In this paper,the polymer chain of rotator(PCOR) equation of state(EOS) was used together with an EOS/G^E mixing rule(MHV1) and the Wilson's equation as an excess-Gibbs-energy model in the proposed approach to ext...In this paper,the polymer chain of rotator(PCOR) equation of state(EOS) was used together with an EOS/G^E mixing rule(MHV1) and the Wilson's equation as an excess-Gibbs-energy model in the proposed approach to extend the capability and improve the accuracy of the PCOR EOS for predicting the Henry's constant of solutions containing polymers.The results of the proposed method compared with two equation of state(van der Waals and GC-Flory) and three activity coefficient models(UNIFAC,UNIFAC-FV and Entropic-FV) indicated that the PCOR EOS/Wilson's equation provided more accurate results.The interaction parameters of Wilson's equation were fitted with Henry's constant experimental data and the property parameters of PCOR,a and b,were fitted with experimental volume data(Tait equation).As a result,the present work provided a simple and useful model for prediction of Henry's constant for polymer solutions.展开更多
The present paper describes experiments aimed at delineating significant chemical characteristics of electrochemical reactions in polymeric solutions, including how rigid solvent environments affect mass transport rat...The present paper describes experiments aimed at delineating significant chemical characteristics of electrochemical reactions in polymeric solutions, including how rigid solvent environments affect mass transport rates, and also discusses the possibility that the microelectrode coated with poly(ethylene oxide)(PEO) film can be used as gas sensor.展开更多
Poly（bisphenol A carbonate） （BPA-PC） was post-polymerized by solid-state polymerization （SSP） after supercritical CO2-induced crystallization in low molecular weight particles prepolymerized via melt transesteri...Poly（bisphenol A carbonate） （BPA-PC） was post-polymerized by solid-state polymerization （SSP） after supercritical CO2-induced crystallization in low molecular weight particles prepolymerized via melt transesterification reaction. The effects of the crystallization conditions on melting behavior and SSP of BPA-PC were investigated with differential scanning calorimetry （DSC）, Ubbelohde viscosity method and gel permeation chromatography （GPC）. The reaction kinetics of the SSP of crystallized prepolymers was studied as a function of reaction temperatures for various reaction periods. As a result, the viscosity average molecular weight of BPA-PC particles （2 mm） increased from 1.9 × 10^4 g/mol to 2.8 × 10^4 g/mol after SSP. More importantly, the significantly enhanced thermal stability and mechanical properties of solid-state polymerized BPA-PC, compared with those of melt transesterification polymerized BPA-PC with the same molecular weight, can be ascribed to the substantial avoidance of undergoing high temperature during polymerization. Our work provides a useful method to obtain practical product of BPA-PC with high quality and high molecular weight.展开更多
A facile one-pot synthesis of solid polymer electrolytes(SPEs), composed of carbonate terminated poly(ethylene glycol)(CH3O-PEG-IC), poly(ethylene glycol)-block-polystyrene(PEG-b-PS) block copolymer nanoparticles cont...A facile one-pot synthesis of solid polymer electrolytes(SPEs), composed of carbonate terminated poly(ethylene glycol)(CH3O-PEG-IC), poly(ethylene glycol)-block-polystyrene(PEG-b-PS) block copolymer nanoparticles containing a conductive PEG corona, fumed SiO2 and Li TFSI salt via polymerization-induced self-assembly is proposed. This method to prepare SPEs has the advantages of one-pot convenient synthesis, avoiding use of organic solvent and conveniently adding inorganic additives. CH3O-PEG-IC combines advantages of PEG and polycarbonate, the in situ synthesized PEG-b-PS nanoparticles containing a rigid polystyrene(PS) core and a PEG corona guarantee continuous lithium ion transport in the synthesized SPEs, and the fumed SiO2 optimizes the interfacial properties and improves the electrochemical stability, all of which afford SPEs a well considerable room temperature ionic conductivity of 1.73 × 10^-4S/cm, high lithium transference number of 0.53, and wide electrochemical stability window of 5.5 V(vs. Li^+/Li). By employing these SPEs, the assembled solid state cells of Li FePO4 |SPEs|Li exhibit considerable cell performance.展开更多
In this work the statistical mechanical equation of state was developed for volumetric properties of crystalline and amorphous polymer blends.The Ihm-Song-Mason equations of state(ISMEOS) based on temperature and dens...In this work the statistical mechanical equation of state was developed for volumetric properties of crystalline and amorphous polymer blends.The Ihm-Song-Mason equations of state(ISMEOS) based on temperature and density at melting point(T_m and ρ_m) as scaling constants were developed for crystalline polymers such as poly(propylene glycol) + poly(ethylene glycol)-200(PPG + PEG-200),poly(ethylene glycol) methyl ether-300(PEGME-350) + PEG-200 and PEGME-350 + PEG-600.Furthermore,for amorphous polymer blends containing poly(2,6-dimethyl-1,4-phenylene oxide)(PPO) + polystyrene(PS) and PS + poly(vinylmethylether)(PVME),the density and surface tension at glass transition(ρ_g and γ_g) were used for estimation of second Virial coefficient.The calculation of second Virial coefficients(B_2),effective van der Waals co-volume(b) and correction factor(α) was required for judgment about applicability of this model.The obtained results by ISMEOS for crystalline and amorphous polymer blends were in good agreement with the experimental data with absolute average deviations of 0.84%and 1.04%,respectively.展开更多
INTRODUCTION The conformational state transition of polymer chains relates to crystallization processes, migration ofthe chains in solution, fluctuation of the end-to-end distance of random coils, and the relaxation a...INTRODUCTION The conformational state transition of polymer chains relates to crystallization processes, migration ofthe chains in solution, fluctuation of the end-to-end distance of random coils, and the relaxation and phasetransitions of polymers. A description of the conformational state transition requires questions about; 1) howmany stable conformational states for a specific σ bond; 2) the barriers between the states; 3) the mechanismof the conformational transition; 4) any cooperative behavior during the transition. Flory and his coworkers展开更多
Solvation structures fundamentally control the ion-transport dynamics and mechanical properties of polymer electrolytes.However,there is a lack of strategies to rationally regulate the solvation structures and fundame...Solvation structures fundamentally control the ion-transport dynamics and mechanical properties of polymer electrolytes.However,there is a lack of strategies to rationally regulate the solvation structures and fundamental understanding on how they control the electrochemical performances.Herein,by harnessing the electrostatic adsorption of one-dimensional nanofiller(i.e.,surface-charged halloysite nanotubes,d-HNTs),we successfully fabricate a high-performance polymer nanocomposite electrolyte enabled by strong surface adsorption,referred as adsorption-state polymer electrolyte(ASPE).This ASPE shows fast ion transport(0.71±0.05 mS cm^(-1)at room temperature),high mechanical strength and toughness(10.3±0.05 MPa;15.73 MJ m^(-3)),improved lithium-ion transference number,and long cycle life with lithium metal anode,in comparison with the sample without the d-HNT adsorption effect.To fundamentally understand these high performances,an anion-rich asymmetric solvent structure model is further proposed and evidenced by both experiments and simulation studies.Results show that the electrostatic adsorption among the d-HNT,ionic liquid electrolyte,and polymer chain generates a nano filler-supported fast ion-conduction pathway with asymmetric Li+-coordination microenvironment.Meanwhile,the anion-rich asymmetric solvent structure model of ASPE also generates a fast de-solvation and anion-derived stable solid-electrolyte interphase for lithium metal anode.The high performance and understanding of the mechanism for ASPE provide a promising path to develop advanced polymer electrolytes.展开更多
Dihexylfluorene and N-butylcarbazole were copolymerized by solid-state oxidative coupling polymerization in the presence of anhydrous FeCl3 at room temperature. The solid-state films of the copolymers emitted blue lig...Dihexylfluorene and N-butylcarbazole were copolymerized by solid-state oxidative coupling polymerization in the presence of anhydrous FeCl3 at room temperature. The solid-state films of the copolymers emitted blue light after beating at 150 ℃ in air for 24 h, no red-shifted emission was observed by fluorescence spectroscopy.展开更多
In order to investigate the partition of initiators for quasi-static precipitation polymerization of acrylamide （AAm） and methacrylic acid （MAc） in ethanol, azo-initiators were employed with various functional gro...In order to investigate the partition of initiators for quasi-static precipitation polymerization of acrylamide （AAm） and methacrylic acid （MAc） in ethanol, azo-initiators were employed with various functional groups such as --COOCH3 （V- 601, dimethyl 2,2＇-azobis（isobutyrate））, --CN （V-65, 2,2＇-Azobis（2,4-diemthylvaleronitrile））, --COOH （V-501, 4,4＇-azobis（4-cyanovaleric acid）） and --NH-（VA-061, 2,2＇-azobis[2-（2-imidazolin-2-yl）propane]）, respectively. Particle size, induction time and kinetics of polymerization were investigated by the scanning electron microscopy （SEM） and gravimetry. It was observed that the polymerization parameters, such as the particle size, induction time and polymerization rate, were considerably affected by the functional groups of initiators. Besides, the monomer concentration also played important roles in the particle formation. By using V-601, the polymerization rate was strongly correlated with the total surface area of particles and the concentration of initiators. However, by using V-50 l, the polymerization rate was strongly related to WoQo, where W0 is the initial concentration of monomers and Ci,0, the initial concentration of initiators. The results indicated that the different functional groups determined the different partition types of initiators between the minimonomer droplets and the continuous phase due to the molecular interactions of initiator and monomers. V-601 was all partitioned in the continuous phase, but a part of V-65 was partitioned in the minimonomer droplets. Besides the V-501 dissolved in the continuous phase, a part of V-501 was adsorbed on the surface of minimonomer droplets. VA-061 destroyed the stability of minimonomer droplets by the formation of zwitterions with MAA.展开更多
Solid-state nuclear magnetic resonance spectroscopy was used to investigate the coordinative states of surface Al species on various alkylaluminum-modified Phillips CrOx/SiO2 catalysts.The alkylaluminum-modified Phill...Solid-state nuclear magnetic resonance spectroscopy was used to investigate the coordinative states of surface Al species on various alkylaluminum-modified Phillips CrOx/SiO2 catalysts.The alkylaluminum-modified Phillips CrOx/SiO2 catalysts were examined via ethylene homopolymerization.1H and 27Al magic angle spinning（MAS） nuclear magnetic resonance（NMR） spectra clearly demonstrated that the existing states of surface Al species in alkylaluminum-modified catalysts strongly depended on the type of alkylaluminum cocatalyst,concentration of alkylaluminum and the calcination temperature.1H MAS NMR spectra of alkylaluminum-modified Phillips CrOx/SiO2 catalysts,calcined at two different temperatures,exhibited similar trends in peak shift.1H spectra showed that with an increase of Al/Cr ratio and calcination temperature,the main peak shifted to high field,indicating that the dominant surface proton species changed from hydroxyl to ethoxyl and ethyl groups.27Al MAS NMR spectra showed the presence of three different coordination states（6-,5-,and 4-coordinated Al species） in the alkylaluminummodified Phillips catalysts.In comparison of different alkylaluminum cocatalysts,it was found that the reactivity of alkylaluminum modified Phillips catalyst decreased in the order of TEA〉DEAH〉DEAE.The amount of 4-coordinated Al species of Phillips catalysts modified by TEA,DEAE and DEAH also decreased in the order of TEA〉DEAH〉DEAE,indicating that the presence of 4-coordinated Al species is related to the polymerization activity.展开更多
During investigating what causes the low yield of the polymerization product of 1,4-bis(quinolyl)-1,3-butadiyne(DQ), we found that the DQ crystals formed on the surface of PDQ cauld be polymerized to give blue cryst...During investigating what causes the low yield of the polymerization product of 1,4-bis(quinolyl)-1,3-butadiyne(DQ), we found that the DQ crystals formed on the surface of PDQ cauld be polymerized to give blue crystals, in which DQ could be sublimated and crystallized on the surface of PDQ film. According to the experimental results, the reason why the DQ crystals can be polymerized is that the sublimation of DQ changes the molecular orientation of DQ in the crystal. The crystals formed in epitaxial growth on the surface of DQ or PDQ during sublimation of DQ are suitable for 1,4-addition polymerization.展开更多
A mathematical model has been developed to handle the reactions in Poly(ethylene terephthalate) (PET) undergoing polycondensation reactions in the solid state. The effect of temperature on chain mobility was considere...A mathematical model has been developed to handle the reactions in Poly(ethylene terephthalate) (PET) undergoing polycondensation reactions in the solid state. The effect of temperature on chain mobility was considered to estimate the rate constants of chemical reactions. The polymer crystalline fraction is modeled as containing only repeat units, thus concentrating end groups and conden-sates in the amorphous fraction. This model is compared with PET reaction data with good results.展开更多
We developed a transient model for actin-based motility.Diffusion of actin monomers was included in the formulation and its influence on the speed of actin-driven cargos was examined in detail.Our results clearly demo...We developed a transient model for actin-based motility.Diffusion of actin monomers was included in the formulation and its influence on the speed of actin-driven cargos was examined in detail.Our results clearly demonstrated how actin polymerization accelerates cargos that are initially stationary,as well as how steady-state is eventually reached.We also found that,due to polymerization and diffusion,actin monomer concentration near the load surface can be significantly lower than that in the rest of the comet tail,suggesting that many previous models may not be very accurate.展开更多
Solid-state polymer sodium–metal batteries(SPSMBs)are considered an essential solution to the safety issues and low energy density of conventional liquid electrolyte sodium-ion batteries.The unstable cathode electrol...Solid-state polymer sodium–metal batteries(SPSMBs)are considered an essential solution to the safety issues and low energy density of conventional liquid electrolyte sodium-ion batteries.The unstable cathode electrolyte interface(CEI)caused by the volume expansion of the cathode hinders the construction of high-energy and long-life SPSMBs.Herein,a quasi-zero-strain layered Nb_(4)P_(2)S_(21) cathode and a localized high-concentration solid-state polymer electrolyte(LHC-SPE)are designed to address the interfacial issues in SPSMBs.The fabricated Na|SPE|Nb_(4)P_(2)S_(21) SPSMBs present a high capacity(315 mA h g^(−1) at 0.5C),high-rate performance(167 mA h g^(−1) at 10C),and good cycling performance(294 mA h g^(−1) at 1C after 150 cycles).Moreover,a high energy density of 500 W h kg^(−1) and a high power density of 2.7 kW kg^(−1) can be achieved,which are superior to the electrochemical performance of the Nb_(4)P_(2)S_(21) cathode in a liquid electrolyte(LE).Further cyclic voltammetry(CV)and in situ Raman characterization studies reveal a dual-redox mechanism based on Nb_(4+)/Nb^(3+)and S^(−)/S^(2−),and in situ XRD manifests quasi-zero-strain sodium insertion behavior.Moreover,a NaF-rich CEI is revealed from the X-ray photoelectron spectroscopy(XPS)results of the cycled electrode.This study has significant implications for the development of SPSMBs with high energy and a long cycling life.展开更多
基金financial support provided by Islamic Azad University of Mahshahr Branch,Iran
文摘In this paper,the polymer chain of rotator(PCOR) equation of state(EOS) was used together with an EOS/G^E mixing rule(MHV1) and the Wilson's equation as an excess-Gibbs-energy model in the proposed approach to extend the capability and improve the accuracy of the PCOR EOS for predicting the Henry's constant of solutions containing polymers.The results of the proposed method compared with two equation of state(van der Waals and GC-Flory) and three activity coefficient models(UNIFAC,UNIFAC-FV and Entropic-FV) indicated that the PCOR EOS/Wilson's equation provided more accurate results.The interaction parameters of Wilson's equation were fitted with Henry's constant experimental data and the property parameters of PCOR,a and b,were fitted with experimental volume data(Tait equation).As a result,the present work provided a simple and useful model for prediction of Henry's constant for polymer solutions.
文摘The present paper describes experiments aimed at delineating significant chemical characteristics of electrochemical reactions in polymeric solutions, including how rigid solvent environments affect mass transport rates, and also discusses the possibility that the microelectrode coated with poly(ethylene oxide)(PEO) film can be used as gas sensor.
基金financially supported by the National Natural Science Foundation of China(No.51173112)
文摘Poly（bisphenol A carbonate） （BPA-PC） was post-polymerized by solid-state polymerization （SSP） after supercritical CO2-induced crystallization in low molecular weight particles prepolymerized via melt transesterification reaction. The effects of the crystallization conditions on melting behavior and SSP of BPA-PC were investigated with differential scanning calorimetry （DSC）, Ubbelohde viscosity method and gel permeation chromatography （GPC）. The reaction kinetics of the SSP of crystallized prepolymers was studied as a function of reaction temperatures for various reaction periods. As a result, the viscosity average molecular weight of BPA-PC particles （2 mm） increased from 1.9 × 10^4 g/mol to 2.8 × 10^4 g/mol after SSP. More importantly, the significantly enhanced thermal stability and mechanical properties of solid-state polymerized BPA-PC, compared with those of melt transesterification polymerized BPA-PC with the same molecular weight, can be ascribed to the substantial avoidance of undergoing high temperature during polymerization. Our work provides a useful method to obtain practical product of BPA-PC with high quality and high molecular weight.
基金supported by the National Science Foundation for Distinguished Young Scholars (No. 21525419)the National Natural Science Foundation of China (No. 21474054)the National Key Research and Development Program of China (No. 2016YFA0202503)
文摘A facile one-pot synthesis of solid polymer electrolytes(SPEs), composed of carbonate terminated poly(ethylene glycol)(CH3O-PEG-IC), poly(ethylene glycol)-block-polystyrene(PEG-b-PS) block copolymer nanoparticles containing a conductive PEG corona, fumed SiO2 and Li TFSI salt via polymerization-induced self-assembly is proposed. This method to prepare SPEs has the advantages of one-pot convenient synthesis, avoiding use of organic solvent and conveniently adding inorganic additives. CH3O-PEG-IC combines advantages of PEG and polycarbonate, the in situ synthesized PEG-b-PS nanoparticles containing a rigid polystyrene(PS) core and a PEG corona guarantee continuous lithium ion transport in the synthesized SPEs, and the fumed SiO2 optimizes the interfacial properties and improves the electrochemical stability, all of which afford SPEs a well considerable room temperature ionic conductivity of 1.73 × 10^-4S/cm, high lithium transference number of 0.53, and wide electrochemical stability window of 5.5 V(vs. Li^+/Li). By employing these SPEs, the assembled solid state cells of Li FePO4 |SPEs|Li exhibit considerable cell performance.
文摘In this work the statistical mechanical equation of state was developed for volumetric properties of crystalline and amorphous polymer blends.The Ihm-Song-Mason equations of state(ISMEOS) based on temperature and density at melting point(T_m and ρ_m) as scaling constants were developed for crystalline polymers such as poly(propylene glycol) + poly(ethylene glycol)-200(PPG + PEG-200),poly(ethylene glycol) methyl ether-300(PEGME-350) + PEG-200 and PEGME-350 + PEG-600.Furthermore,for amorphous polymer blends containing poly(2,6-dimethyl-1,4-phenylene oxide)(PPO) + polystyrene(PS) and PS + poly(vinylmethylether)(PVME),the density and surface tension at glass transition(ρ_g and γ_g) were used for estimation of second Virial coefficient.The calculation of second Virial coefficients(B_2),effective van der Waals co-volume(b) and correction factor(α) was required for judgment about applicability of this model.The obtained results by ISMEOS for crystalline and amorphous polymer blends were in good agreement with the experimental data with absolute average deviations of 0.84%and 1.04%,respectively.
文摘INTRODUCTION The conformational state transition of polymer chains relates to crystallization processes, migration ofthe chains in solution, fluctuation of the end-to-end distance of random coils, and the relaxation and phasetransitions of polymers. A description of the conformational state transition requires questions about; 1) howmany stable conformational states for a specific σ bond; 2) the barriers between the states; 3) the mechanismof the conformational transition; 4) any cooperative behavior during the transition. Flory and his coworkers
基金financial support from the National Natural Science Foundation of China(52203123)the Sichuan Science and Technology Program(2023NSFSC0991)+2 种基金the State Key Laboratory of Polymer Materials Engineering(sklpme 2023-1-05 and sklpme 2024-2-04)the Fundamental Research Funds for the Central Universitiespartially sponsored by the Double First-Class Construction Funds of Sichuan University。
文摘Solvation structures fundamentally control the ion-transport dynamics and mechanical properties of polymer electrolytes.However,there is a lack of strategies to rationally regulate the solvation structures and fundamental understanding on how they control the electrochemical performances.Herein,by harnessing the electrostatic adsorption of one-dimensional nanofiller(i.e.,surface-charged halloysite nanotubes,d-HNTs),we successfully fabricate a high-performance polymer nanocomposite electrolyte enabled by strong surface adsorption,referred as adsorption-state polymer electrolyte(ASPE).This ASPE shows fast ion transport(0.71±0.05 mS cm^(-1)at room temperature),high mechanical strength and toughness(10.3±0.05 MPa;15.73 MJ m^(-3)),improved lithium-ion transference number,and long cycle life with lithium metal anode,in comparison with the sample without the d-HNT adsorption effect.To fundamentally understand these high performances,an anion-rich asymmetric solvent structure model is further proposed and evidenced by both experiments and simulation studies.Results show that the electrostatic adsorption among the d-HNT,ionic liquid electrolyte,and polymer chain generates a nano filler-supported fast ion-conduction pathway with asymmetric Li+-coordination microenvironment.Meanwhile,the anion-rich asymmetric solvent structure model of ASPE also generates a fast de-solvation and anion-derived stable solid-electrolyte interphase for lithium metal anode.The high performance and understanding of the mechanism for ASPE provide a promising path to develop advanced polymer electrolytes.
文摘Dihexylfluorene and N-butylcarbazole were copolymerized by solid-state oxidative coupling polymerization in the presence of anhydrous FeCl3 at room temperature. The solid-state films of the copolymers emitted blue light after beating at 150 ℃ in air for 24 h, no red-shifted emission was observed by fluorescence spectroscopy.
基金financially supported by the National Natural Science Foundation of China(No.51073035)
文摘In order to investigate the partition of initiators for quasi-static precipitation polymerization of acrylamide （AAm） and methacrylic acid （MAc） in ethanol, azo-initiators were employed with various functional groups such as --COOCH3 （V- 601, dimethyl 2,2＇-azobis（isobutyrate））, --CN （V-65, 2,2＇-Azobis（2,4-diemthylvaleronitrile））, --COOH （V-501, 4,4＇-azobis（4-cyanovaleric acid）） and --NH-（VA-061, 2,2＇-azobis[2-（2-imidazolin-2-yl）propane]）, respectively. Particle size, induction time and kinetics of polymerization were investigated by the scanning electron microscopy （SEM） and gravimetry. It was observed that the polymerization parameters, such as the particle size, induction time and polymerization rate, were considerably affected by the functional groups of initiators. Besides, the monomer concentration also played important roles in the particle formation. By using V-601, the polymerization rate was strongly correlated with the total surface area of particles and the concentration of initiators. However, by using V-50 l, the polymerization rate was strongly related to WoQo, where W0 is the initial concentration of monomers and Ci,0, the initial concentration of initiators. The results indicated that the different functional groups determined the different partition types of initiators between the minimonomer droplets and the continuous phase due to the molecular interactions of initiator and monomers. V-601 was all partitioned in the continuous phase, but a part of V-65 was partitioned in the minimonomer droplets. Besides the V-501 dissolved in the continuous phase, a part of V-501 was adsorbed on the surface of minimonomer droplets. VA-061 destroyed the stability of minimonomer droplets by the formation of zwitterions with MAA.
基金project sponsored by the Fundamental Research Funds for the Central Universities (No. 13CX05011A and R1304013A)
文摘Solid-state nuclear magnetic resonance spectroscopy was used to investigate the coordinative states of surface Al species on various alkylaluminum-modified Phillips CrOx/SiO2 catalysts.The alkylaluminum-modified Phillips CrOx/SiO2 catalysts were examined via ethylene homopolymerization.1H and 27Al magic angle spinning（MAS） nuclear magnetic resonance（NMR） spectra clearly demonstrated that the existing states of surface Al species in alkylaluminum-modified catalysts strongly depended on the type of alkylaluminum cocatalyst,concentration of alkylaluminum and the calcination temperature.1H MAS NMR spectra of alkylaluminum-modified Phillips CrOx/SiO2 catalysts,calcined at two different temperatures,exhibited similar trends in peak shift.1H spectra showed that with an increase of Al/Cr ratio and calcination temperature,the main peak shifted to high field,indicating that the dominant surface proton species changed from hydroxyl to ethoxyl and ethyl groups.27Al MAS NMR spectra showed the presence of three different coordination states（6-,5-,and 4-coordinated Al species） in the alkylaluminummodified Phillips catalysts.In comparison of different alkylaluminum cocatalysts,it was found that the reactivity of alkylaluminum modified Phillips catalyst decreased in the order of TEA〉DEAH〉DEAE.The amount of 4-coordinated Al species of Phillips catalysts modified by TEA,DEAE and DEAH also decreased in the order of TEA〉DEAH〉DEAE,indicating that the presence of 4-coordinated Al species is related to the polymerization activity.
基金Supported by Core Research for Evolutional Science and Technology(CREST),Japan Science and Technology Corpo-ration(JST)
文摘During investigating what causes the low yield of the polymerization product of 1,4-bis(quinolyl)-1,3-butadiyne(DQ), we found that the DQ crystals formed on the surface of PDQ cauld be polymerized to give blue crystals, in which DQ could be sublimated and crystallized on the surface of PDQ film. According to the experimental results, the reason why the DQ crystals can be polymerized is that the sublimation of DQ changes the molecular orientation of DQ in the crystal. The crystals formed in epitaxial growth on the surface of DQ or PDQ during sublimation of DQ are suitable for 1,4-addition polymerization.
文摘A mathematical model has been developed to handle the reactions in Poly(ethylene terephthalate) (PET) undergoing polycondensation reactions in the solid state. The effect of temperature on chain mobility was considered to estimate the rate constants of chemical reactions. The polymer crystalline fraction is modeled as containing only repeat units, thus concentrating end groups and conden-sates in the amorphous fraction. This model is compared with PET reaction data with good results.
基金supported by the National Natural Science Foundation of China(Grant Nos.A020307 and 11072094)the program for New Century Excellent Talents in University(NCET-10-0445)
文摘We developed a transient model for actin-based motility.Diffusion of actin monomers was included in the formulation and its influence on the speed of actin-driven cargos was examined in detail.Our results clearly demonstrated how actin polymerization accelerates cargos that are initially stationary,as well as how steady-state is eventually reached.We also found that,due to polymerization and diffusion,actin monomer concentration near the load surface can be significantly lower than that in the rest of the comet tail,suggesting that many previous models may not be very accurate.
基金supported by the Natural Science Foundation of Jiangxi Province(GJJ211320,20224BAB204002)the Jingdezhen Science and Technology Bureau(20212GYZD009-15)+3 种基金the National Key Research and Development Program of China(Grant No.2019YFA0210600)the Science and Technology Commission of Shanghai Municipality(23DZ1200800,22ZR1471300)the National Natural Science Foundation of China(Grant No.51922103 and 51972326)support from the Analytical Instrumentation Center(#SPST-AIC10112914),SPST,ShanghaiTech.
文摘Solid-state polymer sodium–metal batteries(SPSMBs)are considered an essential solution to the safety issues and low energy density of conventional liquid electrolyte sodium-ion batteries.The unstable cathode electrolyte interface(CEI)caused by the volume expansion of the cathode hinders the construction of high-energy and long-life SPSMBs.Herein,a quasi-zero-strain layered Nb_(4)P_(2)S_(21) cathode and a localized high-concentration solid-state polymer electrolyte(LHC-SPE)are designed to address the interfacial issues in SPSMBs.The fabricated Na|SPE|Nb_(4)P_(2)S_(21) SPSMBs present a high capacity(315 mA h g^(−1) at 0.5C),high-rate performance(167 mA h g^(−1) at 10C),and good cycling performance(294 mA h g^(−1) at 1C after 150 cycles).Moreover,a high energy density of 500 W h kg^(−1) and a high power density of 2.7 kW kg^(−1) can be achieved,which are superior to the electrochemical performance of the Nb_(4)P_(2)S_(21) cathode in a liquid electrolyte(LE).Further cyclic voltammetry(CV)and in situ Raman characterization studies reveal a dual-redox mechanism based on Nb_(4+)/Nb^(3+)and S^(−)/S^(2−),and in situ XRD manifests quasi-zero-strain sodium insertion behavior.Moreover,a NaF-rich CEI is revealed from the X-ray photoelectron spectroscopy(XPS)results of the cycled electrode.This study has significant implications for the development of SPSMBs with high energy and a long cycling life.
