Versatile Landscape of Low-k Polyimide: Theories, Synthesis, Synergistic Properties, and Industrial Integration.

The development of microelectronics and large-scale intelligence nowadays promotes the integration, miniaturization, and multifunctionality of electronic and devices but also leads to the increment of signal transmission delays, crosstalk, and energy consumption. The exploitation of materials with low permittivity (low-k) is crucial for realizing innovations in microelectronics. However, due to the high permittivity of conventional interlayer dielectric material (k ∼ 4.0), it is difficult to meet the demands of current microelectronic technology development (k < 3.0). Organic dielectric materials have attracted much attention because of their relatively low permittivity owing to their low material density and low single bond polarization. Polyimide (PI) exhibits better application potential based on its well permittivity tunability (k = 1.1-3.2), high thermal stability (>500 °C), and mechanical property (modulus of elasticity up to 3.0-4.0 GPa). In this review, based on the synergistic relationship of dielectric parameters of materials, the development of nearly 20 years on low-k PI is thoroughly summarized. Moreover, process strategies for modifying low-k PI at the molecular level, multiphase recombination, and interface engineering are discussed exhaustively. The industrial application, technological challenges, and future development of low-k PI are also analyzed, which will provide meaningful guidance for the design and practical application of multifunctional low-k materials.

1D/2D Carbon Nanomaterial-Polymer Dielectric Composites with High Permittivity for Power Energy Storage Applications.

With the development of flexible electronic devices and large-scale energy storage technologies, functional polymer-matrix nanocomposites with high permittivity (high-k) are attracting more attention due to their ease of processing, flexibility, and low cost. The percolation effect is often used to explain the high-k characteristic of polymer composites when the conducting functional fillers are dispersed into polymers, which gives the polymer composite excellent flexibility due to the very low loading of fillers. Carbon nanotubes (CNTs) and graphene nanosheets (GNs), as one-dimensional (1D) and two-dimensional (2D) carbon nanomaterials respectively, have great potential for realizing flexible high-k dielectric nanocomposites. They are becoming more attractive for many fields, owing to their unique and excellent advantages. The progress in dielectric fields by using 1D/2D carbon nanomaterials as functional fillers in polymer composites is introduced, and the methods and mechanisms for improving dielectric properties, breakdown strength and energy storage density of their dielectric nanocomposites are examined. Achieving a uniform dispersion state of carbon nanomaterials and preventing the development of conductive networks in their polymer composites are the two main issues that still need to be solved in dielectric fields for power energy storage. Recent findings, current problems, and future perspectives are summarized.

Dual-Effect Coupling for Superior Dielectric and Thermal Conductivity of Polyimide Composite Films Featuring "Crystal-Like Phase" Structure.

To match the increasing miniaturization and integration of electronic devices, higher requirements are put on the dielectric and thermal properties of the dielectrics to overcome the problems of delayed signal transmission and heat accumulation. Here, a 3D  porous thermal conductivity network is successfully constructed inside the polyimide (PI) matrix by the combination of ionic liquids (IL) and calcium fluoride (CaF2 ) nanofillers, motivated by the bubble-hole forming orientation force. Benefiting from the 3D thermal network formed by IL as a porogenic template and "crystal-like phase" structures induced by CaF2 - polyamide acid charge transfer, IL-10 vol% CaF2 /PI porous film exhibits a low permittivity of 2.14 and a thermal conductivity of 7.22 W m-1 K-1 . This design strategy breaks the bottleneck that low permittivity and high thermal conductivity in microelectronic systems are difficult to be jointly controlled, and provides a feasible solution for the development of intelligent microelectronics.

High-toughness, extensile and self-healing PDMS elastomers constructed by decuple hydrogen bonding.

Elastomers are widely used in traditional industries and new intelligent fields. However, they are inevitably damaged by electricity, heat, force, etc. during the working process. With the continuous improvement of reliability and environmental protection requirements in human production and living, it is vital to develop elastomer materials with good mechanical properties that are not easily damaged and can self-heal after being damaged. Nevertheless, there are often contradictions between mechanical properties and self-healing as well as toughness, strength, and ductility. Herein, a strong and dynamic decuple hydrogen bonding based on carbon hydrazide (CHZ) is reported, accompanied with soft polydimethylsiloxane (PDMS) chains to prepare self-healing (efficiency 98.7%), recyclable, and robust elastomers (CHZ-PDMS). The strategy of decuple hydrogen bonding will significantly impact the study of the mechanical properties of elastomers. High stretchability (1731%) and a high toughness of 23.31 MJ m-3 are achieved due to the phase-separated structure and energy dissipation. The recyclability of CHZ-PDMS further supports the concept of environmental protection. The application of CHZ-PDMS as a flexible strain sensor exhibited high sensitivity.

Advanced Dielectric Materials for Triboelectric Nanogenerators: Principles, Methods, and Applications.

Triboelectric nanogenerator (TENG) manifests distinct advantages such as multiple structural selectivity, diverse selection of materials, environmental adaptability, low cost, and remarkable conversion efficiency, which becomes a promising technology for micro-nano energy harvesting and self-powered sensing. Tribo-dielectric materials are the fundamental and core components for high-performance TENGs. In particular, the charge generation, dissipation, storage, migration of the dielectrics, and dynamic equilibrium behaviors determine the overall performance. Herein, a comprehensive summary is presented to elucidate the dielectric charge transport mechanism and tribo-dielectric material modification principle toward high-performance TENGs. The contact electrification and charge transport mechanism of dielectric materials is started first, followed by introducing the basic principle and dielectric materials of TENGs. Subsequently, modification mechanisms and strategies for high-performance tribo-dielectric materials are highlighted regarding physical/chemical, surface/bulk, dielectric coupling, and structure optimization. Furthermore, representative applications of dielectric materials based TENGs as power sources, self-powered sensors are demonstrated. The existing challenges and promising potential opportunities for advanced tribo-dielectric materials are outlined, guiding the design, fabrication, and applications of tribo-dielectric materials.

Enhanced High-Temperature Capacitive Performance of a Bilayer-Structured Composite Film Employing a Charge Blocking Layer.

The great development potential of polymer dielectric capacitors in harsh environments urgently requires enhancing capacitive performance at high temperatures. However, the exponentially increased conduction loss at high temperature and high field results in a drastic drop in energy density and charge-discharge efficiency. Here, a bilayer-structured polyimide (PI) composite film containing a wide-band gap inorganic layer as a charge blocking layer is designed. The inorganic layer improves the charge trapping ability and regulates the charge mobility at the electrode/dielectric interface. The charge injection mechanism in the interface-optimized PI/boron nitride nanosheet (BNNS) composite films is investigated by finite element simulation, and the effect of the BNNS layer on high temperature conduction is further understood. An appropriate thickness of the charge blocking layer establishes an effective energy barrier. Therefore, the composite films exhibit significantly suppressed conduction loss and excellent capacitive performance at a high temperature. A high energy density of 4.37 J cm-3 with efficiency of 92% is obtained at 200 °C and 500 MV m-1, which is superior to reported high-temperature dielectric polymers and their composite films. This work provides a promising approach to improve the energy storage performance of polymer materials at high temperatures.

Dynamic Covalent Adaptable Polyimide Hybrid Dielectric Films with Superior Recyclability.

Polyimides (PIs) used in advanced electrical and electronic devices can be electrically/mechanically damaged, resulting in a significant waste of resources. Closed-loop chemical recycling may prolong the service life of synthetic polymers. However, the design of dynamic covalent bonds for preparing chemically recyclable crosslinked PIs remains a challenging task. Herein, new crosslinked PI films containing a PI oligomer, chain extender, and crosslinker are reported. They exhibit superior recyclability and excellent self-healable ability owing to the synergistic effect of the chain extender and crosslinker. The produced films can be completely depolymerized in an acidic solution at ambient temperature, leading to efficient monomer recovery. The recovered monomers may be used to remanufacture crosslinked PIs without deteriorating their original performance. In particular, the designed films can serve as corona-resistant films with a recovery rate of approximately 100%. Furthermore, carbon fiber reinforced composites (CFRCs) with PI matrices are suitable for harsh environments and can be recycled multiple times at a non-destructive recycling rate up to 100%. The preparation of high-strength dynamic covalent adaptable PI hybrid films from simple PI oligomers, chain extenders, and crosslinkers may provide a solid basis for sustainable development in the electrical and electronic fields.

Dynamic Sustainable Polyimide Film Combining Hardness with Softness via a "Mimosa-Like" Bionic Strategy.

Dielectric polyimides (PIs) are ubiquitous as insulation in electrical power systems and electronic devices. Generally, dynamic polyimide is required to solve irreversible failure processes of electrical or mechanical damage, for example, under high temperature, pressure, and field strength. The challenge lies in the design of the molecular structure of rigid polyimide to achieve dynamic reversibility. Herein, a low-molecular-weight polyimide gene unit is designed to crosslink with polyimide ligase to prepare the smart film. Interestingly, due to the variability of gene unit and ligase combinations, the polyimide films combining hardness with softness are designed into three forms via a "Mimosa-like" bionic strategy to adapt to different application scenarios. Meanwhile, the films have good degradation efficiency, excellent recyclability, and can be self-healable, which makes them reuse. Clearly, the films can be used in the preparation of ultrafast sensors with a response time ≈0.15 s and the application of corona-resistant films with 100% recovery. Furthermore, the construction of polyimide and carbon-fiber-reinforced composites (CFRCs) has been verified to apply to the worse environment. Nicely, the composites have the property of multiple cycles and the non-destructive recycle rate of carbon fiber (CF) is as high as 100%. The design idea of preparing high-strength dynamic polyimide by crosslinking simple polyimide gene unit with ligase could provide a good foundation and a clear case for the sustainable development of electrical and electronic polyimides, from the perspective of Mimosa bionics.

Green fabrication of durable foam composites with asymmetric wettability by an emulsion spray-coating method for photothermally induced crude oil cleanup.

Chemical spills, especially oil spills, are becoming an increasingly serious environmental issue. It remains a challenge to develop green techniques to prepare mechanically robust oil-water separation materials, especially those capable of separating high-viscosity crude oils. Herein, we propose an environmentally friendly emulsion spray-coating method to fabricate durable foam composites with asymmetric wettability for oil-water separation. After the emulsion, composed of acidified carbon nanotubes (ACNTs), polydimethylsiloxane (PDMS) and its curing agent, is sprayed onto melamine foam (MF), water in the emulsion is first evaporated, while PDMS and ACNTs are finally deposited on the foam skeleton. The foam composite exhibits gradient wettability and turns from superhydrophobicity of the top surface (the water contact angle reaches as high as 155.2°) to hydrophilicity of the interior region. The foam composite can be used for the separation of oils with different densities and has a 97% separation efficiency for chloroform. In particular, the photothermal conversion-induced temperature rise can reduce the oil viscosity and complete the high-efficiency cleanup of crude oil. This emulsion spray-coating technique and asymmetric wettability show promise for the green and low-cost fabrication of high-performance oil/water separation materials.

Rising of Dynamic Polyimide Materials: A Versatile Dielectric for Electrical and Electronic Applications.

Polyimides (PIs) are widely used in circuit components, electrical insulators, and power systems in modern electronic devices and large electrical appliances. Electrical/mechanical damage of materials are important factors that threaten reliability and service lifetime. Dynamic (self-healable, recyclable and degradable) PIs, a promising class of materials that successfully improve electrical/mechanical properties after damage, are anticipated to solve this issue. The viewpoints and perspectives on the status and future trends of dynamic PI based on a few existing documents are shared. The main damage forms of PI dielectric materials in the application process are first introduced, and initial strategies and schemes to solve these problems are proposed. Fundamentally, the bottleneck issues faced by the development of dynamic PIs are indicated, and the relationship between various damage forms and the universality of the method is evaluated. The potential mechanism of the dynamic PI to deal with electrical damage is highlighted and several feasible prospective schemes to address electrical damage are discussed. This study is concluded by presenting a short outlook and future improvements to systems, challenges, and solutions of dynamic PI in electrical insulation. The summary of theory and practice should encourage policy development favoring energy conservation and environmental protection and promoting sustainability.

Intrinsic-designed polyimide dielectric materials with large energy storage density and discharge efficiency at harsh ultra-high temperatures.

Polymer dielectric materials with excellent temperature stability are urgently needed for the ever-increasing energy storage requirements under harsh high-temperature conditions. In this work, a novel diamine monomer (bis(2-cyano-4-aminophenyl)amine) was successfully synthesized to prepare a series of cyano-containing polyimides (CPI-1-3), which possessed excellent dielectric properties and high thermostability. The maximum dielectric permittivity was up to 5.5 at 102 Hz for CPI-3, being 2.5 times higher than that of commercially used BOPP. In comparison, the CPI-1 exhibited an outstanding breakdown strength of 433 MV m-1 and a high energy density of 2.5 J cm-3 even at 250 °C, which was the highest value reported under the same conditions. The synthesized CPIs through such an intrinsic approach are potential candidate materials for energy storage and even other applications under simultaneously harsh electrical and thermal conditions.

Improved Insulation Properties of Polypropylenes in HVDC Cables Using Aqueous Suspension Grafting.

Owing to its lack of crosslinking, polypropylene (PP) is considered an environmentally friendly alternative to crosslinked polyethylene as high-voltage direct current (HVDC) cable insulation. However, pure PP can accumulate space charges under a HVDC, and thus must be modified for use as an insulating material for HVDC cables. In this study, 4-methylstyrene is grafted onto PP using an aqueous suspension grafting method to improve its properties. The effects of the swelling time, reaction time, and 4-methylphenylene concentration on the reaction were investigated. The optimum process conditions were determined, including an optimum grafting ratio of 0.97%. The volume resistivity, ability to suppress space-charge accumulation, and DC breakdown strength of modified PP were also studied. Modified PP with a grafting ratio of 0.88% showed optimal space-charge suppression and the highest volume resistivity and breakdown strength. The work will facilitate the design and development of more efficient insulation materials for HVDC cables.

Low-Permittivity Copolymerized Polyimides with Fluorene Rigid Conjugated Structure.

As the miniaturization of electronic appliances and microprocessors progresses, low-permittivity interlayer materials are becoming increasingly important for their suppression of electronic crosstalk, signal propagation delay and loss, and so forth. Herein, a kind of copolyimide (CPI) film with a "fluorene" rigid conjugated structure was prepared successfully. By introducing 9,9-Bis(3-fluoro-4-aminophenyl) fluorene as the rigid conjugated structure monomer, a series of CPI films with different molecular weights were fabricated by in situ polymerization, which not only achieved the reduction of permittivity but also maintained excellent thermodynamic stability. Moreover, the hydrophobicity of the CPI film was also improved with the increasing conjugated structure fraction. The lowest permittivity reached 2.53 at 106 Hz, while the thermal decomposition temperature (Td5%) was up to 530 °C, and the tensile strength was ≥ 96 MPa. Thus, the CPI films are potential dielectric materials for microelectronic and insulation applications.

Construction of a Three-Dimensional BaTiO3 Network for Enhanced Permittivity and Energy Storage of PVDF Composites.

Three-dimensional BaTiO3 (3D BT)/polyvinylidene fluoride (PVDF) composite dielectrics were fabricated by inversely introducing PVDF solution into a continuous 3D BT network, which was simply constructed via the sol-gel method using a cleanroom wiper as a template. The effect of the 3D BT microstructure and content on the dielectric and energy storage properties of the composites were explored. The results showed that 3D BT with a well-connected continuous network and moderate grain sizes could be easily obtained by calcining a barium source containing a wiper template at 1100 °C for 3 h. The as-fabricated 3D BT/PVDF composites with 21.1 wt% content of 3D BT (3DBT-2) exhibited the best comprehensive dielectric and energy storage performances. An enhanced dielectric constant of 25.3 at 100 Hz, which was 2.8 times higher than that of pure PVDF and 1.4 times superior to the conventional nano-BT/PVDF 25 wt% system, was achieved in addition with a low dielectric loss of 0.057 and a moderate dielectric breakdown strength of 73.8 kV·mm-1. In addition, the composite of 3DBT-2 exhibited the highest discharge energy density of 1.6 × 10-3 J·cm-3 under 3 kV·mm-1, which was nearly 4.5 times higher than that of neat PVDF.

Highly efficient antifogging and antibacterial food packaging film fabricated by novel quaternary ammonium chitosan composite.

In this work, a multifunctional food packaging composite coating with transparent, biodegradable, antifogging and antibacterial properties was designed and fabricated by quaternary ammonium salt modified chitosan (HACC) and poly (vinyl alcohol) (PVA) via a facile and environment-friendly solution casting method. A simple quaternization modification enabled the coating simultaneously to achieve excellent antifogging and antibacterial functions. The excellent antifogging property of the HACC/PVA composite coating was attributed to the strong water absorbency of quaternary ammonium chitosan and PVA. A nearly 98% transmittance ratio of coated glasses was achieved during antifogging test. In addition, the inhibition rate of the HACC/PVA composite coating kill against Escherichia coli (E. coli), Staphylococcus aureus (S. aureus) and Botrytis cinerea were up to ~99%. The antibacterial effect was demonstrated by each group of strawberries after storage for 1, 3, 5 days. The multifunctional coating has broad prospects in the application of fruit and vegetable packaging.

Mechanical, Thermal, and Electrical Properties of BN-Epoxy Composites Modified with Carboxyl-Terminated Butadiene Nitrile Liquid Rubber.

Filled high thermal conductivity epoxy composite solves the problem of the low thermal conductivity of the epoxy resin itself, but the addition of the thermal conductive filler reduces the mechanical properties of the composite, which limits its application in the field of high voltage insulation. In this work, carboxyl-terminated butadiene nitrile liquid rubber (CTBN) was used to toughen the boron nitride-epoxy hybrid system, and the effects of different contents of CTBN on the mechanical properties, thermal conductivity, glass transition temperature, thermal stability, and dielectric properties of the composites were investigated. The results showed that when the content of CTBN was 5-15 wt.%, the CTBN formed a dispersed island structure in the epoxy resin matrix. The toughness of the composite increased by about 32%, the breakdown strength was improved, and the thermal conductivity was about 160% higher than that of pure epoxy resin. As the CTBN content increased, the glass transition temperature and thermal stability of the composite decreased and the dielectric constant and the dielectric loss increased. When the CTBN content is 10-15 wt.%, a toughened epoxy composite material with better comprehensive properties is obtained.

Tailored high cycling performance in a solid polymer electrolyte with perovskite-type Li0.33La0.557TiO3 nanofibers for all-solid-state lithium ion batteries.

Solid polymer electrolytes (SPEs) have drawn considerable attention owing to their reliable safety performance, electrochemical stability and exceptional flexibility, which make them superior to conventional liquid electrolytes. Here, we report a novel composite electrolyte which is composed of homogeneously dispersed Li ion-conducting Li0.33La0.557TiO3 (LLTO) nanowires in a poly(ethylene oxide) (PEO)/LiClO4 matrix. It is demonstrated that only 3 wt% LLTO nanofibers are needed for the optimal performance of SPEs. The PEO-based composite electrolyte shows an excellent Li ion conductivity of 4.01 × 10-4 S cm-1 at 60 °C. In addition, it is worth mentioning that the all-solid-state lithium battery based on this composite electrolyte exhibits a specific capacity of 140 mA h g-1 and an excellent capacity retention of 92.4% after running 100 cycles at a rate of 1C and 60 °C. The study offers a superior alternative for the design of PEO-based solid composite electrolytes.

Ultrasonication assisted preparation of carbonaceous nanoparticles modified polyurethane foam with good conductivity and high oil absorption properties.

In this work, we report a facile, low cost and time-saving method for the fabrication of compressible, electrically conductive, oil absorptive, cost-effective and flexible polyurethane (PU) foam through ultrasonication induced carbonaceous nanoparticles (CNP) onto flexible PU foam (CNP-PU foam). SEM images showed that the CNP could be firmly anchored onto the PU foam, and made the PU foam surface much rougher. Zero-dimensional carbonaceous nanoparticles were easier to anchor onto the PU foam surface than one-dimensional nanoparticles (e.g., carbon nanotube) or two-dimensional nanoparticles (e.g., graphene oxide). The CNP-PU foam exhibited excellent elasticity and high mechanical durability even when it was subjected to 500 cyclic compression. The CNP-PU foam had excellent absorption of organic solvents up to 121 times the weight of the initial PU foam. In addition, the electrical conductivity of PU foams was considerably increased with the anchoring of CNP onto the matrix. In addition, compression experiments confirmed that the electrical conductivity of CNP-PU foams changed with their compression ratios, thus exhibiting excellent pressure sensitivity. The as-prepared materials have significant potential as oil absorbents, elastic conductors, flexible electrodes, pressure sensors, etc.

Improved thermal conductivity and flame retardancy in polystyrene/poly(vinylidene fluoride) blends by controlling selective localization and surface modification of SiC nanoparticles.

The effect of selective localization of silicon carbide (SiC) and polystyrene (PS)-coated SiC (p-SiC) nanoparticles on the thermal conductivity and flame retardancy of immiscible PS/poly(vinylidene fluoride) (PVDF) blends has been systematically studied. The scanning electron microscopy (SEM) images reveal that SiC and p-SiC nanoparticles have different selective localizations in the PS/PVDF blends. The melting and crystallization behaviors of the PVDF component investigated by using differential scanning calorimetry are consistent with the SEM results. To reduce the volume fraction of fillers in the composites, a cocontinuous structure of PS/PVDF has also been built up. The cocontinuity window for PS/PVDF blends is ∼30-70 vol % according to the selective solvent dissolution technique. The selective localization of SiC in the PVDF phase of the PS/PVDF 70/30 blends produces a slightly higher thermal conductivity than that of p-SiC in the PS phase of the PS/PVDF 30/70 blends. However, the composites with selective localization of p-SiC exhibit the best combined properties of thermal conductivity and flame retardancy.