based on oxidation ability of singlet oxygen O₂(¹Δ(g)) that is generated upon irradiation. All tested nanofiber materials exhibited prolonged antibacterial properties, even in the dark after long-duration irradiation. The post-irradiation effect was explained by the photogeneration of H₂O₂, which provided the material with long-lasting antibacterial properties.

Thermal, thermomechanical, tensile and gas transport properties of aliphatic polycarbonate-based polyurethanes (PC-PUs) and their nanocomposites with bentonite for organic systems were studied. Hard segments are formed from hexamethylene diisocyanate and butane-1,4-diol. All PC-PUs and their nanocomposites feature high degree of the phase separation. Three phase transitions were detected by temperature-modulated differential scanning calorimetry (TMDSC) and dynamic mechanical thermal analysis. TMDSC revealed the filler affinity both to soft and hard segments, even though the affinity to hard segments is much stronger. Elongation-at-break at ambient temperatures is mostly over 700%, which leads together with high tensile strength (in some cases) to very high toughness values (over 200 mJ/mm 3 ). The addition of 1 wt % of bentonite does not practically affect mechanical properties implying its very good incorporation into the PU matrix. Permeabilities and other gas transport properties depend on regularity of PC-diol and on hard segment content, but the variations are insignificant.

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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.