Highly Macroporous Polyimide with Chemical Versatility Prepared from Poly(amic acid) Salt-Stabilized High Internal Phase Emulsion Template.

Macroporous polymers have gained significant attention due to their unique mass transport and size-selective properties. In this study, we focused on Polyimide (PI), a high-performance polymer, as an ideal candidate for macroporous structures. Despite various attempts to create macroporous PI (Macro PI) using emulsion templates, challenges remained, including limited chemical diversity and poor control over pore size and porosity. To address these issues, we systematically investigated the role of poly(amic acid) salt (PAAS) polymers as macrosurfactants and matrices. By designing 12 different PAAS polymers with diverse chemical structures, we achieved stable high internal phase emulsions (HIPEs) with >80 vol % internal volume. The resulting Macro PIs exhibited exceptional porosity (>99 vol %) after thermal imidization. We explored the structure-property relationships of these Macro PIs, emphasizing the importance of controlling pore size distribution. Furthermore, our study demonstrated the utility of these Macro PIs as separators in Li-metal batteries, providing stable charging-discharging cycles. Our findings not only enhance the understanding of emulsion-based macroporous polymers but also pave the way for their applications in advanced energy storage systems and beyond.

Density Functional Theory-Based Approach For Dielectric Constant Estimation of Soluble Polyimide Insulators.

Evaluation of the insulating properties of polymers, such as the dielectric constant and dissipation factor, is crucial in electronic devices, including field-effect transistors and wireless communication applications. This study applies density functional theory (DFT) to predict the dielectric constant of soluble polyimides (SPIs). Various SPIs containing trifluoromethyl groups in the backbone with different pendant types, numbers, and symmetries are successfully synthesized, and their dielectric constants are evaluated and compared with the DFT-estimated values. Two types of DFT-optimized SPIs, single-chain and stacked-chain models, are used to describe the local geometries of the SPIs. In addition, to reveal the relationship between the molecular structure and dielectric constant, further investigations are conducted by considering the dielectric constant of composing ionic and electronic components. The DFT-estimated static dielectric constant of the single-chain model accurately reproduces the corresponding experimental value with at least 80% accuracy. Our approach provides a rational and accelerated strategy to evaluate polymer insulators for electronic devices based on cost-effective DFT calculations.

Green and Facile Synthesis of Hybrid Composites with Ultralow Dielectric Properties from Water-Soluble Polyimide and Dual-Porous Silica Nanoparticles.

Here, we proposed an eco-friendly synthetic method for synthesizing hybrid composites with ultralow dielectric properties at high frequencies up to 28 GHz for true 5G communication from aqueous aromatic polyimide (PI) polymers and dual-porous silica nanoparticles (DPS). The "one-step" water-based emulsion template method was used to synthesize the macroporous silica nanoparticles (MPS). A substantially negative ζ potential was produced along the surface of MPS by the poly(vinylpyrrolidone)-based chemical functionalization, enabling excellent aqueous dispersion stability. The water-soluble poly(amic acid) (PAA), as a precursor to PI, was also "one-step" polymerized in an aqueous solution. The MPS were dispersed in a water-soluble PAA matrix to create the hybrid composite films using an entirely water-based approach. The compatibility between the PAA matrix and MPS was elucidated by investigating relatively diverse end-terminated PAAs (with either amine or carboxyl group). It was also discovered that, during a thermally activated imidization reaction, the MPS are in situ converted into the DPS with macro- and microporous structures (with a surface area of 1522.4 m2/g). The thermal, dielectric, mechanical, and morphological characteristics of each composite film were examined, while the amount of DPS in the PI matrix varied from 1 to 20 wt %. With the addition of 5 wt % DPS as an optimum condition, it showed ultralow dielectric properties, with the Dk and Df being 1.615 and 0.003 at a frequency of 28 GHz, respectively, and compatible mechanical properties, with the tensile strength and elastic modulus being 78.2 MPa and 0.32 GPa, respectively. These results can comprehensively satisfy various physical properties required as a substrate material for 5G communication devices.

High-aspect ratio zeolitic imidazolate framework (ZIF) nanoplates for hydrocarbon separation membranes.

Metal-organic frameworks with high aspect ratios have the potential to yield high-performance gas separation membranes. We demonstrate the scalable synthesis of high­aspect ratio zeolitic imidazolate framework (ZIF)­8 nanoplates via a direct template conversion method in which high aspect ratio­layered Zn hydroxide sheets [Zn5(NO3)2(OH)8] were used as the sacrificial precursor. Successful phase conversion occurs as a result of the collaboration of low template stability and delayed delivery of 2-methylimidazole in weakly interacting solvents, particularly using acetone. When the ZIF-8 nanoplates with an average aspect ratio of 20 were shear aligned in the 6FDA-DAM polymer matrix by bar coating, the separation performance for propylene/propane far surpassed that of the previously reported mixed matrix and polymeric membranes, showing a propylene permeability of 164 Barrer and selectivity of 33.4 at 40 weight % loadings.

Eco-Friendly Water-Processable Polyimide Binders with High Adhesion to Silicon Anodes for Lithium-Ion Batteries.

Silicon is an attractive anode material for lithium-ion batteries (LIBs) because of its natural abundance and excellent theoretical energy density. However, Si-based electrodes are difficult to commercialize because of their significant volume changes during lithiation that can result in mechanical damage. To overcome this limitation, we synthesized an eco-friendly water-soluble polyimide (W-PI) precursor, poly(amic acid) salt (W-PAmAS), as a binder for Si anodes via a simple one-step process using water as a solvent. Using the W-PAmAS binder, a composite Si electrode was achieved by low-temperature processing at 150 °C. The adhesion between the electrode components was further enhanced by introducing 3,5-diaminobenzoic acid, which contains free carboxylic acid (-COOH) groups in the W-PAmAS backbone. The -COOH of the W-PI binder chemically interacts with the surface of Si nanoparticles (SiNPs) by forming ester bonds, which efficiently bond the SiNPs, even during severe volume changes. The Si anode with W-PI binder showed improved electrochemical performance with a high capacity of 2061 mAh g-1 and excellent cyclability of 1883 mAh g-1 after 200 cycles at 1200 mA g-1. Therefore, W-PI can be used as a highly effective polymeric binder in Si-based high-capacity LIBs.

Tailored Polymer Gate Dielectric Engineering to Optimize Flexible Organic Field-Effect Transistors and Complementary Integrated Circuits.

The increasing demand for solution-processed and flexible organic electronics has promoted the fabrication of integrated logic circuits using organic field-effect transistors (OFETs) instead of fundamental unit devices. This has been made possible through the rapid development of materials and processes in the past few decades. It is important for the p- and n-type OFETs using different organic semiconductors (OSCs) to have complementarily matched electrical characteristics, which significantly improve the performance of organic logic circuits. In this study, an efficient strategy to optimize the performance of flexible organic electronics, such as OFETs and complementary inverters, is proposed using a combination of polymer insulators tailored to each OSC type. Photopatternable soluble copolyimides (ScoPIs), which exhibit excellent insulating properties and chemical resistance, are synthesized and applied as gate dielectric layers in the OFETs. The material and electrical properties are systematically investigated by varying the molecular ratio of ScoPIs to determine the optimal conditions for each OFET type. As a result, complementary inverters report 1.67 times higher integration density compared to the conventional ones while maintaining gain, switching threshold, and static noise margin of 23.7 V/V, 22.1 V, and 12.1 V, respectively, at a supply voltage of 40 V. The flexible complementary inverters are successfully demonstrated by fully exploiting the advantages of ScoPIs.

Tacky-Free Polyurethanes Pressure-Sensitive Adhesives by Molecular-Weight and HDI Trimer Design.

Polyurethane pressure-sensitive adhesives (PU-PSAs) with satisfactory tack, cohesion, and removability were newly developed through the synthetic process by reacting methylene diisocyanate, poly(ethylene glycol) (PEG), and a 1,4-butanediol chain extender based on the different HDI/HDI trimer ratios. The sticking properties of PU-PSAs depended on both the HDI/HDI trimer ratio and crosslinking-agent composition in the formulation. The molecular weight (MW) dependence of adhesion in PU-PSA was observed in the range of 1000 < Mn < 3000, suggesting that the increase in MW limits the pressure-sensitive adhesion of these samples. The differences in the crosslinking-density significantly affected the cohesion, adhesion, and tack in PU-PSA. The formulation of 50 wt.% 600PEG and 50 wt.% crosslinking-agent and an HDI/HDI trimer ratio of 1.0 led to the optimal balance between the adhesion and cohesion properties owing to the sufficient tack, high 180-peel strength, and good cohesion.

Highly Flexible and Photo-Activating Acryl-Polyurethane for 3D Steric Architectures.

An acryl-functionalized polyurethane (PU) series was successfully synthesized using poly(tetramethylene ether) glycol-methylene diphenyl diisocyanate (PTMG-MDI) oligomer based on urethane methacrylates to control the flexibility of photo-cured 3D printing architectures. The mass ratio of acryl-urethane prepolymer: 1,4-butanediol (BD) chain-extender: diphenyl(2,4,6-trimethylbenzoyl) phosphine oxide (TPO) photoinitiator was 10:0.25:1. To produce suitably hard and precisely curved 3D architectures, the optimal UV absorbance and exposure energy of the acryl-PTMG-MDI resin were controlled precisely. Owing to the optimized viscosity of the acryl-PTMG-MDI resins, they could be printed readily by digital light processing (DLP) to form precisely curved 3D architectures after mixing with 1,6-hexanediol diacrylate (HDDA). The acryl-PTMG-MDI formulations showed much better flexural resolution than the neat resins. The printed 3D structure exhibited high surface hardness, good mechanical strength, and high elasticity for flexible applications in consumer/industrial and biomedical fields.

Synthesis and Characteristics of Eco-Friendly 3D Printing Material Based on Waterborne Polyurethane.

Photo-cured 3D architectures are successfully printed using the designed waterborne polyurethane-acrylate (WPUA) formulation. A WPUA series is synthesized in the presence of polycaprolactone diol (PCL) and 4,4'-methylene dicyclohexyl diisocyanate (H12MDI) as the soft segment part, dimethylolbutanoic acid (DMBA) as the emulsifier, and triethylamine (TEA) as the neutralizer, as a function of prepolymer molecular weight. The compatibility of WPUA and the photo-activating acryl monomer is as a key factor to guarantee the high resolution of 3D digital light processing (DLP) printing. The optimized blending formulations are tuned by using triacrylate monomers instead of diacrylate derivatives. For the high-accuracy and fine features of 3D DLP printing, WPUA are designed to be a suitable molecular structure for a 385 nm wavelength source, and the target viscosity is achieved in the range from 150 to 250 Cp. Photo-cured 3D architectures based on WPUA exhibit good flexural strength and high resolution.

Highly Stable Porous Polyimide Sponge as a Separator for Lithium-metal Secondary Batteries.

To inhibit Li-dendrite growth on lithium (Li)-metal electrodes, which causes capacity deterioration and safety issues in Li-ion batteries, we prepared a porous polyimide (PI) sponge using a solution-processable high internal-phase emulsion technique with a water-soluble PI precursor solution; the process is not only simple but also environmentally friendly. The prepared PI sponge was processed into porous PI separators and used for Li-metal electrodes. The physical properties (e.g., thermal stability, liquid electrolyte uptake, and ionic conductivity) of the porous PI separators and their effect on the Li-metal anodes (e.g., self-discharge and open-circuit voltage properties after storage, cycle performance, rate capability, and morphological changes) were investigated. Owing to the thermally stable properties of the PI polymer, the porous PI separators demonstrated no dimensional changes up to 180 °C. In comparison with commercialized polyethylene (PE) separators, the porous PI separators exhibited improved wetting ability for liquid electrolytes; thus, the latter improved not only the physical properties (e.g., improved the electrolyte uptake and ionic conductivity) but also the electrochemical properties of Li-metal electrodes (e.g., maintained stable self-discharge capacity and open-circuit voltage features after storage and improved the cycle performance and rate capability) in comparison with PE separators.

Low-Temperature Solution-Processed Soluble Polyimide Gate Dielectrics: From Molecular-Level Design to Electrically Stable and Flexible Organic Transistors.

Aromatic soluble polyimides (PIs) have been widely used in organic field-effect transistors (OFETs) as gate dielectric layers due to their promising features such as outstanding chemical resistance, thermal stability, low-temperature processability, and mechanical flexibility. However, the molecular structures of soluble PIs on the electrical characteristics of OFETs are not yet fully understood. In this work, the material, dielectric, and electrical properties are evaluated to systematically investigate the chemical structure effect of aromatic dianhydride and diamine monomers on the device performance. Four soluble PIs based on 4,4'-(Hexafluoroisopropylidene)diphthalic anhydride (6FDA) and 5-(2,5-Dioxotetrahydrofuryl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, in which the monomeric precursors contain different backbones, side groups, and linkages, were employed to compare the chemical structure impact. The dielectric properties, which significantly affect the charge transport and crystallinity of OSC thin films, clearly depended on the soluble PI types as well as the surface energy and the thermal stability. Furthermore, the electrical characteristic measurement and parameter extraction of OFETs based on TIPS-pentacene revealed that the 6FDA-based soluble PIs, which lead to high field-effect mobility, near-zero threshold electric field, and outstanding electrical stability under bias stress, are the most promising gate dielectric candidates. Finally, low-temperature solution-processed OFETs are successfully integrated with ultrathin flexible substrates, and they exhibit no significant electrical performance loss after mechanical flexibility tests. This work presents a step forward in the development of soluble PI gate dielectrics for flexible electronic devices with high device performance.

Polyimide-Coated Glass Microfiber as Polysulfide Perm-Selective Separator for High-Performance Lithium-Sulphur Batteries.

Although numerous research efforts have been made for the last two decades, the chronic problems of lithium-sulphur batteries (LSBs), i.e., polysulfide shuttling of active sulphur material and surface passivation of the lithium metal anode, still impede their practical application. In order to mitigate these issues, we utilized polyimide functionalized glass microfibers (PI-GF) as a functional separator. The water-soluble precursor enabled the formation of a homogenous thin coating on the surface of the glass microfiber (GF) membrane with the potential to scale and fine-tune: the PI-GF was prepared by simple dipping of commercial GF into an aqueous solution of poly(amic acid), (PAA), followed by thermal imidization. We found that a tiny amount of polyimide (PI) of 0.5 wt.% is more than enough to endow the GF separator with useful capabilities, both retarding polysulfide migration. Combined with a free-standing microporous carbon cloth-sulphur composite cathode, the PI-GF-based LSB cell exhibits a stable cycling over 120 cycles at a current density of 1 mA/cm2 and an areal sulphur loading of 2 mgS/cm2 with only a marginal capacity loss of 0.099%/cycle. This corresponds to an improvement in cycle stability by 200%, specific capacity by 16.4%, and capacity loss per cycle by 45% as compared to those of the cell without PI coating. Our study revealed that a simple but synergistic combination of porous carbon supporting material and functional separator enabled us to achieve high-performance LSBs, but could also pave the way for the development of practical LSBs using the commercially viable method without using complicated synthesis or harmful and expensive chemicals.

Investigation of phase separated polyimide blend films containing boron nitride using FTIR imaging.

Immiscible aromatic polyimide (PI) blend films and a PI blend film incorporated with thermally conductive boron nitride (BN) were prepared, and their phase separation behaviors were examined by optical microscopy and FTIR imaging. The 2,2'-bis(trifluoromethyl)benzidine (TFMB)-containing and 4,4'-thiodianiline (TDA)-containing aromatic PI blend films and a PI blend/BN composite film show two clearly separated regions; one region is the TFMB-rich phase, and the other region is the TDA-rich phase. The introduction of BN induces morphological changes in the immiscible aromatic PI blend film without altering the composition of either domain. In particular, the BN is selectively incorporated into the TDA-rich phase in this study.

Comparison of activated clotting times measured using the Hemochron Jr. Signature and Medtronic ACT Plus during cardiopulmonary bypass with acute normovolemic haemodilution.

Objective This study compared the activated clotting time (ACT) measured using the Hemochron Jr. Signature (HACT) with the ACT measured using the Medtronic ACT Plus (MACT) during cardiopulmonary bypass (CPB) with acute normovolemic haemodilution (ANH) in patients undergoing cardiac surgery. Methods The ACT was checked at baseline with both devices after inducing anaesthesia, and 400 to 800 mL of whole blood was withdrawn to induce moderate ANH. Before initiating CPB, a 300-IU/kg bolus dose of heparin was administered to maintain the HACT at >400 s; protamine was later given to reverse the anticoagulation. The ACT was checked using both devices at baseline, during heparinisation, and after protamine administration. Results In total, 106 pairs of samples from 29 patients were analysed. The ACT showed a good correlation between the two devices (r = 0.956). However, Bland-Altman analysis showed that the MACT was higher, particularly at baseline and during heparinisation. Multiple regression analysis showed that the blood glucose concentration significantly influenced the differences between the two ACT devices. Conclusions The HACT was lower than the MACT during CPB with ANH in patients undergoing cardiac surgery. Clinicians should be cautious when using each ACT device within generally accepted reference ACT values.

Highly anisotropic thermal conductivity of discotic nematic liquid crystalline films with homeotropic alignment.

Discotic nematic liquid crystal (DNLC) films are prepared by thermal treatment and a photo-crosslinking reaction inside sandwiched glass plates. The DNLC films exhibit outstanding in-plane thermal conductivity which is much larger than cross-plane thermal conductivity. The homeotropic alignment and higher crosslinking density of DNLCs in the films further increase the thermal conductivity anisotropy.

Metal-oxide assisted surface treatment of polyimide gate insulators for high-performance organic thin-film transistors.

We developed a facile method for treating polyimide-based organic gate insulator (OGI) surfaces with self-assembled monolayers (SAMs) by introducing metal-oxide interlayers, called the metal-oxide assisted SAM treatment (MAST). To create sites for surface modification with SAM materials on polyimide-based OGI (KPI) surfaces, the metal-oxide interlayer, here amorphous alumina (α-Al2O3), was deposited on the KPI gate insulator using spin-coating via a rapid sol-gel reaction, providing an excellent template for the formation of a high-quality SAM with phosphonic acid anchor groups. The SAM of octadecylphosphonic acid (ODPA) was successfully treated by spin-coating onto the α-Al2O3-deposited KPI film. After the surface treatment by ODPA/α-Al2O3, the surface energy of the KPI thin film was remarkably decreased and the molecular compatibility of the film with an organic semiconductor (OSC), 2-decyl-7-phenyl-[1]benzothieno[3,2-b][1]benzothiophene (Ph-BTBT-C10), was increased. Ph-BTBT-C10 molecules were uniformly deposited on the treated gate insulator surface and grown with high crystallinity, as confirmed by atomic force microscopy (AFM) and X-ray diffraction (XRD) analysis. The mobility of Ph-BTBT-C10 thin-film transistors (TFTs) was approximately doubled, from 0.56 ± 0.05 cm2 V-1 s-1 to 1.26 ± 0.06 cm2 V-1 s-1, after the surface treatment. The surface treatment of α-Al2O3 and ODPA significantly decreased the threshold voltage from -21.2 V to -8.3 V by reducing the trap sites in the OGI and improving the interfacial properties with the OSC. We suggest that the MAST method for OGIs can be applied to various OGI materials lacking reactive sites using SAMs. It may provide a new platform for the surface treatment of OGIs, similar to that of conventional SiO2 gate insulators.

Reconfigurable Photonic Capsules Containing Cholesteric Liquid Crystals with Planar Alignment.

Cholesteric liquid crystals (CLCs) reflect selected wavelengths of light owing to their periodic helical structures. The encapsulation of CLCs leads to photonic devices that can be easily processed and might be used as stand-alone microsensors. However, when CLCs are enclosed by polymeric membranes, they usually lose their planar alignment, leading to a deterioration of the optical performance. A microfluidics approach was employed to integrate an ultrathin alignment layer into microcapsules to separate the CLC core and the elastomeric solid membrane using triple-emulsion drops as the templates. The thinness of the alignment layer provides high lubrication resistance, preserving the layer integrity during elastic deformation of the membrane. The CLCs in the microcapsules can thus maintain their planar alignment, rendering the shape and optical properties highly reconfigurable.

Robust microfluidic encapsulation of cholesteric liquid crystals toward photonic ink capsules.

Robust photonic microcapsules are created by microfluidic encapsulation of cholesteric liquid crystals with a hydrogel membrane. The membrane encloses the cholesteric core without leakage in water and the core exhibits pronounced structural colors. The photonic ink capsules, which have a precisely controlled bandgap position and size, provide new opportunities in colorimetric micro-thermometers and optoelectric applications.

Thermally conductive polyamide 6/carbon filler composites based on a hybrid filler system.

We explored the use of a hybrid filler consisting of graphite nanoplatelets (GNPs) and single walled carbon nanotubes (SWCNTs) in a polyamide 6 (PA 6) matrix. The composites containing PA 6, powdered GNP, and SWCNT were melt-processed and the effect of filler content in the single filler and hybrid filler systems on the thermal conductivity of the composites was examined. The thermal diffusivities of the composites were measured by the standard laser flash method. Composites containing the hybrid filler system showed enhanced thermal conductivity with values as high as 8.8 W (m · K)-1, which is a 35-fold increase compared to the thermal conductivity of pure PA 6. Thermographic images of heat conduction and heat release behaviors were consistent with the thermal conductivity results, and showed rapid temperature jumps and drops, respectively, for the composites. A composite model based on the Lewis-Nielsen theory was developed to treat GNP and SWCNT as two separate types of fillers. Two approaches, the additive and multiplicative approaches, give rather good quantitative agreement between the predicted values of thermal conductivity and those measured experimentally.

Thermal conductivity improvement of surface-enhanced polyetherimide (PEI) composites using polyimide-coated h-BN particles.

In this study, we investigated the thermal conductivities and mechanical properties of polyetherimide (PEI) composites using polyimide (PI)-coated h-BN (PI-BN) particles. We found that PI-coated h-BN effectively increased adhesion with the PEI matrix, imparting enhanced mechanical and thermal stability and thermal conductivity with increasing BN content. The thermal conductivity of the PEI composite containing 60 wt% PI-BN was 3.3 W m(-1) K(-1), while the thermal conductivity of the PEI/BN composite without modification was 2.6 W m(-1) K(-1). The PEI/PI-BN composites show higher impact strengths than the PEI/BN composites because of less BN particle agglomeration and good wettability between PEI and h-BN. The results indicate that the PI-coated BN incorporated into the PEI matrix effectively enhances the thermal conductivity and mechanical properties of the PEI composites.