The composition and sequence distribution of monomeric units in polyester polyether multiblock copolymer were studied by pyrolysis? gas chromatography (PGC) and pyrolysis gas chromatography/mass spectrometry (PGC/M...The composition and sequence distribution of monomeric units in polyester polyether multiblock copolymer were studied by pyrolysis? gas chromatography (PGC) and pyrolysis gas chromatography/mass spectrometry (PGC/MS). PGC was applied to study the F t curve of the multiblock copolymer and PGC/MS was used to separate and identify the pyrolyzates. DTA experiment was used to study the decomposition temperature. The results show that the beginning point of elastomer’s decomposition was about 300?℃ and the decomposition temperature of most of the sample was 550?℃. Many pyrolyzates were produced because of the breaking of weak bonds in the sample. The possible microstructure was verified and the pyrolysis pathway of the copolymer was investigated.展开更多
An attempt was made in the paper aiming at imparting flame retardancy to polymers by plasma grafting technique Based on EVA copolymers with different VA contents the author tried to use the Ar plasma followed by graf...An attempt was made in the paper aiming at imparting flame retardancy to polymers by plasma grafting technique Based on EVA copolymers with different VA contents the author tried to use the Ar plasma followed by grafting with/without subsequent saponification and metal ion exchange expediting the charring of polymers upon heationg Characterization of the flammability of the plasma treated EVA copolymers grafted with acrylic monomers(MAA,AA and AAm)indicates that this approach turns out to be a promising way and worthy doing whatever in research and/or applications展开更多
Synthesis of a cold flow improver （MAVA-a） for diesel fuel and its effect on solidifying point （SP） and cold filter plugging point （CFPP） of diesel fuels were investigated, The cold flow improver was prepared by...Synthesis of a cold flow improver （MAVA-a） for diesel fuel and its effect on solidifying point （SP） and cold filter plugging point （CFPP） of diesel fuels were investigated, The cold flow improver was prepared by using maleic anhydride （MA） and vinyl acetate （VA） as raw materials, toluene as solvent, dibenzoyl peroxide （BPO） as initiator, through alternating polymerization under nitrogen to obtain a binary-polymer and then through aminolysis by using a higher carbon amine as aminating agent at a temperature of 80 ℃. A cold flow improver was designed and prepared for No. 0 diesel fuel from Zhang Jia-Gang Petrochemical Company according to the contents of n-paraffin and its carbon number distribution in the No. 0 diesel fuel. It was also used together with two kinds of ethene-vinyl acetate copolymer improvers （EVA） separately. The test result showed that the CFPP of the No. 0 diesel fuel could be lowered by 3-5 ℃ when the improver MAVA-a was used. The CFPP was lowered by 8℃ when the improver MAVA-a was used together with EVA-2.展开更多
The self-assembly of symmetric diblock copolymers confined in the channels of variously shaped cross sections （regu- lar triangles, squares, and ellipses） is investigated using a simulated annealing technique. In th...The self-assembly of symmetric diblock copolymers confined in the channels of variously shaped cross sections （regu- lar triangles, squares, and ellipses） is investigated using a simulated annealing technique. In the bulk, the studied symmetric diblock copolymers form a lamellar structure with period LL. The geometry and surface property of the confining channels have a large effect on the self-assembled structures and the orientation of the lamellar structures. Stacked perpendicular lamellae with period LL are observed for neutral surfaces regardless of the channel shape and size, but each lamella is in the shape of the corresponding channel＇s cross section. In the case of triangle-shaped cross sections, stacked parallel lamel- lae are the majority morphologies for weakly selective surfaces, while morphologies including a triangular-prism-shaped B-cylinder and multiple tridentate lamellae are obtained for strongly selective surfaces. In the cases of square-shaped and ellipse-shaped cross sections, concentric lamellae are the signature morphology for strongly selective surfaces, whereas for weakly selective surfaces, stacked parallel lamellae, and several types of folding lamellae are obtained in the case of square-shaped cross sections, and stacked parallel lamellae are the majority morphologies in the case of ellipse-shaped cross sections when the length of the minor axis is commensurate with the bulk lamellar period. The mean-square end- to-end distance, the average contact number between different species and the surface concentration of the A-monomers are computed to elucidate the mechanisms of the formation of the different morphologies. It is found that the resulting morphology is a consequence of competition among the chain stretching, interfacial energy, and surface energy. Our results suggest that the self-assembled morphology and the orientation of lamellae can be manipulated by the shape, the size, and the surface property of the confining channels.展开更多
The phase behaviours of diblock copolymers under cylindrical confinement are studied in two-dimensional space by using the self-consistent field theory. Several phase parameters are adjusted to investigate the cylindr...The phase behaviours of diblock copolymers under cylindrical confinement are studied in two-dimensional space by using the self-consistent field theory. Several phase parameters are adjusted to investigate the cylindrical-confinement-induced phase behaviours of diblock copolymers. A series of lamella-cylinder mixture phases, such as the mixture of broken-lamellae and cylinders and the mixture of square-lamellae and cylinders, are observed by varying the phase parameters, in which the behaviours of these mixture phases are discussed in the corresponding phase diagrams. Furthermore, the free energies of these mixture phases are investigated to illustrate their evolution processes. Our results are compared with the available observations from the experiments and simulations respectively, and they are in good agreement and provide an insight into the phase behaviours under cylindrical confinement.展开更多
The phase behaviors in a binary mixture of diblock copolymers confined between two parallel walls are investigated by using a cell dynamics simulation of the time-dependent Ginzburg-Landau theory.The morphological dep...The phase behaviors in a binary mixture of diblock copolymers confined between two parallel walls are investigated by using a cell dynamics simulation of the time-dependent Ginzburg-Landau theory.The morphological dependence of the wall-block interaction and the distance between walls（confinement degree） has been systematically studied,and the effect of repulsive interactions between different monomers is also discussed.It is interesting that multiple novel morphological transitions are observed by changing these factors,and various multilayered sandwich structures are formed in the mixture.Furthermore,the parametric dependence and physical reasons for the microdomain growth and orientational order transitions are discussed.From the simulation,we find that much richer morphologies can form in a binary mixture of diblock copolymers than those in a pure diblock copolymer.Our results provide an insight into the phase behaviors under parallel wall confinement and may provide guidance for experimentalists.This model system can also give a simple way to realize orientational order transition in soft materials through confinement.展开更多
Lithium metal batteries are strongly considered as one of the most promising candidates for nextgeneration high-performance battery systems.However,the uncontrollable growth of lithium dendrites and the highly reactiv...Lithium metal batteries are strongly considered as one of the most promising candidates for nextgeneration high-performance battery systems.However,the uncontrollable growth of lithium dendrites and the highly reactive lithium metal result in the severe safety risks and the short lifespan for highenergy-density rechargeable batteries.Here,we demonstrate a hydrophobic and ionically conductive ethylene-vinyl acetate(EVA)copolymer layer can not only endow lithium metal anodes with an air-stable and anti-water surface,but also efficiently suppress the lithium-dendrites growth during the electrochemical cycling process.Therefore,the introduction of the EVA copolymer as a bifunctional protection layer simultaneously improves the anti-water/air performance and electrochemical cycling stability of lithium metal anode.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
We investigated phase transitions in a diblock copolymer–homopolymer hybrid system blended with nanorods(NRs)by using the time-dependent Ginzburg–Landau theory.We systematically studied the effects of the number,len...We investigated phase transitions in a diblock copolymer–homopolymer hybrid system blended with nanorods(NRs)by using the time-dependent Ginzburg–Landau theory.We systematically studied the effects of the number,length and infiltration properties of the NRs on the self-assembly of the composites and the phase transitions occurring in the material.An analysis of the phase diagram was carried out to obtain the formation conditions of sea island structure nanorodbased aggregate,sea island structure nanorod-based dispersion,lamellar structure nanorod-based multilayer arrangement and nanowire structure.Further analysis of the evolution of the domain sizes and the distribution of the nanorod angle microphase structure was performed.Our simulation provides theoretical guidance for the preparation of ordered nanowire structures and a reference to improve the function of a polymer nanocomposite material.展开更多
The new flow improvers for super-viscous crude oils were developed via esterification of polybasic high carbon alcohol with methacrylate and copolymerizafion of monomers followed by amination of copolymers. The struct...The new flow improvers for super-viscous crude oils were developed via esterification of polybasic high carbon alcohol with methacrylate and copolymerizafion of monomers followed by amination of copolymers. The structure of the synthesized polymer flow improver additive was confirmed by IR spectroscopy and the crystal structure of the flow improver additives were determined by X-ray diffrac- tion analysis. The structure of wax crystals was also studied at the same time. The results showed that the wax crystal structure was closely related with the crystal structure of the flow improver, which could change the pour point depression and viscosity reduction behavior of the crude oil. When the wax crystal structure matched well with that of the additive, the wax crystals were dispersed satisfactorily, resulting in favorable effects in terms of pour point depression and viscosity reduction. The new synthe- sized aminated polymer flow improver additive was most efficient for treating super-viscous crude oils. The super-viscous crude oil had a high content of resins and asphaltenes, which might aggregate onto the surface of wax crystals to form blocks to limit the crude oil fluidity. However, amination of copolymers having similar structure with the resins and asphaltenes contained in crude oil could dissolve the huge polar groups to make the deposit formation difficult.展开更多
The lithium-sulfur(Li-S)battery is one of the most promising substitutes for current energy storage systems because of its low cost,high theoretical capacity,and high energy density.However,the high solubility of inte...The lithium-sulfur(Li-S)battery is one of the most promising substitutes for current energy storage systems because of its low cost,high theoretical capacity,and high energy density.However,the high solubility of intermediate products(i.e.,lithium polysulfides)and the resultant shuttle effect lead to rapidly fading capacity and a low coulombic efficiency,which hinder the practical application of Li-S batteries.In this study,block copolymers are constructed with both an ethylene oxide unit and a styrene unit and then used as binders for Li-S batteries.Electrochemical performance improvements are attributed to the synergistic effects contributed by the different units of the block copolymer.The ethylene oxide unit traps polysulfide,which bonds strongly with the intermediate lithium polysulfide,and enhances the transport of lithium ions to reach high capacity.Meanwhile,the styrene unit maintains cathode integrity by improving the mechanical properties and elasticity of the constructed block copolymer to accommodate the large volume changes.By enabling multiple functions via different units in the polymer chain,high sulfur utilization is achieved,polysulfide diffusion is confined,and the shuttle effect is suppressed during the cycle life of Li-S batteries,as revealed by operando ultraviolet-visible spectroscopy and S Kedge X-ray absorption spectroscopy.展开更多
Block copolymers are a class of soft matter that self-assemble to form ordered morphologies on the scale of nanome- ters, making them ideal materials for various applications. These applications directly depend on the...Block copolymers are a class of soft matter that self-assemble to form ordered morphologies on the scale of nanome- ters, making them ideal materials for various applications. These applications directly depend on the shape and size of the self-assembled morphologies, and hence, a high degree of control over the self-assembly is desired. Grafting block copolymer chains onto a substrate to form copolymer brushes is a versatile method to fabricate functional surfaces. Such surfaces demonstrate a response to their environment, i.e., they change their surface topography in response to different external conditions. Furthermore, such surfaces may possess nanoscale patterns, which are important for some applica- tions; however, such patterns may not form with spun-cast films under the same condition. In this review, we summarize the recent progress of the self-assembly of block copolymers grafted onto a flat substrate. We mainly concentrate on the self-assembled morphologies of end-grafted AB dibloek eopolymers, junction p0int-grafted AB diblock copolymers （i.e., Y-shaped brushes）, and end-grafted ABA triblock copolymers. Special emphasis is placed on theoretical and simulation progress.展开更多
In this paper, various kinds of monomers 2-hydroxyethyl methacrylate (HEMA), 2-hydroxyethyl acrylate (HEA), hydroxypropyl methacrylate (HPMA) and methoxy polyethylene glycol methylacrylate (M-23G) were eopolymerized b...In this paper, various kinds of monomers 2-hydroxyethyl methacrylate (HEMA), 2-hydroxyethyl acrylate (HEA), hydroxypropyl methacrylate (HPMA) and methoxy polyethylene glycol methylacrylate (M-23G) were eopolymerized by radiation technique at low temperature (-78℃) and several kinds of copolymer carriers were obtained. Yeast cells were immobilized through adhesion and multiplication of yeast cells themselves on these carriers. The etharol productivity of immobilized yeast cells with these carriers was related to the monomer composition and water content of copolymer carriers and the optimum monomer composition was 20%:10% in poly (HEA-M23G). In this case, the ethanol productivity of immobilized yeast cells was 26 mg /( ml·h), which was 4 times as high as that of free cells. In this study, the effect of adding of crosslinking reagent (4G) in copolymer on activity of yeast cells immobilized with the carriers were also studied. It was found that the effect of adding crosslinking reagent (4G) in lower monomer composition of poly(HEA-M23G) on the ethanol productivity of immobilized cells was better than that in higher one in this work.展开更多
The surface-induced effect on the morphologies of lamella-forming diblock copolymers in nanorod arrays is studied by using the self-consistent field theory. In the simulation study, a rich variety of novel morphologie...The surface-induced effect on the morphologies of lamella-forming diblock copolymers in nanorod arrays is studied by using the self-consistent field theory. In the simulation study, a rich variety of novel morphologies are observed by variations in the strength of the surface field for the diblock copolymers. Different surface-field-induced effects are examined for the diblock copolymers in the arrays with distinct preferential surfaces. It is observed that the majority-block preferential surfaces have more obvious induced effects than those of minority-block preferential surfaces. The strong surface fields exhibit different behaviours from those observed in the weak surface fields, by which the morphologies possess cylindrical symmetries. Results from this research deepen the knowledge of surface-induced effects in a confinement system, which may aid the fabrication of polymer-based na^omaterials.展开更多
Sepiolite （S9, B10, B20, B40） and boehmite have been added to an intumecent flame retardant （IFR） system to produce the halogen-free and fire-resistant ethylene-vinyl acetate copolymer （EVM） rubber. The rubber c...Sepiolite （S9, B10, B20, B40） and boehmite have been added to an intumecent flame retardant （IFR） system to produce the halogen-free and fire-resistant ethylene-vinyl acetate copolymer （EVM） rubber. The rubber contains ammonium polyphosphate （APP） as acid source, double pentaerythritol （D-PER） as carbon source and melamine （MN） as gas source. The effects of nano-filler sepiolite and boehmite on the fire-resistant property of EVM rubber based on IFR system were investigated. The test results show that the system with nano-filler of sepiolite B10 has the best fire-resistant property. The process of smoke emission and thermal decomposition, the element composition of char surface and the micro morphology of intumecent char layer of the EVM IFR system with nano-filler were also studied by NBS chamber, thermogravimetric （TG） analysis, X- ray photoelectron spectroscopy （XPS） and scanning electron microscope （SEM）.展开更多
A novel multifunctional macromolecular organolithium initiator （PD-Sn-（RLi）3） was prepared via living anionic polymerization and used for the synthesis of miktoarm star copolymers in cyclohexane. The average molec...A novel multifunctional macromolecular organolithium initiator （PD-Sn-（RLi）3） was prepared via living anionic polymerization and used for the synthesis of miktoarm star copolymers in cyclohexane. The average molecular weight, polydispersity index, microstructure and unit composition of the miktoarm star copolymers were characterized with GPC and 1H-NMR. Performances of the miktoarm star styrene-butadiene rubbers were investigated in comparison with those of the blend rubbers such as the tin-coupled star-shaped random copolymers of styrene-butadiene rubber（S-SBR）/natural rubber （NR） blend rubber and S-SBR/Cis-1, 4-polybutadiene rubber （Cis-BR） blend rubber.展开更多
A ternary hybrid membrane architecture consisting of sulfonated fluorinated multi-block copolymer （SFMC）, sulfonated （poly ether ether ketone） （SPEEK） and I or 5 wt% graphene oxide （GO） was fabricated through ...A ternary hybrid membrane architecture consisting of sulfonated fluorinated multi-block copolymer （SFMC）, sulfonated （poly ether ether ketone） （SPEEK） and I or 5 wt% graphene oxide （GO） was fabricated through a facile solution casting approach. The simple, but effective monomer sulfonation was performed for SFMC to create compact and rigid hydrophobic backbone structures, while conventional random sulfonation was carried-out for SPEEK. Hydrophilic-hydrophobic-hydrophilic structure of SFMC enhances the compatibility with SPEEK and GO and allows for an unprecedented approach to alter me- chanical strength and proton conductivity of ternary hybrid membrane, as verified from universal test machine （UTM） curves and alternating current （AC） impedance plots. The impact of GO integration on the morphology and roughness of hybrid membrane was scrutinized using field emission scanning electron microscope （FE-SEM） and atomic force microscope （AFM）. Ternary hybrid showed uniform intercalation of GO nanosheets throughout the entire surface of membrane with an increased surface roughness of 8.91 nm. The constructed ternary hybrid membrane revealed excellent water absorption, ion exchange capacity and gas barrier properties, while retaining reasonable dimensional stability. The well-optimized ternary hybrid membrane containing 5 wt% GO revealed a maximum proton conductivity of 111.9 mS/cm, which is higher by a factor of two-fold with respect to that of bare SFMC membrane. The maximum PEMFC power density of 528.07mW/cm2 was yielded by ternary hybrid membrane at a load current density of 1321.1 mA/cm2 when operating the cell at 70 ℃ under 100% relative humidity （RH）. In comparison, a maximum power density of only 182.06 mW/cm2 was exhibited by the bare SFMC membrane at a load current density of 455.56 mA/cm2 under same operating conditions.展开更多
The ground-and the excited-state nonlinearities of two new copolymers are investigated in nanosecond scale at 1064 nm.It is found that the excited-state susceptibility is dramatically larger than the corresponding gro...The ground-and the excited-state nonlinearities of two new copolymers are investigated in nanosecond scale at 1064 nm.It is found that the excited-state susceptibility is dramatically larger than the corresponding ground-state susceptibility for each sample.The experimental results also give evidence that superlattice structure of the copolymers can enhance,especially for the excited state,the molecular hyperpolarizabilities significantly.This enhancement may be attributed to the confinement effect of the pump-induced carriers.展开更多
The electronic properties of xPA/nPPP/yPA sandwiched copolymers with a well-barrier-well structure have been studied by using a tight-binding calculation. It was found that the electronic properties of the neutral sta...The electronic properties of xPA/nPPP/yPA sandwiched copolymers with a well-barrier-well structure have been studied by using a tight-binding calculation. It was found that the electronic properties of the neutral states of these sandwiched copolymers are sensitive to the constitutions of PPP and PA monomers and the interface coupling between PA and PPP. It is verified that the quantum tunnelling effect will occur at the lowest conductive state of xPA/nPPP/xPA copolymers.展开更多
文摘The composition and sequence distribution of monomeric units in polyester polyether multiblock copolymer were studied by pyrolysis? gas chromatography (PGC) and pyrolysis gas chromatography/mass spectrometry (PGC/MS). PGC was applied to study the F t curve of the multiblock copolymer and PGC/MS was used to separate and identify the pyrolyzates. DTA experiment was used to study the decomposition temperature. The results show that the beginning point of elastomer’s decomposition was about 300?℃ and the decomposition temperature of most of the sample was 550?℃. Many pyrolyzates were produced because of the breaking of weak bonds in the sample. The possible microstructure was verified and the pyrolysis pathway of the copolymer was investigated.
文摘An attempt was made in the paper aiming at imparting flame retardancy to polymers by plasma grafting technique Based on EVA copolymers with different VA contents the author tried to use the Ar plasma followed by grafting with/without subsequent saponification and metal ion exchange expediting the charring of polymers upon heationg Characterization of the flammability of the plasma treated EVA copolymers grafted with acrylic monomers(MAA,AA and AAm)indicates that this approach turns out to be a promising way and worthy doing whatever in research and/or applications
基金Supported by the Basic Research Program of the State Key Laboratory of Heavy Oil Processing (200310) China University of Petroleum,Beijing,China
文摘Synthesis of a cold flow improver （MAVA-a） for diesel fuel and its effect on solidifying point （SP） and cold filter plugging point （CFPP） of diesel fuels were investigated, The cold flow improver was prepared by using maleic anhydride （MA） and vinyl acetate （VA） as raw materials, toluene as solvent, dibenzoyl peroxide （BPO） as initiator, through alternating polymerization under nitrogen to obtain a binary-polymer and then through aminolysis by using a higher carbon amine as aminating agent at a temperature of 80 ℃. A cold flow improver was designed and prepared for No. 0 diesel fuel from Zhang Jia-Gang Petrochemical Company according to the contents of n-paraffin and its carbon number distribution in the No. 0 diesel fuel. It was also used together with two kinds of ethene-vinyl acetate copolymer improvers （EVA） separately. The test result showed that the CFPP of the No. 0 diesel fuel could be lowered by 3-5 ℃ when the improver MAVA-a was used. The CFPP was lowered by 8℃ when the improver MAVA-a was used together with EVA-2.
基金Project supported by the National Natural Science Foundation of China(Grant Nos.11204215,51302187,20990234,20925414,21204040,and 91227121)the Natural Science Foundation of Tianjin City,China(Grant Nos.12JCYBJC32500 and 14JCZDJC32100)+1 种基金the Program for Changjiang Scholars and Innovative Research Team in University(PCSIRT)(Grant No.IRT1257)the 111 Project.A.C.Shi gratefully acknowledges the supports from the Natural Sciences and Engineering Research Council(NSERC)of Canada
文摘The self-assembly of symmetric diblock copolymers confined in the channels of variously shaped cross sections （regu- lar triangles, squares, and ellipses） is investigated using a simulated annealing technique. In the bulk, the studied symmetric diblock copolymers form a lamellar structure with period LL. The geometry and surface property of the confining channels have a large effect on the self-assembled structures and the orientation of the lamellar structures. Stacked perpendicular lamellae with period LL are observed for neutral surfaces regardless of the channel shape and size, but each lamella is in the shape of the corresponding channel＇s cross section. In the case of triangle-shaped cross sections, stacked parallel lamel- lae are the majority morphologies for weakly selective surfaces, while morphologies including a triangular-prism-shaped B-cylinder and multiple tridentate lamellae are obtained for strongly selective surfaces. In the cases of square-shaped and ellipse-shaped cross sections, concentric lamellae are the signature morphology for strongly selective surfaces, whereas for weakly selective surfaces, stacked parallel lamellae, and several types of folding lamellae are obtained in the case of square-shaped cross sections, and stacked parallel lamellae are the majority morphologies in the case of ellipse-shaped cross sections when the length of the minor axis is commensurate with the bulk lamellar period. The mean-square end- to-end distance, the average contact number between different species and the surface concentration of the A-monomers are computed to elucidate the mechanisms of the formation of the different morphologies. It is found that the resulting morphology is a consequence of competition among the chain stretching, interfacial energy, and surface energy. Our results suggest that the self-assembled morphology and the orientation of lamellae can be manipulated by the shape, the size, and the surface property of the confining channels.
基金supported by the National Natural Science Foundation of China (Grant Nos. 20574052 and 20774066)the Program for New Century Excellent Talents in University, China (Grant No. NCET-05-0538)the Natural Science Foundation of Zhejiang Province, China (Grant Nos. R404047, Y4090174, and Y405553)
文摘The phase behaviours of diblock copolymers under cylindrical confinement are studied in two-dimensional space by using the self-consistent field theory. Several phase parameters are adjusted to investigate the cylindrical-confinement-induced phase behaviours of diblock copolymers. A series of lamella-cylinder mixture phases, such as the mixture of broken-lamellae and cylinders and the mixture of square-lamellae and cylinders, are observed by varying the phase parameters, in which the behaviours of these mixture phases are discussed in the corresponding phase diagrams. Furthermore, the free energies of these mixture phases are investigated to illustrate their evolution processes. Our results are compared with the available observations from the experiments and simulations respectively, and they are in good agreement and provide an insight into the phase behaviours under cylindrical confinement.
基金Project supported by the National Natural Science Foundation of China (Grant No. 20673070)the Natural Science Foundation of Shanxi Province (Grant No. 2007011055)+1 种基金the Natural Science Foundation for Young Scientists of Shanxi Province (Grant No. 2011021008-1)the Soft Science Program of Shanxi Province (Grant No. 2011041015-01)
文摘The phase behaviors in a binary mixture of diblock copolymers confined between two parallel walls are investigated by using a cell dynamics simulation of the time-dependent Ginzburg-Landau theory.The morphological dependence of the wall-block interaction and the distance between walls（confinement degree） has been systematically studied,and the effect of repulsive interactions between different monomers is also discussed.It is interesting that multiple novel morphological transitions are observed by changing these factors,and various multilayered sandwich structures are formed in the mixture.Furthermore,the parametric dependence and physical reasons for the microdomain growth and orientational order transitions are discussed.From the simulation,we find that much richer morphologies can form in a binary mixture of diblock copolymers than those in a pure diblock copolymer.Our results provide an insight into the phase behaviors under parallel wall confinement and may provide guidance for experimentalists.This model system can also give a simple way to realize orientational order transition in soft materials through confinement.
基金supported by the National Key Research and Development Program(2016YFA0202500)National Natural Science Foundation of China(21776019,21808124,51972121)+1 种基金Tip-top Scientific and Technical Innovative Youth Talents of Guangdong Special Support Program(2017TQ04C419)Beijing Natural Science Foundation(L182021)。
文摘Lithium metal batteries are strongly considered as one of the most promising candidates for nextgeneration high-performance battery systems.However,the uncontrollable growth of lithium dendrites and the highly reactive lithium metal result in the severe safety risks and the short lifespan for highenergy-density rechargeable batteries.Here,we demonstrate a hydrophobic and ionically conductive ethylene-vinyl acetate(EVA)copolymer layer can not only endow lithium metal anodes with an air-stable and anti-water surface,but also efficiently suppress the lithium-dendrites growth during the electrochemical cycling process.Therefore,the introduction of the EVA copolymer as a bifunctional protection layer simultaneously improves the anti-water/air performance and electrochemical cycling stability of lithium metal anode.
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Project supported by the National Natural Science Foundation of China(Grant No.21373131)the Provincial Natural Science Foundation of Shanxi,China(Grant No.2015011004)the Research Foundation for Excellent Talents of Shanxi Provincial Department of Human Resources and Social Security,China
文摘We investigated phase transitions in a diblock copolymer–homopolymer hybrid system blended with nanorods(NRs)by using the time-dependent Ginzburg–Landau theory.We systematically studied the effects of the number,length and infiltration properties of the NRs on the self-assembly of the composites and the phase transitions occurring in the material.An analysis of the phase diagram was carried out to obtain the formation conditions of sea island structure nanorodbased aggregate,sea island structure nanorod-based dispersion,lamellar structure nanorod-based multilayer arrangement and nanowire structure.Further analysis of the evolution of the domain sizes and the distribution of the nanorod angle microphase structure was performed.Our simulation provides theoretical guidance for the preparation of ordered nanowire structures and a reference to improve the function of a polymer nanocomposite material.
文摘The new flow improvers for super-viscous crude oils were developed via esterification of polybasic high carbon alcohol with methacrylate and copolymerizafion of monomers followed by amination of copolymers. The structure of the synthesized polymer flow improver additive was confirmed by IR spectroscopy and the crystal structure of the flow improver additives were determined by X-ray diffrac- tion analysis. The structure of wax crystals was also studied at the same time. The results showed that the wax crystal structure was closely related with the crystal structure of the flow improver, which could change the pour point depression and viscosity reduction behavior of the crude oil. When the wax crystal structure matched well with that of the additive, the wax crystals were dispersed satisfactorily, resulting in favorable effects in terms of pour point depression and viscosity reduction. The new synthe- sized aminated polymer flow improver additive was most efficient for treating super-viscous crude oils. The super-viscous crude oil had a high content of resins and asphaltenes, which might aggregate onto the surface of wax crystals to form blocks to limit the crude oil fluidity. However, amination of copolymers having similar structure with the resins and asphaltenes contained in crude oil could dissolve the huge polar groups to make the deposit formation difficult.
基金supported by the Assistant Secretary for Energy Efficiency and Renewable Energy,Vehicle Technologies Office,under the Advanced Battery Materials Research(BMR)Program of the U.S.Department of Energy under Contract No.DE-AC02-05CH11231support by the U.S.Department of Energy under Contract No.106298-001+2 种基金the funding from Polish Ministry of Science and Higher Education No.1670/MOB/V/2017/0funding support of SUSTechthe resources of the National Energy Research Scientific Computing Center(NERSC)that is supported by the Office of Science of the U.S.Department of Energy。
文摘The lithium-sulfur(Li-S)battery is one of the most promising substitutes for current energy storage systems because of its low cost,high theoretical capacity,and high energy density.However,the high solubility of intermediate products(i.e.,lithium polysulfides)and the resultant shuttle effect lead to rapidly fading capacity and a low coulombic efficiency,which hinder the practical application of Li-S batteries.In this study,block copolymers are constructed with both an ethylene oxide unit and a styrene unit and then used as binders for Li-S batteries.Electrochemical performance improvements are attributed to the synergistic effects contributed by the different units of the block copolymer.The ethylene oxide unit traps polysulfide,which bonds strongly with the intermediate lithium polysulfide,and enhances the transport of lithium ions to reach high capacity.Meanwhile,the styrene unit maintains cathode integrity by improving the mechanical properties and elasticity of the constructed block copolymer to accommodate the large volume changes.By enabling multiple functions via different units in the polymer chain,high sulfur utilization is achieved,polysulfide diffusion is confined,and the shuttle effect is suppressed during the cycle life of Li-S batteries,as revealed by operando ultraviolet-visible spectroscopy and S Kedge X-ray absorption spectroscopy.
基金supported by the National Natural Science Foundation of China(Grant Nos.20990234,20925414,and 91227121)the Program for Changjiang Scholars and Innovative Research Team in University,China(Grant No.IRT1257)+1 种基金the Programme of Introducing Talents of Discipline to Universities,Chinaby the Tianhe No.1,China
文摘Block copolymers are a class of soft matter that self-assemble to form ordered morphologies on the scale of nanome- ters, making them ideal materials for various applications. These applications directly depend on the shape and size of the self-assembled morphologies, and hence, a high degree of control over the self-assembly is desired. Grafting block copolymer chains onto a substrate to form copolymer brushes is a versatile method to fabricate functional surfaces. Such surfaces demonstrate a response to their environment, i.e., they change their surface topography in response to different external conditions. Furthermore, such surfaces may possess nanoscale patterns, which are important for some applica- tions; however, such patterns may not form with spun-cast films under the same condition. In this review, we summarize the recent progress of the self-assembly of block copolymers grafted onto a flat substrate. We mainly concentrate on the self-assembled morphologies of end-grafted AB dibloek eopolymers, junction p0int-grafted AB diblock copolymers （i.e., Y-shaped brushes）, and end-grafted ABA triblock copolymers. Special emphasis is placed on theoretical and simulation progress.
基金This research projcct was financed by applied base research fund of jiangsu provicial Scicntific and Tcchniquuc Committee from 1989-1991
文摘In this paper, various kinds of monomers 2-hydroxyethyl methacrylate (HEMA), 2-hydroxyethyl acrylate (HEA), hydroxypropyl methacrylate (HPMA) and methoxy polyethylene glycol methylacrylate (M-23G) were eopolymerized by radiation technique at low temperature (-78℃) and several kinds of copolymer carriers were obtained. Yeast cells were immobilized through adhesion and multiplication of yeast cells themselves on these carriers. The etharol productivity of immobilized yeast cells with these carriers was related to the monomer composition and water content of copolymer carriers and the optimum monomer composition was 20%:10% in poly (HEA-M23G). In this case, the ethanol productivity of immobilized yeast cells was 26 mg /( ml·h), which was 4 times as high as that of free cells. In this study, the effect of adding of crosslinking reagent (4G) in copolymer on activity of yeast cells immobilized with the carriers were also studied. It was found that the effect of adding crosslinking reagent (4G) in lower monomer composition of poly(HEA-M23G) on the ethanol productivity of immobilized cells was better than that in higher one in this work.
基金Project supported by the National Natural Science Foundation of China (Grant Nos.20374050,20934004,21074096,50773072,and 90403022)the Outstanding Youth Fund of China (Grant No.20525416)+3 种基金the National Basic Research Program of China(Grant No.2005CB623800)Program for New Century Excellent Talents in University (Grant No.NCET-05-0538)the Natural Science Foundation of Zhejiang Province (Grant Nos.Y4090174 and Y6100033)the Science Technology Development Plan of Wenzhou City,China (Grant No.H20080041)
文摘The surface-induced effect on the morphologies of lamella-forming diblock copolymers in nanorod arrays is studied by using the self-consistent field theory. In the simulation study, a rich variety of novel morphologies are observed by variations in the strength of the surface field for the diblock copolymers. Different surface-field-induced effects are examined for the diblock copolymers in the arrays with distinct preferential surfaces. It is observed that the majority-block preferential surfaces have more obvious induced effects than those of minority-block preferential surfaces. The strong surface fields exhibit different behaviours from those observed in the weak surface fields, by which the morphologies possess cylindrical symmetries. Results from this research deepen the knowledge of surface-induced effects in a confinement system, which may aid the fabrication of polymer-based na^omaterials.
基金Sponsored by Project in National Key Technology R&D Program(2006BAE03B05-2)
文摘Sepiolite （S9, B10, B20, B40） and boehmite have been added to an intumecent flame retardant （IFR） system to produce the halogen-free and fire-resistant ethylene-vinyl acetate copolymer （EVM） rubber. The rubber contains ammonium polyphosphate （APP） as acid source, double pentaerythritol （D-PER） as carbon source and melamine （MN） as gas source. The effects of nano-filler sepiolite and boehmite on the fire-resistant property of EVM rubber based on IFR system were investigated. The test results show that the system with nano-filler of sepiolite B10 has the best fire-resistant property. The process of smoke emission and thermal decomposition, the element composition of char surface and the micro morphology of intumecent char layer of the EVM IFR system with nano-filler were also studied by NBS chamber, thermogravimetric （TG） analysis, X- ray photoelectron spectroscopy （XPS） and scanning electron microscope （SEM）.
基金Supported by the National Natural Science Foundation of China(50573005)
文摘A novel multifunctional macromolecular organolithium initiator （PD-Sn-（RLi）3） was prepared via living anionic polymerization and used for the synthesis of miktoarm star copolymers in cyclohexane. The average molecular weight, polydispersity index, microstructure and unit composition of the miktoarm star copolymers were characterized with GPC and 1H-NMR. Performances of the miktoarm star styrene-butadiene rubbers were investigated in comparison with those of the blend rubbers such as the tin-coupled star-shaped random copolymers of styrene-butadiene rubber（S-SBR）/natural rubber （NR） blend rubber and S-SBR/Cis-1, 4-polybutadiene rubber （Cis-BR） blend rubber.
基金supported by the Korea Institute of Energy Technology Evaluation and Planning(KETEP)the Ministry of Trade,Industry&Energy(MOTIE)of the Republic of Korea(No.20164030201070)supported by Basic Science Research Program through the National Research Foundation of Korea(NRF)funded by the Ministry of Science,ICT and future Planning(NRF-2017R1A2B4005230)
文摘A ternary hybrid membrane architecture consisting of sulfonated fluorinated multi-block copolymer （SFMC）, sulfonated （poly ether ether ketone） （SPEEK） and I or 5 wt% graphene oxide （GO） was fabricated through a facile solution casting approach. The simple, but effective monomer sulfonation was performed for SFMC to create compact and rigid hydrophobic backbone structures, while conventional random sulfonation was carried-out for SPEEK. Hydrophilic-hydrophobic-hydrophilic structure of SFMC enhances the compatibility with SPEEK and GO and allows for an unprecedented approach to alter me- chanical strength and proton conductivity of ternary hybrid membrane, as verified from universal test machine （UTM） curves and alternating current （AC） impedance plots. The impact of GO integration on the morphology and roughness of hybrid membrane was scrutinized using field emission scanning electron microscope （FE-SEM） and atomic force microscope （AFM）. Ternary hybrid showed uniform intercalation of GO nanosheets throughout the entire surface of membrane with an increased surface roughness of 8.91 nm. The constructed ternary hybrid membrane revealed excellent water absorption, ion exchange capacity and gas barrier properties, while retaining reasonable dimensional stability. The well-optimized ternary hybrid membrane containing 5 wt% GO revealed a maximum proton conductivity of 111.9 mS/cm, which is higher by a factor of two-fold with respect to that of bare SFMC membrane. The maximum PEMFC power density of 528.07mW/cm2 was yielded by ternary hybrid membrane at a load current density of 1321.1 mA/cm2 when operating the cell at 70 ℃ under 100% relative humidity （RH）. In comparison, a maximum power density of only 182.06 mW/cm2 was exhibited by the bare SFMC membrane at a load current density of 455.56 mA/cm2 under same operating conditions.
基金Supported by the National Natural Science Foundation of China under Grant No.19734004。
文摘The ground-and the excited-state nonlinearities of two new copolymers are investigated in nanosecond scale at 1064 nm.It is found that the excited-state susceptibility is dramatically larger than the corresponding ground-state susceptibility for each sample.The experimental results also give evidence that superlattice structure of the copolymers can enhance,especially for the excited state,the molecular hyperpolarizabilities significantly.This enhancement may be attributed to the confinement effect of the pump-induced carriers.
基金Supported by the National Natural Science Foundation of China under Grant Nos.10074040 and 59871024.
文摘The electronic properties of xPA/nPPP/yPA sandwiched copolymers with a well-barrier-well structure have been studied by using a tight-binding calculation. It was found that the electronic properties of the neutral states of these sandwiched copolymers are sensitive to the constitutions of PPP and PA monomers and the interface coupling between PA and PPP. It is verified that the quantum tunnelling effect will occur at the lowest conductive state of xPA/nPPP/xPA copolymers.
