A ternary hybrid membrane architecture consisting of sulfonated fluorinated multi-block copolymer (SFMC), sulfonated (poly ether ether ketone) (SPEEK) and I or 5 wt% graphene oxide (GO) was fabricated through ...A ternary hybrid membrane architecture consisting of sulfonated fluorinated multi-block copolymer (SFMC), sulfonated (poly ether ether ketone) (SPEEK) and I or 5 wt% graphene oxide (GO) was fabricated through a facile solution casting approach. The simple, but effective monomer sulfonation was performed for SFMC to create compact and rigid hydrophobic backbone structures, while conventional random sulfonation was carried-out for SPEEK. Hydrophilic-hydrophobic-hydrophilic structure of SFMC enhances the compatibility with SPEEK and GO and allows for an unprecedented approach to alter me- chanical strength and proton conductivity of ternary hybrid membrane, as verified from universal test machine (UTM) curves and alternating current (AC) impedance plots. The impact of GO integration on the morphology and roughness of hybrid membrane was scrutinized using field emission scanning electron microscope (FE-SEM) and atomic force microscope (AFM). Ternary hybrid showed uniform intercalation of GO nanosheets throughout the entire surface of membrane with an increased surface roughness of 8.91 nm. The constructed ternary hybrid membrane revealed excellent water absorption, ion exchange capacity and gas barrier properties, while retaining reasonable dimensional stability. The well-optimized ternary hybrid membrane containing 5 wt% GO revealed a maximum proton conductivity of 111.9 mS/cm, which is higher by a factor of two-fold with respect to that of bare SFMC membrane. The maximum PEMFC power density of 528.07mW/cm2 was yielded by ternary hybrid membrane at a load current density of 1321.1 mA/cm2 when operating the cell at 70 ℃ under 100% relative humidity (RH). In comparison, a maximum power density of only 182.06 mW/cm2 was exhibited by the bare SFMC membrane at a load current density of 455.56 mA/cm2 under same operating conditions.展开更多
A series of liquid crystalline multi-block copolymers poly[1.6-bis(4-oxybenzoyl-oxy)hexane terephthalate]-b-bisphenol A polycarbonate (PHTH-6-b-PC) with different segment lengths were synthesized in tetrachloroethane ...A series of liquid crystalline multi-block copolymers poly[1.6-bis(4-oxybenzoyl-oxy)hexane terephthalate]-b-bisphenol A polycarbonate (PHTH-6-b-PC) with different segment lengths were synthesized in tetrachloroethane by solution polycondensation in which hydroxyl terminated PC and acyl chloride terminated PHTH-6 were used. It is found that block copolymers with high molecular weight and well-defined structures were obtained. All the block copolymers exhibit a nematic liquid crystalline texture.展开更多
Liquid crystalline multi-block copolymers poly[1,6-bis(4-oxybenzoyl-oxy)hexane terephthalate]-b-bisphenol A polycarbonate (PHTH-6-b-PC) with different segments of polycarbonate (PC) and thermotropic polyester PHTH-6 w...Liquid crystalline multi-block copolymers poly[1,6-bis(4-oxybenzoyl-oxy)hexane terephthalate]-b-bisphenol A polycarbonate (PHTH-6-b-PC) with different segments of polycarbonate (PC) and thermotropic polyester PHTH-6 were synthesized in tetrachloroethane at 144 similar to 146 degrees C. The influence of segment length on the resulting phase structure and thermal behavior of block copolymers was also discussed. It is demonstrated by TEM and DMA that the resulting block copolymers show a considerable microphase separation. The degree of phase separation and the thermal behavior of the block copolymers are strongly dependent on the molecular weight of the segments incorporated.展开更多
Increasing environmental concerns about limiting harmful emissions has necessitated sulfur-and phosphorus-free green lubricant additives.Although boron-containing compounds have been widely investigated as green lubri...Increasing environmental concerns about limiting harmful emissions has necessitated sulfur-and phosphorus-free green lubricant additives.Although boron-containing compounds have been widely investigated as green lubricant additives,their macromolecular analogs have been rarely considered yet to develop environmentally friendly lubricant additives.In this work,a series of boron-containing copolymers have been synthesized by free-radical copolymerization of stearyl methacrylate and isopropenyl boronic acid pinacol ester with different feeding ratios(S_(n)-r-B_(m),n=1,m=1/3,1,2,3,5,9).The resulting copolymers of S_(n)-r-B_(m)(n=1,m=1/3,1,2,3,5)are readily dispersed in the PAO-10 base oil and form micelle-like aggregates with hydrodynamic diameters ranging from 9.7 to 52 nm.SRV-IV oscillating reciprocating tribological tests on ball-on-flat steel pairs show that compared with the base oil of PAO-10,the friction coefficients and wear volumes of the base oil solutions of S_(n)-r-B_(m)decrease considerably up to 62%and 97%,respectively.Moreover,the base oil solution of S_(1)-r-B_(1)exhibits an excellent load-bearing capacity of(850±100)N.These superior lubricating properties are due to the formation of protective tribofilms comprising S_(n)-r-B_(m),boron oxide,and iron oxide compounds on the lubricated steel surface.Therefore,the boron-containing copolymers can be regarded as a novel class of environmentally friendly lubricating oil macroadditives for efficient friction and wear reduction without sulfur and phosphorus elements.展开更多
High-voltage LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)(NCM811)cathodes are critical for enhancing the energy density of lithium-ion batteries(LIBs).The development of binders compatible with high-voltage NCM811 cathode material...High-voltage LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)(NCM811)cathodes are critical for enhancing the energy density of lithium-ion batteries(LIBs).The development of binders compatible with high-voltage NCM811 cathode materials is crucial to enhance the electrochemical performance of LIBs.However,the traditional fluoropolymer binder,poly(vinylidene difluoride)(PVDF),can potentially leach components or break down into poly(fluoroalkyl substances)(PFAS)chemicals,thereby contributing to PFAS contamination.A novel fluorine-free polymer,polysulfone-polyamide-polyimide(SPIO),was designed and synthesized as a binder for NCM811 cathodes.The SPIO binder exhibits exceptional mechanical properties and superior electrochemical characteristics.The cathode film fabricated with SPIO demonstrated a remarkable delamination force of 8 N(390 N·m^(-1)),indicating robust adhesion.The Li‖NCM811 cell incorporating the SPIO binder retained 80%of its initial capacity after 300 cycles at a current density of 0.2 C.In comparison,the control cells assem bled with the PVDF binder retained only 52%of their capacities under the same cycling conditions.Furthermore,the SPIO binder exhibited improved compatibility with the electrolyte.Transmission electron microscopy analysis of the cathode films after 100 cycles revealed the formation of a unifo rm,dense,and continuous chemical-electrochemical interface(CEI)by the SPIO binder on the surface of the NCM811 particles,which significantly contributed to the enhancement of the electrochemical performance.These results highlight the potential of SPIO as an advanced binder material for high-perfo rmance lithium-ion batteries.展开更多
Amphiphilic asymmetric brush copolymers(AABCs)possess unique self-assembly behaviors owing to their asymmetric brush architecture and multiple functionalities of multicomponent side chains.However,the synthesis of AAB...Amphiphilic asymmetric brush copolymers(AABCs)possess unique self-assembly behaviors owing to their asymmetric brush architecture and multiple functionalities of multicomponent side chains.However,the synthesis of AABCs presents challenges,which greatly limits the exploration of their self-assembly behaviors.In this work,we employed dissipative particle dynamics(DPD)simulations to investigate the self-assembly behaviors of AABCs in selective solution.By varying the copolymer concentration and structure,we conducted the self-assembly phase diagrams of AABCs,revealing complex morphologies such as channelized micelles with one or more solvophilic channels.Moreover,the number,surface area,and one-dimensional density distribution of the channelized micelles were calculated to demonstrate the internal structure and morphological transformation during the self-assembly process.Our findings indicate that the morphology of the internal solvophilic channels is greatly influenced by the copolymer structure,concentration,and interaction parameters between the different side chains.The simulation results are consistent with available experimental observations,which can offer theoretical insights into the self-assembly of AABCs.展开更多
A significant challenge in developing block copolymer photonic crystals is constructing low-symmetric ordered phases,which are essential for achieving a complete photonic band gap.Here,we propose a promising strategy ...A significant challenge in developing block copolymer photonic crystals is constructing low-symmetric ordered phases,which are essential for achieving a complete photonic band gap.Here,we propose a promising strategy to create low-symmetric ordered morphologies by incorporating shape-anisotropic rod-like side chains into block copolymers.Using dissipative particle dynamics simulations,we demonstrate that block copolymers with longer rod-like side chains can self-assemble into a hexagonally packed columnar phase characterized by a low-symmetric rectangular cross-section.Photonic band structure calculations reveal that this low-symmetric columnar phase can exhibit a complete photonic band gap,with the gap size dependent on the aspect ratio of the rectangular cross-sections of the columns.Our findings suggest an effective approach to constructing low-symmetric photonic crystals through the self-assembly of block copolymers with shape-anisotropic segments.展开更多
The design of low-cost and high-performance cyclic olefin copolymers remains challenging.Ethylene copolymers with dicyclopentadiene(DCPD)were prepared using Ph_(2)C(Cp)(Flu)ZrCl_(2)(Cat.1),rac-Et(Ind)_(2)ZrCl_(2)(Cat....The design of low-cost and high-performance cyclic olefin copolymers remains challenging.Ethylene copolymers with dicyclopentadiene(DCPD)were prepared using Ph_(2)C(Cp)(Flu)ZrCl_(2)(Cat.1),rac-Et(Ind)_(2)ZrCl_(2)(Cat.2),Me_(2)C(Cp)(Flu)ZrCl_(2)(Cat.3)andMe_(2)Si(Ind)_(2)ZrCl_(2)(Cat.4)combined with[Ph_(3)C][B(C_(6)F_(5))_(4)]/iBu_(3)Al.Ni(acac)_(2)/iBu_(3)Al was then used to catalyze the hydrogenation of the intracyclic double bonds of ethylene/DCPD copolymers.The results showed that compared to C_(2) symmetric catalysts(Cat.2 and Cat.4),Cs symmetric catalysts(Cat.1 and Cat.3)facilitated the incorporation of copolymers with higher DCPD.1H-and ^(13)C-NMR spectra indicated that ethylene/DCPD copolymerization occurred via enhancement of the norbornene ring.Additionally,measurement of the reactivity ratios provided further confirmation that the copolymers had random sequence distributions.All these samples demonstrated transmittance values above 90%in the visible wavelength range from 400 nm to 800 nm.By changing the fraction of monomers,the glass transition temperature,refractive index,Young's modulus,and tensile strength of the copolymer increased as the incorporation of DCPD increased,whereas the Abbe number and elongation at break decreased.Compared with ethylene/norbornene and ethylene/tetracyclicdodecene copolymers,ethylene/DCPD copolymers,with excellent optical and mechanical properties,are promising materials.展开更多
The optimization of polymer structures aims to determine an optimal sequence or topology that achieves a given target property or structural performance.This inverse design problem involves searching within a vast com...The optimization of polymer structures aims to determine an optimal sequence or topology that achieves a given target property or structural performance.This inverse design problem involves searching within a vast combinatorial phase space defined by components,se-quences,and topologies,and is often computationally intractable due to its NP-hard nature.At the core of this challenge lies the need to evalu-ate complex correlations among structural variables,a classical problem in both statistical physics and combinatorial optimization.To address this,we adopt a mean-field approach that decouples direct variable-variable interactions into effective interactions between each variable and an auxiliary field.The simulated bifurcation(SB)algorithm is employed as a mean-field-based optimization framework.It constructs a Hamiltonian dynamical system by introducing generalized momentum fields,enabling efficient decoupling and dynamic evolution of strongly coupled struc-tural variables.Using the sequence optimization of a linear copolymer adsorbing on a solid surface as a case study,we demonstrate the applica-bility of the SB algorithm to high-dimensional,non-differentiable combinatorial optimization problems.Our results show that SB can efficiently discover polymer sequences with excellent adsorption performance within a reasonable computational time.Furthermore,it exhibits robust con-vergence and high parallel scalability across large design spaces.The approach developed in this work offers a new computational pathway for polymer structure optimization.It also lays a theoretical foundation for future extensions to topological design problems,such as optimizing the number and placement of side chains,as well as the co-optimization of sequence and topology.展开更多
Spatial confinement of block copolymers can induce frustrations,which can further be utilized to regulate self-assembled structures,thus providing an efficient route for fabricating novel structures.We studied the sel...Spatial confinement of block copolymers can induce frustrations,which can further be utilized to regulate self-assembled structures,thus providing an efficient route for fabricating novel structures.We studied the self-assembly of AB di-block copolymers(di-BCPs)confined in Janus spherical nanocavities using simulations,and explained the structure formation mechanisms.In the case of a strongly selective cavity wall,all the lamella-forming,gyroid-forming,and cylinder-forming di-BCPs can form interfacial frustration-induced Janus concentric perforated lamellar nanoparticles,whose outermost is a Janus spherical shell and the internal is a sphere with concentric perforated lamellar structure.In particular,Janus concentric perforated lamellar nanoparticles with holes distributed only near the equatorial plane were obtained in both lamella-forming and gyroid-forming di-BCPs,directly reflecting the effect of interfacial frustration.The minority-block domain of the cylider-forming di-BCPs may form hemispherical perforated lamellar structures with holes distributed in parallel layers with a specific orientation.For symmetric di-BCPs,both the A and B domains in each nanoparticle are continuous,interchangeable,and have rotational symmetry.While for gyroid-forming and cylinder-forming di-BCPs,only the majority-block domains are continuous in each nanoparticle,and holes in the minority-block domains usually have rotational symmetry.In the case of a weakly selective cavity wall,the inhomogeneity of the cavity wall results in structures having a specific orientation(such as flower-like and branched structures in gyroid-forming and cylinder-forming di-BCPs)and a perforated wetting layer with uniformly distributed holes.The novel nanoparticles obtained may have potential applications in nanotechnology as functional nanostructures or nanoparticles.展开更多
The self-assembly of block copolymers serves as an effective approach for fabricating various periodic ordered nanostructures. By employing self-consistent field theory (SCFT) to calculate the phase diagrams of block ...The self-assembly of block copolymers serves as an effective approach for fabricating various periodic ordered nanostructures. By employing self-consistent field theory (SCFT) to calculate the phase diagrams of block copolymers, one can accurately predict their self-assembly behaviors, thus providing guidance for the fabrication of various novel structures. However, SCFT is highly sensitive to initial conditions because it finds the free energy minima through an iterative process. Consequently, constructing phase diagrams using SCFT typically requires predefined candidate structures based on the experience of researchers. Such experience-dependent strategies often miss some structures and thus result in inaccurate phase diagrams. Recently, artificial intelligence (AI) techniques have demonstrated significant potential across diverse fields of science and technology. By leveraging AI methods, it is possible to reduce reliance on human experience, thereby constructing more robust and reliable phase diagrams. In this work, we demonstrate how to combine AI with SCFT to automatically search for self-assembled structures of block copolymers and construct phase diagrams. Our aim is to realize automatic construction of block copolymer phase diagrams while minimizing reliance on human prior knowledge.展开更多
Cutting-edge research has primarily focused on flow synthesis of linear block copolymers,lacking the ability for manipulating chain architectures for more extensive applications.Herein,we develop a flow chemistry plat...Cutting-edge research has primarily focused on flow synthesis of linear block copolymers,lacking the ability for manipulating chain architectures for more extensive applications.Herein,we develop a flow chemistry platform for the continuous microflow synthesis of bottlebrush block copolymers(BBCPs)using a grafting-through method.This involves performing ring-opening metathesis polymerization(ROMP)of two different macromonomers within two microfluidic reactors connected in series.The microflow environment allows for complete monomer conversion within a few tens of seconds,benefiting from the superior mixing efficiency achieved in Z-shaped channels as indicated by both theoretical simulations and experimental results.Consequently,a library of well-defined BBCPs of up to 528 distinct samples can be produced within one day through automation of the continuous procedure,while keeping precise control on degree of polymerization(DP<4)and polydispersity indices(PDI<1.2).The synthetic method is generally applicable to different macromonomers with different compositions and contour lengths,yielding libraries of branched block copolymers with great diversity in physiochemical properties and chain architectures.This work presents a powerful platform for high-throughput production of branched copolymers,significantly lowering the costs of the materials for real applications.展开更多
The hydration state of amphiphilic block copolymers during the self-assembly transition is closely related to the structure and properties of copolymers. In this study, the temperature-induced self-assembly of copolym...The hydration state of amphiphilic block copolymers during the self-assembly transition is closely related to the structure and properties of copolymers. In this study, the temperature-induced self-assembly of copolymer poly(N,N-dimethylacrylamide)-poly(diacetone acrylamide)(PDMAA_(30)-PDAAM_(60))_(2)in aqueous solution was monitored by near-infrared spectroscopy with water as a probe. The wavelet packet transform was employed to improve the spectral resolution. The spectral information of hydrated water surrounding the hydrophilic PDMAA and hydrophobic PDAAM blocks was then extracted, revealing the significant roles of water in morphological transition of the copolymer from spherical to worm-like micelles. Specifically, water molecules interacting with N atoms and C=O groups of the hydrophilic block gradually decrease during the morphological transition, while hydrogen-bond structures NH–CO of the hydrophobic block gradually break, bringing more water molecules into contact with the hydrophobic block. This work provides a foundation for exploring the role of water molecules during the self-assembly transition of complex block copolymers.展开更多
Smart low-solid drilling fluids(SLSDFs)with thermo-controllable rheological properties and attractive thickening characteristics have recently captivated profound attention due to their low formation damage and enhanc...Smart low-solid drilling fluids(SLSDFs)with thermo-controllable rheological properties and attractive thickening characteristics have recently captivated profound attention due to their low formation damage and enhanced cuttings lifting capacity.However,their applications to deep hole drilling at high temperatures have remained limited because of the thermal instability and environmental constraints of the thermo-associating polymers as additives.This work explored the synergistic benefits of thermo-associating polymer and biogenic nano-silica(B-SiNP)extracted from rice husk to improve the thermo-stability of SLSDF.This study shows that the nano-hybrid,TAP-S based on vinyl-terminated B-SiNP could potentially mitigate the limiting performance of conventional LSDF(F-2)caused by the failure of thermo-associating copolymers under elevated temperatures.TAP-S bearing drilling fluid(F-3)could preserve more than 5.6-fold of its initial properties(ca.apparent viscosity,plastic viscosity,yield point,and gel strength)with a nearly flat-gel profile in the temperature range of 25-230℃,which was higher than those of the counterpart F-2 and base fluid according to the results of rheological tests analysis.In addition,TAP-S exhibited an abrupt thermo-thickening characteristic with a magnitude declining by only 1.05-fold and the activation Gibbs free energy of 1339 kJ/mol above the plateau(ca.130℃),reflecting its less sensitivity compared to F-2 under a continuous heating process.As a result,a lower temperature was required to drive the dehydration of the residual fraction of lower critical solution temperature(LCST)in nano-hybrid structures than TAP according to the results of DSC analysis.Thus,lower energy was expected to disintegrate the residual hydrogen bonds formed between the LCST chains and surrounding water molecules at elevated temperatures.Moreover,TAP-S formed a solid-micro-crosslinking structure network which exhibited a more stable hydrodynamic diameter as revealed by DLS analysis.Compared with TAP,TAP-S consisted of a larger composite B-SiNP-TAP integrated spatial network structure based on the results of environmental scanning electron microscope,which conferred a degree of thermal conductivity characteristic for improved temperature resistance.This contributed to the effective binding onto bentonite particles for protection and maintained a relatively stable bentonite particle dispersion according to the results of EPM and particle size distribution analyses.Consequently,TAP-S fortified drilling fluid demonstrates improved rheological and filtration performance under severe downhole conditions.Therefore,TAP-S,the thermo-associating copolymer integrated with B-SiNP could find potential application as an eco-friendly viscosifier in LSDFs for deep-well drilling operations.展开更多
Mechanochromic materials respond to external stimuli and provide early warnings of material damage.Perylene diimide(PDI)-based materials have attracted attention because of their outstanding fluorescence performance.H...Mechanochromic materials respond to external stimuli and provide early warnings of material damage.Perylene diimide(PDI)-based materials have attracted attention because of their outstanding fluorescence performance.However,the application of PDI in mechanochromism is limited by the difficulty for mechanical forces to disrupt the aggregation of PDI and its derivatives,as well as the fluorescence quenching caused by continuousπ-πstacking between PDI molecules.To eliminate the fluorescence quenching effect caused by the aggregation of PDI and broaden its application fields,polyhedral oligomeric silsesquioxane(POSS)-PDI-POSS(PPP)was screened as PDI doping.The photophysical properties of PPP in both monomeric and aggregated states in different solvents were studied.Then,PPP and styrene-butadiene-styrene block copolymer(SBS)were mixed to prepare the PPP/SBS film.The mechanochromic properties of PPP/SBS film were explored.The fluorescence emission spectra confirmed that when the PPP mass fraction increased to 0.30%,the PPP/SBS film exhibited mechanochromic behavior under uniaxial deformation due to the changes in the molecular packing.展开更多
Flexible polymer-based foam sensors have significant potential for application in wearable electronics and motion monitoring.However,these prospects are hindered by the complex and unenvironmentally friendly manufactu...Flexible polymer-based foam sensors have significant potential for application in wearable electronics and motion monitoring.However,these prospects are hindered by the complex and unenvironmentally friendly manufacturing processes.In this study,we employed melt blending and supercritical carbon dioxide foaming to fabricate an ethylene-vinyl acetate copolymer(EVA)/low-density polyethylene(LDPE)/carbon nanotube(CNT)piezoresistive foam sensor.The cross-linking agent bis(tert-butyldioxyisopropyl)benzene and the conductive filler CNT were incorporated into the EVA/LDPE composite,successfully achieving a chemically cross-linked and physically entangled composite structure that significantly enhanced the storage modulus and complex viscosity.Additionally,the compressive strength of EVA/LDPE/CNT foam with 10 parts per hundred rubber(phr)CNT reached 1.37 MPa at 50%compression,marking a 340%increase compared to the 0.31 MPa of the CNT-free sample.Furthermore,the EVA/LDPE/CNT composite foams,which incorporated 10 phr CNT,were prepared under specific foaming conditions,resulting in an ultra-low density of 0.11 g/cm^(3) and a higher sensitivity,with a gauge factor of–2.3.The piezoresistive foam sensors developed in this work could accurately detect human motion,thereby expanding their applications in the field of piezoresistive foam sensors and providing an effective strategy for the advancement of high-performance piezoresistive foam sensors.展开更多
Power cables are important pieces of equipment for energy transmission,but achieving a good balance between flame retardancy and mechanical properties of cable sheaths remains a challenge.In this work,a novel intumesc...Power cables are important pieces of equipment for energy transmission,but achieving a good balance between flame retardancy and mechanical properties of cable sheaths remains a challenge.In this work,a novel intumescent flame retardant(IFR)system containing silicone-containing macromolecular charring agent(Si-MCA)and ammonium polyphosphate(APP)was designed to synergistically improve the flame retardancy and mechanical properties of ethylene-butyl acrylate copolymer(EBA)composites.The optimal mass ratio of APP/Si-MCA was 3/1 in EBA composites(EBA/APP-Si-31),corresponding to the best flame retardancy with 31.2% of limited oxygen index(LOI),V-0 rating in UL-94 vertical burning test,and 76.4%reduction on the peak of heat release rate(PHRR)in cone calorimeter test.The enhancement mechanism was attributed to the synergistic effect of APP/Si-MCA during combustion,including the radical-trapping effect,the dilution effect of non-flammable gases,and the barrier effect of the intumescent char layer.Meanwhile,the tensile results indicated that EBA/APP-Si-31 also exhibited good mechanical properties with the addition of maleic anhydride-grafted polyethylene(PE-g-MA)as the compatibilizer.Thus,the APP/Si-MCA combination is an effective IFRs system for preparing high-performance EBA composites,and it will promote their applications as cable sheath materials.展开更多
Solid-state polymer electrolytes are crucial for advancing solid-state lithium-metal batteries owing to their flexibility,excellent manufacturability,and strong interfacial compatibility.However,their widespread appli...Solid-state polymer electrolytes are crucial for advancing solid-state lithium-metal batteries owing to their flexibility,excellent manufacturability,and strong interfacial compatibility.However,their widespread applications are hindered by low ionic conductivity at room temperature and lithium dendrite growth.Herein,we report a novel solid-state composite membrane electrolyte design that combines the vertically aligned channel structure and copolymer with a radial gradient composition.Within the vertically aligned channels,the composition of poly(vinyl ethylene carbonate-co-poly(ethylene glycol)diacrylate)(P(VEC-PEGDA)varies in a gradient along the radial direction:from the center to the wall of vertically aligned channels,the proportion of vinyl ethylene carbonate(VEC)in the copolymer decreases,while the proportion of poly(ethylene glycol)diacrylate(PEGDA)increases accordingly.It can be functionally divided into a mechanical-reinforcement layer and a fast-ion-conducting layer.The resulting solid-state composite membrane electrolyte achieves a high critical current density of 1.2 mA cm^(-2)and high ionic conductivity of 2.03 mS cm^(-1)at room temperature.Employing this composite membrane electrolyte,a Li//Li symmetric cell exhibits stable cycling for over 1850 h at 0.2 m A cm^(-2)/0.2 m A h cm^(-2),and a Li//LiFePO4(LFP)battery maintains 77.3% capacity retention at 2 C after 300 cycles.Our work provides insight into the rational design of safer and more efficient solidstate batteries through electrolyte structural engineering.展开更多
The strategic dispersion of carbon nanotubes(CNTs)within triblock copolymer matrix is key to fabricating nanocomposites with the desired electrical properties.This study investigated the self-assembly and electrical b...The strategic dispersion of carbon nanotubes(CNTs)within triblock copolymer matrix is key to fabricating nanocomposites with the desired electrical properties.This study investigated the self-assembly and electrical behavior of a polystyrene-polybutadiene-polystyrene(SBS)matrix with CNTs of different aspect ratios using hybrid particle-field molecular dynamics simulations.Structural factor analysis of the nanocomposites indicated that CNTs with higher aspect ratios promoted the transition of the SBS matrix from a bicontinuous to a lamellar phase.The resistor network algorithm method showed that the electrical conductivity of SBS and CNTs nanocomposites was influenced by the interplay between the CNTs aspect ratios,concentrations,and domain sizes of the triblock copolymer SBS.Our research sheds light on the relationship between CNTs dispersion and the electrical behavior of SBS/CNTs nanocomposites,guiding the engineering of materials to achieve desired electrical properties through the modulation of CNTs aspect ratios and tailored sizing of triblock copolymer domains.展开更多
This review paper provides a comprehensive introduction to various numerical methods for the phase-field model used to simulate the phase separation dynamics of diblock copolymer melts.Diblock copolymer systems form c...This review paper provides a comprehensive introduction to various numerical methods for the phase-field model used to simulate the phase separation dynamics of diblock copolymer melts.Diblock copolymer systems form complex structures at the nanometer scale and play a significant role in various applications.The phase-field model,in particular,is essential for describing the formation and evolution of these structures and is widely used as a tool to effectively predict the movement of phase boundaries and the distribution of phases over time.In this paper,we discuss the principles and implementations of various numerical methodologies for this model and analyze the strengths,limitations,stability,accuracy,and computational efficiency of each method.Traditional approaches such as Fourier spectral methods,finite difference methods and alternating direction explicit methods are reviewed,as well as recent advancements such as the invariant energy quadratization method and the scalar auxiliary variable scheme are also presented.In addition,we introduce examples of the phase-field model,which are fingerprint image restoration and 3D printing.These examples demonstrate the extensive applicability of the reviewed methods and models.展开更多
基金supported by the Korea Institute of Energy Technology Evaluation and Planning(KETEP)the Ministry of Trade,Industry&Energy(MOTIE)of the Republic of Korea(No.20164030201070)supported by Basic Science Research Program through the National Research Foundation of Korea(NRF)funded by the Ministry of Science,ICT and future Planning(NRF-2017R1A2B4005230)
文摘A ternary hybrid membrane architecture consisting of sulfonated fluorinated multi-block copolymer (SFMC), sulfonated (poly ether ether ketone) (SPEEK) and I or 5 wt% graphene oxide (GO) was fabricated through a facile solution casting approach. The simple, but effective monomer sulfonation was performed for SFMC to create compact and rigid hydrophobic backbone structures, while conventional random sulfonation was carried-out for SPEEK. Hydrophilic-hydrophobic-hydrophilic structure of SFMC enhances the compatibility with SPEEK and GO and allows for an unprecedented approach to alter me- chanical strength and proton conductivity of ternary hybrid membrane, as verified from universal test machine (UTM) curves and alternating current (AC) impedance plots. The impact of GO integration on the morphology and roughness of hybrid membrane was scrutinized using field emission scanning electron microscope (FE-SEM) and atomic force microscope (AFM). Ternary hybrid showed uniform intercalation of GO nanosheets throughout the entire surface of membrane with an increased surface roughness of 8.91 nm. The constructed ternary hybrid membrane revealed excellent water absorption, ion exchange capacity and gas barrier properties, while retaining reasonable dimensional stability. The well-optimized ternary hybrid membrane containing 5 wt% GO revealed a maximum proton conductivity of 111.9 mS/cm, which is higher by a factor of two-fold with respect to that of bare SFMC membrane. The maximum PEMFC power density of 528.07mW/cm2 was yielded by ternary hybrid membrane at a load current density of 1321.1 mA/cm2 when operating the cell at 70 ℃ under 100% relative humidity (RH). In comparison, a maximum power density of only 182.06 mW/cm2 was exhibited by the bare SFMC membrane at a load current density of 455.56 mA/cm2 under same operating conditions.
文摘A series of liquid crystalline multi-block copolymers poly[1.6-bis(4-oxybenzoyl-oxy)hexane terephthalate]-b-bisphenol A polycarbonate (PHTH-6-b-PC) with different segment lengths were synthesized in tetrachloroethane by solution polycondensation in which hydroxyl terminated PC and acyl chloride terminated PHTH-6 were used. It is found that block copolymers with high molecular weight and well-defined structures were obtained. All the block copolymers exhibit a nematic liquid crystalline texture.
文摘Liquid crystalline multi-block copolymers poly[1,6-bis(4-oxybenzoyl-oxy)hexane terephthalate]-b-bisphenol A polycarbonate (PHTH-6-b-PC) with different segments of polycarbonate (PC) and thermotropic polyester PHTH-6 were synthesized in tetrachloroethane at 144 similar to 146 degrees C. The influence of segment length on the resulting phase structure and thermal behavior of block copolymers was also discussed. It is demonstrated by TEM and DMA that the resulting block copolymers show a considerable microphase separation. The degree of phase separation and the thermal behavior of the block copolymers are strongly dependent on the molecular weight of the segments incorporated.
文摘Increasing environmental concerns about limiting harmful emissions has necessitated sulfur-and phosphorus-free green lubricant additives.Although boron-containing compounds have been widely investigated as green lubricant additives,their macromolecular analogs have been rarely considered yet to develop environmentally friendly lubricant additives.In this work,a series of boron-containing copolymers have been synthesized by free-radical copolymerization of stearyl methacrylate and isopropenyl boronic acid pinacol ester with different feeding ratios(S_(n)-r-B_(m),n=1,m=1/3,1,2,3,5,9).The resulting copolymers of S_(n)-r-B_(m)(n=1,m=1/3,1,2,3,5)are readily dispersed in the PAO-10 base oil and form micelle-like aggregates with hydrodynamic diameters ranging from 9.7 to 52 nm.SRV-IV oscillating reciprocating tribological tests on ball-on-flat steel pairs show that compared with the base oil of PAO-10,the friction coefficients and wear volumes of the base oil solutions of S_(n)-r-B_(m)decrease considerably up to 62%and 97%,respectively.Moreover,the base oil solution of S_(1)-r-B_(1)exhibits an excellent load-bearing capacity of(850±100)N.These superior lubricating properties are due to the formation of protective tribofilms comprising S_(n)-r-B_(m),boron oxide,and iron oxide compounds on the lubricated steel surface.Therefore,the boron-containing copolymers can be regarded as a novel class of environmentally friendly lubricating oil macroadditives for efficient friction and wear reduction without sulfur and phosphorus elements.
基金supported by the Shenzhen Science and Technology Program(No.JCYJ20220818100407016)the National Natural Science Foundation of China(No.22275059)+1 种基金Guangdong Special Support Program(No.2021TX06L775)high-level special funds(No.G03050K002)。
文摘High-voltage LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)(NCM811)cathodes are critical for enhancing the energy density of lithium-ion batteries(LIBs).The development of binders compatible with high-voltage NCM811 cathode materials is crucial to enhance the electrochemical performance of LIBs.However,the traditional fluoropolymer binder,poly(vinylidene difluoride)(PVDF),can potentially leach components or break down into poly(fluoroalkyl substances)(PFAS)chemicals,thereby contributing to PFAS contamination.A novel fluorine-free polymer,polysulfone-polyamide-polyimide(SPIO),was designed and synthesized as a binder for NCM811 cathodes.The SPIO binder exhibits exceptional mechanical properties and superior electrochemical characteristics.The cathode film fabricated with SPIO demonstrated a remarkable delamination force of 8 N(390 N·m^(-1)),indicating robust adhesion.The Li‖NCM811 cell incorporating the SPIO binder retained 80%of its initial capacity after 300 cycles at a current density of 0.2 C.In comparison,the control cells assem bled with the PVDF binder retained only 52%of their capacities under the same cycling conditions.Furthermore,the SPIO binder exhibited improved compatibility with the electrolyte.Transmission electron microscopy analysis of the cathode films after 100 cycles revealed the formation of a unifo rm,dense,and continuous chemical-electrochemical interface(CEI)by the SPIO binder on the surface of the NCM811 particles,which significantly contributed to the enhancement of the electrochemical performance.These results highlight the potential of SPIO as an advanced binder material for high-perfo rmance lithium-ion batteries.
基金supported by the National Science Foundation for Distinguished Young Scholars(No.52325308)the National Natural Science Foundation of China(Nos.52273008 and 52073092)+1 种基金Shanghai Scientific and Technological Innovation Projects(No.22ZR1479300)Shanghai Rising-Star Program(No.23QA1402500).
文摘Amphiphilic asymmetric brush copolymers(AABCs)possess unique self-assembly behaviors owing to their asymmetric brush architecture and multiple functionalities of multicomponent side chains.However,the synthesis of AABCs presents challenges,which greatly limits the exploration of their self-assembly behaviors.In this work,we employed dissipative particle dynamics(DPD)simulations to investigate the self-assembly behaviors of AABCs in selective solution.By varying the copolymer concentration and structure,we conducted the self-assembly phase diagrams of AABCs,revealing complex morphologies such as channelized micelles with one or more solvophilic channels.Moreover,the number,surface area,and one-dimensional density distribution of the channelized micelles were calculated to demonstrate the internal structure and morphological transformation during the self-assembly process.Our findings indicate that the morphology of the internal solvophilic channels is greatly influenced by the copolymer structure,concentration,and interaction parameters between the different side chains.The simulation results are consistent with available experimental observations,which can offer theoretical insights into the self-assembly of AABCs.
基金financially supported by the National Key R&D Program of China(No.2022YFB3707300)the National Natural Science Foundation of China(Nos.22133002,22373089)the support from the Excellent Youth Foundation of Henan Scientific Committee(No.242300421032).
文摘A significant challenge in developing block copolymer photonic crystals is constructing low-symmetric ordered phases,which are essential for achieving a complete photonic band gap.Here,we propose a promising strategy to create low-symmetric ordered morphologies by incorporating shape-anisotropic rod-like side chains into block copolymers.Using dissipative particle dynamics simulations,we demonstrate that block copolymers with longer rod-like side chains can self-assemble into a hexagonally packed columnar phase characterized by a low-symmetric rectangular cross-section.Photonic band structure calculations reveal that this low-symmetric columnar phase can exhibit a complete photonic band gap,with the gap size dependent on the aspect ratio of the rectangular cross-sections of the columns.Our findings suggest an effective approach to constructing low-symmetric photonic crystals through the self-assembly of block copolymers with shape-anisotropic segments.
基金supported by the National Natural Science Foundation of China(Nos.52130307 and 5240031453).
文摘The design of low-cost and high-performance cyclic olefin copolymers remains challenging.Ethylene copolymers with dicyclopentadiene(DCPD)were prepared using Ph_(2)C(Cp)(Flu)ZrCl_(2)(Cat.1),rac-Et(Ind)_(2)ZrCl_(2)(Cat.2),Me_(2)C(Cp)(Flu)ZrCl_(2)(Cat.3)andMe_(2)Si(Ind)_(2)ZrCl_(2)(Cat.4)combined with[Ph_(3)C][B(C_(6)F_(5))_(4)]/iBu_(3)Al.Ni(acac)_(2)/iBu_(3)Al was then used to catalyze the hydrogenation of the intracyclic double bonds of ethylene/DCPD copolymers.The results showed that compared to C_(2) symmetric catalysts(Cat.2 and Cat.4),Cs symmetric catalysts(Cat.1 and Cat.3)facilitated the incorporation of copolymers with higher DCPD.1H-and ^(13)C-NMR spectra indicated that ethylene/DCPD copolymerization occurred via enhancement of the norbornene ring.Additionally,measurement of the reactivity ratios provided further confirmation that the copolymers had random sequence distributions.All these samples demonstrated transmittance values above 90%in the visible wavelength range from 400 nm to 800 nm.By changing the fraction of monomers,the glass transition temperature,refractive index,Young's modulus,and tensile strength of the copolymer increased as the incorporation of DCPD increased,whereas the Abbe number and elongation at break decreased.Compared with ethylene/norbornene and ethylene/tetracyclicdodecene copolymers,ethylene/DCPD copolymers,with excellent optical and mechanical properties,are promising materials.
基金supported by the Fundamental Research Funds for the Central Universities(No.2024JBZX029)Shijiazhuang High Level Science and Technology Innovation and Entrepreneurship Talent Project(No.08202307)the National Natural Science Foundation of China(NSFC)(No.22173004).
文摘The optimization of polymer structures aims to determine an optimal sequence or topology that achieves a given target property or structural performance.This inverse design problem involves searching within a vast combinatorial phase space defined by components,se-quences,and topologies,and is often computationally intractable due to its NP-hard nature.At the core of this challenge lies the need to evalu-ate complex correlations among structural variables,a classical problem in both statistical physics and combinatorial optimization.To address this,we adopt a mean-field approach that decouples direct variable-variable interactions into effective interactions between each variable and an auxiliary field.The simulated bifurcation(SB)algorithm is employed as a mean-field-based optimization framework.It constructs a Hamiltonian dynamical system by introducing generalized momentum fields,enabling efficient decoupling and dynamic evolution of strongly coupled struc-tural variables.Using the sequence optimization of a linear copolymer adsorbing on a solid surface as a case study,we demonstrate the applica-bility of the SB algorithm to high-dimensional,non-differentiable combinatorial optimization problems.Our results show that SB can efficiently discover polymer sequences with excellent adsorption performance within a reasonable computational time.Furthermore,it exhibits robust con-vergence and high parallel scalability across large design spaces.The approach developed in this work offers a new computational pathway for polymer structure optimization.It also lays a theoretical foundation for future extensions to topological design problems,such as optimizing the number and placement of side chains,as well as the co-optimization of sequence and topology.
基金supported by the National Natural Science Foundation of China(NSFC)(Nos.22173051,21829301,21774066)College Discipline Innovation and Intelligence Introduction Program(111 Project(B16027)+1 种基金the International Cooperation Base(2016D01025)Tianjin International Joint Research and Development Center。
文摘Spatial confinement of block copolymers can induce frustrations,which can further be utilized to regulate self-assembled structures,thus providing an efficient route for fabricating novel structures.We studied the self-assembly of AB di-block copolymers(di-BCPs)confined in Janus spherical nanocavities using simulations,and explained the structure formation mechanisms.In the case of a strongly selective cavity wall,all the lamella-forming,gyroid-forming,and cylinder-forming di-BCPs can form interfacial frustration-induced Janus concentric perforated lamellar nanoparticles,whose outermost is a Janus spherical shell and the internal is a sphere with concentric perforated lamellar structure.In particular,Janus concentric perforated lamellar nanoparticles with holes distributed only near the equatorial plane were obtained in both lamella-forming and gyroid-forming di-BCPs,directly reflecting the effect of interfacial frustration.The minority-block domain of the cylider-forming di-BCPs may form hemispherical perforated lamellar structures with holes distributed in parallel layers with a specific orientation.For symmetric di-BCPs,both the A and B domains in each nanoparticle are continuous,interchangeable,and have rotational symmetry.While for gyroid-forming and cylinder-forming di-BCPs,only the majority-block domains are continuous in each nanoparticle,and holes in the minority-block domains usually have rotational symmetry.In the case of a weakly selective cavity wall,the inhomogeneity of the cavity wall results in structures having a specific orientation(such as flower-like and branched structures in gyroid-forming and cylinder-forming di-BCPs)and a perforated wetting layer with uniformly distributed holes.The novel nanoparticles obtained may have potential applications in nanotechnology as functional nanostructures or nanoparticles.
基金supported by the National Natural Science Foundation of China(Nos.52394272,22333002,22203018,22303017).
文摘The self-assembly of block copolymers serves as an effective approach for fabricating various periodic ordered nanostructures. By employing self-consistent field theory (SCFT) to calculate the phase diagrams of block copolymers, one can accurately predict their self-assembly behaviors, thus providing guidance for the fabrication of various novel structures. However, SCFT is highly sensitive to initial conditions because it finds the free energy minima through an iterative process. Consequently, constructing phase diagrams using SCFT typically requires predefined candidate structures based on the experience of researchers. Such experience-dependent strategies often miss some structures and thus result in inaccurate phase diagrams. Recently, artificial intelligence (AI) techniques have demonstrated significant potential across diverse fields of science and technology. By leveraging AI methods, it is possible to reduce reliance on human experience, thereby constructing more robust and reliable phase diagrams. In this work, we demonstrate how to combine AI with SCFT to automatically search for self-assembled structures of block copolymers and construct phase diagrams. Our aim is to realize automatic construction of block copolymer phase diagrams while minimizing reliance on human prior knowledge.
基金financially supported by the National Natural Science Foundation of China(No.22071176)。
文摘Cutting-edge research has primarily focused on flow synthesis of linear block copolymers,lacking the ability for manipulating chain architectures for more extensive applications.Herein,we develop a flow chemistry platform for the continuous microflow synthesis of bottlebrush block copolymers(BBCPs)using a grafting-through method.This involves performing ring-opening metathesis polymerization(ROMP)of two different macromonomers within two microfluidic reactors connected in series.The microflow environment allows for complete monomer conversion within a few tens of seconds,benefiting from the superior mixing efficiency achieved in Z-shaped channels as indicated by both theoretical simulations and experimental results.Consequently,a library of well-defined BBCPs of up to 528 distinct samples can be produced within one day through automation of the continuous procedure,while keeping precise control on degree of polymerization(DP<4)and polydispersity indices(PDI<1.2).The synthetic method is generally applicable to different macromonomers with different compositions and contour lengths,yielding libraries of branched block copolymers with great diversity in physiochemical properties and chain architectures.This work presents a powerful platform for high-throughput production of branched copolymers,significantly lowering the costs of the materials for real applications.
基金supported by the National Natural Science Foundation of China (Nos. 22174075 and 22374082)the Haihe Laboratory of Sustainable Chemical Transformations。
文摘The hydration state of amphiphilic block copolymers during the self-assembly transition is closely related to the structure and properties of copolymers. In this study, the temperature-induced self-assembly of copolymer poly(N,N-dimethylacrylamide)-poly(diacetone acrylamide)(PDMAA_(30)-PDAAM_(60))_(2)in aqueous solution was monitored by near-infrared spectroscopy with water as a probe. The wavelet packet transform was employed to improve the spectral resolution. The spectral information of hydrated water surrounding the hydrophilic PDMAA and hydrophobic PDAAM blocks was then extracted, revealing the significant roles of water in morphological transition of the copolymer from spherical to worm-like micelles. Specifically, water molecules interacting with N atoms and C=O groups of the hydrophilic block gradually decrease during the morphological transition, while hydrogen-bond structures NH–CO of the hydrophobic block gradually break, bringing more water molecules into contact with the hydrophobic block. This work provides a foundation for exploring the role of water molecules during the self-assembly transition of complex block copolymers.
基金supported by the National Natural Science Foundation for International Young Scientists of China(Grant No.52150410427)funding of Scientific Research Startup Project for High-Level Talents of Shandong Institute of Petroleum and Chemical Technology(Grant No.DJB2023020 and Grant No.2023SS019).
文摘Smart low-solid drilling fluids(SLSDFs)with thermo-controllable rheological properties and attractive thickening characteristics have recently captivated profound attention due to their low formation damage and enhanced cuttings lifting capacity.However,their applications to deep hole drilling at high temperatures have remained limited because of the thermal instability and environmental constraints of the thermo-associating polymers as additives.This work explored the synergistic benefits of thermo-associating polymer and biogenic nano-silica(B-SiNP)extracted from rice husk to improve the thermo-stability of SLSDF.This study shows that the nano-hybrid,TAP-S based on vinyl-terminated B-SiNP could potentially mitigate the limiting performance of conventional LSDF(F-2)caused by the failure of thermo-associating copolymers under elevated temperatures.TAP-S bearing drilling fluid(F-3)could preserve more than 5.6-fold of its initial properties(ca.apparent viscosity,plastic viscosity,yield point,and gel strength)with a nearly flat-gel profile in the temperature range of 25-230℃,which was higher than those of the counterpart F-2 and base fluid according to the results of rheological tests analysis.In addition,TAP-S exhibited an abrupt thermo-thickening characteristic with a magnitude declining by only 1.05-fold and the activation Gibbs free energy of 1339 kJ/mol above the plateau(ca.130℃),reflecting its less sensitivity compared to F-2 under a continuous heating process.As a result,a lower temperature was required to drive the dehydration of the residual fraction of lower critical solution temperature(LCST)in nano-hybrid structures than TAP according to the results of DSC analysis.Thus,lower energy was expected to disintegrate the residual hydrogen bonds formed between the LCST chains and surrounding water molecules at elevated temperatures.Moreover,TAP-S formed a solid-micro-crosslinking structure network which exhibited a more stable hydrodynamic diameter as revealed by DLS analysis.Compared with TAP,TAP-S consisted of a larger composite B-SiNP-TAP integrated spatial network structure based on the results of environmental scanning electron microscope,which conferred a degree of thermal conductivity characteristic for improved temperature resistance.This contributed to the effective binding onto bentonite particles for protection and maintained a relatively stable bentonite particle dispersion according to the results of EPM and particle size distribution analyses.Consequently,TAP-S fortified drilling fluid demonstrates improved rheological and filtration performance under severe downhole conditions.Therefore,TAP-S,the thermo-associating copolymer integrated with B-SiNP could find potential application as an eco-friendly viscosifier in LSDFs for deep-well drilling operations.
基金Yunfu 2023 Innovation Team Project,China(CYRC202305)。
文摘Mechanochromic materials respond to external stimuli and provide early warnings of material damage.Perylene diimide(PDI)-based materials have attracted attention because of their outstanding fluorescence performance.However,the application of PDI in mechanochromism is limited by the difficulty for mechanical forces to disrupt the aggregation of PDI and its derivatives,as well as the fluorescence quenching caused by continuousπ-πstacking between PDI molecules.To eliminate the fluorescence quenching effect caused by the aggregation of PDI and broaden its application fields,polyhedral oligomeric silsesquioxane(POSS)-PDI-POSS(PPP)was screened as PDI doping.The photophysical properties of PPP in both monomeric and aggregated states in different solvents were studied.Then,PPP and styrene-butadiene-styrene block copolymer(SBS)were mixed to prepare the PPP/SBS film.The mechanochromic properties of PPP/SBS film were explored.The fluorescence emission spectra confirmed that when the PPP mass fraction increased to 0.30%,the PPP/SBS film exhibited mechanochromic behavior under uniaxial deformation due to the changes in the molecular packing.
基金supported by the National Natural Science Foundation of China(No.52473026)。
文摘Flexible polymer-based foam sensors have significant potential for application in wearable electronics and motion monitoring.However,these prospects are hindered by the complex and unenvironmentally friendly manufacturing processes.In this study,we employed melt blending and supercritical carbon dioxide foaming to fabricate an ethylene-vinyl acetate copolymer(EVA)/low-density polyethylene(LDPE)/carbon nanotube(CNT)piezoresistive foam sensor.The cross-linking agent bis(tert-butyldioxyisopropyl)benzene and the conductive filler CNT were incorporated into the EVA/LDPE composite,successfully achieving a chemically cross-linked and physically entangled composite structure that significantly enhanced the storage modulus and complex viscosity.Additionally,the compressive strength of EVA/LDPE/CNT foam with 10 parts per hundred rubber(phr)CNT reached 1.37 MPa at 50%compression,marking a 340%increase compared to the 0.31 MPa of the CNT-free sample.Furthermore,the EVA/LDPE/CNT composite foams,which incorporated 10 phr CNT,were prepared under specific foaming conditions,resulting in an ultra-low density of 0.11 g/cm^(3) and a higher sensitivity,with a gauge factor of–2.3.The piezoresistive foam sensors developed in this work could accurately detect human motion,thereby expanding their applications in the field of piezoresistive foam sensors and providing an effective strategy for the advancement of high-performance piezoresistive foam sensors.
基金supported by the National Natural Science Foundation of China(52473059)Taishan Scholar Constructive Engineering Foundation of Shandong Province(tsqn202103079)Key Research and Development Plan of Shandong Province(2024TSGC0264).
文摘Power cables are important pieces of equipment for energy transmission,but achieving a good balance between flame retardancy and mechanical properties of cable sheaths remains a challenge.In this work,a novel intumescent flame retardant(IFR)system containing silicone-containing macromolecular charring agent(Si-MCA)and ammonium polyphosphate(APP)was designed to synergistically improve the flame retardancy and mechanical properties of ethylene-butyl acrylate copolymer(EBA)composites.The optimal mass ratio of APP/Si-MCA was 3/1 in EBA composites(EBA/APP-Si-31),corresponding to the best flame retardancy with 31.2% of limited oxygen index(LOI),V-0 rating in UL-94 vertical burning test,and 76.4%reduction on the peak of heat release rate(PHRR)in cone calorimeter test.The enhancement mechanism was attributed to the synergistic effect of APP/Si-MCA during combustion,including the radical-trapping effect,the dilution effect of non-flammable gases,and the barrier effect of the intumescent char layer.Meanwhile,the tensile results indicated that EBA/APP-Si-31 also exhibited good mechanical properties with the addition of maleic anhydride-grafted polyethylene(PE-g-MA)as the compatibilizer.Thus,the APP/Si-MCA combination is an effective IFRs system for preparing high-performance EBA composites,and it will promote their applications as cable sheath materials.
基金supported by the National Natural Science Foundation of China(52372099,52202328,22461142135,22479046)the Shanghai Sailing Program(22YF1455500)the Shanghai Magnolia Talent Plan Pujiang Project(24PJD128)。
文摘Solid-state polymer electrolytes are crucial for advancing solid-state lithium-metal batteries owing to their flexibility,excellent manufacturability,and strong interfacial compatibility.However,their widespread applications are hindered by low ionic conductivity at room temperature and lithium dendrite growth.Herein,we report a novel solid-state composite membrane electrolyte design that combines the vertically aligned channel structure and copolymer with a radial gradient composition.Within the vertically aligned channels,the composition of poly(vinyl ethylene carbonate-co-poly(ethylene glycol)diacrylate)(P(VEC-PEGDA)varies in a gradient along the radial direction:from the center to the wall of vertically aligned channels,the proportion of vinyl ethylene carbonate(VEC)in the copolymer decreases,while the proportion of poly(ethylene glycol)diacrylate(PEGDA)increases accordingly.It can be functionally divided into a mechanical-reinforcement layer and a fast-ion-conducting layer.The resulting solid-state composite membrane electrolyte achieves a high critical current density of 1.2 mA cm^(-2)and high ionic conductivity of 2.03 mS cm^(-1)at room temperature.Employing this composite membrane electrolyte,a Li//Li symmetric cell exhibits stable cycling for over 1850 h at 0.2 m A cm^(-2)/0.2 m A h cm^(-2),and a Li//LiFePO4(LFP)battery maintains 77.3% capacity retention at 2 C after 300 cycles.Our work provides insight into the rational design of safer and more efficient solidstate batteries through electrolyte structural engineering.
基金financially supported by the National Natural Science Foundation of China(Nos.52273019,62173065,22133002,22273031,and 12274056)Fundamental Research Funds for the Central Universities(No.04442024074)+2 种基金NationalKey R&D Program of China(No.2022YFB3707300)Beijing Natural Science Foundation(No.4242040)Scientific Research Funds Project of Liaoning Provincial Department of Education(No.LJKZ0034)。
文摘The strategic dispersion of carbon nanotubes(CNTs)within triblock copolymer matrix is key to fabricating nanocomposites with the desired electrical properties.This study investigated the self-assembly and electrical behavior of a polystyrene-polybutadiene-polystyrene(SBS)matrix with CNTs of different aspect ratios using hybrid particle-field molecular dynamics simulations.Structural factor analysis of the nanocomposites indicated that CNTs with higher aspect ratios promoted the transition of the SBS matrix from a bicontinuous to a lamellar phase.The resistor network algorithm method showed that the electrical conductivity of SBS and CNTs nanocomposites was influenced by the interplay between the CNTs aspect ratios,concentrations,and domain sizes of the triblock copolymer SBS.Our research sheds light on the relationship between CNTs dispersion and the electrical behavior of SBS/CNTs nanocomposites,guiding the engineering of materials to achieve desired electrical properties through the modulation of CNTs aspect ratios and tailored sizing of triblock copolymer domains.
文摘This review paper provides a comprehensive introduction to various numerical methods for the phase-field model used to simulate the phase separation dynamics of diblock copolymer melts.Diblock copolymer systems form complex structures at the nanometer scale and play a significant role in various applications.The phase-field model,in particular,is essential for describing the formation and evolution of these structures and is widely used as a tool to effectively predict the movement of phase boundaries and the distribution of phases over time.In this paper,we discuss the principles and implementations of various numerical methodologies for this model and analyze the strengths,limitations,stability,accuracy,and computational efficiency of each method.Traditional approaches such as Fourier spectral methods,finite difference methods and alternating direction explicit methods are reviewed,as well as recent advancements such as the invariant energy quadratization method and the scalar auxiliary variable scheme are also presented.In addition,we introduce examples of the phase-field model,which are fingerprint image restoration and 3D printing.These examples demonstrate the extensive applicability of the reviewed methods and models.