Semi-alicyclic colorless and transparent polyimide (CPI) films usually suffer from the high linear coefficients of thermal expansion (CTEs) due to the intrinsic thermo-sensitive alicyclic segments in the polymers. A series of semi-alicyclic CPI films containing rigid-rod amide moieties were successfully prepared in the current work in order to reduce the CTEs of the CPI films while maintaining their original optical transparency and solution-processability. For this purpose, two alicyclic dianhydrides, hydrogenated pyromellitic anhydride (HPMDA, I), and hydrogenated 3,3’,4,4’-biphenyltetracarboxylic dianhydride (HBPDA, II) were polymerized with two amide-bridged aromatic diamines, 2-methyl-4,4’-diaminobenzanilide (MeDABA, a) and 2-chloro-4,4’-diaminobenzanilide (ClDABA, b) respectively to afford four CPI resins. The derived CPI resins were all soluble in polar aprotic solvents, including N-methyl-2-pyrrolidone (NMP) and N,N-dimethylacetamide (DMAc). Flexible and tough CPI films were successfully prepared by casing the PI solutions onto glass substrates followed by thermally cured at elevated temperatures from 80 °C to 250 °C. The MeDABA derived PI-I_a (HPMDA-MeDABA) and PI-II_a (HBPDA-MeDABA) exhibited superior optical transparency compared to those derived from ClDABA (PI-I_b and PI-II_b). PI-I_a and PI-II_a showed the optical transmittances of 82.3% and 85.8% at the wavelength of 400 nm with a thickness around 25 μm, respectively. Introduction of rigid-rod amide moiety endowed the HPMDA-PI films good thermal stability at elevated temperatures with the CTE values of 33.4 × 10⁻⁶/K for PI-I_a and 27.7 × 10⁻⁶/K for PI-I_b in the temperature range of 50–250 °C. Comparatively, the HBPDA-PI films exhibited much higher CTE values. In addition, the HPMDA-PI films exhibited good thermal stability with the 5% weight loss temperatures (T_5%) higher than 430 °C and glass transition temperatures (T_g) in the range of 349–351 °C.

Oscillation, widely existing in nature, is of vital importance for human society (e.g., energy utilization, signal transmission and communication), but preparing soft self-oscillators with facile accessibility, fatigue resistance, precise and noncontact control in multi-way tunable approaches is still desirable and challenging. Here, we report the fabrication of a light-driven tunable self-oscillator based on bimorph films of commercial Kapton and photoactive liquid-crystalline polymers with physical crosslinking sites, which can be remotely powered under constant irradiation of UV/visible light. The photomechanical behaviors of the bimorph actuators are acquired from the photoinduced changes in the volume of the photoactive polymer, and both the cis-azobenzene content and the trans–cis dynamic isomerization process are determinant factors. By combining the self-shadowing effect and inertia effect of the actuator, self-sustained oscillation is obtained. In nature, only leaves with particular size and weight could sway as appropriate strong wind blows from a specific direction, which inspires us to tune the oscillating frequency and amplitude with multiple approaches, like light intensity/wavelength (from UV to visible light), irradiated position, and size/weight of the oscillator for regulating the inertia effect. Such autonomously light-fueled self-oscillators are found to have potential applications in detecting charges and signal transmission.

Protection of polymeric materials from the atomic oxygen erosion in low-earth orbit spacecrafts has become one of the most important research topics in aerospace science. In the current research, a series of novel organic/inorganic nanocomposite films with excellent atomic oxygen (AO) resistance are prepared from the phosphorous-containing polyimide (FPI) matrix and trisilanolphenyl polyhedral oligomeric silsesquioxane (TSP–POSS) additive. The PI matrix derived from 2,2’-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride (6FDA) and 2,5-bis[(4-amino- phenoxy)phenyl]diphenylphosphine oxide (BADPO) itself possesses the self-healing feature in AO environment. Incorporation of TSP–POSS further enhances the AO resistance of the FPI/TSP composite films via a Si–P synergic effect. Meanwhile, the thermal stability of the pristine film is maintained. The FPI-25 composite film with a 25 wt % loading of TSP–POSS in the FPI matrix exhibits an AO erosion yield of 3.1 × 10⁻²⁶ cm³/atom after an AO attack of 4.0 × 10²⁰ atoms/cm², which is only 5.8% and 1.0% that of pristine FPI-0 film (6FDA-BADPO) and PI-ref (PMDA-ODA) film derived from 1,2,4,5-pyromellitic anhydride (PMDA) and 4,4’-oxydianline (ODA), respectively. Inert phosphorous and silicon-containing passivation layers are observed at the surface of films during AO exposure.