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The formation of polymeric micro-patterns on various substrates via a photolithography procedure has been widely used in semiconductor fabrication. Standard polymer patterns are usually fabricated via photosensitive polymer varnishes, in which large amounts of potentially harmful solvents with weight ratios over 50 wt% have to be removed. In the current work, a novel pattern-formation methodology via solvent-free electrospun photosensitive polymeric fibrous membranes (NFMs) instead of the conventional photosensitive solutions as the starting photoresists was proposed and practiced. For this purpose, a series of preimidized negative auto-photosensitive polyimide (PSPI) resins were first prepared via the two-step chemical imidization procedure from the copolymerization reactions of 3,3′,4,4′-benzophenonetetracarboxylic- dianhydride (BTDA) and two ortho-methyl-substituted aromatic diamines, including 3,3′,5,5′-tetramethyl-4,4′-diaminodiphenylmethane (TMMDA) and 3,7-diamino-2,8-dimethyl- dibenzothiophene sulfone (TSN). The derived homopolymer PI-1 (BTDA-TMMDA) and the copolymers, including SPI-2~SPI-6, with the molar ratio of 5~25% for TSN in the diamine units, showed good solubility in polar solvents. Then, a series of PSPI NFMs were fabricated via standard electrospinning procedure with the developed PSPI solutions in N,N-dimethylacetamide (DMAc) with a solid content of 25 wt% as the starting materials. The derived PSPI NFMs showed good thermal stability with 5% weight loss temperatures higher than 500 °C in nitrogen. Meanwhile, the derived PSPIs showed good photosensitivity to the ultraviolet (UV) emitting wavelengths of i-line (365 nm), g-line (405 nm) and h-line (436 nm) of the high-pressure mercury lamps in both forms of transparent films and opaque NFMs. Fine micro-patterns with a line width of around 100 μm were directly obtained from the representative SPI-4 NFM via standard photolithography procedure. [ABSTRACT FROM AUTHOR]

Optically transparent polyimide (PI) films with good dielectric properties and long-term sustainability in atomic-oxygen (AO) environments have been highly desired as antenna substrates in low earth orbit (LEO) aerospace applications. However, PI substrates with low dielectric constant (low-Dk), low dielectric dissipation factor (low-Df) and high AO resistance have rarely been reported due to the difficulties in achieving both high AO survivability and good dielectric parameters simultaneously. In the present work, an intrinsically low-Dk and low-Df optically transparent PI film matrix, poly[4,4′-(hexafluoroisopropylidene)diphthalic anhydride-co-2,2-bis(4-(4-aminophenoxy)phenyl)hexafluoropropane] (6FPI) was combined with a nanocage trisilanolphenyl polyhedral oligomeric silsesquioxane (TSP-POSS) additive in order to afford novel organic–inorganic nanocomposite films with enhanced AO-resistant properties and reduced dielectric parameters. The derived 6FPI/POSS films exhibited the Dk and Df values as low as 2.52 and 0.006 at the frequency of 1 MHz, respectively. Meanwhile, the composite films showed good AO resistance with the erosion yield as low as 4.0 × 10−25 cm3/atom at the exposure flux of 4.02 × 1020 atom/cm2, which decreased by nearly one order of magnitude compared with the value of 3.0 × 10−24 cm3/atom of the standard PI-ref Kapton® film. [ABSTRACT FROM AUTHOR]

High-temperature-resistant polymeric adhesives with high servicing temperatures and high adhesion strengths are highly desired in aerospace, aviation, microelectronic and other high-tech areas. The currently used high-temperature resistant polymeric adhesives, such as polyamic acid (PAA), are usually made from the high contents of solvents in the composition, which might cause adhesion failure due to the undesirable voids caused by the evaporation of the solvents. In the current work, electrospun preimidized polyimide (PI) nano-fibrous membranes (NFMs) were proposed to be used as solvent-free or solvent-less adhesives for stainless steel adhesion. In order to enhance the adhesion reliability of the PI NFMs, thermally crosslinkable phenylethynyl end-cappers were incorporated into the PIs derived from 3,3',4,4'-oxydiphthalic anhydride (ODPA) and 3,3-bis[4-(4-aminophenoxy)phenyl]phthalide (BAPPT). The derived phenylethynyl-terminated PETI-10K and PETI-20K with the controlled molecular weights of 10,000 g mol−1 and 20,000 g mol−1, respectively, showed good solubility in polar aprotic solvents, such as N-methyl-2-pyrrolidinone (NMP) and N,N-dimethylacetamide (DMAc). The PI NFMs were successfully fabricated by electrospinning with the PETI/DMAc solutions. The ultrafine PETI NFMs showed the average fiber diameters (dav) of 627 nm for PETI-10K 695 nm for PETI-20K, respectively. The PETI NFMs showed good thermal resistance, which is reflected in the glass transition temperatures (Tgs) above 270 °C. The PETI NFMs exhibited excellent thermoplasticity at elevated temperatures. The stainless steel adherends were successfully adhered using the PETI NFMs as the adhesives. The PI NFMs provided good adhesion to the stainless steels with the single lap shear strengths (LSS) higher than 20.0 MPa either at room temperature (25 °C) or at an elevated temperature (200 °C). [ABSTRACT FROM AUTHOR]

The rapid development of advanced high-frequency mobile communication techniques has advanced urgent requirements for polymer materials with high-temperature resistance and good dielectric properties, including low dielectric constants (low-Dk) and low dielectric dissipation factors (low-Df). The relatively poor dielectric properties of common polymer candidates, such as standard polyimides (PIs) greatly limited their application in high-frequency areas. In the current work, benzoxazole units were successfully incorporated into the molecular structures of the fluoro-containing PIs to afford the poly(imide-benzoxazole) (PIBO) nano-fibrous membranes (NFMs) via electrospinning fabrication. First, the PI NFMs were prepared by the electrospinning procedure from organo-soluble PI resins derived from 2,2′-bis(3,4-dicarboxy-phenyl)hexafluoropropane dianhydride (6FDA) and aromatic diamines containing ortho-hydroxy-substituted benzamide units, including 2,2-bis[3-(4-aminobenzamide)-4-hydroxylphenyl]hexafluoropropane (p6FAHP) and 2,2-bis[3-(3-aminobenzamide)-4-hydroxyphenyl]hexafluoropropane (m6FAHP). Then, the PI NFMs were thermally dehydrated at 350 °C in nitrogen to afford the PIBO NFMs. The average fiber diameters (dav) for the PIBO NFMs were 1225 nm for PIBO-1 derived from PI-1 (6FDA-p6FAHP) precursor and 816 nm for PIBO-2 derived from PI-2 (6FDA-m6FAHP). The derived PIBO NFMs showed good thermal stability with the glass transition temperatures (Tgs) over 310 °C and the 5% weight loss temperatures (T5%) higher than 500 °C in nitrogen. The PIBO NFMs showed low dielectric features with the Dk value of 1.64 for PIBO-1 and 1.82 for PIBO-2 at the frequency of 1 MHz, respectively. The Df values were in the range of 0.010~0.018 for the PIBO NFMs. [ABSTRACT FROM AUTHOR]