The morphology and properties of HDPE blends with Zn-SEPDM and GR were studied through SEM and mechanical property test. The results show that as Zn-SEPDM/GR content amounts to 20%, the blend becomes an IPN in structu...The morphology and properties of HDPE blends with Zn-SEPDM and GR were studied through SEM and mechanical property test. The results show that as Zn-SEPDM/GR content amounts to 20%, the blend becomes an IPN in structure, and that a rather high impact and tensile strength of HDPE may be obtained after blending. The antistatic effect, the softening point,and HDT of the blend are higher as compared to HDPE/Zn-SEPDM/ZnSt (zinc stearate).The effect of Zn-SEPDM on the compatibility the morphology and properties of IPP blends were studied by DSC, TEM and mechanical properties test. The results show that as Zn-SEPDM content exceeds 20%. Zn-SEPDM in the blend becomes continuous and an abrupt change in impact strength is incurred there from. Owing to the incorporation of ionic groups into EPDM.the strong interactions betWeen the chains make both the impact and the tensile strength of IPP remarkably higher展开更多
Serratia marcescens strain 9986 is a producer of prodigiosin used as a dye of polyolefines (polyethylene, ultratene). The biosynthesis of pigment was closely connected with controlled growth parameters. A prodigiosin ...Serratia marcescens strain 9986 is a producer of prodigiosin used as a dye of polyolefines (polyethylene, ultratene). The biosynthesis of pigment was closely connected with controlled growth parameters. A prodigiosin yield 0.2 - 0.4 mg per l of culture medium in the batch culture under aerobic conditions was obtained. Prodigiosin was extracted from crude biomass treated by 0.1% of sodium dodecyl sulfate (SDS). This novel elaborated stage is necessary for thermostability a dye in polymer. The consumption of prodigiosin preparation is more economical in the technology of the coloration of polyolefines. The elaborated method has been manufactured for dyeing polyethylene by biological pigment-articles of the common use corresponding to the technological standard.展开更多
The inert carbon–carbon(C–C) bonds cleavage is a main bottleneck in the chemical upcycling of recalcitrant polyolefin plastics waste. Here we develop an efficient strategy to catalyze the complete cleavage of C–C b...The inert carbon–carbon(C–C) bonds cleavage is a main bottleneck in the chemical upcycling of recalcitrant polyolefin plastics waste. Here we develop an efficient strategy to catalyze the complete cleavage of C–C bonds in mixed polyolefin plastics over non-noble metal catalysts under mild conditions. The nickelbased catalyst involving Ni_(2)Al_(3) phase enables the direct transformation of mixed polyolefin plastics into natural gas, and the gas carbon yield reaches up to 89.6%. Reaction pathway investigation reveals that natural gas comes from the stepwise catalytic cleavage of C–C bonds in polypropylene, and the catalyst prefers catalytic cleavage of terminal C–C bond in the side-chain with the low energy barrier.Additionally, our developed approach is evaluated by the technical economic analysis for an economically competitive production process.展开更多
Boosting of rechargeable lithium metal batteries(LMBs) holds challenges because of lithium dendrites germination and high-reactive surface feature.Separators may experience structure-determined chemical deterioration ...Boosting of rechargeable lithium metal batteries(LMBs) holds challenges because of lithium dendrites germination and high-reactive surface feature.Separators may experience structure-determined chemical deterioration and worsen Li plating-stripping behaviors when smoothly shifting from lithium-ion batteries(LIBs) to LMBs.This study precisely regulations the crystal structure of β-polypropylene and separator porous construction to investigate the intrinsic porous structure and mechanical properties determined electrochemical performances and cycling durability of LMBs.Crystal structure characterizations,porous structure analyses,and electrochemical cycling tests uncover appropriate annealing thermal stimulation concentrates β-lamellae thickness and enhances lamellae thermal stability by rearranging molecular chain in inferior β-lamellae,maximally homogenizing biaxial tensile deformation and resultant porous constructions.These even pores with high connectivity lower ion migration barriers,alleviate heterogeneous Li^(+) flux dispersion,stabilize reversible Li plating-stripping behaviors,and hinder coursing and branching of Li dendrites,endowing steady cell cycling durability,especially at higher currents due to the highlighted uncontrollable cumulation of dead Li,which offers new insights for the current pursuit of high-power density battery and fast charging technology.The suggested separator structure-chemical nature functions in ensuring cyclic cell stability and builds reliable relationships between separator structure design and practical LMBs applications.展开更多
Development of practical lithium(Li)metal batteries(LMBs)remains challenging despite promises of Li metal anodes(LMAs),owing to Li dendrite formation and highly reactive surface nature.Polyolefin separators used in LM...Development of practical lithium(Li)metal batteries(LMBs)remains challenging despite promises of Li metal anodes(LMAs),owing to Li dendrite formation and highly reactive surface nature.Polyolefin separators used in LMBs may undergo severe mechanical and chemical deterioration when contacting with LMAs.To identify the best polyolefin separator for LMBs,this study investigated the separator-deterministic cycling stability of LMBs under practical conditions,and redefined the key influencing factors,including pore structure,mechanical stability,and chemical affinity,using 12 different commercial separators,including polyethylene(PE),polypropylene(PP),and coated separators.At extreme compression triggered by LMA swelling,isotropic stress release by balancing the machine direction and transverse direction tensile strengths was found to be crucial for mitigating cell short-circuiting.Instead of PP separators,a PE separator that possesses a high elastic modulus and a highly connected pore structure can uniformly regulate LMA swelling.The ceramic coating reinforced short-circuiting resistance,while the cycling efficiency degraded rapidly owing to the detrimental interactions between ceramics and LMAs.This study identified the design principle of separators for practical LMBs with respect to mechanical stability and chemical affinity toward LMAs by elucidating the impacts of separator modification on the cycling performance.展开更多
The Henry’s law constant of volatiles in polymer systems is a crucial parameter reflecting the gas-liquid equilibrium,which is very important for devolatilization.In this research,polyolefin elastomer(POE)-cyclohexan...The Henry’s law constant of volatiles in polymer systems is a crucial parameter reflecting the gas-liquid equilibrium,which is very important for devolatilization.In this research,polyolefin elastomer(POE)-cyclohexane and polydimethylsiloxane(PDMS)-hexane systems were studied,and the Henry’s law constant was obtained by measuring the gas phase equilibrium partial pressure when polymer solutions containing different mass fractions of volatiles reached a saturated state.The effects of temperature,type of volatiles,and polymer viscosity on the gas phase equilibrium partial pressure and Henry’s law constant of the volatiles were investigated.The results indicate that,with the increase of temperature and polymer viscosity,the gas phase equilibrium partial pressure and Henry’s law constant of volatiles increase.As temperature increases,the solubility of gas in liquid decreases.The relationship between the Henry’s law constant and temperature is consistent with the Arrhenius law.In the PDMS-hexane system,the gas phase equilibrium partial pressure and Henry’s law constant of n-hexane are higher than those of cyclohexane.The obtained Henry’s law constants can be used as a reference for perfecting the devolatilization process and improving the devolatilization effect.展开更多
Biaxial-oriented polypropylene (BOPP) thin films are currently used as dielectrics in state-of-the-art capacitors that show many advantages, such as low energy loss and high breakdown strength, but a limited energy de...Biaxial-oriented polypropylene (BOPP) thin films are currently used as dielectrics in state-of-the-art capacitors that show many advantages, such as low energy loss and high breakdown strength, but a limited energy density ( 600 MV/m. The PP-OH dielectric demonstrates a linear reversible charge storage behavior with high releasing energy density > 7 J/cm3 (2 - 3 times of BOPP) after an applied electric field at E = 600 MV/m, without showing any significant increase of energy loss and remnant polarization at zero electric field. On the other hand, a cross-linked polypropylene (x-PP) exhibits an ε ~ 3, which is independent of a wide range of temperatures and frequencies, slim polarization loops, high breakdown strength (E = 650 MV/m), narrow breakdown distribution, and reliable energy storage capacity > 5 J/cm3 (double that of state-of-the-art BOPP capacitors), without showing any increase in energy loss.展开更多
As a long-term project aimed at developing super polyolefin blends, in this paper we summarize our work on themechanical reinforcement and phase morphology of polyolefin blends achieved by dynamic packing injection mo...As a long-term project aimed at developing super polyolefin blends, in this paper we summarize our work on themechanical reinforcement and phase morphology of polyolefin blends achieved by dynamic packing injection molding(DPIM). The main feature of this technology is that the specimen is forced to move repeatedly in the model by two pistonsthat move reversibly with the same frequency during cooling, which results in preferential orientation of the dispersed phaseas well as the matrix. The typical morphology of samples obtained via DPIM is a shear-induced morphology with a core inthe center, an oriented zone surrounding the core and a skin layer in the cross-section areas. Shear-induced phase dissolutionat a higher shear rate but phase separation at low shear rates is evident from AFM examination of LLDPE/PP (50/50) blends.The super polyolefin blends having high modulus (1.9-2.2 GPa), high tensile strength (100-120 MPa) and high impactstrength (6 times as that of pure HDPE) have been prepared by controlling the phase separation, molecular orientation andcrystal morphology.展开更多
The diffusion coefficient of volatiles in polymer solutions is a crucial parameter to describe the mass transfer efficiency and ability of volatiles.In this research,polyolefin elastomer(POE)was used as a polymer,and ...The diffusion coefficient of volatiles in polymer solutions is a crucial parameter to describe the mass transfer efficiency and ability of volatiles.In this research,polyolefin elastomer(POE)was used as a polymer,and cyclohexane was used as a volatile.A gravimetric analysis was applied to measure the diffusion coefficient of cyclohexane in POE.The devolatilization rate of the POE-cyclohexane system under different conditions was measured.The effects of temperature,film sample thickness,and initial concentration of volatiles on the devolatilization rate were discussed.Based on the devolatilization rate data,the average diffusion coefficient of cyclohexane in POE was obtained by fitting with a mathematical model.The experimental results indicate that the devolatilization rate increased with increasing temperature and initial concentration of volatiles,but it decreased with increasing sample thickness.As the thickness increased,the overall diffusion resistance increased.As the temperature increased,the molecular movement increased,resulting in the increase of average diffusion coefficient.The relationship between the diffusion coefficient of the POE-cyclohexane system and temperature follows the Arrhenius law.The diffusion activation energy E=6201.73 J/mol,and the pre-exponential factor of the diffusion coefficient D0=2.64×10^(-10) m^(2)/s.This work can provide basic data for exploring the devolatilization of POE polymers and serves as a useful reference for enhancing the effect of devolatilization.展开更多
A neutral nickel(Ⅱ)catalyst D,{[O-(3-cyclohexyl)(5-Cl)C_6H_2-ortho-C(H)=N-2,6-C_6H_3(i-Pr)_2]Ni(Ph_3P)(Ph)}hasbeen synthesized and characterized by IH-NMR,FTIR and elemental analysis.The results indicate that Al(i-Bu...A neutral nickel(Ⅱ)catalyst D,{[O-(3-cyclohexyl)(5-Cl)C_6H_2-ortho-C(H)=N-2,6-C_6H_3(i-Pr)_2]Ni(Ph_3P)(Ph)}hasbeen synthesized and characterized by IH-NMR,FTIR and elemental analysis.The results indicate that Al(i-Bu)_3 is aneffective cocatalyst for the neutral nickel catalyst.With bis(1,5-cyclooctadiene)nickel(0)[Ni(COD)_2]or Al(i-Bu)_3 as a co-catalyst,the neutral nickel catalyst D is active for ethylene polymerisation and copolymerisation with polar monomers(tert-butyl 10-undecenoate(BU),methyl 10-undecenoate(MU),allyl alcohol(AA)and 4-penten-1-ol(PO))under mild conditions.The resulting polymers were characterized by (?)H-NMR,FTIR,DSC,and GPC.From the comparative studies,Ni(COD)_2 ismore active than Al(i-Bu)_3 for ethylene homopolymerization,while Al(i-Bu)_3 is more effective than Ni(COD)_2 for ethylenecopolymerisation with polar monomers.The polymerization parameters which affect both the catalytic activity and propertiesof the resulting polyethylene were investigated in detail.Under the conditions of 20 μmol catalyst D and Ni(COD)_2/D=3(molar ratio) in 30 mL toluene solution at 45℃,12×105 Pa ethylene for 20 min,the polymerization activity reaches ashigh as 7.29×105 gPE.(mol.Ni.h)^(-1) and M_η,is 7.16×104 g.mol^(-1).For ethylene copolymerization with polar monomers,theeffect of comonomer concentrations was examined.As high as 0.97 mol% of MU,1.06 mol% of BU,1.04 mol% of AA and1.37 mol% of PO were incorporated into the polymer,respectively,catalyzed by D/Al(i-Bu)_3 system.展开更多
Polyolefins that bear a chiral side chain(typically an isobutyl group)experience a so-called macromolecularamplification of chirality:the chiral side-chain induces a slight preference for either tg or tg(?) main chain...Polyolefins that bear a chiral side chain(typically an isobutyl group)experience a so-called macromolecularamplification of chirality:the chiral side-chain induces a slight preference for either tg or tg(?) main chain conformation.Thisslight conformational bias is amplified cooperatively along the chain,and results in preferred chirality of the main chainhelical conformations.As a result,these polymers display a liquid-crystal(LC)phase both in solution and,in the melt as atransient phase on the way to crystallization.The existence of two processes(melt-LC and LC-crystal transitions)results inunconventional behaviors that were first analyzed by Pino and collaborators back in 1975.These polymers also offer a meansto test the structural consequences of recently introduced crystallization schemes.These schemes postulate the formation of atransient liquid-crystal phase as a general scheme for polymer crystallization.展开更多
A method to quantify crazing deformations by tensile tests for polystyrene (PS) and polyolefin elastomer (POE) blends was investigated. The toughness of PS/POE blends, reflected by the Charpy impact strength, incr...A method to quantify crazing deformations by tensile tests for polystyrene (PS) and polyolefin elastomer (POE) blends was investigated. The toughness of PS/POE blends, reflected by the Charpy impact strength, increased with the content of POE. SEM micrographs showed the poor compatibility between PS and POE. In simple tensile tests, it is very easy to achieve the ratio of crazing deformation, i.e. K by measuring the size changes of samples. The K values decreased with increasing the content of POE, and the deformations of PS/POE blends were dominated by crazing. The plots of the change of volume (△V) against longitudinal variation (△I) showed a linear relationship, and the slope of lines decreased with the content of POE. Measuring samples at the tensile velocities of 5 mm/min, 50 mm/min, and 500 mm/min respectively, the K values kept unchanged for each PS/POE blends.展开更多
The morphology of PE in the in-situ CB/PE composites prepared from in-situ polymerization via a catalyst-supported approach was studied by DSC. It is found that both the melting peak temperature and crystallinity of t...The morphology of PE in the in-situ CB/PE composites prepared from in-situ polymerization via a catalyst-supported approach was studied by DSC. It is found that both the melting peak temperature and crystallinity of the PE shelldecrease as filler level increases. The unexpected phenomena are ascribed to the strong interaction between PE and CB andthe very high specific area of CB. It is suggested that the lamellar thickness should be well correlated to the PE shell thickness. A two-layer PE model is successfully used to explain the experiment results.展开更多
In this communication, by means of stress relaxation experiments, the viscous stress at various strains during tensile deformation of oriented polyolefin samples including high density polyethylene (HDPE), linear lo...In this communication, by means of stress relaxation experiments, the viscous stress at various strains during tensile deformation of oriented polyolefin samples including high density polyethylene (HDPE), linear low density polyethylene (LLDPE) and isotactic polypropylene (iPP), has been determined. The viscous stress in the oriented samples takes up to 50%-70% of the total stress, which is unusually high compared with their isotropic counterparts. The unusual high viscous stress was discussed based on mainly the existence of shish structure in oriented polyolefins, which could enhance the inter-lamella coupling significantly.展开更多
Recent successful examples for synthesis of new polyolefins containing (polar) functionalities by adopting the approaches by controlled incorporation of reactive functionalities (and the subsequent introduction of pol...Recent successful examples for synthesis of new polyolefins containing (polar) functionalities by adopting the approaches by controlled incorporation of reactive functionalities (and the subsequent introduction of polar functionalities under mild conditions) by coordination polymerization in the presence of transition metal complex catalysts have been described. Related methods (such as direct copolymerization of olefin with polar monomer using living radical or coordination insertion methods) have also been demonstrated for comparison. Our recent efforts for precise synthesis of polyolefins containing polar functionalities by efficient incorporation of reactive functionality by copolymerization of ethylene with nonconjugateddiene (1,7-octadiene, vinylcyclohexene etc.) or divinyl-biphenyl using nonbridged half-titanocene [ex. Cp’TiCl2(O-2,6-iPr2C6H3), Cp’ = C5Me5, tBuC5H4 etc.] catalysts have been introduced.展开更多
The cracking of polyolefins, especially polyethylene in the molten state was effectively catalyzed by the powdery spent FCC (Fluid Catalytic Cracking) catalyst which was dispersed in it. The activation energy of the...The cracking of polyolefins, especially polyethylene in the molten state was effectively catalyzed by the powdery spent FCC (Fluid Catalytic Cracking) catalyst which was dispersed in it. The activation energy of the catalytic cracking of polyethylene was about 74 kJ/mol. The cracked product was naphtha and middle distillate as the major product and gaseous hydrocarbon (C1-C4) as the minor product while little heavy oil was produced. The chemical compositions of the product were: aromatic hydrocarbons, isoparaffins and branched olefins, whereas that of the non-catalyzed products were: n-olefins and n-paraffins with minor amount of dienes with increasing the process time. Additionally, the product pattern shifted from naphtha rich product to kerosene and gas-oil rich product. However, any catalytic product showed low fluid point (〈 -10 ℃), while that of the non-catalyzed product was as high as 40 ℃. Catalyst could process, more than 100 times by weight of polyethylene with fairly small amount (- 30 wt%) of coke deposition. Spent catalyst gave higher hydrocarbons while fresh catalyst gave gaseous product as the major product. Other polyolefins such as polypropylene and polystyrene were tested on same catalyst to show that their reactivity is higher than that of polyethylene and gave the aliphatic products, alkyl benzenes and C6-C9 iso-paraffins as the major product. Product pattern of the cracked product suggested that the reaction proceeded via the primary reactions making paraffins and olefins which were followed by the isomerization, secondary cracking, aromatization and hydrogen transfer which based on the carbenium ion mechanism.展开更多
A range of blends of polypropylene-polyethylene are investigated for their mechanical performances. These speciality polymer blends are chemically designed to suit high modulus/high load bearing mining wire rope appli...A range of blends of polypropylene-polyethylene are investigated for their mechanical performances. These speciality polymer blends are chemically designed to suit high modulus/high load bearing mining wire rope applications subjected to continued bending and tensile stresses and fluctuating loads and are exposed to extreme weather conditions. In this paper we study the influence of different parameters on the performance of the wire ropes: chemistry of polymer, crystallinity of the polymer matrix, and the morphology. The FTIR and SEM studies revealed that the high fraction of polypropylene in polypropylene-polyethylene matrix lead to early failure as a result of incompatibility and phase segregation and high spherulite sizes of the polymer matrix.展开更多
Oxidized (GO) and expanded (G-Exp) graphite were employed to prepare composites with ultrahigh molecular weight polyethylene (UHMWPE) matrix using masterbatches of polyethylene with different compositions. The materia...Oxidized (GO) and expanded (G-Exp) graphite were employed to prepare composites with ultrahigh molecular weight polyethylene (UHMWPE) matrix using masterbatches of polyethylene with different compositions. The materials and a blend of UHMWPE/HDPE were prepared by extrusion and their properties were evaluated. The effect of carbon fillers on the crystalline structure, thermo dynamic-mechanical (DMTA) and thermal properties (melting and crystallization temperatures) of the composites were discussed. The thermogravimetric analysis (TGA), differential scanning calorimetry (DSC) and wide-angle X-ray diffraction (WAXD) measurements showed that the addition of masterbatch with GO and G-Exp significantly increased the crystallite size of composites, increasing the temperatures of melting, degradation, glass transition and the degree of crystallinity of polyethylene. DMTA analysis indicated the storage and loss moduli of composites in relation to neat UHMWPE, the blend and UHMWPE/composites. SEM micrographs showed a flatter, continuous and uniform surface meaning a compact lamellar structure. The present work resulted in interesting findings on the effects of GO on the crystalline structures, mechanical and thermal properties of UHMWPE, which can lead to generalizations useful for future work.展开更多
Cyclic polyolefin (COP) is an inexpensive hydrophobic material with low auto-fluorescence, high light transmittance and thermal stability, broad chemical resistance and no non-specific protein binding. Here, the hydro...Cyclic polyolefin (COP) is an inexpensive hydrophobic material with low auto-fluorescence, high light transmittance and thermal stability, broad chemical resistance and no non-specific protein binding. Here, the hydrophobic alkane COP was modified to have carbonyl functionalities through oxygen plasma and chemical etching treatments to increase usefulness for chemical and biochemical applications. Then, biotin-hydrazide was used to create biotinylated surfaces that bound streptavidin. A biotinylated target oligonucleotide was subsequently bound to the immobilized biotin-streptavidin and ligation mediated rolling circle amplification-based (L-RCA) SNP detection was demonstrated.展开更多
文摘The morphology and properties of HDPE blends with Zn-SEPDM and GR were studied through SEM and mechanical property test. The results show that as Zn-SEPDM/GR content amounts to 20%, the blend becomes an IPN in structure, and that a rather high impact and tensile strength of HDPE may be obtained after blending. The antistatic effect, the softening point,and HDT of the blend are higher as compared to HDPE/Zn-SEPDM/ZnSt (zinc stearate).The effect of Zn-SEPDM on the compatibility the morphology and properties of IPP blends were studied by DSC, TEM and mechanical properties test. The results show that as Zn-SEPDM content exceeds 20%. Zn-SEPDM in the blend becomes continuous and an abrupt change in impact strength is incurred there from. Owing to the incorporation of ionic groups into EPDM.the strong interactions betWeen the chains make both the impact and the tensile strength of IPP remarkably higher
文摘Serratia marcescens strain 9986 is a producer of prodigiosin used as a dye of polyolefines (polyethylene, ultratene). The biosynthesis of pigment was closely connected with controlled growth parameters. A prodigiosin yield 0.2 - 0.4 mg per l of culture medium in the batch culture under aerobic conditions was obtained. Prodigiosin was extracted from crude biomass treated by 0.1% of sodium dodecyl sulfate (SDS). This novel elaborated stage is necessary for thermostability a dye in polymer. The consumption of prodigiosin preparation is more economical in the technology of the coloration of polyolefines. The elaborated method has been manufactured for dyeing polyethylene by biological pigment-articles of the common use corresponding to the technological standard.
基金supported by the National Natural Science Foundation of China (grant 22208339)the China Postdoctoral Science Foundation (2021M693132)+2 种基金the National Key R&D Program of China (2019YFC1905303)the Doctoral Scientific Research Foundation of Liaoning Province (2021-BS-006)the Youth Innovation Fund of Dalian Institute of Chemical Physics (DICP I202132)。
文摘The inert carbon–carbon(C–C) bonds cleavage is a main bottleneck in the chemical upcycling of recalcitrant polyolefin plastics waste. Here we develop an efficient strategy to catalyze the complete cleavage of C–C bonds in mixed polyolefin plastics over non-noble metal catalysts under mild conditions. The nickelbased catalyst involving Ni_(2)Al_(3) phase enables the direct transformation of mixed polyolefin plastics into natural gas, and the gas carbon yield reaches up to 89.6%. Reaction pathway investigation reveals that natural gas comes from the stepwise catalytic cleavage of C–C bonds in polypropylene, and the catalyst prefers catalytic cleavage of terminal C–C bond in the side-chain with the low energy barrier.Additionally, our developed approach is evaluated by the technical economic analysis for an economically competitive production process.
基金the Natural Science Foundation of Shandong Province (ZR2022QB050)the Liaocheng University Doctoral Initial Fund (318052137) for Financial Support。
文摘Boosting of rechargeable lithium metal batteries(LMBs) holds challenges because of lithium dendrites germination and high-reactive surface feature.Separators may experience structure-determined chemical deterioration and worsen Li plating-stripping behaviors when smoothly shifting from lithium-ion batteries(LIBs) to LMBs.This study precisely regulations the crystal structure of β-polypropylene and separator porous construction to investigate the intrinsic porous structure and mechanical properties determined electrochemical performances and cycling durability of LMBs.Crystal structure characterizations,porous structure analyses,and electrochemical cycling tests uncover appropriate annealing thermal stimulation concentrates β-lamellae thickness and enhances lamellae thermal stability by rearranging molecular chain in inferior β-lamellae,maximally homogenizing biaxial tensile deformation and resultant porous constructions.These even pores with high connectivity lower ion migration barriers,alleviate heterogeneous Li^(+) flux dispersion,stabilize reversible Li plating-stripping behaviors,and hinder coursing and branching of Li dendrites,endowing steady cell cycling durability,especially at higher currents due to the highlighted uncontrollable cumulation of dead Li,which offers new insights for the current pursuit of high-power density battery and fast charging technology.The suggested separator structure-chemical nature functions in ensuring cyclic cell stability and builds reliable relationships between separator structure design and practical LMBs applications.
基金supported by the National Research Foundation of Korea(NRF),Government of Korea(MSIT)(2020R1A4A4079810 and 2020R1C1C1009159).
文摘Development of practical lithium(Li)metal batteries(LMBs)remains challenging despite promises of Li metal anodes(LMAs),owing to Li dendrite formation and highly reactive surface nature.Polyolefin separators used in LMBs may undergo severe mechanical and chemical deterioration when contacting with LMAs.To identify the best polyolefin separator for LMBs,this study investigated the separator-deterministic cycling stability of LMBs under practical conditions,and redefined the key influencing factors,including pore structure,mechanical stability,and chemical affinity,using 12 different commercial separators,including polyethylene(PE),polypropylene(PP),and coated separators.At extreme compression triggered by LMA swelling,isotropic stress release by balancing the machine direction and transverse direction tensile strengths was found to be crucial for mitigating cell short-circuiting.Instead of PP separators,a PE separator that possesses a high elastic modulus and a highly connected pore structure can uniformly regulate LMA swelling.The ceramic coating reinforced short-circuiting resistance,while the cycling efficiency degraded rapidly owing to the detrimental interactions between ceramics and LMAs.This study identified the design principle of separators for practical LMBs with respect to mechanical stability and chemical affinity toward LMAs by elucidating the impacts of separator modification on the cycling performance.
基金Polyolefin Elastomer Technology Development project(2020B-2619).
文摘The Henry’s law constant of volatiles in polymer systems is a crucial parameter reflecting the gas-liquid equilibrium,which is very important for devolatilization.In this research,polyolefin elastomer(POE)-cyclohexane and polydimethylsiloxane(PDMS)-hexane systems were studied,and the Henry’s law constant was obtained by measuring the gas phase equilibrium partial pressure when polymer solutions containing different mass fractions of volatiles reached a saturated state.The effects of temperature,type of volatiles,and polymer viscosity on the gas phase equilibrium partial pressure and Henry’s law constant of the volatiles were investigated.The results indicate that,with the increase of temperature and polymer viscosity,the gas phase equilibrium partial pressure and Henry’s law constant of volatiles increase.As temperature increases,the solubility of gas in liquid decreases.The relationship between the Henry’s law constant and temperature is consistent with the Arrhenius law.In the PDMS-hexane system,the gas phase equilibrium partial pressure and Henry’s law constant of n-hexane are higher than those of cyclohexane.The obtained Henry’s law constants can be used as a reference for perfecting the devolatilization process and improving the devolatilization effect.
文摘Biaxial-oriented polypropylene (BOPP) thin films are currently used as dielectrics in state-of-the-art capacitors that show many advantages, such as low energy loss and high breakdown strength, but a limited energy density ( 600 MV/m. The PP-OH dielectric demonstrates a linear reversible charge storage behavior with high releasing energy density > 7 J/cm3 (2 - 3 times of BOPP) after an applied electric field at E = 600 MV/m, without showing any significant increase of energy loss and remnant polarization at zero electric field. On the other hand, a cross-linked polypropylene (x-PP) exhibits an ε ~ 3, which is independent of a wide range of temperatures and frequencies, slim polarization loops, high breakdown strength (E = 650 MV/m), narrow breakdown distribution, and reliable energy storage capacity > 5 J/cm3 (double that of state-of-the-art BOPP capacitors), without showing any increase in energy loss.
基金This work was supported by the National Natural Science Foundation of China (Grant No. 29992535) and the China National Distinguished Young Investigator Fund.
文摘As a long-term project aimed at developing super polyolefin blends, in this paper we summarize our work on themechanical reinforcement and phase morphology of polyolefin blends achieved by dynamic packing injection molding(DPIM). The main feature of this technology is that the specimen is forced to move repeatedly in the model by two pistonsthat move reversibly with the same frequency during cooling, which results in preferential orientation of the dispersed phaseas well as the matrix. The typical morphology of samples obtained via DPIM is a shear-induced morphology with a core inthe center, an oriented zone surrounding the core and a skin layer in the cross-section areas. Shear-induced phase dissolutionat a higher shear rate but phase separation at low shear rates is evident from AFM examination of LLDPE/PP (50/50) blends.The super polyolefin blends having high modulus (1.9-2.2 GPa), high tensile strength (100-120 MPa) and high impactstrength (6 times as that of pure HDPE) have been prepared by controlling the phase separation, molecular orientation andcrystal morphology.
基金The authors wish to express their thanks for the financial support from the Polyolefin Elastomer Technology Development project(2020B-2619).
文摘The diffusion coefficient of volatiles in polymer solutions is a crucial parameter to describe the mass transfer efficiency and ability of volatiles.In this research,polyolefin elastomer(POE)was used as a polymer,and cyclohexane was used as a volatile.A gravimetric analysis was applied to measure the diffusion coefficient of cyclohexane in POE.The devolatilization rate of the POE-cyclohexane system under different conditions was measured.The effects of temperature,film sample thickness,and initial concentration of volatiles on the devolatilization rate were discussed.Based on the devolatilization rate data,the average diffusion coefficient of cyclohexane in POE was obtained by fitting with a mathematical model.The experimental results indicate that the devolatilization rate increased with increasing temperature and initial concentration of volatiles,but it decreased with increasing sample thickness.As the thickness increased,the overall diffusion resistance increased.As the temperature increased,the molecular movement increased,resulting in the increase of average diffusion coefficient.The relationship between the diffusion coefficient of the POE-cyclohexane system and temperature follows the Arrhenius law.The diffusion activation energy E=6201.73 J/mol,and the pre-exponential factor of the diffusion coefficient D0=2.64×10^(-10) m^(2)/s.This work can provide basic data for exploring the devolatilization of POE polymers and serves as a useful reference for enhancing the effect of devolatilization.
基金This work was supported by the NSFC(No.2007402820374043)SINOPEC(X500030).
文摘A neutral nickel(Ⅱ)catalyst D,{[O-(3-cyclohexyl)(5-Cl)C_6H_2-ortho-C(H)=N-2,6-C_6H_3(i-Pr)_2]Ni(Ph_3P)(Ph)}hasbeen synthesized and characterized by IH-NMR,FTIR and elemental analysis.The results indicate that Al(i-Bu)_3 is aneffective cocatalyst for the neutral nickel catalyst.With bis(1,5-cyclooctadiene)nickel(0)[Ni(COD)_2]or Al(i-Bu)_3 as a co-catalyst,the neutral nickel catalyst D is active for ethylene polymerisation and copolymerisation with polar monomers(tert-butyl 10-undecenoate(BU),methyl 10-undecenoate(MU),allyl alcohol(AA)and 4-penten-1-ol(PO))under mild conditions.The resulting polymers were characterized by (?)H-NMR,FTIR,DSC,and GPC.From the comparative studies,Ni(COD)_2 ismore active than Al(i-Bu)_3 for ethylene homopolymerization,while Al(i-Bu)_3 is more effective than Ni(COD)_2 for ethylenecopolymerisation with polar monomers.The polymerization parameters which affect both the catalytic activity and propertiesof the resulting polyethylene were investigated in detail.Under the conditions of 20 μmol catalyst D and Ni(COD)_2/D=3(molar ratio) in 30 mL toluene solution at 45℃,12×105 Pa ethylene for 20 min,the polymerization activity reaches ashigh as 7.29×105 gPE.(mol.Ni.h)^(-1) and M_η,is 7.16×104 g.mol^(-1).For ethylene copolymerization with polar monomers,theeffect of comonomer concentrations was examined.As high as 0.97 mol% of MU,1.06 mol% of BU,1.04 mol% of AA and1.37 mol% of PO were incorporated into the polymer,respectively,catalyzed by D/Al(i-Bu)_3 system.
文摘Polyolefins that bear a chiral side chain(typically an isobutyl group)experience a so-called macromolecularamplification of chirality:the chiral side-chain induces a slight preference for either tg or tg(?) main chain conformation.Thisslight conformational bias is amplified cooperatively along the chain,and results in preferred chirality of the main chainhelical conformations.As a result,these polymers display a liquid-crystal(LC)phase both in solution and,in the melt as atransient phase on the way to crystallization.The existence of two processes(melt-LC and LC-crystal transitions)results inunconventional behaviors that were first analyzed by Pino and collaborators back in 1975.These polymers also offer a meansto test the structural consequences of recently introduced crystallization schemes.These schemes postulate the formation of atransient liquid-crystal phase as a general scheme for polymer crystallization.
文摘A method to quantify crazing deformations by tensile tests for polystyrene (PS) and polyolefin elastomer (POE) blends was investigated. The toughness of PS/POE blends, reflected by the Charpy impact strength, increased with the content of POE. SEM micrographs showed the poor compatibility between PS and POE. In simple tensile tests, it is very easy to achieve the ratio of crazing deformation, i.e. K by measuring the size changes of samples. The K values decreased with increasing the content of POE, and the deformations of PS/POE blends were dominated by crazing. The plots of the change of volume (△V) against longitudinal variation (△I) showed a linear relationship, and the slope of lines decreased with the content of POE. Measuring samples at the tensile velocities of 5 mm/min, 50 mm/min, and 500 mm/min respectively, the K values kept unchanged for each PS/POE blends.
文摘The morphology of PE in the in-situ CB/PE composites prepared from in-situ polymerization via a catalyst-supported approach was studied by DSC. It is found that both the melting peak temperature and crystallinity of the PE shelldecrease as filler level increases. The unexpected phenomena are ascribed to the strong interaction between PE and CB andthe very high specific area of CB. It is suggested that the lamellar thickness should be well correlated to the PE shell thickness. A two-layer PE model is successfully used to explain the experiment results.
基金This work was financially supported by the National Natural Science Foundation of China (Nos. 20404008, 50533050 and 20490220)This work was subsidized by the Special Funds for Major State Basic Research Projects of China (No. 2003CB615600).
文摘In this communication, by means of stress relaxation experiments, the viscous stress at various strains during tensile deformation of oriented polyolefin samples including high density polyethylene (HDPE), linear low density polyethylene (LLDPE) and isotactic polypropylene (iPP), has been determined. The viscous stress in the oriented samples takes up to 50%-70% of the total stress, which is unusually high compared with their isotropic counterparts. The unusual high viscous stress was discussed based on mainly the existence of shish structure in oriented polyolefins, which could enhance the inter-lamella coupling significantly.
文摘Recent successful examples for synthesis of new polyolefins containing (polar) functionalities by adopting the approaches by controlled incorporation of reactive functionalities (and the subsequent introduction of polar functionalities under mild conditions) by coordination polymerization in the presence of transition metal complex catalysts have been described. Related methods (such as direct copolymerization of olefin with polar monomer using living radical or coordination insertion methods) have also been demonstrated for comparison. Our recent efforts for precise synthesis of polyolefins containing polar functionalities by efficient incorporation of reactive functionality by copolymerization of ethylene with nonconjugateddiene (1,7-octadiene, vinylcyclohexene etc.) or divinyl-biphenyl using nonbridged half-titanocene [ex. Cp’TiCl2(O-2,6-iPr2C6H3), Cp’ = C5Me5, tBuC5H4 etc.] catalysts have been introduced.
文摘The cracking of polyolefins, especially polyethylene in the molten state was effectively catalyzed by the powdery spent FCC (Fluid Catalytic Cracking) catalyst which was dispersed in it. The activation energy of the catalytic cracking of polyethylene was about 74 kJ/mol. The cracked product was naphtha and middle distillate as the major product and gaseous hydrocarbon (C1-C4) as the minor product while little heavy oil was produced. The chemical compositions of the product were: aromatic hydrocarbons, isoparaffins and branched olefins, whereas that of the non-catalyzed products were: n-olefins and n-paraffins with minor amount of dienes with increasing the process time. Additionally, the product pattern shifted from naphtha rich product to kerosene and gas-oil rich product. However, any catalytic product showed low fluid point (〈 -10 ℃), while that of the non-catalyzed product was as high as 40 ℃. Catalyst could process, more than 100 times by weight of polyethylene with fairly small amount (- 30 wt%) of coke deposition. Spent catalyst gave higher hydrocarbons while fresh catalyst gave gaseous product as the major product. Other polyolefins such as polypropylene and polystyrene were tested on same catalyst to show that their reactivity is higher than that of polyethylene and gave the aliphatic products, alkyl benzenes and C6-C9 iso-paraffins as the major product. Product pattern of the cracked product suggested that the reaction proceeded via the primary reactions making paraffins and olefins which were followed by the isomerization, secondary cracking, aromatization and hydrogen transfer which based on the carbenium ion mechanism.
文摘A range of blends of polypropylene-polyethylene are investigated for their mechanical performances. These speciality polymer blends are chemically designed to suit high modulus/high load bearing mining wire rope applications subjected to continued bending and tensile stresses and fluctuating loads and are exposed to extreme weather conditions. In this paper we study the influence of different parameters on the performance of the wire ropes: chemistry of polymer, crystallinity of the polymer matrix, and the morphology. The FTIR and SEM studies revealed that the high fraction of polypropylene in polypropylene-polyethylene matrix lead to early failure as a result of incompatibility and phase segregation and high spherulite sizes of the polymer matrix.
文摘Oxidized (GO) and expanded (G-Exp) graphite were employed to prepare composites with ultrahigh molecular weight polyethylene (UHMWPE) matrix using masterbatches of polyethylene with different compositions. The materials and a blend of UHMWPE/HDPE were prepared by extrusion and their properties were evaluated. The effect of carbon fillers on the crystalline structure, thermo dynamic-mechanical (DMTA) and thermal properties (melting and crystallization temperatures) of the composites were discussed. The thermogravimetric analysis (TGA), differential scanning calorimetry (DSC) and wide-angle X-ray diffraction (WAXD) measurements showed that the addition of masterbatch with GO and G-Exp significantly increased the crystallite size of composites, increasing the temperatures of melting, degradation, glass transition and the degree of crystallinity of polyethylene. DMTA analysis indicated the storage and loss moduli of composites in relation to neat UHMWPE, the blend and UHMWPE/composites. SEM micrographs showed a flatter, continuous and uniform surface meaning a compact lamellar structure. The present work resulted in interesting findings on the effects of GO on the crystalline structures, mechanical and thermal properties of UHMWPE, which can lead to generalizations useful for future work.
文摘Cyclic polyolefin (COP) is an inexpensive hydrophobic material with low auto-fluorescence, high light transmittance and thermal stability, broad chemical resistance and no non-specific protein binding. Here, the hydrophobic alkane COP was modified to have carbonyl functionalities through oxygen plasma and chemical etching treatments to increase usefulness for chemical and biochemical applications. Then, biotin-hydrazide was used to create biotinylated surfaces that bound streptavidin. A biotinylated target oligonucleotide was subsequently bound to the immobilized biotin-streptavidin and ligation mediated rolling circle amplification-based (L-RCA) SNP detection was demonstrated.