3D Printing of Periodic Porous Metamaterials for Tunable Electromagnetic Shielding Across Broad Frequencies

The new-generation electronic components require a balance between electromagnetic interference shielding efficiency and open structure factors such as ventilation and heat dissipation.In addition,realizing the tunable shielding of porous shields over a wide range of wavelengths is even more challenging.In this study,the well-prepared thermoplastic polyurethane/carbon nanotubes composites were used to fabricate the novel periodic porous flexible metamaterials using fused deposition modeling 3D printing.Particularly,the investigation focuses on optimization of pore geometry,size,dislocation configuration and material thickness,thus establishing a clear correlation between structural parameters and shielding property.Both experimental and simulation results have validated the superior shielding performance of hexagon derived honeycomb structure over other designs,and proposed the failure shielding size(D_(f)≈λ/8-λ/5)and critical inclined angle(θf≈43°-48°),which could be used as new benchmarks for tunable electromagnetic shielding.In addition,the proper regulation of the material thickness could remarkably enhance the maximum shielding capability(85-95 dB)and absorption coefficient A(over 0.83).The final innovative design of the porous shielding box also exhibits good shielding effectiveness across a broad frequency range(over 2.4 GHz),opening up novel pathways for individualized and diversified shielding solutions.

Polymer Fiber Rigid Network with High Glass Transition Temperature Reinforces Stability of Organic Photovoltaics

Organic photovoltaics(OPVs)need to overcome limitations such as insufficient thermal stability to be commercialized.The reported approaches to improve stability either rely on the development of new materials or on tailoring the donor/acceptor morphology,however,exhibiting limited applicability.Therefore,it is timely to develop an easy method to enhance thermal stability without having to develop new donor/acceptor materials or donor–acceptor compatibilizers,or by introducing another third component.Herein,a unique approach is presented,based on constructing a polymer fiber rigid network with a high glass transition temperature(T_(g))to impede the movement of acceptor and donor molecules,to immobilize the active layer morphology,and thereby to improve thermal stability.A high-T_(g) one-dimensional aramid nanofiber(ANF)is utilized for network construction.Inverted OPVs with ANF network yield superior thermal stability compared to the ANF-free counterpart.The ANF network-incorporated active layer demonstrates significantly more stable morphology than the ANF-free counterpart,thereby leaving fundamental processes such as charge separation,transport,and collection,determining the device efficiency,largely unaltered.This strategy is also successfully applied to other photovoltaic systems.The strategy of incorporating a polymer fiber rigid network with high T_(g) offers a distinct perspective addressing the challenge of thermal instability with simplicity and universality.

Visualization of adaptive polymer flow and displacement in medium-permeable 3D core-on-a-chip

Polymer flooding has been witnessed an effective technology for enhancing oil recovery from medium-to low-permeability reservoirs;however, direct visualization of polymer solution flow in such reservoir condition is still lacking. In this work, a three-dimensional (3D) core-on-a-chip device with a permeability of around 200 mD was prepared and employed to visualize the pore-scale flow and displacement of a self-adaptive polymer (SAP, 8.7 × 106 g·mol−1)−whose microscopic association structure and macroscopic viscosity can reversibly change in response to shear action−versus partially hydrolyzed polyacrylamide (HPAM), by recording their flow curves, monitoring dynamic transportation process via particle imaging velocimetry, and building 3D structure of remaining oil. The results show that, in single-phase flow, all polymer solutions exhibit flow thinning and then thickening regions as flow rate increases, but the transition between two regimes occurs at a small Weissenberg number (10−3−10−1) in this medium-permeable condition. In contrast to HPAM-1 with close weight-average molecular weight (Mw), the adaptive character not only extends SAP's shear-govern region, allowing SAP to propagate piece by piece and achieve higher accessible pore volume, but it also enhances the elastic resistibility of polymer in the extension-dominated regime, increasing the microscopic displacement efficiency. These two effects result in 1.5–3 times more oil recovery factor for SAP than for HPAM-1. Regarding ultra-high-Mw HPAM-2 (25 × 106 g·mol−1), plugging and chain degradation do occur, thus producing lower oil recovery than SAP. This work provides a direct approach for in-situ assessment of polymer-based displacing system under a more authentic condition of practical reservoirs.

3D printing encouraging desired in-situ polypyrrole seed-polymerization for ultra-high energy density supercapacitors

The tireless pursuit of supercapacitors with high energy density entails the parallel advancement of wellsuited electrode materials and elaborately engineered architectures.Polypyrrole(PPy)emerges as an exceedingly conductive polymer and a prospective pseudocapacitive materials for supercapacitors,yet the inferior cyclic stability and unpredictable polymerization patterns severely impede its real-world applicability.Here,for the first time,an innovative seed-induced in-situ polymerization assisted 3D printing strategy is proposed to fabricate PPy-reduced graphene oxide/poly(vinylidene difluoride-cohexafluoropropylene)(PVDF-HFP)(PPy-rGO/PH)electrodes with controllable polymerization behavior and exceptional areal mass loading.The preferred active sites uniformly pre-planted on the 3D-printed graphene substrates serve as reliable seeds to induce efficient polypyrrole deposition,achieving an impressive mass loading of 185.6 mg cm^(-2)(particularly 79.2 mg cm^(-2)for polypyrrole)and a superior areal capacitance of 25.2 F cm^(-2)at 2 mA cm^(-2)for a 12-layer electrode.In agreement with theses appealing features,an unprecedented areal energy density of 1.47 mW h cm^(-2)for a symmetrical device is registered,a rarely achieved value for other PPy/rGO-based supercapacitors.This work highlights a promising route to preparing high energy density energy storage modules for real-world applications.

Structure Regulation of Electric Double Layer via Hydrogen Bonding Effect to Realize High-Stability Lithium-Metal Batteries

The interfacial chemistry of solid electrolyte interphases(SEI)on lithium(Li)electrode is directly determined by the structural chemistry of the electric double layer(EDL)at the interface.Herein,a strategy for regulating the structural chemistry of EDL via the introduction of intermolecular hydrogen bonds has been proposed(p-hydroxybenzoic acid(pHA)is selected as proof-of-concept).According to the molecular dynamics(MD)simulation and density functional theory(DFT)calculation results,the existence of hydrogen bonds realizes the anion structural rearrangement in the EDL,reduces the lowest unoccupied molecular orbital(LUMO)energy level of anions in the EDL,and the number of free solvent molecules,which promotes the formation of inorganic species-enriched SEI and eventually achieves the dendrite-free Li deposition.Based on this strategy,Li‖Cu cells can stably run over 185 cycles with an accumulated active Li loss of only 2.27 mAh cm^(-2),and the long-term cycle stability of Li‖Li cells is increased to 1200 h.In addition,the full cell pairing with the commercial LiFePO_(4)(LFP)cathodes exhibits stable cycling performance at 1C,with a capacity retention close to 90%after 200 cycles.

Design of AI-Enhanced and Hardware-Supported Multimodal E-Skin for Environmental Object Recognition and Wireless Toxic Gas Alarm

Post-earthquake rescue missions are full of challenges due to the unstable structure of ruins and successive aftershocks.Most of the current rescue robots lack the ability to interact with environments,leading to low rescue efficiency.The multimodal electronic skin(e-skin)proposed not only reproduces the pressure,temperature,and humidity sensing capabilities of natural skin but also develops sensing functions beyond it—perceiving object proximity and NO2 gas.Its multilayer stacked structure based on Ecoflex and organohydrogel endows the e-skin with mechanical properties similar to natural skin.Rescue robots integrated with multimodal e-skin and artificial intelligence(AI)algorithms show strong environmental perception capabilities and can accurately distinguish objects and identify human limbs through grasping,laying the foundation for automated post-earthquake rescue.Besides,the combination of e-skin and NO2 wireless alarm circuits allows robots to sense toxic gases in the environment in real time,thereby adopting appropriate measures to protect trapped people from the toxic environment.Multimodal e-skin powered by AI algorithms and hardware circuits exhibits powerful environmental perception and information processing capabilities,which,as an interface for interaction with the physical world,dramatically expands intelligent robots’application scenarios.

Exploring Trade-offs in Thermal Interface Materials:The Impact of Polymer-Filler Interfaces on Thermal Conductivity and Thixotropy

Effective thermal transport across solid-solid interfaces which is essential in thermal interface materials(TIMs),necessitates both optimal thixotropy and high thermal conductivity.The role of filler surface modification,a fundamental aspect of TIM fabrication,in the influence of these properties is not fully understood.This study employs the use of a silane coupling agent(SCA)to modify alumina,integrating experimental approaches with molecular dynamics simulations,to elucidate the interface effects on thixotropy and thermal conductivity in polydimethylsiloxane(PDMS)-based TIMs.Our findings reveal that the variations of SCAs modify both interface binding energy and transition layer thickness.The interface binding energy restricts macromolecular segmental relaxation near the interface,hindering desirable thixotropy and bond line thickness.On the contrary,the thickness of the transition layer at the interface positively influences thermal conductivity,facilitating the transport of phonons between the polymer and filler.Consequently,selecting an optimal SCA allows a balance between traditionally conflicting goals of high thermal conductivity and minimal bond line thickness,achieving an impressively low interface thermal resistance of just 2.45-4.29 K·mm^(2)·W^(-1)at275.8 kPa.

Thermotolerant and fireproof gel polymer electrolyte toward high-performance and safe lithium-ion battery

Poly(ethylene oxide)(PEO)and its derivatives based gel polymer electrolytes(GPEs)are severely limited in advanced and safe lithium-ion batteries(LIBs)owing to the intrinsically high flammability of liquid electrolytes and PEO.Directly adding flame retardants to the GPEs can suppress their flammability and thus improve the safety of LIBs,but results in deteriorative electrochemical performance.Herein,a novel GPE with chemically bonded flame retardant(i.e.diethyl vinylphosphonate)in cross-linked polyethylene glycol diacrylate matrix,featuring both high-safety and high-performance,is designed.This as-prepared GPE storing the commercial 1 mol L^(-1) LiPF6 electrolyte resists high temperature of 200℃and cannot be ignited as well as possesses a high ionic conductivity(0.60 m S cm^(-1))and good compatibility with lithium.Notably,the LiFePO_(4)/Li battery with this GPE delivers a satisfactory capacity of 142.2 m A h g^(-1) and a superior cycling performance with a capacity retention of 96.3%and a coulombic efficiency of close to 100%for 350 cycles at 0.2 C under ambient temperature.Furthermore,the battery can achieve steady charge–discharge for 100 cycles with a coulombic efficiency of 99.5%at 1 C under 80℃and run normally even at a high temperature of 150℃or under the exposure to butane flame.Differential scanning calorimetry manifests significantly improved battery safety compared to commercial battery systems.This work provides a new pathway for developing next-generation advanced LIBs with enhanced performance and high safety.

From trash to treasure: Chemical recycling and upcycling of commodity plastic waste to fuels, high-valued chemicals and advanced materials

Of all the existing materials, plastics are no doubt among the most versatile ones. However, the extreme increases in plastic production as well as the difficulty of the material for degradation have led to a huge number of plastic wastes. Their recycling rate after disposal is less than 10%, resulting in a series of serious environmental and ecological problems as well as a significant waste of resources. Current recycling methods generally suffer from large energy consumption, the low utilization rate of recycled products with low added value, and produce other waste during the process. Here, we summarized recentlydeveloped chemical recycling ways on commodity plastics, especially new catalytic paths in production of fuels, high-valued chemicals and advanced materials from a single virgin or a mixture of plastic waste,which have emerged as promising ways to valorize waste plastics more economically and environmentally friendly. The new catalyst design criteria as well as innovative catalytic paths and technologies for plastic upcycling are highlighted. Beyond energy recovery by incineration, these approaches demonstrate how waste plastics can be a viable feedstock for energy use with the generation of clean H_(2), high-quality liquid fuels and materials for energy storage, and help inspiring more catalytic process on plastic upcycling to overcome the economical hurdle and building a circular plastic economy.

Fabrication of segregated poly(arylene sulfide sulfone)/graphene nanoplate composites reinforced by polymer fibers for electromagnetic interference shielding

Poly(arylene sulfide sulfone)/graphene nanoplate(PASS/GNP) composites with segregated structure based on continuous polymer fiber skeletons were fabricated by coating a thin conductive layer on the PASS fibers and then performing compression molding. The formation of a unique segregated conductive network endowed the PASS/GNP composites with high electrical conductivity and excellent electromagnetic interference(EMI) shielding effectiveness(SE), reaching 17.8 S/m and 30.1 d B, respectively, when the content of the GNPs in the conductive layer was 20 wt%. The PASS/GNP composites also exhibited outstanding mechanical properties, which was attributed to the continuous PASS fiber skeletons that could withstand large loads and the strong interfacial interaction between the conductive layers and the PASS fibers that could provide good stress transfer. This approach is suitable for most soluble polymers.

Corrigendum to“Functional Capsules Encapsulating Molecular-Recognizable Nanogels for Facile Removal of Organic Micro- Pollutants from Water”[Engineering 7 (2021) 636–646]

In section 3.6,page 643,right column,lines 8–9 from bottom,“dsorption/regeneration of the capsules is performed for five cycles,”where“five”should be“six.”

Composition Dependence of the Thermal Behavior,Morphology and Properties of Biodegradable PBS/PTMO Segment Block Copolymer

A series of aliphatic biodegradable poly（ether-ester）s based on poly（butylene succinate）（PBS）as hard segment and poly（tetramethylene oxide）（PTMO,M_n=1 000 g/mol） as soft segment were synthesized.The composition dependence of thermal behavior,morphology and mechanical properties was investigated by differential scanning calorimetry（DSC）,atomic force microscopy（AFM）,and tensile testing.The crystallization temperature（T_c） and melting temperature（T_m） of the PBS block within poly（ether-ester）s decrease steadily at first,but decrease sharply with PTMO content above 50 wt%.Two crystallization peaks were detected for PTMO in PBSPTMO60 sample,suggesting the occurrence of fractionated crystallization.The crystallization enthalpies（△H_c） and melting enthalpies（△H_m） of PBS block decrease at first,then increase as PTMO content increases further.AFM has demonstrated that phase-separated morphology transforms from a phase of continuous hard matrix to one of continuous soft matrix containing isolated hard domain as PTMO content is increased.Finally,the results of tensile testing show that the poly（ether-ester）s present the behavior of plastics when PTMO content is below 40 wt%,and of thermoplastic elastomers with PTMO content above 50 wt%.By varying the composition of copolymer,the aliphatic poly（ether-ester）s plastics,or especially biodegradable aliphatic poly（ether-ester）s thermoplastic elastomers can be obtained.

“Toolbox”for the Processing of Functional Polymer Composites

Functional polymer composites(FPCs)have attracted increasing attention in recent decades due to their great potential in delivering a wide range of functionalities.These functionalities are largely determined by functional fillers and their network morphology in polymer matrix.In recent years,a large number of studies on morphology control and interfacial modification have been reported,where numerous preparation methods and exciting performance of FPCs have been reported.Despite the fact that these FPCs have many similarities because they are all consisting of functional inorganic fillers and polymer matrices,review on the overall progress of FPCs is still missing,and especially the overall processing strategy for these composites is urgently needed.Herein,a"Toolbox"for the processing of FPCs is proposed to summarize and analyze the overall processing strategies and corresponding morphology evolution for FPCs.From this perspective,the morphological control methods already utilized for various FPCs are systematically reviewed,so that guidelines or even predictions on the processing strategies of various FPCs as well as multi-functional polymer composites could be given.This review should be able to provide interesting insights for the field of FPCs and boost future intelligent design of various FPCs.

Solid-state mechanochemistry advancing two dimensional materials for lithium-ion storage applications:A mini review

The vigorous development of two-dimensional(2D)materials brings about numerous opportunities for lithiumion batteries(LIBs)due to their unique 2D layered structure,large specific surface area,outstanding mechanical and flexibility properties,etc.Modern technologies for production of 2D materials include but are not limited to mechanochemical(solid-state/liquid-phase)exfoliation,the solvothermal method and chemical vapor deposition.In this review,strategies leading to the production of 2D materials via solid-state mechanochemistry featuring traditional high energy ball-milling and Sichuan University patented pan-milling are highlighted.The mechanism involving exfoliation,edge selective carbon radical generation of the 2D materials is delineated and this is followed by detailed discussion on representative mechanochemical techniques for tailored and improved lithium-ion storage performance.In the light of the advantages of the solid-state mechanochemical method,there is great promise for the commercialization of 2D materials for the next-generation high performance LIBs.

A Thermochromic, Viscoelastic Nacre-like Nanocomposite for the Smart Thermal Management of Planar Electronics

Cutting-edge heat spreaders for soft and planar electronics require not only high thermal conductivity and a certain degree of flexibility but also remarkable self-adhesion without thermal interface materials, elasticity, arbitrary elongation along with soft devices, and smart properties involving thermal self-healing, thermochromism and so on. Nacre-like composites with excellent in-plane heat dissipation are ideal as heat spreaders for thin and planar electronics. However, the intrinsically poor viscoelasticity, i.e., adhesion and elasticity, prevents them from simultaneous self-adhesion and arbitrary elongation along with current flexible devices as well as incurring high interfacial thermal impedance. In this paper, we propose a soft thermochromic composite(STC) membrane with a layered structure, considerable stretchability, high in-plane thermal conductivity(~30 Wm^(-1) K^(-1)), low thermal contact resistance(~12 mm^2 KW^(-1), 4–5 times lower than that of silver paste), strong yet sustainable adhesion forces(~4607 Jm^(-2), 2220 Jm^(-2) greater than that of epoxy paste) and self-healing efficiency. As a self-adhesive heat spreader, it implements efficient cooling of various soft electronics with a temperature drop of 20℃ than the polyimide case. In addition to its self-healing function, the chameleon-like behavior of STC facilitates temperature monitoring by the naked eye, hence enabling smart thermal management.

Swift Assembly of Adaptive Thermocell Arrays for Device‑Level Healable and Energy‑Autonomous Motion Sensors

The evolution of wearable technology has prompted the need for adaptive,self-healable,and energy-autonomous energy devices.This study innovatively addresses this challenge by introducing an MXene-boosted hydrogel electrolyte,which expedites the assembly process of flexible thermocell(TEC)arrays and thus circumvents the complicated fabrication of typical wearable electronics.Our findings underscore the hydrogel electrolyte’s superior thermoelectrochemical performance under substantial deformations and repeated self-healing cycles.The resulting hydrogel-based TEC yields a maximum power output of 1032.1 nW under theΔT of 20 K when being stretched to 500%for 1000 cycles,corresponding to 80%of its initial state;meanwhile,it sustains 1179.1 nW under theΔT of 20 K even after 60 cuthealing cycles,approximately 92%of its initial state.The as-assembled TEC array exhibits device-level self-healing capability and high adaptability to human body.It is readily applied for touch-based encrypted communication where distinct voltage signals can be converted into alphabet letters;it is also employed as a self-powered sensor to in-situ monitor a variety of body motions for complex human actions.The swift assembly approach,combined with the versatile functionality of the TEC device,paves the way for future advancements in wearable electronics targeting at fitness monitoring and human–machine interfaces.

Inner-pore reduction nucleation of palladium nanoparticles in highly conductive wurster-type covalent organic frameworks for efficient oxygen reduction electrocatalysis

Covalent organic frameworks(COFs)have emerged as a class of promising supports for electrocatalysis because of their advantages including good crystallinity,highly ordered pores,and structural diversity.However,their poor conductivity represents the main obstruction to their practical application.Here,we reported a novel synthesis strategy for synergistically endowing a triphenylamine-based COFs with improved electrical conductivity and excellent catalytic activity for oxygen reduction,via the in-situ redox deposition and confined growth of palladium nanoparticles inside the porous structure of COFs using reductive triphenylamine frameworks as reducing agent;meanwhile,the triphenylamine unit was oxidized to radical cation structure and affords radical cation COFs with conductivity as high as3.2*10^(-1) S m^(-1).Such a uniform confine palladium nanoparticle on highly conductive COFs makes it an efficient electrocatalyst for four-electron oxygen reduction reaction(4e-ORR),showing excellent activities and fast kinetics with a remarkable half-wave potential(E_(1/2))of 0.865 V and an ultralow Tafel slope of 39.7 mV dec^(-1) in alkaline media even in the absence of extra commercial conductive fillers.The generality of this strategy was proved by preparing the different metal and metal alloy nanoparticles supported on COFs(Au@COF,Pt@COF,AuPd@COF,AgPd@COF,and PtPd@COF)using reductive triphenylamine frameworks as reducing agent.This work not only provides a facile strategy for the fabrication of highly conductive COF supported ORR electrocatalysts,but also sheds new light on the practical application of Zn-air battery.

Crystallization Behavior of Poly(Tetramethylene Oxide) Influenced by the Crystallization Condition of Poly(Butylene Succinate) in Their Copolymers

The effect of crystallization conditions of poly(butylene succinate)(PBS) component on the crystallization of poly(tetramethylene oxide)(PTMO) component in their segment block copolymer, with a higher PTMO content(PTMO mass fraction is 67%), was investigated by DSC and temperature-dependent FTIR. It is found that the isothermal crystallization time(tIC) of PBS has an effect on the crystallization behavior of PTMO component. Perturbation correlation move-window two-dimensional(PCMW2 D) correlation analysis and generalized 2 D correlation analysis(2 DIR) were performed to explore the origin of this phenomenon. The PCMW2 D and 2 DIR results show that the correlation intensity peak observed at around 20 ℃ for PTMO is due to the PTMO chains movements forced by the PBS chains folded movements. If tIC of PBS at temperature of 20 ℃ is prolonged, more PTMO components are incorporated in the region between PBS lamellae and the peak at-7.6 ℃(belonging to less-constricted PTMO chains) changes smaller and even disappears, while the peak at-16.3 ℃ belonging to more-constricted PTMO chains gets bigger. A crystallization model was also established in this study. The results of tensile testing showed that tensile strength slightly increased and elongation at break decreased with increasing heat treatment time at 40 ℃.

Microemulsion Polymerization of Methyl Methacrylate

The microemulsion polymerization of methyl methacrylate was studied. The effects of feeding modes on the structure and the properties of the obtained polymer microlatex were investigated by measuring the conversion, the transmittance and the refractive index of the latex, and by measuring the particle size, the molecular weight and the glass transition temperature (T_g) of the polymers. The results show that compared to the batch feeding mode, the semi-continuous feeding mode is more favorable to form a PMMA microlatex with a higher transmittance, a smaller particle size, a higher molecular weight and a higher T_g. And the obtained PMMA microlatex has a 30%—40% (mass fraction) polymer content, a 0. 03 emulsifier/water weight ratio, a 0. 05 emulsifier/monomer weight ratio and a 17 nm average particle diameter, which is very important for the industrialization of the microemulsion polymerization technique.