Polymer adhesives have emerged as a promising dielectric passivation layer in hybrid bonding for 3D integration while they raise misalignment problems during curing. In this work, the synergistic effect of oxygen plasma surface activation and wetting is utilized to achieve bonding between completed cured polyimides. The optimized process achieves a void-less bonding with a maximum shear strength of 35.3 MPa at a low temperature of 250 °C in merely 2 min, significantly shortening the bonding period and decreasing thermal stress. It is found that the plasma activation generated hydrophilic groups on the polyimide surface, and the wetting process further introduced more -OH groups and water molecular on the activated polyimide surface. The synergistic process of plasma activation and wetting facilitate bridging polyimide interfaces to achieve bonding, providing an alternative path for adhesive bonding in 3D integration.

To improve the wear resistance of polyimide (PI), surface modification was developed. In this study, the tribological properties of graphene (GN), graphene oxide (GO), and KH550-grafted graphene oxide (K5-GO) modified PI were evaluated by molecular dynamics (MD) at the atomic level. The findings indicated that the addition of nanomaterials can significantly enhance the friction performance of PI. The friction coefficient of PI composites decreased from 0.253 to 0.232, 0.136, and 0.079 after coating GN, GO and K5-GO, respectively. Among them, the K5-GO/PI exhibited the best surface wear resistance. Importantly, the mechanism behind the modification of PI was thoroughly revealed by observing the wear state, analyzing the changes of interfacial interactions, interfacial temperature, and relative concentration.

A set of aromatic copolyimides was obtained by reaction of 4,4′-(hexafluoroisopropylidene) diphthalic anhydride (6FDA), and mixtures of the diamines 1,4-bis(4-amino-2-trifluoromethylphenoxy)-2,5-di-tert-butylbenzene (CF3TBAPB) and 3,5-diamino benzoic acid (DABA). These polymers were characterized and compared with the homopolymer derived from 6FDA and CF3TBAPB. All copolyimides showed high molecular weight values and good mechanical properties. The presence of carboxylic groups in these copolymers allowed their cross-linking by reaction with 1,4-butanediol. The crosslinked polymer films were extensively characterized and it was observed that the degree of crosslinking was low in the copolyimides possessing a small number of carboxyl groups. The degradation temperature of these crosslinked copolyimides was lower than their corresponding non-crosslinked ones. Glass transition temperatures were higher than 260 oC, showing the non-crosslinked copolyimides the highest values. Young moduli of these crosslinked showed values higher than 1.9 GPa, and slightly lower elongation at break when compared with the precursor copolyimides. All copolyimides (precursor, and crosslinked ones) films could be tested as gas separation membranes. It was seen that CO2 permeability values were around 100 barrer, having better selectivity than that of the homopolymer. Moreover, the plasticization resistance of the crosslinked material having a large number of carboxylic groups was excellent.

The polymer binder, poly(imide-co-siloxane) (PIS), was synthesized and applied to form a thin cathode layer composites for a thermal battery that has an unusually high operating temperature of 450 °C. The PIS was prepared through cross-linking of the polyimide with polysiloxane. The morphology of FeS₂/PIS composites showed that FeS₂ particles was coated with the PIS cross-linked gel. The FeS₂/PIS composites enabled to fabricate mechanically stable thin cathode layer that was 20–10% of the thickness of a conventional pellet-type cathode. The FeS₂/PIS composites were stable up to 400 °C and maintained their morphology at this temperature. PIS coating layers decomposed at 450 °C and a new residue was generated, which was observed by transmission electron microscopy and the compositional change was analyzed. The FeS₂/PIS composites showed enhanced thermal stability over that of FeS₂ in thermogravimetric analysis. The thermal battery with the PIS polymer binder showed a 20% discharge capacity increase when compared to a conventional pellet-type cathode.

Three polyimides and six inorganic fillers in a form of nanometer-sized particles were studied as thick film solution cast mixed matrix membranes (MMMs) for transport of CO₂, CH₄ and H₂O. Gas transport properties and electron microscopy images indicate good polymer-filler compatibility for all membranes. The only filler type which demonstrated good distribution throughout the membrane thickness at 10 wt. % loading was BaCe_0.2Zr_0.7Y_0.1O₃ (BCZY). The influence of this filler on MMM gas transport properties was studied in detail for 6FDA-6FpDA in a filler content range from 1 to 20 wt.% and for Matrimid^® and P84^® at 10 wt. % loading. The most promising result was obtained for Matrimid^® - 10wt% BCZY MMM, which showed improvement in CO₂ and H₂O permeabilities accompanied by increased CO₂/CH₄ selectivity and high water selective membrane at elevated temperatures without H₂O/permanent gas selectivity loss.

Random copolymers made of both (PIM-polyimide) and (6FDA-durene-PI) were prepared for the first time by a facile one-step polycondensation reaction. By combining the highly porous and contorted structure of PIM (polymers with intrinsic microporosity) and high thermomechanical properties of PI (polyimide), the membranes obtained from these random copolymers [(PIM-PI)x-(6FDA-durene-PI)y] showed high CO₂ permeability (> 1047 Barrer) with moderate CO₂/N₂ (> 16.5) and CO₂/CH₄ (> 18) selectivity, together with excellent thermal and mechanical properties. The membranes prepared from three different compositions of two comonomers (1:4, 1:6 and 1:10 of x:y), all showed similar morphological and physical properties, and gas separation performance, indicating ease of synthesis and practicability for large-scale production. The gas separation performance of these membranes at various pressure ranges (100–1500 torr) was also investigated.

Light-colored and transparent polyimide (PI) films with good high-temperature dimensional stability are highly desired for advanced optoelectronic applications. However, in practice, the simultaneous achievement of good optical and thermal properties in one PI film is usually difficult due to the inter-conflicting molecular design for the polymers. In the present work, a series of PI-SiO2 nanocomposite films (ABTFCPI) were developed based on the PI matrix derived from hydrogenated pyromellitic anhydride (HPMDA) and an aromatic diamine containing benzanilide and trifluoromethyl substituents in the structure, 2,2'-bis(trifluoromethyl)-4,4'-bis[4-(4-aminobenzamide)]biphenyl (ABTFMB). The inorganic SiO2 fillers were incorporated into the nanocomposite films with the form of colloidal nanoparticles dispersed in the good solvent of N,N-dimethylacetamide (DMAc) for the PI matrix. The derived ABTFCPI nanocomposite films showed good film-forming ability, flexible and tough nature, good optical transparency, and good thermal properties with the loading amounts of SiO2 up to 30 wt% in the system. The ABTFCPI-30 film with the SiO2 content of 30 wt% in the film showed the optical transmittance of 79.6% at the wavelength of 400 nm (T400) with a thickness of 25 μm, the yellow index (b*) of 2.15, and the 5% weight loss temperatures (T5%) of 491 oC, which are all comparable to those the pristine ABTFCPI-0 matrix without filler (T400=81.8%; b*=1.77; T5%=492 oC). Meanwhile, the ABTFCPI-30 film exhibited obviously enhanced high-temperature dimensional stability with the linear coefficients of thermal expansion (CTE) of 25.4×10-6/K in the temperature range of 50 to 250 oC, which is much lower than that of the AMTFCPI-0 film (CTE=32.7×10-6/K).

Polyimide (PI) films are widely used in electronic devices owing to their excellent mechanical and electrical properties and high thermal and chemical stabilities. In particular, PI films play an important role in flexible printed circuit boards (FPCBs). However, one challenge currently faced with their use is that the adhesives used in FPCBs cause a high dielectric loss in high-frequency applications. Therefore, it is envisioned that PI films with a low dielectric loss and Cu films can be used to prepare two-layer flexible copper clad laminates (FCCLs) without any adhesive. However, the preparation of ultra-thin FCCLs with no adhesives is difficult owing to the low peel strength between the PI films and Cu films. To address this technical challenge, an FCCL with no adhesive was prepared by high-power helicon wave plasma (HWP) treatment. The surface roughness of the PI film and the peel strength between the PI film and Cu film were measured. The experimental results showed that the surface roughness of the PI film increased by 40-65% and the PI film demonstrated improved adhesion (the peel strength was >8.0 N/cm) with the Cu film following plasma treatment and Cu plating.

A nanocomposite rod-shaped structure with single-walled carbon nanotube (SWCNT) embedded in polypyrrole (PPy) doped with nonafluorobutanesulfonic acid (C4F), SWCNT/C4F-PPy, was synthesized using emulsion polymerization. The hybrid ink was then directly coated on a polyimide film interdigitated with the Cu/Ni/Au electrodes via a screen-printing technique to create a flexible film sensor. The sensor film showed a response of 1.72% at 25 °C/atmospheric pressure when acetone gas of 5 ppm was injected, which corresponds to almost 95% compared to the Si wafer-based array interdigitated with the Au electrode. Additionally, C4F was used as a hydrophobic dopant of PPy to improve the stability of humidity and to produce a highly sensitive film-type gas sensor that provides stable detection even in humid conditions.

The development of photocurable compositions is in high demand for the manufacture of func-tional materials for electronics, optics, medicine, energy, etc. The properties of the final pho-to-cured material are primarily determined by the initial mixture, which needs to be tuned for each application. In this study we propose to use simple systems based on di(meth)acrylate, polyimide and photoinitiator for the preparation of new photo-curable compositions. It was es-tablished that a fluorinated cardo copolymide (FCPI) based on 2,2-bis-(3,4-dicarboxydiphenyl)hexafluoropropane dianhydride, 9,9-bis-(4-aminophenyl)fluorene and 2,2-bis-(4-aminophenyl)hexafluoropropane (1.00:0.75:0.25 mol) has excellent solubility in di(met)acrylates. This made it possible to prepare solutions of FCPI in such monomers, to study the effect of FCPI on the kinetics of their photopolymerization in situ and the properties of the resulting polymers. According to the obtained data, the solutions of FCPI (23 wt.%) in 1,4-butanediol diacrylate (BDDA) and FCPI (15 wt.%) in tetraethylene glycol diacrylate were tested for the formation of the primary protective coatings of the silica optical fibers. It was found that the new coating of poly(BDDA–FCPI23%) can withstand prolonged annealing at 200°C (72 h), which is comparable or superior to the known most thermally stable photo-curable coatings. The proposed approach can be applied to obtain other functional materials.

Neat polyimide films are known to be dense and rigid. They are therefore not suitable for use in membranes, sensors and sustainable energy storage applications. In this study a novel technique has been used to simulta-neously improve the rigidity, damping ability and impact resistance of polyimide membranes. It is demonstrated that dispersion of a small amount of polyaniline copolymer-modified clay of about 0.25-0.5 wt.% into the pol-yimide matrix, resulted in enhanced storage modulus while maintaining high damping ability and glass transition temperature, Tg. Novel polyimide/substituted polyaniline-copolymer-clay nanocomposite membranes containing poly(N-ethyl-aniline-co-aniline-2-sulfonic-acid-modified-clay (SPNEAC) was successfully prepared and in-corporated into polyimide matrix to form modified clay/polyimide nanocomposites. UV-Vis analysis of the nanocomposite films show that the optical transparency of the SPNEAC-PI nanocomposite membranes de-creased with increasing SPNEAC concentration due to the high UV-Vis absorption of SPNEAC. Transmittance of about 3 % was observed in the nanocomposite membrane containing 5wt.% modified clay at 500 nm wave-length, which is significantly lower than that for the neat PI membrane of about 36 %. The dispersion of SPNEAC containing high concentration of clay (≥ 40 wt.% clay), SPNEAC2 in polyimide matrix, resulted in attainment of a higher degree of imidization than was possible for the neat organoclay/polyimide nanocomposite. This behavior is believed to be due to the synergistic interaction between PI and polyaniline copolymer modified clay. The viscoelastic property of polyimide and the nanocomposite membranes was measured by using the dynamic mechanical spectroscopy, DMS. It was shown that the glass transition temperature, Tg of the nano-composites decreased, while the damping ability and impact energy increased with increasing weight fraction of fillers.