Polyimide Research Articles

Preparation of printable copper submicron particle paste

Abstract Thanks to the rise of flexible printed electronics, printable conductive pastes have received more and more attention, especially copper paste that can be prepared on a large scale at low cost. We first prepared submicron copper particles by reducing copper sulfate solution with glucose and hydrazine as the reducing agents and then modified the surface of copper submicron particles with formate and ethylene glycol for antioxidant treatment. The surface-modified copper particles exhibit better corrosion and oxidation resistance. Next, the copper submicron particles were dispersed in propylene glycol to make copper slurry. The copper conductive pattern with a low resistivity of 6.09×10−4 Ω·cm can be fabricated by printing copper paste with a dispensing machine, followed by a sintering process in an argon atmosphere at 200°C for 10 min. As prepared copper conductive patterns have excellent mechanical flexibility on polyimide (PI) substrate, which will be conducive to the large-scale application of copper paste on flexible substrates.

97‐1: Late‐News Paper: Mechanism for the Irreversible Threshold Voltage Behavior by Polyimide Charging in Thin Film Transistors

The irreversible threshold voltage (Vth) shift by polyimide (PI) charging is experimentally demonstrated. The Vth of device without PI electrode is positively moved during the release. Interestingly, the shifted Vth is not recovered to initial value up to one month. The mechanism for the irreversibility is suggested.

Flexible, wearable and sensitive laser‐induced graphene sensors for human health monitoring

AbstractBio‐compatible strain sensors are indispensable for human monitoring devices, requiring a delicate balance of robustness, flexibility, and sensitivity. However, achieving these attributes concurrently remains a formidable challenge. This article presents a pioneering approach to fabricate three‐dimensional flexible strain sensors using laser‐induced graphene (LIG) on polyimide (PI) substrates. Through a one‐step laser direct writing (LDW) technique, durable LIG/CuSO4 composites with closed‐pore porous structures are synthesized. The integration of copper sulfate within the closed‐cell architecture of LIG establishes a resilient conducting pathway, enhancing sensitivity to deformation under tensile stress. The resulting sensor exhibits exceptional performance in monitoring a wide range of human movements, from vigorous activities to subtle oscillations and physiological signals. Notably, the sensor boasts a remarkable sensing range of up to 25% strain, coupled with a high sensitivity characterized by a gauge factor of approximately 597. Rapid response times of 175 ms and quick recovery times of 200 ms further underscore its efficiency. Moreover, the sensor demonstrates outstanding stability and durability, maintaining consistent performance over 5600 cyclic experiments. This innovative approach represents a significant advancement in bio‐compatible strain sensor technology, offering a versatile solution for diverse monitoring applications.

P‐96: Alignment Optimization on Gen. 4.5 G for High‐framerate Ultra‐high‐resolution Ferroelectric Liquid Crystal Displays

We achieve high‐framerate (< 100 μs) high‐contrast‐ratio ferroelectric liquid crystal displays (FLCD) on Gen 4.5. Innovatively, a new polyimide (PI) that is suitable for ferroelectric liquid crystal (FLC) alignment is synthesized and tested on the production line. It replaces Nylon 6 (N6), which was the barrier to the commercialization of FLCD. Moreover, a new FLC is synthesized to match requirements in mass production. Additionally, various materials were studied to investigate the surface energy and relative performance. It is not only proof of the feasibility on the production line, but also a significant step towards the commercialization of field‐sequential‐color high‐resolution FLCDs.

Utilizing photodeposition to fabricate micro-nano structured microcapsules for enhancing mechanical and high-temperature tribological performance of fabric composites

Fabric composite materials face significant challenges in maintaining excellent tribological properties at high temperatures. This study employed photodeposition to deposit gold (Au) and copper (Cu) nanoparticles on the surface of titanium dioxide-coated jojoba oil microcapsules (TiO2 @jojoba), yielding micro-nanostructured Au-TiO2 @jojoba and Cu-TiO2 @jojoba microcapsules. Subsequently, microcapsules participated in the in-situ polymerization of polyimide (PI), serving as crosslinking points in PEEK/PTFE fabric-reinforced composites. PEEK/PTFE-Au composites containing Au-TiO2 @jojoba microcapsules exhibited outstanding tribological and mechanical properties. Compared to microcapsule-free samples, PEEK/PTFE-Au composites showed a 30.26 % reduction in friction coefficient at 250 °C and a 24.28 % increase in tensile strength. In addition, mechanistic studies indicated that TiO2 underwent a friction chemical reaction converting to TiNF during friction accompanying by friction-induced phase transitions. The release of jojoba oil during friction and the occurrence of friction chemical reactions were the main friction reduction mechanisms of PEEK/PTFE-Au composites at high temperatures.

Halloysite nanotubes enhanced polyimide/oxidized-lignin nanofiber separators for long-cycling lithium metal batteries

The high energy density and robust cycle properties of lithium-ion batteries contribute to their extensive range of applications. Polyolefin separators are often used for the purpose of storing electrolytes, hence ensuring the efficient internal ion transport. Nevertheless, the electrochemical performance of lithium-ion batteries is constrained by its limited interaction with electrolytes and poor capacity for cation transport. This work presents the preparation of a new bio-based nanofiber separator by combining oxidized lignin (OL) and halloysite nanotubes (HNTs) with polyimide (PI) using an electrospinning technique. Analysis was conducted to examine and compare the structure, morphology, thermal characteristics, and EIS of the separator with those of commercially available polypropylene separator (PP). The results indicate that the PI@OL and PI-OL@ 10 % HNTs separators exhibit higher lithium ion transference number and ionic conductivity. Moreover, the use of HNTs successfully impeded the proliferation of lithium dendrites, hence exerting a beneficial impact on both the cycle performance and multiplier performance of the battery. Consequently, after undergoing 300 iterations, the battery capacity of LiFePO4|PI-OL@ 10 % HNTs|Li stays at 92.1 %, surpassing that of PP (86.8 %) and PI@OL (89.6 %). These findings indicate that this new bio-based battery separator (PI-OL@HNTs) has the great potential to serve as a substitute for the commonly used PP separator in lithium metal batteries.

Regulating porous microstructure of polyimide aerogels toward efficient shape memory performance

The development of lightweight shape memory materials with exceptional thermal insulation properties is highly important in aerospace applications. Herein, shape memory polyimide (PI) aerogels was fabricated by molecularly designed PI molecular chains through freeze gelation and subsequent thermal imidization. The freezing conditions were controlled to regulate the porous microstructures of the aerogels. The interactions between PI chains formed physically crosslinked netpoints, which could overcome the expansive force and capillary force, thereby creating a stable porous structure. Because shape memory was thermally activated, the shape memory mechanisms associated with the thermal conductivity of the aerogels were comprehensively explored. Upon decreasing the pore size, dense frameworks were formed, contributing to the improved thermo-mechanical and compressive properties. Moreover, the heat transfer efficiency in the aerogel skeleton was enhanced, resulting in a rapid shape recovery response. Benefiting from the physically crosslinked structures, including entangled chains and π-π interactions, the fabricated PI aerogels demonstrated exceptional shape fixation and recovery capabilities. These findings may provide guidelines for designing smart aerogels for aerospace applications.

Laser‐Induced Porous Graphene/CuO Composite for Efficient Interfacial Solar Steam Generation

AbstractInterfacial solar steam generation can produce clean water in an environmentally friendly and efficient way. The evaporator employing graphene as a photothermal conversion material represents an excellent paradigm within the realm of interfacial evaporators. However, existing graphene materials exhibit a certain degree of hydrophobicity and are associated with intricate manufacturing processes. Hence, the study proposes a hydrophilic composite graphene‐based material incorporating CuO, which is fabricated through a straightforward laser‐induced graphene synthesis method directly onto a polyimide film coated with CuCl2. Due to the fast capillary performance endowed by the enhanced hydrophilicity and hierarchical structural morphology, the assembled laser‐induced‐graphene evaporator achieves an evaporation rate of 2.54 kg m−2 h−1 under 1 sun irradiation with an evaporation efficiency of 91.1%, while also demonstrating excellent desalination capabilities. The as‐prepared graphene‐based evaporator has significant potential for desalination and wastewater treatment applications, offering an effective solution to address clean water challenges in remote areas.

Multifunctional polyimide/boron nitride nanosheet/Ti3C2Tx MXene composite film with three-dimensional conductive network for integrated thermal conductive, electromagnetic interference shielding, and Joule heating performances

With the demand for further miniaturization and higher frequency operation of electronic devices, polymer films with high thermal conductivity and electromagnetic interference (EMI) shielding effectiveness (SE) are urgently required. Herein, polyimide (PI)/boron nitride nanosheets (BNNS) aerogels with oriented porous structure are fabricated by unidirectional-freezing and freeze-drying methods. Subsequently, hierarchical PI/BNNS/Ti3C2Tx composite films with consecutively electrically and thermally conductive networks are successfully prepared via a unidirectional PI/BNNS aerogels-assisted immersion and hot-pressing strategy. Owing to the three-dimensional conductive dual networks of BNNS and Ti3C2Tx, the composite film exhibits excellent thermal conductivity with the maximum in-plane value of 4.73 W/(m·K), increased by 456 % compared to pure PI film. Moreover, the conductive network of Ti3C2Tx is conducive to the excellent EMI shielding performance, endowing the PI/BNNS/Ti3C2Tx composite film with an outstanding EMI SE value of 49.2 dB at 8.2 GHz with a low MXene content of 6 wt% and thickness of 300 μm. Furthermore, the composite film shows the superior Joule heating performance with fast thermal response and sufficient reliability. Therefore, the resulting composite film exhibits excellent thermal conductive, EMI shielding and Joule heating performance, which enables the potential application of multifunctional composites for thermal management and EMI shielding.

Polyacrylonitrile In-Situ reinforced polyimide superhydrophobic porous fibers: A miraculous thermal insulation and flame-retardant material

In response to the demand for safety protective textiles suitable for extreme conditions such as intense heat and humidity, we have innovatively developed a novel approach using polyacrylonitrile (PAN) in-situ reinforced polyimide (PI) superhydrophobic porous fibers. We blended fluorinated polyamic acid (PAA) with PAN and prepared PI/pre-oxidized fiber (panof) porous fibers using a process that includes wet phase separation spinning and integrated synchronous imidization/pre-oxidation. Special emphasis was placed on the chemical mechanisms during the heat treatment stage of the preparation process. The uncapped PAA underwent imidization reactions and also facilitated PAN’s pre-oxidation, which notably enhanced the structural stability of the PI porous fibers. This novel enhancement mechanism effectively addresses the challenges of structural collapse and volume shrinkage encountered in the preparation of traditional PI porous fibers. In addition, our investigation into the impact of thermal imidization temperature on the structure of porous fibers led to the evaluation of PI/panof porous fibers. The PI/panof-320 porous fibers, produced by the combined enhancement effect of fluorinated PI and PAN, showcased exceptional features: superhydrophobicity (water contact angle = 168.9°), low density (0.078 g/cm3), reduced thermal conductivity (0.0251 W/(m·K)), high strength (22.18 MPa), outstanding flexibility (bend radius = 205 μm), and superior flame retardancy and insulation. The outstanding performance of these composite porous fibers paves the way for innovative, comfortable, and safe wearable devices in high heat and humidity environments, highlighting their extensive applicability and potential.

A Flexible Double-Sided Curvature Sensor Array for Use in Soft Robotics.

This paper describes the design, fabrication, integration, characterization, and demonstration of a novel flexible double-sided curvature sensor array for use in soft robotics. The paper explores the performance and potential applications of a piezoresistive sensor array consisting of four gold strain gauges on a flexible polyimide (PI) substrate arranged in a Wheatstone bridge configuration. Multiple sensor strips were arranged like the fingers of a hand. Integrating Shape Memory Alloy (SMA) foils alongside the fingers was explored to mimic a human hand-gripping motion controlled with temperature, while curvature sensor array strips measure the resulting finger shapes. Moreover, object sensing in a flexible granular material gripper was demonstrated. The sensors were embedded within Polydimethylsiloxane (PDMS) to enhance their tactile feel and adhesive properties. The findings of this study are promising for future applications, particularly in robotics and prosthetics, as the ability to accurately mimic human hand movements and reconstruct sensor surfaces paves the way for robotic hand functionality.

Highly reversible zinc anode enabled by composite tailored polyimide separator

Zinc-ion batteries (ZIBs) are highly suitable for storing energy due to their exceptional safety and efficiency. However, uncontrolled Zn2+ deposition builds and quickly penetrates the separator. To surmount this obstacle, a fundamental coating of polyimide (PI) on commercial GF separator (PI@GF) is used enabling quick kinetics and minimal overpotential in 0.5 M Zn triflate TMP electrolyte. The separator has widespread imide –CO–N–CO– groups that interact strongly with Zn2+, therefore, it increases anode-electrolyte wettability and modifies Zn2+ solvation structure. The composite separator efficiently protected the Zn anode, for 6000 hours at 1 mA cm-2, compared to 110 hours with the standard GF separator even surviving till 6 mA cm-2 and more importantly, has excellent safety at high temperature (50 ⁰C) with ultra-large areal capacity of 10 mAh cm-2. Due to its exceptional characteristics, the PI@GF separator enhances the transference of Zn2+ ions from 0.45 to 0.53, by facilitating the guidance of zinc ion nucleation, growth, and deposition while maintaining 99.7% coulombic efficiency for 1000 hours. Undoubtedly, the energy barrier for Zn2+ transport across the PI@GF separator was decreased via simulation studies. This study reveals how functional separator design may influence Zn2+ deposition activity and provide a dendrite-free Zn anode.

Robust and transparent dust removal coating applied to polyimide-based photovoltaic modules for lunar rovers

Dust removal coatings for polyimide (PI)-based photovoltaic modules used in lunar rovers were fabricated successfully through the blade-coating method using silicon dioxide (SiO2) nanoparticles and γ-aminopropyltriethoxysilane (KH550). The dust removal performance, morphology, transparency, and adhesive force of the coating can be optimized by adjusting the pH and the mass ratios of SiO2 and KH550. The designed coating demonstrates excellent dust removal performance, achieving an percentage of over 85 %. Moreover, the coating has minimal impact on the transparency of the PI substrate and exhibits strong adhesion to it. Additionally, the coating shows remarkable resistance to both high and low temperatures. Even after undergoing five cycles of thermal treatment ranging from −196 to 160 °C, there were no significant changes in the morphology or dust removal performance of the coating. Therefore, this coating exhibits tremendous potential for application in the dust removal of photovoltaic modules in lunar rovers.

A Water-Soluble Thermoplastic Polyamide Acid Sizing Agents for Enhancing Interfacial Properties of Carbon Fibre Reinforced Polyimide Composites.

Carbon-fiber-reinforced polyimide (PI) resin composites have gained significant attention in the field of continuous-fiber-reinforced polymers, in which the interfacial bonding between carbon fiber and matrix resin has been an important research direction. This study designed and prepared a water-soluble thermoplastic polyamide acid sizing agent to improve the wettability of carbon fiber, enhance the van der Waals forces between carbon fiber and resin and strengthen the chemical bonding between the sizing agent and the alkyne-capped polyimide resin by introducing alkyne-containing functional groups into the sizing agent. This study found that the addition of a sizing layer effectively bridged the large modulus difference between the fiber and resin regions, resulting in the formation of an interfacial layer approximately 85 nm thick. This layer facilitated the transfer of stress from the matrix to the reinforced carbon fiber, leading to a significant improvement in the interfacial properties of the composites. Adjusting the concentration of the sizing agent showed that composites treated with 3% had the best interfacial properties. The interfacial shear strength increased from 82.08 MPa to 108.62 MPa (32.33%) compared to unsized carbon fiber. This research is significant for developing sizing agents suitable for carbon-fiber-reinforced polyimide composites.

A flexible sensor fabricated by laser-induced graphene on PI fabric with macroscopic crack array for GF modulation strategy

In numerous fields such as digital health, soft robotics, and artificial intelligence, there is a growing demand for sensing various types of weak signals. In response to this need, flexible sensors should possess characteristics such as high sensitivity (i.e., gauge factor, GF), good conformability and high cyclic stability. So, in this study a simple method was employed to prepare flexible sensors using a polyimide (PI) fabric as a flexible substrate and hot-press molding technique. Furthermore, a strategy was proposed to adjust the GF using a macroscopic crack array. Compared to traditional film substrates, fabric substrates exhibit better conformability and can be designed into variable curvature structures, presenting greater potential for various applications. Experimental data illustrate that the designed flexible fabric sensor exhibits exceptional linearity within the 0–10% strain range, with a linearity value of 0.99747. Subsequently, an extremely simple and cheap strategy for modulating the GF was proposed based on such fabric structure. The strategy is engraving an array of cracks on the surface of the sensor. The GF of the crack arrays sensors was boosted to 25 times of that without engraved crack arrays. The sensors with and without crack arrays finally accomplished the sensing tests of finger bending signal, breathing signal, blinking signal, and speech signal successfully. Therefore, the proposed sensor preparation scheme and GF enhancement strategy in this study exhibit strong potential for applications in the field of wearable flexible electronics.

Mechanically robust poly(urethane-imide) aerogels with excellent thermal insulation and sound absorption by ambient drying

Polyimide (PI) aerogels are the great candidates for sound absorption, thermal insulation and mechanical cushioning materials due to their low density, excellent mechanical properties and good thermal stability. However, the high shrinkage and hydrophilicity of PI aerogels, as well as the time-consuming and complexity of the process directly limit their wide application in many fields. Herein, a facile one-step method for the synthesis of porous monolithic poly(urethane-imide) (PUI) aerogels was successfully developed. Hydrothermal synthesis and ambient drying methods were adopted in the construction of monolithic chemically cross-linked PUI aerogels, which avoids the complex imidization process. PUI aerogels were homogeneously produced by a chemical cross-linking copolymerization reaction between polyurethane (PU) oligomers, Benzene-1,2,4,5-tetracarboxylic dianhydride (PMDA) and 1, 3, 5-tris (6-isocyanatohexyl)-1, 3, 5-triazine-2, 4, 6(1H, 3H, 5H)-trione without any catalysts. Interestingly, the introduction of linear flexible PU oligomers chain segments effectively prevented the shrinkage of the network backbone and enhanced the hydrophobicity of PUI aerogels. The obtained PUI aerogels have low density (0.196 g/cm3), low shrinkage (9.30%), high porosity (79.54%) and hydrophobicity (water contact angle of 129.2°). Under high pressure, PUI aerogel was compressed but not break and the compression Young's modulus as high as 3.638 MPa. Moreover, the thermal conductivity of PUI aerogels was only 59.92 mW/m/K at 150 °C. When the back cavity depth was 5 mm, the highest sound absorption coefficient of PUI aerogel was up to 0.7219. This work provides a new method for the development of lightweight, high-mechanical-strength polymer aerogels, and the prepared aerogels have a potential application in the field of multifunctional integrated sound absorption materials.

Effect of Various Polyimide (PI) Ratios on the Wear Resistance and Mechanical Properties of PI/Polytetrafluoroethylene (PTFE) Blends

Filling polytetrafluoroethylene (PTFE) with polyimide (PI) could effectively improve the properties of PTFE-based blends. In our research described in this article, five PI/PTFE-blend specimens with various conditions were prepared by a cold-pressing, sintering method using various ratios of PI. The PI/PTFE blends were tested for mechanical and wear resistance properties. The surface morphology of the blends was observed using an ultra-field electron microscope. The maximum tensile strength was 32.18 MPa at a PI ratio of 12.5 wt.%. The variation of the PI ratio caused changes in the dispersion of the filler in the matrix, which affected the mechanical properties of the blends. When the PI content was 15 wt.%, the lowest volumetric wear degree of the PI/PTFE blends occurred, 7.8327 × 10−7 mm3/Nm. When the ratio of PI was too high, the PI filler was more likely to be detached from the PTFE matrix in a large area during the friction experiments. This would lead to the blends being more prone to generating abrasive debris during friction, and the buildup and sliding of these abrasive debris on the friction interfaces increased the volumetric wear rate and the coefficient of friction of the blends.

Surface Modification of Polyimide Aerogel by Thermoplastic Polyurethane for Enhanced Mechanical Strength and Thermal Insulation Performance.

Polyimide (PI) aerogel is a good thermal insulation material with the highest temperature resistance in practical application. But the mechanical strength of PI aerogels prepared by freeze-drying or thermoimide methods is weak. In this research, TPU was selected as an aging solution to solve the problem of the low mechanical strength of PI aerogel prepared by the freeze-drying method. Previous work has certified that the coupling of PI and thermoplastic polyurethane (TPU) can enhance the mechanical strength of PI aerogel to a certain extent due to the flexibility of TPU. But excessive TPU will change the PI structure in the cross-linking process and decrease the mechanical strength of the aerogel. Thus, a new kind of PI gel modification method was provided by using TPU as an aging solution, and the mechanical strength of PI aerogel is improved to 3.06 MPa. Furthermore, the shrinkage, specific surface area, waterproof angle, and thermal conductivity all show good performance, thus enabling PI aerogel to be used in many aspects. Specially, the method is simple and can be used to prepare some other high-strength aerogels.

Fabrication of high-performance polyimide films by tailoring coordination bond and chain rigidity

Coordination bonds and chain rigidities play severe roles in crystalline structure and property of polyimides (PIs). This study developed various polyimides with metal-diimine coordination bonds and varying chain rigidities. How coordination bonds and chain stiffness affect the semi-crystalline structure of polyimide films was investigated. Results from Fourier transform infrared (FTIR) and X-ray photoelectron spectroscopy (XPS) spectra confirmed the successful synthesis of coordinated polyimide films. Wide-angle diffraction (WAXD) results revealed that the crystallization behavior of PIs with flexible chains is significantly affected by additional coordination bonds, while the crystallization of PIs with rigid structures is primarily influenced by the chain rigidities. Compared to coordinated PIs with amorphous structure, PIs with both coordination bonds and semi-crystalline structures exhibited enhanced heat resistance, crystallinity, and dimensional stability. Notably, the coordinated PI-BP-Cu film with the highest chain rigidity in this study demonstrated excellent mechanical properties, with a tensile strength of 280 MPa, initial modulus of 5.7 GPa, and outstanding dimensional stability, characterized by a linear thermal expansion coefficient of 8.9 ppm/K (40–300 °C). These findings significantly enhance its suitability for use in metal/non-metal bonding composite materials.

Synergies and applications of polyimides featured low permittivity and high thermal conductivity

The continuous upgrading of electronic technology has facilitated the integration and miniaturization of electronic and electrical equipment, as well as putting great pressure on the multifunctional demand for internal materials. Developing insulating materials with both low permittivity and high thermal conductivity has become imperative. This perspective focuses on polyimide (PI), which is the top material of the polymer material pyramid, discusses the characteristic parameters that affect its dielectric property and thermal conductivity. A series of basic schemes to regulate the dielectric/thermal properties of PI are summarized, revealing the bottlenecks and drawbacks of the current research. Future development trends of PIs featured low permittivity-high thermal conductivity are anticipated, and novel ideas are proposed for the development of new generation of multifunctional PIs.