In this work,we proposed a strategy for the hydrolysis of native corn starch after the treatment of corn starch in an ionic liquid aqueous solution,and it is an awfully“green”and simple means to obtain starch with l...In this work,we proposed a strategy for the hydrolysis of native corn starch after the treatment of corn starch in an ionic liquid aqueous solution,and it is an awfully“green”and simple means to obtain starch with low molecular weight and amorphous state.X-ray diffraction results revealed that the natural starch crystalline region was largely disrupted by ionic liquid owing to the broken intermolecular and intramolecular hydrogen bonds.After hydrolysis,the morphology of starch changed from particles of native corn starch into little pieces,and their molecular weight could be effectively regulated during the hydrolysis process,and also the hydrolyzed starch samples exhibited decreased thermal stability with the extension of hydrolysis time.This work would counsel as a powerful tool for the development of native starch in realistic applications.展开更多
In 2024,the MOE Key Laboratory of Macromolecular Synthesis and Functionalization at Zhejiang University continued its impactful researches across five core areas.In controllable catalytic polymerization,organoboron ca...In 2024,the MOE Key Laboratory of Macromolecular Synthesis and Functionalization at Zhejiang University continued its impactful researches across five core areas.In controllable catalytic polymerization,organoboron catalysts were developed for CO₂copolymerization and novel photoresist materials.Studies in microstructure and rheology elucidated universal deformation modes in graphene-based 2D membranes and improved graphene fiber properties through shear alignment engineering,defect control,and enhanced interlayer entanglement.For separating functional polymers,Janus membranes and channels were created for multiphase separation,liquid-phase molecular layer-by-layer deposition technique was developed to fabricate aromatic polyamide nanofilms,and the harmonic amide bond density was established as a valuable parameter for polyamide structural analysis.In biomedical functional polymers,a sustainable carboxyl-ester transesterification strategy was proposed for upcycling poly(ethylene terephthalate)(PET)waste into biodegradable plastics.Additionally,immunocompatible biomaterials were designed utilizing zwitterionic polypeptides and albumin-derived coatings,and Cu2+-phenolic nanoflower was designed to combat fungal infections by combining cuproptosis and cell wall digestion.Further,the researchers developed a gelatin-DOPA-knob/fibrinogen hydrogel to achieve rapid and robust hemostatic sealing,utilized a double-network polyelectrolyte-coated hydrogel for enhancing endothelialization of left atrial appendage(LAA)occluders,and the researchers also demonstrated that image-guided high-intensity focused ultrasound enables manipulation of shape-memory polymers.Finally,in the realm of photo-electro-magnetic functional polymers,precise control of through-space conjugation was shown to enhance organic luminescence.Topologically structured hydrogels were revealed to exhibit autonomous actuation.Also,solar-driven photothermal ion pumps were developed for selective lithium extraction from seawater,and high-performance non-solvated C60 single-crystal films were prepared via facile bar coating.Lastly,the researchers demonstrated outstanding dielectric properties of polyethylene(PE)lamellar single crystals.The relevant works are reviewed in this paper.展开更多
The complex interactions and conflicting performance demands in multi-component composites pose significant challenges for achieving balanced multi-property optimization through conventional trial-and-error approaches...The complex interactions and conflicting performance demands in multi-component composites pose significant challenges for achieving balanced multi-property optimization through conventional trial-and-error approaches.Machine learning(ML)offers a promising solution,markedly improving materials discovery efficiency.However,the high dimensionality of feature spaces in such systems has long impeded effective ML-driven feature representation and inverse design.To overcome this,we present an Intelligent Screening System(ISS)framework to accelerate the discovery of optimal formulations balancing four key properties in 15-component PTFE-based copper-clad laminate composites(PTFE-CCLCs).ISS adopts modular descriptors based on the physical information of component volume fractions,thereby simplifying the feature representation.By leveraging the inverse prediction capability of ML models and constructing a performance-driven virtual candidate database,ISS significantly reduced the computational complexity associated with high-dimensional spaces.Experimental validation confirmed that ISSoptimized formulations exhibited superior synergy,notably resolving the trade-off between thermal conductivity and peel strength,and outperform many commercial counterparts.Despite limited data and inherent process variability,ISS achieved an average prediction accuracy of 76.5%,with thermal conductivity predictions exceeding 90%,demonstrating robust reliability.This work provides an innovative,efficient strategy for multifunctional optimization and accelerated discovery in ultra-complex composite systems,highlighting the integration of ML and advanced materials design.展开更多
To address the poor mechanical performance and improve the tribological properties of self-lubricating polyphenylene sulfide/irradiation treated polytetrafluoroethylene(PPS/i-PTFE)blends,different aspect ratio carbon ...To address the poor mechanical performance and improve the tribological properties of self-lubricating polyphenylene sulfide/irradiation treated polytetrafluoroethylene(PPS/i-PTFE)blends,different aspect ratio carbon fibers(i.e.,PSCF:50,SCF:about 429)were introduced as reinforcement fillers.The results showed that the hybriding of PSCF and SCF at certain mass ratios exhibited simultaneous enhancement of mechanical and tribological performance for PPS/i-PTFE blend through the construction of synergistic lubrication and mechanical interlocking network.Specifically,the flexural strength and modulus of PPS/i-PTFE were increased by 125.6% and 389.3%,the friction coefficient and specific wear rate were decreased by 13.9% and 95%,respectively.It was worth noting that PPS composites possessed excellent integrated performance which were able to withstand sliding action under high PV(≥10 MPa·m/s)conditions,as assessed by a customized pin-on-disc tester.This work demonstrated that the formation of intact lubricating film combined with the enhanced thermal and mechanical properties were favorable for improving the tribological properties of PPS-based composites,which makes them suitable for advanced engineering applications.展开更多
There are limitations to using hard carbon(HC)in K^(+)storage due to its insufficient high-current reversible capacity and plateau potential,which result from the lack of effective active sites and low intercalation c...There are limitations to using hard carbon(HC)in K^(+)storage due to its insufficient high-current reversible capacity and plateau potential,which result from the lack of effective active sites and low intercalation capabilities.The construction of HC cathodes with more available functional groups and ordered carbon nanocrystal structures is essential for improving K^(+)storage efficiency.Herein,a new perspective is proposed for synthesizing hard carbon nanosheets(HCNS)with abundant hydroxyl groups(O-H)/carboxylic groups(O-C=O)and rational carbon nanocrystals by interfacial assembly and carbonization.Systematic in ex-situ observations,dynamic analysis and theory calculations elucidate that the superior electrochemical capability of HCNS is ascribed to the synergistic effect of abundant available functional groups and ordered graphitic microcrystalline.Consequently,the HCNS exhibits outstanding K^(+)storage capabilities in terms of superb energy density(146.2 Wh/kg),high power density(1,7800 Wh/kg),and ultralong lifespan(102.9%capacity retention after 10,000 cycles).It was also found that the HC structure correlates with the discharge/charge plateau,confirming the'adsorption-insertion'charge storage mechanism.Furthermore,the proposed work provides a theoretical basis for making high-performance HC anodes by understanding the effect of their microstructure on K^(+)storage.展开更多
Hard carbon(HC)remains a leading anode candidate for sodium-ion storage,yet its application is hindered by low initial Coulombic efficiency(ICE)and limited plateau capacity due to uncontrolled defect density and open ...Hard carbon(HC)remains a leading anode candidate for sodium-ion storage,yet its application is hindered by low initial Coulombic efficiency(ICE)and limited plateau capacity due to uncontrolled defect density and open porosity.Here,we propose a scalable dual-regulation strategy that simultaneously tunes pore mouth size and defect chemistry to enhance sodium storage performance.Using phenol-formaldehyde resin as the carbon precursor and phosphorus pentoxide(P_(2)O_(5))as a bifunctional sacrificial template and dopant source,we synthesize phosphorus-functionalized hard carbon(PF-PHC)featuring a high density of closed pores with well-confined sub-nanometer pore entrances.The in-situ sublimation of P_(2)O_(5) during pyrolysis promotes the formation of closed-pore architectures,while residual phosphorus atoms effectively passivate vacancy-type defects,thereby reducing irreversible Na+adsorption and mitigating excessive solid electrolyte interphase(SEI)formation.As a result,PF-PHC achieves an ICE of 89.3%and a plateau capacity of 289 mAh g^(−1).In-situ characterizations reveal that regulating pore mouth dimensions decouples Na+and solvent access,enabling highly selective ion transport and stable interfacial chemistry.Sodium-ion hybrid capacitors(SIHCs)assembled based on PF-PHC deliver exceptional rate performance and outstanding long-term cycling stability,retaining 98.2%after 10,000 cycles at 2 A g^(−1).This study establishes pore mouth engineering as a robust and scalable design principle for advancing next-generation HC-based sodium storage materials.展开更多
Composite polymer electrolytes(CPEs)offer a promising solution for all-solid-state lithium-metal batteries(ASSLMBs).However,conventional nanofillers with Lewis-acid-base surfaces make limited contribution to improving...Composite polymer electrolytes(CPEs)offer a promising solution for all-solid-state lithium-metal batteries(ASSLMBs).However,conventional nanofillers with Lewis-acid-base surfaces make limited contribution to improving the overall performance of CPEs due to their difficulty in achieving robust electrochemical and mechanical interfaces simultaneously.Here,by regulating the surface charge characteristics of halloysite nanotube(HNT),we propose a concept of lithium-ion dynamic interface(Li^(+)-DI)engineering in nano-charged CPE(NCCPE).Results show that the surface charge characteristics of HNTs fundamentally change the Li^(+)-DI,and thereof the mechanical and ion-conduction behaviors of the NCCPEs.Particularly,the HNTs with positively charged surface(HNTs+)lead to a higher Li^(+)transference number(0.86)than that of HNTs-(0.73),but a lower toughness(102.13 MJ m^(-3)for HNTs+and 159.69 MJ m^(-3)for HNTs-).Meanwhile,a strong interface compatibilization effect by Li^(+)is observed for especially the HNTs+-involved Li^(+)-DI,which improves the toughness by 2000%compared with the control.Moreover,HNTs+are more effective to weaken the Li^(+)-solvation strength and facilitate the formation of Li F-rich solid-electrolyte interphase of Li metal compared to HNTs-.The resultant Li|NCCPE|LiFePO4cell delivers a capacity of 144.9 m Ah g^(-1)after 400 cycles at 0.5 C and a capacity retention of 78.6%.This study provides deep insights into understanding the roles of surface charges of nanofillers in regulating the mechanical and electrochemical interfaces in ASSLMBs.展开更多
UHMWPE fibers exhibit impressive modulus and strength,but they have not reached their theoretical limits.Researchers focus on molecular weight,orientation,and crystallinity of UHMWPE,yet their contributions to mechani...UHMWPE fibers exhibit impressive modulus and strength,but they have not reached their theoretical limits.Researchers focus on molecular weight,orientation,and crystallinity of UHMWPE,yet their contributions to mechanical properties are unclear.Molecular dynamics simulations are valuable but often limited by computational constraints.Our aim is to simulate higher molecular weights to better represent real UHMWPE fibers.We used Packmol and Polyply methodologies to construct PE systems,with Polyply reproducing more reasonable properties of UHMWPE fibers.Additionally,tensile simulations showed that orientation and crystallinity greatly impact Young's modulus more than molecular weight.Energy decomposition indicated that higher molecular weights lead to covalent bonds that can withstand more energy during stretching,thus increasing breaking strength.Combining simulations with machine learning,we found that orientation has the most significant impact on Young's modulus,contributing 60%,and molecular weight plays the most crucial role in determining the breaking strength,accounting for 65%.This study provides a theoretical basis and guidelines for enhancing UHMWPE's modulus and strength.展开更多
An effective strategy for enhancing the heat resistance of polystyrene(PS)with regard to its glass transition temperature(T_(g))involves the anionic solution copolymerization of a-methylstyrene(AMS)with styrene(St),ty...An effective strategy for enhancing the heat resistance of polystyrene(PS)with regard to its glass transition temperature(T_(g))involves the anionic solution copolymerization of a-methylstyrene(AMS)with styrene(St),typically requires much lower temperature(-25℃)and multistep monomer feeding to achieve higher number-average molecular weight(M_(n))block copolymers.However,the anionic copolymerization of AMS and St under the mild temperature remains largely unexplored.This study systematically investigated the anionic copolymerization of AMS and St using n-BuLi in nonpolar solvent(-25℃ to 25℃)through both one-step and two-step approaches.We demonstrated that one-step copolymerization at 25℃ yielded only 1-3 terminal AMS units,with higher feed ratios(5 wt%-20 wt%)increasing AMS incorporation but reducing the exact molecular weight(MW)due to enhanced depolymerization,as evidenced by MALDI-TOF MS.Temperature-controlled AMS conversion at-15℃ achieved 98%AMS conversion(5 wt% feed)by suppressing side reactions and lowering the[M]_(e),while 50℃(near T_(C))almost prevented incorporation.Despite t-BuOK regulation induced broader PDI(1.24)via reactive[(polymer-Li)OR]K intermediates,while other systems showed narrow distributions,t-BuOK outperformed THF in enhancing AMS incorporation via efficient ion pair dissociation.In comparison,the two-step polymerization approach demonstrated superior performance,achieving both higher AMS conversion efficiency and preferential incorporation at the initiation end.At a 20 wt%AMS feed ratio,this method yielded copolymer chains containing up to 6 AMS units on average.Thermal analysis revealed a composition-dependent single T_(g),which exhibited a systematic increase with higher AMS incorporation content.These results collectively demonstrate the precise control over AMS incorporation and heat resistance achievable through the manipulation of polymerization conditions.展开更多
Aqueous Zn-ion storage offers high capacity and safety,but practical use is hindered by dendrite formation,side reactions,and hydrogen evolution,affecting stability and efficiency.Herein,tetramethylol acetylenediurea(...Aqueous Zn-ion storage offers high capacity and safety,but practical use is hindered by dendrite formation,side reactions,and hydrogen evolution,affecting stability and efficiency.Herein,tetramethylol acetylenediurea(TA)is proposed as an effective electrolyte additive that modulates the Zn^(2+)deposition environment via coordination competition.The polar functional groups of TA restructure the solvation sheath,while its molecular dipoles generate localized electric fields that accelerate Zn^(2+)migration and promote directional(002)-oriented deposition.These effects collectively suppress side reactions and enhance Zn plating/stripping reversibility.The four hydroxyl(–OH)and conjugated ketone groups(C=O)in the TA molecule have strong coordination ability(Lewis basicity)and can form a stable[Zn(TA)(H_(2)O)_(n)]^(2+)with Zn^(2+),reducing the number of free water molecules and the proportion of active water in the solvation sheath.The TA molecules are adsorbed onto the Zn anode surface,leading to the redistribution of the local spatial electric field and homogenization of ion flux dynamics.Its conjugated planar structure can induce Zn^(2+)to preferentially deposit along the(002)crystal plane.Zn//Zn symmetric cell using TA-containing ZnSO4 electrolyte exhibits stable cycling for more than 2240 h at 1 mA cm^(−2),1 mAh cm^(−2).The Zn//activated carbon(AC)full-cell can stably cycle 30,000 cycles at 5 A g^(−1)with a capacity retention rate of 90%.This study provides important insights into electrolyte engineering strategies for stabilizing Zn anodes,highlighting the potential of molecular design additives in next-generation Zn^(2+)energy storage systems.展开更多
Vitrimers belong to a class of polymeric materials capable of bond exchange reactions,showing great promise for environmental protection and sustainable development.However,studies on the coupling mechanism between th...Vitrimers belong to a class of polymeric materials capable of bond exchange reactions,showing great promise for environmental protection and sustainable development.However,studies on the coupling mechanism between the bond exchange kinetics and segmental dynamics near the glass transition temperature(T_(g))remain scarce.Herein,we employed molecular dynamics simulations to investigate the dynamic heterogeneity of the segment motion and bond exchange in vitrimers.The simulation results revealed that the bond exchange energy barrier exerts a much stronger influence on the bond exchange kinetics than on the segmental dynamics.At lower temperatures,slower segmental relaxation further constraind the bond exchange rate.Additionally,increasing the bond exchange energy barrier markedly enhanced the dynamic heterogeneity of segment motion.A close correlation was observed between heterogeneity and bond exchange.This study elucidated the coupling mechanism between bond exchange and segmental dynamics at the molecular scale,thereby providing a theoretical basis for designing vitrimer materials with tunable dynamic properties.展开更多
Hospital wastewater contains complex pollutants,including residual organic dyes and antibiotic-resistant pathogens,posing severe risks to ecosystems and human health.Conventional adsorbents,constrained by monopolar fu...Hospital wastewater contains complex pollutants,including residual organic dyes and antibiotic-resistant pathogens,posing severe risks to ecosystems and human health.Conventional adsorbents,constrained by monopolar functional groups and limited surface sites,fail to remove both pollutants simultaneously.Here,we report an intelligent responsive polyurethane microsphere adsorbent doped with diallyl dimethylammonium chloride modified carbon nanotubes,termed as PUCD microspheres.The PUCD integrates bipolar adsorption sites,tunable micrometer-scale pores,and a near-infrared(NIR)-triggered in situ capture mechanism within a single platform,which achieves up to 98.3%dye removal,maintains strong adsorption performance across a wide pH range and retains 83.3%efficiency for rhodamine B after five cycles.Notably,the PUCD employs a temperature-responsive phase transition:under NIR irradiation,the microspheres undergo shrinkage,reducing the pore size to generate a‘polymer trap',enabling in situ capture of bacteria with>99%efficiencies for both Staphylococcus aureus and Escherichia coli.By immobilizing live bacteria,the PUCD microspheres substantially reduces the risk of pathogen desorption and toxin release.This promising platform offers a safe,efficient,and single-stage strategy for hospital wastewater purification,enabling the simultaneous elimination of dyes and pathogenic bacteria.展开更多
The development of shape-customizable and bulk flexible electrochemical devices through processing technologies as versatile as those used for plastics promises to revolutionize the future of battery technology.Howeve...The development of shape-customizable and bulk flexible electrochemical devices through processing technologies as versatile as those used for plastics promises to revolutionize the future of battery technology.However,this pursuit has been fundamentally hindered by the absence of transformative battery materials capable of delivering the necessary electrochemical functions,robust interface adhesion,and,crucially,the suitable rheological properties required for on-demand shaping.In this work,we introduce a concept of a multifunctional plasticine electrode matrix(PEM)featuring nano-interpenetrating networks(nano-IPN)to address this challenge.Utilizing the nonflammable liquid-electrolyte hydration combined with conductive nanomaterials,we have realized a PEM in the form of a multifunctional nanocomposite that integrates ion and electron conduction,component binding,non-flammability,and plasticine-like moldability.With this PEM,we have successfully fabricated a variety of bulk-flexible electrodes with high mass loading of active material(AM)(>70 wt%)using industry-friendly extrusion and compression molding techniques.Moreover,these high AM-loading composite electrodes achieve an unparalleled bulk conformability and flexibility,remaining structurally intact even under severe mechanical stress.Ultimately,we have successfully produced shape-patternable and flexible batteries via extrusion molding.This study underscores the potential of the PEM to revolutionize battery microstructures,interfaces,manufacturing processes,and performance characteristics.展开更多
Heterogeneous polymerization represents a widely employed method in the polyolefin industry.In recent years,various heterogenization strategies for late transition metal catalysts have been developed,enabling effectiv...Heterogeneous polymerization represents a widely employed method in the polyolefin industry.In recent years,various heterogenization strategies for late transition metal catalysts have been developed,enabling effective control of polymer morphology and optimization of catalytic performance.However,while most studies have focused on designing anchoring groups and advancing support approaches,systematic investigations into how the support influences the catalytic behavior of the late transition metal catalysts.In this work,we fabricated supported α-diimine nickel catalysts by functionalizing the ligand with alkyl alcohol chains of varying lengths and supporting them onto MgCl_(2)supports.The ethylene polymerization behavior of these catalysts was then investigated.By precisely adjusting the alkyl alcohol chain length,the distance between the catalytically active metal center and the support surface was modulated.This approach demonstrates that support-induced steric hindrance effect can be effectively regulated by controlling the separation distance between the metal center and the support surface.展开更多
Achieving high thermal conductivity in polymer composites with micro or nanoparticle fillers are challenging.Typically,over 50 vol%filler loading is necessary to form a thermal conductive network.However,even with suc...Achieving high thermal conductivity in polymer composites with micro or nanoparticle fillers are challenging.Typically,over 50 vol%filler loading is necessary to form a thermal conductive network.However,even with such a network in place,the increase in thermal conductivity may not be significant compared to that in electrically conductive composites.To clarify the ideal filler network structure,we endeavored to selectively disperse nano-sized Al_(2)O_(3)nanoparticles at the interface of co-continuous SEBS/PA6 blends,with and without various filler surface modification methods.A thermal conductive network forms when all interface areas are fully covered by 2.56 vol%of Al_(2)O_(3)nanoparticles(very close to theoretical loading content 2.29 vol%).In this case,the Al_(2)O_(3)nanoparticle has the highest thermal conductive contribution(TCC).However,the absolute TCC values are extremely low because of the interfacial thermal resistance and it will decrease when the filler content exceeds 2.56 vol%,indicating that some nanoparticles are dispersed separately out of the existed thermal conductive network.These findings suggest that the construction of a connected thermal conductive network,relatively lower interfacial thermal resistance and the precise positioning of fillers within this network are essential for achieving high thermal conductivity composites.展开更多
The equilibrium dynamics and nonlinear rheology of unentangled polymer blends remain inadequately understood,especially regarding the influence of short-chain matrix length N_(S) on the structure and rheological behav...The equilibrium dynamics and nonlinear rheology of unentangled polymer blends remain inadequately understood,especially regarding the influence of short-chain matrix length N_(S) on the structure and rheological behavior of dispersed long chains.Using molecular dynamics simulations based on the Kremer-Grest model,we systematically explore the N_(S)-dependence of static conformations,equilibrium dynamics,and nonlinear shear responses in unentangled long-chain/short-chain polymer blends.Our results demonstrate a decoupling between the static and dynamic sensitivity to N_(S):while the static chain size,R_g,follows Flory theory with slight swelling at small N_(S) due to incomplete excluded volume screening,the diffusion coefficient,D,and the relaxation time,τ_(0),exhibit a strong,non-monotonic N_(S)-dependence,transitioning from monomeric friction dominance at small N_(S) to collective segmental rearrangement at large N_(S).Additionally,we observe partial decoupling between the viscous and normal stress responses:while the zero-shear viscosity,η,is strongly N_(S)-dependent,the first and second normal stress coefficients,Ψ_(1) and Ψ_(2),collapse onto universal curves when scaled by the dimensionless shear rate,γτ_(0),suggesting a common mechanism of orientation and stretching.Under shear,long chains compress in the vorticity direction λ_(z)~Wi^(-0.2),which reduces collision frequency and contributes to shear thinning,while the scaling of weaker orientation resistance m_(G)~Wi^(0.35)reflects hydrodynamic screening by the short-chain matrix.These findings highlight the limitations of single-chain models and emphasize the necessity of considering N_(S)-dependent matrix dynamics and flow-induced structural changes in understanding the rheology of unentangled polymer blends.展开更多
The development of epoxy(EP)nanocomposites has emerged as a prominent research area across diverse sectors,including automotive,construction,and aerospace industries.Recently,adopting biomimetic strategies for the pre...The development of epoxy(EP)nanocomposites has emerged as a prominent research area across diverse sectors,including automotive,construction,and aerospace industries.Recently,adopting biomimetic strategies for the preparation of nanomaterials to design multifunctional epoxy resins has emerged as a prominent research hotspot.Inspired by the growth pattern of coral reefs,this study successfully engineered a novel hierarchical nanostructured material(Fe-NiPS-PBA)with the aim of creating EP nanocomposites that exhibit highly flame-retardant efficiency,exceptional mechanical strength,and distinguished wear-resisting property even at low additive concentrations.With a 3 wt%addition of Fe-NiPS-PBA,the limiting oxygen index of the EP/3Fe-NiPS-PBA nanocomposite increased from 23.5 to 25.9,achieving a UL-94 V-0 rating.Compared to pure EP,EP/3Fe-NiPSPBA nanocomposite reduced the peak heat release rate(PHRR),total heat release(THR),peak smoke production rate(PSPR),total smoke production(TSP),and maximum CO emission(MCO)by 44.1%,66.7%,47.0%,67.8%,and 51.7%,respectively.Moreover,the incorporation of a 1 wt%additive resulted in significant enhancements of tensile strength from 76.7 MPa to 96.9 MPa,while the wear rate demonstrated a remarkable reduction of 77.8%.The Fe-NiPS-PBA significantly enhanced the fire performance and mechanical strength of EP nanocomposites,demonstrating exceptional overall performance in various applications.展开更多
In this review,the synthesis,functions,and applications of the polymers containing germanium and tin,which are heavy group 14 elements,in their polymer frameworks are summarized.Germanium and tin can form similar skel...In this review,the synthesis,functions,and applications of the polymers containing germanium and tin,which are heavy group 14 elements,in their polymer frameworks are summarized.Germanium and tin can form similar skeletal structures with their homologues carbon and silicon,whereas the polymers containing germanium and tin show unique properties derived from their large atomic radii and weak binding energies.For example,polygermane and polystannane exhibited light absorption in the UV–visible region and conductivity because of theσ-conjugation through the polymer main-chain constructed byσ-bonds between heavy elements.Theσ-conjugation was affected by the conformational change of the polymer main-chain,and thermochromic properties can be induced.Furthermore,the weak bonds were able to be cleaved homolytically upon photoirradiation,and radicals were subsequently generated.By incorporating hypervalent heavy elements into theπ-conjugated system,it was possible to modulate the electronic structures of theπ-conjugated system throughσ*–π*conjugation with highly coordinated elements.Finally,applications for organic solar cells,organic lightemitting materials,and chemical sensors have been achieved.Herein,representative synthetic methods and unique properties for creating smart materials with germanium and tin will be explained.展开更多
Catalysts are key for olefin polymerization reactions and are also ubiquitous in catalysis science.Multinuclear metal catalysts have witnessed enhanced performances in catalytic reactions relative to mononuclear catal...Catalysts are key for olefin polymerization reactions and are also ubiquitous in catalysis science.Multinuclear metal catalysts have witnessed enhanced performances in catalytic reactions relative to mononuclear catalysts,but which substantially involve multi-step,tedious,and difficult synthesis.Herein,this study reports an intriguing approach to construct multi-nuclear catalysts for the milestoneα-diimine nickel catalysts using an oligomeric strategy.A polymerizable norbornene unit is incorporated into theα-diimine ligand backbone,leading to the formation of the monomeric nickel catalyst Ni_(1)and its corresponding oligomeric nickel catalysts(Ni_(3)and Ni_(5))with varying degrees of polymerization(DP=3 and 5).Notably,the oligomeric catalyst Ni_(5)was facilely scaled up(50 g-level),showed enhanced thermal stability,exhibited 4.6 times higher activity,and yielded polyethylene elastomer with a 379%increased molecular weight in ethylene polymerization,compared to the monomeric catalyst Ni_(1).Catalytic performance enhancements of oligomeric catalysts were found to be DP-dependent.The kilogram-scale polyethylene,produced using Ni_(5)in a 20 L reactor,presented a highly branched all-hydrocarbon structure,which demonstrated typical elastic properties(tensile strength:4 MPa,elastic recovery:SR=72%)along with great processability(MFI=3.0 g/10 min),insulating characteristics(volume resistivity=2×10^(16)Ω/m),and hydrophobicity(water vapor permeability:0.03 g/m^(2)/day),suggesting potentially practical applications.展开更多
文摘In this work,we proposed a strategy for the hydrolysis of native corn starch after the treatment of corn starch in an ionic liquid aqueous solution,and it is an awfully“green”and simple means to obtain starch with low molecular weight and amorphous state.X-ray diffraction results revealed that the natural starch crystalline region was largely disrupted by ionic liquid owing to the broken intermolecular and intramolecular hydrogen bonds.After hydrolysis,the morphology of starch changed from particles of native corn starch into little pieces,and their molecular weight could be effectively regulated during the hydrolysis process,and also the hydrolyzed starch samples exhibited decreased thermal stability with the extension of hydrolysis time.This work would counsel as a powerful tool for the development of native starch in realistic applications.
基金supported by the Fundamental Research Funds for the Central Universities(No.226-2025-00031).
文摘In 2024,the MOE Key Laboratory of Macromolecular Synthesis and Functionalization at Zhejiang University continued its impactful researches across five core areas.In controllable catalytic polymerization,organoboron catalysts were developed for CO₂copolymerization and novel photoresist materials.Studies in microstructure and rheology elucidated universal deformation modes in graphene-based 2D membranes and improved graphene fiber properties through shear alignment engineering,defect control,and enhanced interlayer entanglement.For separating functional polymers,Janus membranes and channels were created for multiphase separation,liquid-phase molecular layer-by-layer deposition technique was developed to fabricate aromatic polyamide nanofilms,and the harmonic amide bond density was established as a valuable parameter for polyamide structural analysis.In biomedical functional polymers,a sustainable carboxyl-ester transesterification strategy was proposed for upcycling poly(ethylene terephthalate)(PET)waste into biodegradable plastics.Additionally,immunocompatible biomaterials were designed utilizing zwitterionic polypeptides and albumin-derived coatings,and Cu2+-phenolic nanoflower was designed to combat fungal infections by combining cuproptosis and cell wall digestion.Further,the researchers developed a gelatin-DOPA-knob/fibrinogen hydrogel to achieve rapid and robust hemostatic sealing,utilized a double-network polyelectrolyte-coated hydrogel for enhancing endothelialization of left atrial appendage(LAA)occluders,and the researchers also demonstrated that image-guided high-intensity focused ultrasound enables manipulation of shape-memory polymers.Finally,in the realm of photo-electro-magnetic functional polymers,precise control of through-space conjugation was shown to enhance organic luminescence.Topologically structured hydrogels were revealed to exhibit autonomous actuation.Also,solar-driven photothermal ion pumps were developed for selective lithium extraction from seawater,and high-performance non-solvated C60 single-crystal films were prepared via facile bar coating.Lastly,the researchers demonstrated outstanding dielectric properties of polyethylene(PE)lamellar single crystals.The relevant works are reviewed in this paper.
基金financially supported by the National Key Research and Development Project of China(No.2022YFB3806900)。
文摘The complex interactions and conflicting performance demands in multi-component composites pose significant challenges for achieving balanced multi-property optimization through conventional trial-and-error approaches.Machine learning(ML)offers a promising solution,markedly improving materials discovery efficiency.However,the high dimensionality of feature spaces in such systems has long impeded effective ML-driven feature representation and inverse design.To overcome this,we present an Intelligent Screening System(ISS)framework to accelerate the discovery of optimal formulations balancing four key properties in 15-component PTFE-based copper-clad laminate composites(PTFE-CCLCs).ISS adopts modular descriptors based on the physical information of component volume fractions,thereby simplifying the feature representation.By leveraging the inverse prediction capability of ML models and constructing a performance-driven virtual candidate database,ISS significantly reduced the computational complexity associated with high-dimensional spaces.Experimental validation confirmed that ISSoptimized formulations exhibited superior synergy,notably resolving the trade-off between thermal conductivity and peel strength,and outperform many commercial counterparts.Despite limited data and inherent process variability,ISS achieved an average prediction accuracy of 76.5%,with thermal conductivity predictions exceeding 90%,demonstrating robust reliability.This work provides an innovative,efficient strategy for multifunctional optimization and accelerated discovery in ultra-complex composite systems,highlighting the integration of ML and advanced materials design.
基金financially supported by the National Natural Science Foundation of China(No.52103040)China Postdoctoral Science Foundation(No.2020M673217)the Fundamental Research Funds for the Central Universities(No.2023SCU12022)。
文摘To address the poor mechanical performance and improve the tribological properties of self-lubricating polyphenylene sulfide/irradiation treated polytetrafluoroethylene(PPS/i-PTFE)blends,different aspect ratio carbon fibers(i.e.,PSCF:50,SCF:about 429)were introduced as reinforcement fillers.The results showed that the hybriding of PSCF and SCF at certain mass ratios exhibited simultaneous enhancement of mechanical and tribological performance for PPS/i-PTFE blend through the construction of synergistic lubrication and mechanical interlocking network.Specifically,the flexural strength and modulus of PPS/i-PTFE were increased by 125.6% and 389.3%,the friction coefficient and specific wear rate were decreased by 13.9% and 95%,respectively.It was worth noting that PPS composites possessed excellent integrated performance which were able to withstand sliding action under high PV(≥10 MPa·m/s)conditions,as assessed by a customized pin-on-disc tester.This work demonstrated that the formation of intact lubricating film combined with the enhanced thermal and mechanical properties were favorable for improving the tribological properties of PPS-based composites,which makes them suitable for advanced engineering applications.
基金supported by the National Natural Science Foundation of China(Nos.22269020,42167068,U23A20582)Gansu Province Higher Education Industry Support Plan Project(No.2023CYZC-17)2024 Major Cultivation Projectfor University Research and Innovation Platforms(No.2024CXPT-10).
文摘There are limitations to using hard carbon(HC)in K^(+)storage due to its insufficient high-current reversible capacity and plateau potential,which result from the lack of effective active sites and low intercalation capabilities.The construction of HC cathodes with more available functional groups and ordered carbon nanocrystal structures is essential for improving K^(+)storage efficiency.Herein,a new perspective is proposed for synthesizing hard carbon nanosheets(HCNS)with abundant hydroxyl groups(O-H)/carboxylic groups(O-C=O)and rational carbon nanocrystals by interfacial assembly and carbonization.Systematic in ex-situ observations,dynamic analysis and theory calculations elucidate that the superior electrochemical capability of HCNS is ascribed to the synergistic effect of abundant available functional groups and ordered graphitic microcrystalline.Consequently,the HCNS exhibits outstanding K^(+)storage capabilities in terms of superb energy density(146.2 Wh/kg),high power density(1,7800 Wh/kg),and ultralong lifespan(102.9%capacity retention after 10,000 cycles).It was also found that the HC structure correlates with the discharge/charge plateau,confirming the'adsorption-insertion'charge storage mechanism.Furthermore,the proposed work provides a theoretical basis for making high-performance HC anodes by understanding the effect of their microstructure on K^(+)storage.
基金supported by the National Natural Science Foundation of China(22269020,U23A20582,42167068)the Gansu Province Higher Education Industry Support Plan Project(2023CYZC-17)+1 种基金2024 Major Cultivation Project for University Research and Innovation Platforms(2024CXPT-10)the Key Project of the Natural Science Foundation of Gansu Province(25JRRA004).
文摘Hard carbon(HC)remains a leading anode candidate for sodium-ion storage,yet its application is hindered by low initial Coulombic efficiency(ICE)and limited plateau capacity due to uncontrolled defect density and open porosity.Here,we propose a scalable dual-regulation strategy that simultaneously tunes pore mouth size and defect chemistry to enhance sodium storage performance.Using phenol-formaldehyde resin as the carbon precursor and phosphorus pentoxide(P_(2)O_(5))as a bifunctional sacrificial template and dopant source,we synthesize phosphorus-functionalized hard carbon(PF-PHC)featuring a high density of closed pores with well-confined sub-nanometer pore entrances.The in-situ sublimation of P_(2)O_(5) during pyrolysis promotes the formation of closed-pore architectures,while residual phosphorus atoms effectively passivate vacancy-type defects,thereby reducing irreversible Na+adsorption and mitigating excessive solid electrolyte interphase(SEI)formation.As a result,PF-PHC achieves an ICE of 89.3%and a plateau capacity of 289 mAh g^(−1).In-situ characterizations reveal that regulating pore mouth dimensions decouples Na+and solvent access,enabling highly selective ion transport and stable interfacial chemistry.Sodium-ion hybrid capacitors(SIHCs)assembled based on PF-PHC deliver exceptional rate performance and outstanding long-term cycling stability,retaining 98.2%after 10,000 cycles at 2 A g^(−1).This study establishes pore mouth engineering as a robust and scalable design principle for advancing next-generation HC-based sodium storage materials.
基金the financial support from the National Natural Science Foundation of China(52203123 and 52473248)State Key Laboratory of Polymer Materials Engineering(sklpme2024-2-04)+1 种基金the Fundamental Research Funds for the Central Universitiessponsored by the Double First-Class Construction Funds of Sichuan University。
文摘Composite polymer electrolytes(CPEs)offer a promising solution for all-solid-state lithium-metal batteries(ASSLMBs).However,conventional nanofillers with Lewis-acid-base surfaces make limited contribution to improving the overall performance of CPEs due to their difficulty in achieving robust electrochemical and mechanical interfaces simultaneously.Here,by regulating the surface charge characteristics of halloysite nanotube(HNT),we propose a concept of lithium-ion dynamic interface(Li^(+)-DI)engineering in nano-charged CPE(NCCPE).Results show that the surface charge characteristics of HNTs fundamentally change the Li^(+)-DI,and thereof the mechanical and ion-conduction behaviors of the NCCPEs.Particularly,the HNTs with positively charged surface(HNTs+)lead to a higher Li^(+)transference number(0.86)than that of HNTs-(0.73),but a lower toughness(102.13 MJ m^(-3)for HNTs+and 159.69 MJ m^(-3)for HNTs-).Meanwhile,a strong interface compatibilization effect by Li^(+)is observed for especially the HNTs+-involved Li^(+)-DI,which improves the toughness by 2000%compared with the control.Moreover,HNTs+are more effective to weaken the Li^(+)-solvation strength and facilitate the formation of Li F-rich solid-electrolyte interphase of Li metal compared to HNTs-.The resultant Li|NCCPE|LiFePO4cell delivers a capacity of 144.9 m Ah g^(-1)after 400 cycles at 0.5 C and a capacity retention of 78.6%.This study provides deep insights into understanding the roles of surface charges of nanofillers in regulating the mechanical and electrochemical interfaces in ASSLMBs.
基金financially supported by the National Natural Science Foundation of China(Nos.52303298 and 52233002)。
文摘UHMWPE fibers exhibit impressive modulus and strength,but they have not reached their theoretical limits.Researchers focus on molecular weight,orientation,and crystallinity of UHMWPE,yet their contributions to mechanical properties are unclear.Molecular dynamics simulations are valuable but often limited by computational constraints.Our aim is to simulate higher molecular weights to better represent real UHMWPE fibers.We used Packmol and Polyply methodologies to construct PE systems,with Polyply reproducing more reasonable properties of UHMWPE fibers.Additionally,tensile simulations showed that orientation and crystallinity greatly impact Young's modulus more than molecular weight.Energy decomposition indicated that higher molecular weights lead to covalent bonds that can withstand more energy during stretching,thus increasing breaking strength.Combining simulations with machine learning,we found that orientation has the most significant impact on Young's modulus,contributing 60%,and molecular weight plays the most crucial role in determining the breaking strength,accounting for 65%.This study provides a theoretical basis and guidelines for enhancing UHMWPE's modulus and strength.
基金financially supported by the National Natural Science Foundation of China(No.52373052)Fundamental Research Funds for the Central Universities(No.DUT24MS011)。
文摘An effective strategy for enhancing the heat resistance of polystyrene(PS)with regard to its glass transition temperature(T_(g))involves the anionic solution copolymerization of a-methylstyrene(AMS)with styrene(St),typically requires much lower temperature(-25℃)and multistep monomer feeding to achieve higher number-average molecular weight(M_(n))block copolymers.However,the anionic copolymerization of AMS and St under the mild temperature remains largely unexplored.This study systematically investigated the anionic copolymerization of AMS and St using n-BuLi in nonpolar solvent(-25℃ to 25℃)through both one-step and two-step approaches.We demonstrated that one-step copolymerization at 25℃ yielded only 1-3 terminal AMS units,with higher feed ratios(5 wt%-20 wt%)increasing AMS incorporation but reducing the exact molecular weight(MW)due to enhanced depolymerization,as evidenced by MALDI-TOF MS.Temperature-controlled AMS conversion at-15℃ achieved 98%AMS conversion(5 wt% feed)by suppressing side reactions and lowering the[M]_(e),while 50℃(near T_(C))almost prevented incorporation.Despite t-BuOK regulation induced broader PDI(1.24)via reactive[(polymer-Li)OR]K intermediates,while other systems showed narrow distributions,t-BuOK outperformed THF in enhancing AMS incorporation via efficient ion pair dissociation.In comparison,the two-step polymerization approach demonstrated superior performance,achieving both higher AMS conversion efficiency and preferential incorporation at the initiation end.At a 20 wt%AMS feed ratio,this method yielded copolymer chains containing up to 6 AMS units on average.Thermal analysis revealed a composition-dependent single T_(g),which exhibited a systematic increase with higher AMS incorporation content.These results collectively demonstrate the precise control over AMS incorporation and heat resistance achievable through the manipulation of polymerization conditions.
基金supported by the National Natural Science Foundation of China(22269020,42167068,U23A20582)the Gansu Province Higher Education Industry Support Plan Project(2023CYZC-17,2023CYZC-68)+1 种基金the Key Project of Natural Science Foundation of Gansu Province(25JRRA004)2024 Major Cultivation Project for University Research and Innovation Platforms(2024CXPT-10).
文摘Aqueous Zn-ion storage offers high capacity and safety,but practical use is hindered by dendrite formation,side reactions,and hydrogen evolution,affecting stability and efficiency.Herein,tetramethylol acetylenediurea(TA)is proposed as an effective electrolyte additive that modulates the Zn^(2+)deposition environment via coordination competition.The polar functional groups of TA restructure the solvation sheath,while its molecular dipoles generate localized electric fields that accelerate Zn^(2+)migration and promote directional(002)-oriented deposition.These effects collectively suppress side reactions and enhance Zn plating/stripping reversibility.The four hydroxyl(–OH)and conjugated ketone groups(C=O)in the TA molecule have strong coordination ability(Lewis basicity)and can form a stable[Zn(TA)(H_(2)O)_(n)]^(2+)with Zn^(2+),reducing the number of free water molecules and the proportion of active water in the solvation sheath.The TA molecules are adsorbed onto the Zn anode surface,leading to the redistribution of the local spatial electric field and homogenization of ion flux dynamics.Its conjugated planar structure can induce Zn^(2+)to preferentially deposit along the(002)crystal plane.Zn//Zn symmetric cell using TA-containing ZnSO4 electrolyte exhibits stable cycling for more than 2240 h at 1 mA cm^(−2),1 mAh cm^(−2).The Zn//activated carbon(AC)full-cell can stably cycle 30,000 cycles at 5 A g^(−1)with a capacity retention rate of 90%.This study provides important insights into electrolyte engineering strategies for stabilizing Zn anodes,highlighting the potential of molecular design additives in next-generation Zn^(2+)energy storage systems.
基金financially supported by the National Natural Science Foundation of China(Nos.52173020 and 52573023)。
文摘Vitrimers belong to a class of polymeric materials capable of bond exchange reactions,showing great promise for environmental protection and sustainable development.However,studies on the coupling mechanism between the bond exchange kinetics and segmental dynamics near the glass transition temperature(T_(g))remain scarce.Herein,we employed molecular dynamics simulations to investigate the dynamic heterogeneity of the segment motion and bond exchange in vitrimers.The simulation results revealed that the bond exchange energy barrier exerts a much stronger influence on the bond exchange kinetics than on the segmental dynamics.At lower temperatures,slower segmental relaxation further constraind the bond exchange rate.Additionally,increasing the bond exchange energy barrier markedly enhanced the dynamic heterogeneity of segment motion.A close correlation was observed between heterogeneity and bond exchange.This study elucidated the coupling mechanism between bond exchange and segmental dynamics at the molecular scale,thereby providing a theoretical basis for designing vitrimer materials with tunable dynamic properties.
基金financially supported by the National Natural Science Foundation of China(Nos.52473139 and U21A2098)。
文摘Hospital wastewater contains complex pollutants,including residual organic dyes and antibiotic-resistant pathogens,posing severe risks to ecosystems and human health.Conventional adsorbents,constrained by monopolar functional groups and limited surface sites,fail to remove both pollutants simultaneously.Here,we report an intelligent responsive polyurethane microsphere adsorbent doped with diallyl dimethylammonium chloride modified carbon nanotubes,termed as PUCD microspheres.The PUCD integrates bipolar adsorption sites,tunable micrometer-scale pores,and a near-infrared(NIR)-triggered in situ capture mechanism within a single platform,which achieves up to 98.3%dye removal,maintains strong adsorption performance across a wide pH range and retains 83.3%efficiency for rhodamine B after five cycles.Notably,the PUCD employs a temperature-responsive phase transition:under NIR irradiation,the microspheres undergo shrinkage,reducing the pore size to generate a‘polymer trap',enabling in situ capture of bacteria with>99%efficiencies for both Staphylococcus aureus and Escherichia coli.By immobilizing live bacteria,the PUCD microspheres substantially reduces the risk of pathogen desorption and toxin release.This promising platform offers a safe,efficient,and single-stage strategy for hospital wastewater purification,enabling the simultaneous elimination of dyes and pathogenic bacteria.
基金financial support from the National Natural Science Foundation of China(52473248,52203123,52125301,22279070 and U21A20170)the State Key Laboratory of Polymer Materials Engineering(Grant No:sklpme 2023-1-05 and sklpme 2024-2-04)+3 种基金the Ministry of Science and Technology of China(No.2019YFA0705703)the Sichuan Science and Technology Program(2023NSFSC0991 and 2025ZNSFSC1411)the Fundamental Research Funds for the Central Universitiespartially sponsored by the Double First-Class Construction Funds of Sichuan University.
文摘The development of shape-customizable and bulk flexible electrochemical devices through processing technologies as versatile as those used for plastics promises to revolutionize the future of battery technology.However,this pursuit has been fundamentally hindered by the absence of transformative battery materials capable of delivering the necessary electrochemical functions,robust interface adhesion,and,crucially,the suitable rheological properties required for on-demand shaping.In this work,we introduce a concept of a multifunctional plasticine electrode matrix(PEM)featuring nano-interpenetrating networks(nano-IPN)to address this challenge.Utilizing the nonflammable liquid-electrolyte hydration combined with conductive nanomaterials,we have realized a PEM in the form of a multifunctional nanocomposite that integrates ion and electron conduction,component binding,non-flammability,and plasticine-like moldability.With this PEM,we have successfully fabricated a variety of bulk-flexible electrodes with high mass loading of active material(AM)(>70 wt%)using industry-friendly extrusion and compression molding techniques.Moreover,these high AM-loading composite electrodes achieve an unparalleled bulk conformability and flexibility,remaining structurally intact even under severe mechanical stress.Ultimately,we have successfully produced shape-patternable and flexible batteries via extrusion molding.This study underscores the potential of the PEM to revolutionize battery microstructures,interfaces,manufacturing processes,and performance characteristics.
基金financially supported by the National Natural Science Foundation of China(No.52473338)the National Natural Science Foundation of China(Nos.52173004 and 51873055)+3 种基金Strategic Priority Research Program of the Chinese Academy of Sciences(No.XDA0540000)Advanced Materials-National Science and Technology Major Project(No.2025ZD0614000)Hebei Natural Science Foundation(No.E2022202015)Anhui Province Science and Technology Innovation Tackling Key Project(No.202423i08050025)。
文摘Heterogeneous polymerization represents a widely employed method in the polyolefin industry.In recent years,various heterogenization strategies for late transition metal catalysts have been developed,enabling effective control of polymer morphology and optimization of catalytic performance.However,while most studies have focused on designing anchoring groups and advancing support approaches,systematic investigations into how the support influences the catalytic behavior of the late transition metal catalysts.In this work,we fabricated supported α-diimine nickel catalysts by functionalizing the ligand with alkyl alcohol chains of varying lengths and supporting them onto MgCl_(2)supports.The ethylene polymerization behavior of these catalysts was then investigated.By precisely adjusting the alkyl alcohol chain length,the distance between the catalytically active metal center and the support surface was modulated.This approach demonstrates that support-induced steric hindrance effect can be effectively regulated by controlling the separation distance between the metal center and the support surface.
基金supported by the National Natural Science Foundation of China(Nos.51973052 and 51473047)。
文摘Achieving high thermal conductivity in polymer composites with micro or nanoparticle fillers are challenging.Typically,over 50 vol%filler loading is necessary to form a thermal conductive network.However,even with such a network in place,the increase in thermal conductivity may not be significant compared to that in electrically conductive composites.To clarify the ideal filler network structure,we endeavored to selectively disperse nano-sized Al_(2)O_(3)nanoparticles at the interface of co-continuous SEBS/PA6 blends,with and without various filler surface modification methods.A thermal conductive network forms when all interface areas are fully covered by 2.56 vol%of Al_(2)O_(3)nanoparticles(very close to theoretical loading content 2.29 vol%).In this case,the Al_(2)O_(3)nanoparticle has the highest thermal conductive contribution(TCC).However,the absolute TCC values are extremely low because of the interfacial thermal resistance and it will decrease when the filler content exceeds 2.56 vol%,indicating that some nanoparticles are dispersed separately out of the existed thermal conductive network.These findings suggest that the construction of a connected thermal conductive network,relatively lower interfacial thermal resistance and the precise positioning of fillers within this network are essential for achieving high thermal conductivity composites.
基金financially supported by the National Natural Science Foundation of China(Nos.22341304,22303100 and 12205270)the National Key R&D Program of China(Nos.2023YFA1008800 and 2020YFA0713601)the Strategic Priority Research Program of the Chinese Academy of Sciences(No.XDC0180303)。
文摘The equilibrium dynamics and nonlinear rheology of unentangled polymer blends remain inadequately understood,especially regarding the influence of short-chain matrix length N_(S) on the structure and rheological behavior of dispersed long chains.Using molecular dynamics simulations based on the Kremer-Grest model,we systematically explore the N_(S)-dependence of static conformations,equilibrium dynamics,and nonlinear shear responses in unentangled long-chain/short-chain polymer blends.Our results demonstrate a decoupling between the static and dynamic sensitivity to N_(S):while the static chain size,R_g,follows Flory theory with slight swelling at small N_(S) due to incomplete excluded volume screening,the diffusion coefficient,D,and the relaxation time,τ_(0),exhibit a strong,non-monotonic N_(S)-dependence,transitioning from monomeric friction dominance at small N_(S) to collective segmental rearrangement at large N_(S).Additionally,we observe partial decoupling between the viscous and normal stress responses:while the zero-shear viscosity,η,is strongly N_(S)-dependent,the first and second normal stress coefficients,Ψ_(1) and Ψ_(2),collapse onto universal curves when scaled by the dimensionless shear rate,γτ_(0),suggesting a common mechanism of orientation and stretching.Under shear,long chains compress in the vorticity direction λ_(z)~Wi^(-0.2),which reduces collision frequency and contributes to shear thinning,while the scaling of weaker orientation resistance m_(G)~Wi^(0.35)reflects hydrodynamic screening by the short-chain matrix.These findings highlight the limitations of single-chain models and emphasize the necessity of considering N_(S)-dependent matrix dynamics and flow-induced structural changes in understanding the rheology of unentangled polymer blends.
基金Outstanding Youth Scientific Research Project in Anhui Province(2022AH020055)Key Research and Development Projects in Anhui Province(2022i01020016)。
文摘The development of epoxy(EP)nanocomposites has emerged as a prominent research area across diverse sectors,including automotive,construction,and aerospace industries.Recently,adopting biomimetic strategies for the preparation of nanomaterials to design multifunctional epoxy resins has emerged as a prominent research hotspot.Inspired by the growth pattern of coral reefs,this study successfully engineered a novel hierarchical nanostructured material(Fe-NiPS-PBA)with the aim of creating EP nanocomposites that exhibit highly flame-retardant efficiency,exceptional mechanical strength,and distinguished wear-resisting property even at low additive concentrations.With a 3 wt%addition of Fe-NiPS-PBA,the limiting oxygen index of the EP/3Fe-NiPS-PBA nanocomposite increased from 23.5 to 25.9,achieving a UL-94 V-0 rating.Compared to pure EP,EP/3Fe-NiPSPBA nanocomposite reduced the peak heat release rate(PHRR),total heat release(THR),peak smoke production rate(PSPR),total smoke production(TSP),and maximum CO emission(MCO)by 44.1%,66.7%,47.0%,67.8%,and 51.7%,respectively.Moreover,the incorporation of a 1 wt%additive resulted in significant enhancements of tensile strength from 76.7 MPa to 96.9 MPa,while the wear rate demonstrated a remarkable reduction of 77.8%.The Fe-NiPS-PBA significantly enhanced the fire performance and mechanical strength of EP nanocomposites,demonstrating exceptional overall performance in various applications.
基金supported by Japan Society for the Promotion of Science(JSPS),a Grant-in-Aid for Scientific Research(B)(JP23K23398)(for M.G.)and(JP24K01570)(for K.T.).
文摘In this review,the synthesis,functions,and applications of the polymers containing germanium and tin,which are heavy group 14 elements,in their polymer frameworks are summarized.Germanium and tin can form similar skeletal structures with their homologues carbon and silicon,whereas the polymers containing germanium and tin show unique properties derived from their large atomic radii and weak binding energies.For example,polygermane and polystannane exhibited light absorption in the UV–visible region and conductivity because of theσ-conjugation through the polymer main-chain constructed byσ-bonds between heavy elements.Theσ-conjugation was affected by the conformational change of the polymer main-chain,and thermochromic properties can be induced.Furthermore,the weak bonds were able to be cleaved homolytically upon photoirradiation,and radicals were subsequently generated.By incorporating hypervalent heavy elements into theπ-conjugated system,it was possible to modulate the electronic structures of theπ-conjugated system throughσ*–π*conjugation with highly coordinated elements.Finally,applications for organic solar cells,organic lightemitting materials,and chemical sensors have been achieved.Herein,representative synthetic methods and unique properties for creating smart materials with germanium and tin will be explained.
基金financial support from the National Natural Science Foundation of China(Nos.22401274,U23B6011)the Jilin Provincial Science and Technology Department Program(No.20250102070JC)。
文摘Catalysts are key for olefin polymerization reactions and are also ubiquitous in catalysis science.Multinuclear metal catalysts have witnessed enhanced performances in catalytic reactions relative to mononuclear catalysts,but which substantially involve multi-step,tedious,and difficult synthesis.Herein,this study reports an intriguing approach to construct multi-nuclear catalysts for the milestoneα-diimine nickel catalysts using an oligomeric strategy.A polymerizable norbornene unit is incorporated into theα-diimine ligand backbone,leading to the formation of the monomeric nickel catalyst Ni_(1)and its corresponding oligomeric nickel catalysts(Ni_(3)and Ni_(5))with varying degrees of polymerization(DP=3 and 5).Notably,the oligomeric catalyst Ni_(5)was facilely scaled up(50 g-level),showed enhanced thermal stability,exhibited 4.6 times higher activity,and yielded polyethylene elastomer with a 379%increased molecular weight in ethylene polymerization,compared to the monomeric catalyst Ni_(1).Catalytic performance enhancements of oligomeric catalysts were found to be DP-dependent.The kilogram-scale polyethylene,produced using Ni_(5)in a 20 L reactor,presented a highly branched all-hydrocarbon structure,which demonstrated typical elastic properties(tensile strength:4 MPa,elastic recovery:SR=72%)along with great processability(MFI=3.0 g/10 min),insulating characteristics(volume resistivity=2×10^(16)Ω/m),and hydrophobicity(water vapor permeability:0.03 g/m^(2)/day),suggesting potentially practical applications.
