Block copolymer(BCP) nanolithography offers potential beyond traditional photolithographic limits, yet reliably producing low-defect, perpendicular domains remains challenging. We introduce a microenvironmentdriven is...Block copolymer(BCP) nanolithography offers potential beyond traditional photolithographic limits, yet reliably producing low-defect, perpendicular domains remains challenging. We introduce a microenvironmentdriven isothermal annealing method for directed self-assembly of BCP thin films. By annealing films at stable temperature in a quasi-sealed, inert-gas chamber, our approach promotes highly uniform perpendicular lamellar nanopatterns over large areas, effectively mitigating environmental fluctuations and emulating solvent-vapor annealing without solvent exposure. Resulting BCP structures demonstrate enhanced spatial coherence and notably low defect density. Furthermore, we successfully transfer these nanopatterns into precise metal nano-line arrays,confirming the method's capability for high-fidelity pattern replication. This scalable, solvent-free technique provides a robust, reliable route for high-resolution nanopatterning in advanced semiconductor manufacturing.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
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
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
The rich phase behavior of block copolymers(BCPs)has drawn great attention in recent years.However,the double diamond(DD)phase is rarely obtained because of the competition between the minimization of interfacial ener...The rich phase behavior of block copolymers(BCPs)has drawn great attention in recent years.However,the double diamond(DD)phase is rarely obtained because of the competition between the minimization of interfacial energy and packing frustration.Here,a rod-coil BCP containing mesogen-jacketed liquid crystalline polymer is designed to acquire ordered bicontinuous network nanostructures.The reduction of internal energy originating from the orientational interaction among the rod blocks can compensate for the free energy penalty of packing frustration to stabilize the DD structure.The resulting BCP can also experience lamellae-to-DD and double gyroid-to-lamellae transitions by changing the annealing temperature.These results make the rod-coil BCP an excellent candidate for the self-assembly of ordered network structures,demonstrating great potential in nanopatterning and metamaterials.展开更多
Salt-doped block copolymers have widespread applications in batteries,fuel cells,semiconductors,and various industries,where their properties crucially depend on phase separation behavior.Traditionally,investigations ...Salt-doped block copolymers have widespread applications in batteries,fuel cells,semiconductors,and various industries,where their properties crucially depend on phase separation behavior.Traditionally,investigations into salt-doped diblock copolymers have predominantly focused on microphase separation,overlooking the segregation between ionic and polymeric species.This study employs weak segregation theory to explore the interplay between phase separation dominated by the polymer-modulated mode and the salt-out-modulated mode,corresponding to microscopic and macroscopic phase separations,respectively.By comparing diblock copolymers doped with salts to those doped with neutral solvents,we elucidate the significant role of charged species in modulating phase behavior.The phase separation mode exhibits a transition between the polymer-modulated and salt-out-modulated modes at different wavenumbers.In systems doped with neutral solvents,this transition is stepwise,while in salt-ion-doped systems,it is continuous.With a sufficiently large Flory-Huggins parameter between ions and polymers,the salt-out-modulated mode becomes dominant,promoting macrophase separation.Due to the solvation effect of salt ions,salt-doped systems are more inclined to undergo microphase separation.Furthermore,we explore factors influencing the critical wavenumber of phase separation,including doping level and the Flory-Huggins parameters between two blocks and between ions and polymeric species.Our findings reveal that in a neutral solvent environment,these factors alter only the boundary between micro-and macro-phase separations,leaving the critical wavenumber unchanged in microphase separation cases.However,in a salt-doped environment,the critical wavenumber of microphase separation varies with these parameters.This provides valuable insights into the pivotal role of electrostatics in the phase separation of salt-doped block copolymers.展开更多
Ethylene-propylene block copolymer(EbP) is a vital component in impact polypropylene copolymer(IPC), yet its distribution in the multiphase composite material and how it influences the phase structure and the mechanic...Ethylene-propylene block copolymer(EbP) is a vital component in impact polypropylene copolymer(IPC), yet its distribution in the multiphase composite material and how it influences the phase structure and the mechanical properties are not well understood. In this work,four IPCs were investigated by atomic force microscopy-infrared(AFM-IR) to assess the phase compositions in situ, based on which in conjunction with the chain microstructure information obtained ex situ the distributions of the copolymer components were derived for each alloy. For the IPCs whose EbP comprises long P and long E segments, the EbP fraction was found to phase separate from the rubber and the PP matrix to form the cores of the disperse particles with the E-P segmented copolymer(EsP). In contrast, in the IPC with EbP composed of long P and short E segments, the EbP fraction formed an outer shell for the rubber particles with the cores comprising the EsP alone, and this IPC, containing a lower E comonomer content than its counterpart, exhibited both better impact resistance and higher flexural modulus. These results clarify how the chain structure of EbP governs the phase morphology in IPC, which in turn impacts the properties of the composite material.展开更多
Temperature-responsive polymers have garnered significant attention due to their ability to respond to external stimuli.In this work,dual temperature-responsive block copolymers are synthesized via reversible addition...Temperature-responsive polymers have garnered significant attention due to their ability to respond to external stimuli.In this work,dual temperature-responsive block copolymers are synthesized via reversible addition-fragmentation chain transfer polymerization(RAFT)polymerization utilizing zwitterionic monomer methacryloyl ethyl sulfobetaine(SBMA) and N-isopropyl acrylamide(NIPAAm) as monomers.The thermal responsive behaviors can be easily modulated by incorporating additional hydrophobic monomer benzyl acrylate(BN) or hydrophilic monomer acrylic acid(AA),adjusting concentration or pH,or varying the degree of polymerization of the block chain segments.The cloud points of the copolymers are determined by UV-Vis spectrophotometry,and these copolymers exhibit both controlled upper and lower critical solu bility temperatures(LCST and UCST) in aqueous solution.This study analyzes and summarizes the influencing factors of dual temperature responsive block copolymers by exploring the effects of various conditions on the phase transition temperature of temperature-sensitive polymers to explore the relationship between their properties and environment and structure to make them more selective in terms of temperature application range and regulation laws.It is very interesting that the introduction of poly-acrylic acid(PAA) segments in the middle of di-block copolymer PSBMA_(55)-b-PNIPAAm_(80) to form PSBMA_(55)-b-PAA_(x)-b-PNIPAAm_(80) results in a reversal of temperature-responsive behaviors from 'U'(LCST UCST) type,while the copolymer PSBMA_(55)-b-P(NIPAAm_(80)-co-AA_(x)) not.This work provides a clue for tuning the phase transition behavior of polymers for manufacture of extreme smart materials.展开更多
Organocatalysis has shown special potency for simplifying the construction of complex polymer structures.We are reporting here a one-pot synthetic pathway using amine as a selectivity-switching agent in the two-compon...Organocatalysis has shown special potency for simplifying the construction of complex polymer structures.We are reporting here a one-pot synthetic pathway using amine as a selectivity-switching agent in the two-component catalytic system consisting of triethylborane(Et_(3)B)and a phosphazene base.We first modelled the interactions of a variety of amines with Et_(3)B by density functional theory calculations.The results indicate that the aliphatic diamines comprising both primary and tertiary amino groups,capable of forming stable intramolecular hydrogen bonds,undergo the strongest complexation with Et_(3)B.Accordingly,experimental results demonstrate that the addition of such amines promptly actuates the in situ selectivity switch from Lewis pair-catalyzed ring-opening polymerization(ROP)of epoxide(propylene oxide,n-butylglycidyl ether,or glycidyl phenyl ether)to organobase-catalyzed ROP ofδ-valerolactone,allowing one-pot continuous synthesis of ether-ester type block copolymers.We thus exploited the noncovalent interaction between amine and Et_(3)B to refine the catalyst switch strategy by exempting it from loading of extra catalyst.展开更多
We consider the inverse problem of finding guiding pattern shapes that result in desired self-assembly morphologies of block copolymer melts.Specifically,we model polymer selfassembly using the self-consistent field t...We consider the inverse problem of finding guiding pattern shapes that result in desired self-assembly morphologies of block copolymer melts.Specifically,we model polymer selfassembly using the self-consistent field theory and derive,in a non-parametric setting,the sensitivity of the dissimilarity between the desired and the actual morphologies to arbitrary perturbations in the guiding pattern shape.The sensitivity is then used for the optimization of the confining pattern shapes such that the dissimilarity between the desired and the actual morphologies is minimized.The efficiency and robustness of the proposed gradient-based algorithm are demonstrated in a number of examples related to templating vertical interconnect accesses(VIA).展开更多
In unit cell simulations,identification of ordered phases in block copolymers(BCPs)is a tedious and time-consuming task,impeding the advancement of more streamlined and potentially automated research workflows.In this...In unit cell simulations,identification of ordered phases in block copolymers(BCPs)is a tedious and time-consuming task,impeding the advancement of more streamlined and potentially automated research workflows.In this study,we propose a scattering-based automated identification strategy(SAIS)for characterization and identification of ordered phases of BCPs based on their computed scattering patterns.Our approach leverages the scattering theory of perfect crystals to efficiently compute the scattering patterns of periodic morphologies in a unit cell.In the first stage of the SAIS,phases are identified by comparing reflection conditions at a sequence of Miller indices.To confirm or refine the identification results of the first stage,the second stage of the SAIS introduces a tailored residual between the test phase and each of the known candidate phases.Furthermore,our strategy incorporates a variance-like criterion to distinguish background species,enabling its extension to multi-species BCP systems.It has been demonstrated that our strategy achieves exceptional accuracy and robustness while requiring minimal computational resources.Additionally,the approach allows for real-time expansion and improvement to the candidate phase library,facilitating the development of automated research workflows for designing specific ordered structures and discovering new ordered phases in BCPs.展开更多
Poly(N,N-dimethyl acrylamide)-block-poly(styrene)-block-poly(N,N-dimethyl acrylamide)(PDMAc-bPSt-b-PDMAc)amphiphilic triblock copolymer micro/nano-objects were synthesized through reversible addition-fragmentation cha...Poly(N,N-dimethyl acrylamide)-block-poly(styrene)-block-poly(N,N-dimethyl acrylamide)(PDMAc-bPSt-b-PDMAc)amphiphilic triblock copolymer micro/nano-objects were synthesized through reversible addition-fragmentation chain transfer(RAFT)dispersion polymerization of St mediated with poly(N,Ndimethyl acrylamide)trithiocarbonate(PDMAc-TTC-PDMAc)bi-functional macromolecular RAFT agent.It is found that the morphology of the PDMAc-b-PSt-b-PDMAc copolymer micro/nano-objects like spheres,vesicles and vesicle with hexagonally packed hollow hoops(HHHs)wall can be tuned by changing the solvent composition.In addition,vesicles with two sizes(600 nm,264 nm)and vesicles with HHHs features were also synthesized in high solid content systems(30 wt%and 40 wt%,respectively).Besides,as compared with typical AB diblock copolymers(A is the solvophilic,stabilizer block,and B is the solvophobic block),ABA triblock copolymers tend to form higher order morphologies,such as vesicles,under similar conditions.The finding of this study provides a new and robust approach to prepare block copolymer vesicles and other higher order micelles with special structure via PISA.展开更多
The self-assembly of block copolymer in solution has proven to be an effective strategy for building up a wide range of nanomaterials with diverse structures and applications.This paper reports a facile self-assembly ...The self-assembly of block copolymer in solution has proven to be an effective strategy for building up a wide range of nanomaterials with diverse structures and applications.This paper reports a facile self-assembly approach towards two-dimensional(2D)sandwich-like mesoporous nitrogen-doped carbon/reduced graphene oxide nanocomposites(denoted as mNC/rGO)with well-defined large mesopores.The strategy involves the synergistic self-assembly ofpolystyrene-block-poly(ethylene oxide)(PS-b-PEO)spherical micelles,m-phenylenediamine(mPD)monomers and GO in solution and the subsequent carbonization at 900~C.The resultant mNC/rGO nanosheets have an average pore size of 19 nm,a high specific surface of 812 m^(2)'g^(-1)and a nitrogen content of 2.2 wt%.As an oxygen reduction reaction(ORR)catalyst,the unique structural features render the metal-free nanosheets excellent electrocatalytic performance.In a 0.1 mol.L-~KOH alkaline medium,mNC/rGO exhibits a four-electron transfer pathway with a high half-wave-potential(El/2)of+0.77 V versus reversible hydrogen electrode(RHE)and a limiting current density(JL)of 5.2 mA'cm^(-2),which are well comparable with those of the commercial Pt/C catalysts.展开更多
A novel fluorinated triblock copolymer incorporating 2-ethylhexyl methacrylate （EHMA）, tert-butyl methacrylate （tBMA） and 1H,1H,2H,2H-perfluorodecyl acrylate （FA） （PEHMA-b-PtBMA-b-PFA） was first synthesized us...A novel fluorinated triblock copolymer incorporating 2-ethylhexyl methacrylate （EHMA）, tert-butyl methacrylate （tBMA） and 1H,1H,2H,2H-perfluorodecyl acrylate （FA） （PEHMA-b-PtBMA-b-PFA） was first synthesized using three successive reversible addition fragmentation chain transfer （RAFT） polymerization and the subsequent hydrolyzing at acidic condition. The as-fabricated triblock copolymer exhibited an interesting morphology evolution from the multi-compartment rod-like structure to spherical structure along with the addition of a selective solution. At the same time, a visible phase separation domain could be seen in the core area due to the existence of fluorocarbon segments. Furthermore, the self- assembly behavior of the triphilic copolymer at different pH was also verified by transmission electron microscopy, as well as the dynamic light scattering. These stimuli-responsive multi-compartment nanostructures may have potential applications in drug delivery.展开更多
This feature article summarizes the synthesis of novel olefin block copolymers using fast syndiospecific living homo- and copolymerization of propylene, higher 1-alkene, and norbornene with ansa-fluorenylamidodimethyl...This feature article summarizes the synthesis of novel olefin block copolymers using fast syndiospecific living homo- and copolymerization of propylene, higher 1-alkene, and norbornene with ansa-fluorenylamidodimethyltitanium- based catalyst according to the authors＇ recent results. The catalytic synthesis of monodisperse polyolefin and olefin block copolymer was also described using this living system.展开更多
Controlled synthesis of amphiphilic block copolymer nanoparticles in a convenient way is an important and interest topic in polymer science. In this review, three formulations of polymerization-induced self-assembly t...Controlled synthesis of amphiphilic block copolymer nanoparticles in a convenient way is an important and interest topic in polymer science. In this review, three formulations of polymerization-induced self-assembly to in situ synthesize block copolymer nanoparticles are briefly introduced, which perform by reversible addition-fragmentation chain transfer （RAFT） polymerization under heterogeneous conditions, e.g., aqueous emulsion RAFT polymerization, dispersion RAFT polymerization and especially the recently proposed seeded RAFT polymerization. The latest developments in several selected areas on the synthesis of block copolymer nano-assemblies are highlighted.展开更多
A series of new amphiphilic poly[methyl（3,3,3-trifluoropropyl）siloxane]-b-poly（ethylene oxide） （PMTFPS-b-PEO） diblock copolymers with different ratios of hydrophobic segment to hydrophilic segment were prepared ...A series of new amphiphilic poly[methyl（3,3,3-trifluoropropyl）siloxane]-b-poly（ethylene oxide） （PMTFPS-b-PEO） diblock copolymers with different ratios of hydrophobic segment to hydrophilic segment were prepared by coupling reactions of end-functlonal PMTFPS and PEO homopolymers. Copolymers were shown to be well defined and narrow molecular weight distribution （MWD） （1.07-1.3） by characterizations such as gel permeation chromatography （GPC） and ^1H-nudear magnetic resonance （^1H-NMR）.展开更多
Block copolymer lithography is emerging as one of the leading technologies for patteming nanoscale dense features. In almost all potential applications of this technology, control over the orientation of cylindrical a...Block copolymer lithography is emerging as one of the leading technologies for patteming nanoscale dense features. In almost all potential applications of this technology, control over the orientation of cylindrical and lamellar domains is required for pattern transfer from the block copolymer film. This review highlights the state-of-art development of brushes to modify the substrates to control the assembly behaviors of block copolymers in films. Selected important contributions to the development of self-assembled monolayers, polymer brushes and mats, and chemically patterned brushes are discussed.展开更多
Solid polymer electrolytes have been considered as the promising candidates to improve the safety and stability of high-energy lithium metal batteries.However,the practical applications of solid polymer electrolytes a...Solid polymer electrolytes have been considered as the promising candidates to improve the safety and stability of high-energy lithium metal batteries.However,the practical applications of solid polymer electrolytes are still limited by the low ionic conductivity,poor interfacial contact with electrodes,narrow electrochemical window and weak mechanical strength.Here,a series of novel block copolymer electrolytes with three-dimensional networks are designed by cross-linked copolymerization of the polyethylene glycol soft segments and hexamethylene diisocyanate trimer hard segments.Their ionic migration performances and interface compatibilities with Li metal anode have been optimized delicately by tailoring the ratio of these functional units.The optimized block copolymer electrolyte has shown an amorphous crystalline structure,a high ionic conductivity of ~5.7×10^(-4)S cm^(-1),high lithium ion transference number(~0.49),wide electrochemical window up to ~4.65 V(vs.Li+/Li) and favorable mechanical strength at 55℃.Furthermore,the enhanced interface compatibility can well support the normal operations of lithium metal batteries using both LiFePO4 and LiNi0.8Co0.15Al0.05O2 cathodes.This study not only paves a new way to develop solid polymer electrolyte with optimizing functional units,but also provides a polymer electrolyte design strategy for the application demand of lithium metal battery.展开更多
pH-sensitive wettability of polystyrene-b-poly（4-vinylpyridine） （PS-b-P4VP） self assembled films, exhibiting superoleophobicity under water and hydrophilicity at low pH value, and oleophobicity under water and hyd...pH-sensitive wettability of polystyrene-b-poly（4-vinylpyridine） （PS-b-P4VP） self assembled films, exhibiting superoleophobicity under water and hydrophilicity at low pH value, and oleophobicity under water and hydrophobicity at neutral condition, has been realized. The wettability properties resulted from the surface topological and chemical transition, which were confirmed by in situ AFM measurements under water at different pH. At low pH, P4VP chains, which were confined in the hexagonal-packed nanodomains, got protonated into a swollen state, while at high pH, P4VP chains were deprotonated into a collapsed state. The reversible protonation/deprotonation procedure on the molecular scale leads to surface topological and chemical transition, thereby pH-sensitive wettability.展开更多
基金supported by the National Natural Science Foundation of China (Grant Nos.U20A20168 and 62404120)the National Key R&D Program (Grant No.2022YFB3204100)+2 种基金the Postdoctoral Fellowship Program of CPSF (Grant Nos.GZB20240335 and GZC20231216)the China Postdoctoral Science Foundation (Grant No.2025T180151)the Initiative Scientific Research Program of the School of Integrated Circuits,Tsinghua University。
文摘Block copolymer(BCP) nanolithography offers potential beyond traditional photolithographic limits, yet reliably producing low-defect, perpendicular domains remains challenging. We introduce a microenvironmentdriven isothermal annealing method for directed self-assembly of BCP thin films. By annealing films at stable temperature in a quasi-sealed, inert-gas chamber, our approach promotes highly uniform perpendicular lamellar nanopatterns over large areas, effectively mitigating environmental fluctuations and emulating solvent-vapor annealing without solvent exposure. Resulting BCP structures demonstrate enhanced spatial coherence and notably low defect density. Furthermore, we successfully transfer these nanopatterns into precise metal nano-line arrays,confirming the method's capability for high-fidelity pattern replication. This scalable, solvent-free technique provides a robust, reliable route for high-resolution nanopatterning in advanced semiconductor manufacturing.
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 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This work was financially supported by the National Natural Science Foundation of China(Nos.51921002,22203015 and 51725301)Natural Science Foundation of Fujian Province(No.2021J01591)the National Key R&D Program of China(No.2018YFB0703702).The suggestions and help offered by Prof.Rong-Ming Ho of National Tsing Hua University are greatly appreciated.The authors acknowledge the scientists at the synchrotron X-ray beamline 1W2A at Beijing Synchrotron Radiation Facility(BSRF)and the synchrotron X-ray beamline BL16B1 at Shanghai Synchrotron Radiation Facility(SSRF)for their assistance on the SAXS experiments.
文摘The rich phase behavior of block copolymers(BCPs)has drawn great attention in recent years.However,the double diamond(DD)phase is rarely obtained because of the competition between the minimization of interfacial energy and packing frustration.Here,a rod-coil BCP containing mesogen-jacketed liquid crystalline polymer is designed to acquire ordered bicontinuous network nanostructures.The reduction of internal energy originating from the orientational interaction among the rod blocks can compensate for the free energy penalty of packing frustration to stabilize the DD structure.The resulting BCP can also experience lamellae-to-DD and double gyroid-to-lamellae transitions by changing the annealing temperature.These results make the rod-coil BCP an excellent candidate for the self-assembly of ordered network structures,demonstrating great potential in nanopatterning and metamaterials.
基金supported by the Major Research Plan of the National Natural Science Foundation of China(No.92372104)Guangdong Basic and Applied Basic Research Foundation(No.2022A1515110016)the Recruitment Program of Guangdong(No.2016ZT06C322),and TCL Science and Technology Innovation Fund.
文摘Salt-doped block copolymers have widespread applications in batteries,fuel cells,semiconductors,and various industries,where their properties crucially depend on phase separation behavior.Traditionally,investigations into salt-doped diblock copolymers have predominantly focused on microphase separation,overlooking the segregation between ionic and polymeric species.This study employs weak segregation theory to explore the interplay between phase separation dominated by the polymer-modulated mode and the salt-out-modulated mode,corresponding to microscopic and macroscopic phase separations,respectively.By comparing diblock copolymers doped with salts to those doped with neutral solvents,we elucidate the significant role of charged species in modulating phase behavior.The phase separation mode exhibits a transition between the polymer-modulated and salt-out-modulated modes at different wavenumbers.In systems doped with neutral solvents,this transition is stepwise,while in salt-ion-doped systems,it is continuous.With a sufficiently large Flory-Huggins parameter between ions and polymers,the salt-out-modulated mode becomes dominant,promoting macrophase separation.Due to the solvation effect of salt ions,salt-doped systems are more inclined to undergo microphase separation.Furthermore,we explore factors influencing the critical wavenumber of phase separation,including doping level and the Flory-Huggins parameters between two blocks and between ions and polymeric species.Our findings reveal that in a neutral solvent environment,these factors alter only the boundary between micro-and macro-phase separations,leaving the critical wavenumber unchanged in microphase separation cases.However,in a salt-doped environment,the critical wavenumber of microphase separation varies with these parameters.This provides valuable insights into the pivotal role of electrostatics in the phase separation of salt-doped block copolymers.
基金financially supported by the National Natural Science Foundation of China (No.52073277)the Science and Technology Department of Fujian Province (No.2020HZ06019)。
文摘Ethylene-propylene block copolymer(EbP) is a vital component in impact polypropylene copolymer(IPC), yet its distribution in the multiphase composite material and how it influences the phase structure and the mechanical properties are not well understood. In this work,four IPCs were investigated by atomic force microscopy-infrared(AFM-IR) to assess the phase compositions in situ, based on which in conjunction with the chain microstructure information obtained ex situ the distributions of the copolymer components were derived for each alloy. For the IPCs whose EbP comprises long P and long E segments, the EbP fraction was found to phase separate from the rubber and the PP matrix to form the cores of the disperse particles with the E-P segmented copolymer(EsP). In contrast, in the IPC with EbP composed of long P and short E segments, the EbP fraction formed an outer shell for the rubber particles with the cores comprising the EsP alone, and this IPC, containing a lower E comonomer content than its counterpart, exhibited both better impact resistance and higher flexural modulus. These results clarify how the chain structure of EbP governs the phase morphology in IPC, which in turn impacts the properties of the composite material.
基金financially supported by the National Natural Science Foundation of China (No. 22271207)the Project Funded by the Priority Academic Program Development of Jiangsu Higher Education Institutions (PAPD)。
文摘Temperature-responsive polymers have garnered significant attention due to their ability to respond to external stimuli.In this work,dual temperature-responsive block copolymers are synthesized via reversible addition-fragmentation chain transfer polymerization(RAFT)polymerization utilizing zwitterionic monomer methacryloyl ethyl sulfobetaine(SBMA) and N-isopropyl acrylamide(NIPAAm) as monomers.The thermal responsive behaviors can be easily modulated by incorporating additional hydrophobic monomer benzyl acrylate(BN) or hydrophilic monomer acrylic acid(AA),adjusting concentration or pH,or varying the degree of polymerization of the block chain segments.The cloud points of the copolymers are determined by UV-Vis spectrophotometry,and these copolymers exhibit both controlled upper and lower critical solu bility temperatures(LCST and UCST) in aqueous solution.This study analyzes and summarizes the influencing factors of dual temperature responsive block copolymers by exploring the effects of various conditions on the phase transition temperature of temperature-sensitive polymers to explore the relationship between their properties and environment and structure to make them more selective in terms of temperature application range and regulation laws.It is very interesting that the introduction of poly-acrylic acid(PAA) segments in the middle of di-block copolymer PSBMA_(55)-b-PNIPAAm_(80) to form PSBMA_(55)-b-PAA_(x)-b-PNIPAAm_(80) results in a reversal of temperature-responsive behaviors from 'U'(LCST UCST) type,while the copolymer PSBMA_(55)-b-P(NIPAAm_(80)-co-AA_(x)) not.This work provides a clue for tuning the phase transition behavior of polymers for manufacture of extreme smart materials.
基金This work was financially supported by the National Natural Science Foundation of China(Nos.52022031 and 21734004).
文摘Organocatalysis has shown special potency for simplifying the construction of complex polymer structures.We are reporting here a one-pot synthetic pathway using amine as a selectivity-switching agent in the two-component catalytic system consisting of triethylborane(Et_(3)B)and a phosphazene base.We first modelled the interactions of a variety of amines with Et_(3)B by density functional theory calculations.The results indicate that the aliphatic diamines comprising both primary and tertiary amino groups,capable of forming stable intramolecular hydrogen bonds,undergo the strongest complexation with Et_(3)B.Accordingly,experimental results demonstrate that the addition of such amines promptly actuates the in situ selectivity switch from Lewis pair-catalyzed ring-opening polymerization(ROP)of epoxide(propylene oxide,n-butylglycidyl ether,or glycidyl phenyl ether)to organobase-catalyzed ROP ofδ-valerolactone,allowing one-pot continuous synthesis of ether-ester type block copolymers.We thus exploited the noncovalent interaction between amine and Et_(3)B to refine the catalyst switch strategy by exempting it from loading of extra catalyst.
文摘We consider the inverse problem of finding guiding pattern shapes that result in desired self-assembly morphologies of block copolymer melts.Specifically,we model polymer selfassembly using the self-consistent field theory and derive,in a non-parametric setting,the sensitivity of the dissimilarity between the desired and the actual morphologies to arbitrary perturbations in the guiding pattern shape.The sensitivity is then used for the optimization of the confining pattern shapes such that the dissimilarity between the desired and the actual morphologies is minimized.The efficiency and robustness of the proposed gradient-based algorithm are demonstrated in a number of examples related to templating vertical interconnect accesses(VIA).
基金This work was supported by the National Natural Science Foundation of China(Grants No.21873021).
文摘In unit cell simulations,identification of ordered phases in block copolymers(BCPs)is a tedious and time-consuming task,impeding the advancement of more streamlined and potentially automated research workflows.In this study,we propose a scattering-based automated identification strategy(SAIS)for characterization and identification of ordered phases of BCPs based on their computed scattering patterns.Our approach leverages the scattering theory of perfect crystals to efficiently compute the scattering patterns of periodic morphologies in a unit cell.In the first stage of the SAIS,phases are identified by comparing reflection conditions at a sequence of Miller indices.To confirm or refine the identification results of the first stage,the second stage of the SAIS introduces a tailored residual between the test phase and each of the known candidate phases.Furthermore,our strategy incorporates a variance-like criterion to distinguish background species,enabling its extension to multi-species BCP systems.It has been demonstrated that our strategy achieves exceptional accuracy and robustness while requiring minimal computational resources.Additionally,the approach allows for real-time expansion and improvement to the candidate phase library,facilitating the development of automated research workflows for designing specific ordered structures and discovering new ordered phases in BCPs.
文摘Poly(N,N-dimethyl acrylamide)-block-poly(styrene)-block-poly(N,N-dimethyl acrylamide)(PDMAc-bPSt-b-PDMAc)amphiphilic triblock copolymer micro/nano-objects were synthesized through reversible addition-fragmentation chain transfer(RAFT)dispersion polymerization of St mediated with poly(N,Ndimethyl acrylamide)trithiocarbonate(PDMAc-TTC-PDMAc)bi-functional macromolecular RAFT agent.It is found that the morphology of the PDMAc-b-PSt-b-PDMAc copolymer micro/nano-objects like spheres,vesicles and vesicle with hexagonally packed hollow hoops(HHHs)wall can be tuned by changing the solvent composition.In addition,vesicles with two sizes(600 nm,264 nm)and vesicles with HHHs features were also synthesized in high solid content systems(30 wt%and 40 wt%,respectively).Besides,as compared with typical AB diblock copolymers(A is the solvophilic,stabilizer block,and B is the solvophobic block),ABA triblock copolymers tend to form higher order morphologies,such as vesicles,under similar conditions.The finding of this study provides a new and robust approach to prepare block copolymer vesicles and other higher order micelles with special structure via PISA.
基金financially supported by the National Natural Science Foundation of China(Nos.51573091,21774076,21320102006 and 91527304)Program of the Shanghai Committee of Science and Technology(Nos.17JC1403200 and 16JC1400703)Program for Shanghai Eastern Scholar
文摘The self-assembly of block copolymer in solution has proven to be an effective strategy for building up a wide range of nanomaterials with diverse structures and applications.This paper reports a facile self-assembly approach towards two-dimensional(2D)sandwich-like mesoporous nitrogen-doped carbon/reduced graphene oxide nanocomposites(denoted as mNC/rGO)with well-defined large mesopores.The strategy involves the synergistic self-assembly ofpolystyrene-block-poly(ethylene oxide)(PS-b-PEO)spherical micelles,m-phenylenediamine(mPD)monomers and GO in solution and the subsequent carbonization at 900~C.The resultant mNC/rGO nanosheets have an average pore size of 19 nm,a high specific surface of 812 m^(2)'g^(-1)and a nitrogen content of 2.2 wt%.As an oxygen reduction reaction(ORR)catalyst,the unique structural features render the metal-free nanosheets excellent electrocatalytic performance.In a 0.1 mol.L-~KOH alkaline medium,mNC/rGO exhibits a four-electron transfer pathway with a high half-wave-potential(El/2)of+0.77 V versus reversible hydrogen electrode(RHE)and a limiting current density(JL)of 5.2 mA'cm^(-2),which are well comparable with those of the commercial Pt/C catalysts.
基金financially supported by the National Natural Science Foundation of China(Nos.51622301 and 51573046)Fundamental Research Funds for the Central Universities(Nos.B14018,WD1616010 and 222201717001)
文摘A novel fluorinated triblock copolymer incorporating 2-ethylhexyl methacrylate （EHMA）, tert-butyl methacrylate （tBMA） and 1H,1H,2H,2H-perfluorodecyl acrylate （FA） （PEHMA-b-PtBMA-b-PFA） was first synthesized using three successive reversible addition fragmentation chain transfer （RAFT） polymerization and the subsequent hydrolyzing at acidic condition. The as-fabricated triblock copolymer exhibited an interesting morphology evolution from the multi-compartment rod-like structure to spherical structure along with the addition of a selective solution. At the same time, a visible phase separation domain could be seen in the core area due to the existence of fluorocarbon segments. Furthermore, the self- assembly behavior of the triphilic copolymer at different pH was also verified by transmission electron microscopy, as well as the dynamic light scattering. These stimuli-responsive multi-compartment nanostructures may have potential applications in drug delivery.
文摘This feature article summarizes the synthesis of novel olefin block copolymers using fast syndiospecific living homo- and copolymerization of propylene, higher 1-alkene, and norbornene with ansa-fluorenylamidodimethyltitanium- based catalyst according to the authors＇ recent results. The catalytic synthesis of monodisperse polyolefin and olefin block copolymer was also described using this living system.
基金financially supported by the National Science Foundation for Distinguished Young Scholars(No.21525419)the National Natural Science Foundation of China(Nos.21274066 and 21474054)the National Key Research and Development Program of China(No.2016YFA0202503)
文摘Controlled synthesis of amphiphilic block copolymer nanoparticles in a convenient way is an important and interest topic in polymer science. In this review, three formulations of polymerization-induced self-assembly to in situ synthesize block copolymer nanoparticles are briefly introduced, which perform by reversible addition-fragmentation chain transfer （RAFT） polymerization under heterogeneous conditions, e.g., aqueous emulsion RAFT polymerization, dispersion RAFT polymerization and especially the recently proposed seeded RAFT polymerization. The latest developments in several selected areas on the synthesis of block copolymer nano-assemblies are highlighted.
基金the National Natural Science Foundation of China (No. 20606029)the Postdoctoral Science Foundation of China (No. 20070420230)
文摘A series of new amphiphilic poly[methyl（3,3,3-trifluoropropyl）siloxane]-b-poly（ethylene oxide） （PMTFPS-b-PEO） diblock copolymers with different ratios of hydrophobic segment to hydrophilic segment were prepared by coupling reactions of end-functlonal PMTFPS and PEO homopolymers. Copolymers were shown to be well defined and narrow molecular weight distribution （MWD） （1.07-1.3） by characterizations such as gel permeation chromatography （GPC） and ^1H-nudear magnetic resonance （^1H-NMR）.
基金financially supported by the National Natural Science Foundation of China(Nos.51173181 and 51373166)“The Hundred Talents Program”from the Chinese Academy of Sciences and the International S&T Cooperation Program from Department of Science and Technology of Jilin Province(No.20160414032GH)
文摘Block copolymer lithography is emerging as one of the leading technologies for patteming nanoscale dense features. In almost all potential applications of this technology, control over the orientation of cylindrical and lamellar domains is required for pattern transfer from the block copolymer film. This review highlights the state-of-art development of brushes to modify the substrates to control the assembly behaviors of block copolymers in films. Selected important contributions to the development of self-assembled monolayers, polymer brushes and mats, and chemically patterned brushes are discussed.
基金supported financially by the National Key R&D Program of China (Grant No. 2018YFB0104300)Beijing Natural Science Foundation (JQ19003, KZ201910005002 and L182009)+1 种基金National Natural Science Foundation of China (Grants 21875007, 51622202, and 21974007)the Project of Youth Talent Plan of Beijing Municipal Education Commission (CIT&TCD201804013)。
文摘Solid polymer electrolytes have been considered as the promising candidates to improve the safety and stability of high-energy lithium metal batteries.However,the practical applications of solid polymer electrolytes are still limited by the low ionic conductivity,poor interfacial contact with electrodes,narrow electrochemical window and weak mechanical strength.Here,a series of novel block copolymer electrolytes with three-dimensional networks are designed by cross-linked copolymerization of the polyethylene glycol soft segments and hexamethylene diisocyanate trimer hard segments.Their ionic migration performances and interface compatibilities with Li metal anode have been optimized delicately by tailoring the ratio of these functional units.The optimized block copolymer electrolyte has shown an amorphous crystalline structure,a high ionic conductivity of ~5.7×10^(-4)S cm^(-1),high lithium ion transference number(~0.49),wide electrochemical window up to ~4.65 V(vs.Li+/Li) and favorable mechanical strength at 55℃.Furthermore,the enhanced interface compatibility can well support the normal operations of lithium metal batteries using both LiFePO4 and LiNi0.8Co0.15Al0.05O2 cathodes.This study not only paves a new way to develop solid polymer electrolyte with optimizing functional units,but also provides a polymer electrolyte design strategy for the application demand of lithium metal battery.
基金financially supported by the National Natural Science Foundation of China(No.21204002)Specialized Research Fund for the Doctoral Program of Higher Education(No.20111102120050)+1 种基金Program for New Century Excellent Talents in Universities(2010)the Fundamental Research Funds for the Central Universities
文摘pH-sensitive wettability of polystyrene-b-poly（4-vinylpyridine） （PS-b-P4VP） self assembled films, exhibiting superoleophobicity under water and hydrophilicity at low pH value, and oleophobicity under water and hydrophobicity at neutral condition, has been realized. The wettability properties resulted from the surface topological and chemical transition, which were confirmed by in situ AFM measurements under water at different pH. At low pH, P4VP chains, which were confined in the hexagonal-packed nanodomains, got protonated into a swollen state, while at high pH, P4VP chains were deprotonated into a collapsed state. The reversible protonation/deprotonation procedure on the molecular scale leads to surface topological and chemical transition, thereby pH-sensitive wettability.
