With the aim to effectively depolymerize polyethylene terephthalate(PET)under mild reaction conditions,PET methanolysis and dimethyl terephthalate(DMT)hydrolysis are integrated in a catalyst system.Firstly,methanolysi...With the aim to effectively depolymerize polyethylene terephthalate(PET)under mild reaction conditions,PET methanolysis and dimethyl terephthalate(DMT)hydrolysis are integrated in a catalyst system.Firstly,methanolysis of PET to DMT is achieved over Cu-Mg-Al oxide catalyst.Next,terephthalic acid(TPA)is prepared by DMT hydrolysis.It is found that hydrolysis of DMT to TPA can be promoted by introducing trace amount of water in this catalyst system.CuO-MgO-4.5Al_2O_(3)catalyst demonstrates the excellent catalytic performance for the depolymerization of PET with high conversion rate and TPA yield(100%and 99.5%,respectively)after reaction at 160℃for 6 h,which provides a new idea for the depolymerization of PET.展开更多
This work proposed a strategy to improve the caking index of polyethylene terephthalate(PET)waste,in which low-temperature pyrolysis treatment(LTPT)was used to depolymerize PET waste.The mechanism of G modification wa...This work proposed a strategy to improve the caking index of polyethylene terephthalate(PET)waste,in which low-temperature pyrolysis treatment(LTPT)was used to depolymerize PET waste.The mechanism of G modification was revealed combining thermogravimetric(TG)analysis,Fourier transform infrared spectroscopy,pyrolysis-gas chromatography with mass spectrometric detection,and solid-state 13C nuclear magnetic resonance spectroscopy.Furthermore,crucible coking experiments were also conducted using industrial coal mixture and treated PET with the optimum G(PET300)or raw PET to evaluate the applicability of PET waste in coal-blending coking.According to characterization results of coke reactivity(CR),coke strength after reaction(CSR)indices,TG-related curves,pore volumes,and Raman spectra of the resultant cokes,LTPT could greatly increase the G of PET,and the optimum temperature was 300℃.Specifically,compared with the coke obtained from the blend with PET,the CR of the coke produced from the blend with PET300 decreased by 4.9%,whereas the CSR of the increased by 7.4%,suggesting that LTPT could increase the proportion of PET used for coal-blending coking.The improvement in G is attributed to the changes in C-O/C=O ratio,aliphatic H and aromaticity caused by LTPT.展开更多
In this work,a novel alcohol alkali hydrolysis method was explored for the preparation of terephthalic acid(TPA)from waste polyethylene terephthalate(PET).First,a series of single factor experiments on the depolymeriz...In this work,a novel alcohol alkali hydrolysis method was explored for the preparation of terephthalic acid(TPA)from waste polyethylene terephthalate(PET).First,a series of single factor experiments on the depolymerization rate of waste PET bottles and the yield of TPA were conducted to determine the optimized experimental conditions,in terms of reaction time,reaction temperature,dosage of ethylene glycol and sodium bicarbonate,amount of distilled water and stirring rate.Then IR spectra and elemental analysis were carried out for the characterization of obtained product.Under optimal experimental conditions,over 98%PET can be depolymerized into the target product(TPA)and the purity and yield of TPA are over 97%and 94%,respectively.Both the experimental and analytical results support a feasible process for the preparation of TPA from waste PET.It is expected that this alcohol alkali hydrolysis method can promise an effective way for the sustainable recycling of waste PET.展开更多
The rheological behavior of fumed silica suspensions in polyethylene glycol(PEG) was studied at steady and oscillatory shear stress using AR 2000 stress controlled rheometer. The systems show reversible shear thickeni...The rheological behavior of fumed silica suspensions in polyethylene glycol(PEG) was studied at steady and oscillatory shear stress using AR 2000 stress controlled rheometer. The systems show reversible shear thickening behavior and the shear-thickening behavior can be explained by the clustering mechanism. The viscosity and the degree of shear-thickening of the systems strongly depend on the mass fraction of the silica, the molecular weigh of PEG and the frequency used in the rheological measurement. The silica volume fraction of the systems is 1.16% 3.62%, corresponding to the mass fraction of 4%9%. The shear-thickening taking place in the low volume fraction may contribute to the fractal nature of the silica. At oscillatory shear stress, when the shear stress is less than the critical stress, the storage modulus decreases significantly, meanwhile the loss modulus and the complex viscosity almost remain unchanged; when the shear stress is larger than the critical stress, the storage modulus, the loss modulus and the complex viscosity increase with the increase of shear stress. The loss modulus is larger than the storage modulus in the range of stress studied and both moduli depend on frequency.展开更多
The experimental observations about remarkable influence of the substrates on the isothermal crystallization rate of a high density polyethylene(HDPE) were presented.Two methods were used to characterize the crystalli...The experimental observations about remarkable influence of the substrates on the isothermal crystallization rate of a high density polyethylene(HDPE) were presented.Two methods were used to characterize the crystallization rate:the change of turbidity of the HDPE specimen and the changes of the complex viscosity and storage modulus measured by a rotational rheometer,which gave consistent results showing that the isothermal crystallization rate decreased in sequence as the specimen contacted with aluminum,brass and stainless steel plates,respectively.As to the dominant influence factor,the chemical composition of the substrates can be excluded via insulating the plate by an aluminum foil.Instead,we propose the plate's ability of removing the latent heat of crystallization from the specimen.Rheological measurement is sensitive to the crystallization process.The colloid like model proposed by BOUTAHAR et al for the crystallization of HDPE gives reasonable predictions of the crystallized fraction from the measured storage modulus.展开更多
Mesoporous polyethylene glycol-resorcinol and formaldehyde（PEG-RF） carbon xerogels were prepared by a new polymer blend method in which PEG-RF mixed organic xerogels were synthesized by blending thermally unstable p...Mesoporous polyethylene glycol-resorcinol and formaldehyde（PEG-RF） carbon xerogels were prepared by a new polymer blend method in which PEG-RF mixed organic xerogels were synthesized by blending thermally unstable polyethylene glycol with organic monomers, resorcinol and formaldehyde and then subjected to pyrolization at 1 000 ℃. The influences of mass ratio of PEG to the theoretical yield of RF xerogel, m（PEG）/m（RF） and the （relative） molecular mass of PEG on the pore structure and electric double layer capacitance（EDLC） performance of PEG-RF carbon xerogels were investigated. The results show that PEG under different conditions leads to the difference of phase separation structure of the polymer blend and thus the change of pore structure of PEG-RF carbon xerogels. Specific surface area and capacity of PEG-RF carbon xerogels in 30% H2SO4 solution can reach （755 m2/g） and 150 F/g, respectively. Their surface can be fully utilized to form electric double layer. However, the pore structure differences of PEG-RF carbon xerogels result in their different EDLC performances. The distributed capacitance effect increases with decreasing the pore size of PEG-RF carbon xerogels.展开更多
Metal hydroxides （MAH） consisting of magnesium hydroxide and aluminum hydroxide with a mass ratio of 1：2 were surface-modified by y-diethoxyphosphorous ester propyldiethoxymethylsilane, boric acid and diphenylsilan...Metal hydroxides （MAH） consisting of magnesium hydroxide and aluminum hydroxide with a mass ratio of 1：2 were surface-modified by y-diethoxyphosphorous ester propyldiethoxymethylsilane, boric acid and diphenylsilanediol in xylene under dibutyl tin dilaurate catalyst at 140 ℃. Phosphorus, silicon and boron elements covalently bonded to metal hydroxide particles were detected by X-ray photoelectron spectroscopy. The degradation behavior of the surface-modified MAH was characterized by thermogravimetric analysis. The results show that linear low density polyethylene （LLDPE） composite, filled with 50% （mass fraction） of MAH modified by 5.0% （mass fraction） of modifiers, passes the V-0 rating of UL-94 test and shows the limited oxygen index of 34%, and its heat release rate and average effective heat combustion in a cone calorimeter measurement decrease obviously; The mechanical properties of MAH can be improved by surface-modification. The uniform dispersion of particles and strong interfacial bonding between particles and matrix are obtained.展开更多
In order to explore the mechanism of improving the surface wettability of low-energy polytetrafluoroethylene(PTFE)by new extended surfactants,five kinds of extended anionic surfactants with different numbers of oxypro...In order to explore the mechanism of improving the surface wettability of low-energy polytetrafluoroethylene(PTFE)by new extended surfactants,five kinds of extended anionic surfactants with different numbers of oxypropylene(PO)and oxyethylene(EO),octadecyl-(PO)_(m)-(EO)_(n)-sodium carboxylate(C_(18)PO_(m)EO_(n)C,m=5,10,15,n=5,10,15),were studied.The surface tension and contact angle of C_(18)PO_(m)EO_(n)C solution with different concentrations were measured,and the adhesion tension,PTFE-water interfacial tension,and adhesion work were calculated.It was found that the extended surfactant molecules adsorb on the surface of the solution and the PTFE-liquid interface simultaneously when the concentration is lower than the critical micelle concentration(cmc),and there was a linear relationship between surface tension and adhesion tension.The adsorption amount of C_(18)PO_(m)EO_(n)C at the PTFE-water interface was significantly lower than that on the surface of the solution.As the concentration increases above cmc,semi-micelle aggregates on the surface of PTFE are formed by C_(18)PO_(m)EO_(n)C molecules through hydrophobic interaction,and the hydrophilic group faces the solution to modify the surface of PTFE with high efficiency.展开更多
A nanomicelle(denoted as TPGS/Ppa)was fabricated via the coassembly of the amphiphilic D-α-tocopheryl polyethylene glycol 1000 succinate(TPGS)and the hydrophobic photosensitizer pyropheophorbide a(Ppa)for photodynami...A nanomicelle(denoted as TPGS/Ppa)was fabricated via the coassembly of the amphiphilic D-α-tocopheryl polyethylene glycol 1000 succinate(TPGS)and the hydrophobic photosensitizer pyropheophorbide a(Ppa)for photodynamic therapy(PDT).The obtained nanomicelle possessed a spherical structure with a diameter of(18.0±2.2)nm and a zeta potential of approximately -18 mV.Besides,the nanomicelle exhibited excellent photostability,biocompatibility,and phototoxicity,and could effectively reach the tumor region via the enhanced permeability and retention effect.Additionally,it could be found that the TPGS/Ppa nanomicelle exhibited higher phototoxicity against 4T1 murine mammary cancer cells than free Ppa.In the 4T1 tumor-bearing mouse model,the nanomicelle showed an excellent antitumor therapeutic effect.This study develops a new type of photodynamic nanomicelle TPGS/Ppa,which can increase the accumulation of drugs and prolong their tumor retention time,providing a feasible strategy for realizing the delivery of small-molecule hydrophobic drugs and tumor PDT.展开更多
A new multifunctional mPEG-b-PAA-grafted chitosan copolymer possessing amino and carboxyl groups,mPEG-b-PAA-g-CHI(compound 6) ,was designed for a potential application in gene/drug delivery and synthesized by the meth...A new multifunctional mPEG-b-PAA-grafted chitosan copolymer possessing amino and carboxyl groups,mPEG-b-PAA-g-CHI(compound 6) ,was designed for a potential application in gene/drug delivery and synthesized by the methods of reversible addition-fragmentation chain transfer(RAFT) polymerization of acrylic acid(AA) and grafting reaction of a biodegradable chitosan(CHI) derivative.Completion of the reactions and characterization of the resulting compounds were demonstrated by 1 H NMR,FTIR and gel permeation chtomatography(GPC) studies.The results show that the molar ratio of amino groups to carboxyl groups in the copolymer(compound 6) is 0.41-0.59.展开更多
Composite polymer electrolytes based on polyethylene oxide(PEO) were prepared by using LiClO4 as doping salt and silane-modified SiO2 as filler. SiO2 was formed in-situ in (PEO)8LiClO4 matrix by the hydrolysis and con...Composite polymer electrolytes based on polyethylene oxide(PEO) were prepared by using LiClO4 as doping salt and silane-modified SiO2 as filler. SiO2 was formed in-situ in (PEO)8LiClO4 matrix by the hydrolysis and condensation reaction of Si(OC4H9)4. The crystallinity,morphology and ionic conductivity of composite polymer electrolyte films were examined by differential scanning calorimetry,scanning electron microscopy,atom force microscopy and alternating current impedance spectroscopy,respectively. Compared with the crystallinity of the unmodified SiO2 as inert filler,that of composite polymer electrolytes is decreased. The results show that silane-modified SiO2 particles are uniformly dispersed in (PEO)8LiClO4 composite polymer electrolyte film and the addition of silane-modified SiO2 increases the ionic conductivity of the (PEO)8LiClO4 more noticeably. When the mass fraction of SiO2 is about 10%,the conductivity of (PEO)8LiClO4-modified SiO2 attains a maximum value of 4.8×10-5 S·cm-1.展开更多
Nitrocellulose,or cellulose nitrate,has received considerable interest due to its various applications,such as propellants,coating agents and gas generators.However,its high mechanical sensitivity caused many accident...Nitrocellulose,or cellulose nitrate,has received considerable interest due to its various applications,such as propellants,coating agents and gas generators.However,its high mechanical sensitivity caused many accidents during its storage and usage in ammunition.In this work,two kinds of insensitive step ladderstructured nitrocellulose(LNC)with different nitrogen contents were synthesized.The products were characterized by FT-IR,Raman,XRD,SEM,elemental analysis,TGA,DSC,accelerating rate calorimeter analysis(ARC),and drop weight test to study their molecular structure,thermal characteristics and desensitization performance.Compared with raw nitrocellulose,LNC has a sharper exothermic peak in the DSC and ARC curves.The H50values of the two kinds of LNC increased from 25.76 to 30.01 cm for low nitrogen content and from 18.02 to 21.84 cm for high nitrogen content,respectively.The results show that the ladder-structure of LNC which provides regular molecular arrangement and a soft buffer made with polyethylene glycol could affect the energy releasing process of LNC and reduce the sensitivity of LNC.Insensitive LNC provides an alternative to be used as a binder in insensitive propellants formulation.展开更多
(PEO)8LiClO4-SiO2 composite polymer electrolytes(CPEs)were prepared by in-situ reaction,in which ethyl-orthosilicate(TEOS)was catalyzed by HCl and NH3.H2O,respectively.The ionic conductivity,the contact angle and the ...(PEO)8LiClO4-SiO2 composite polymer electrolytes(CPEs)were prepared by in-situ reaction,in which ethyl-orthosilicate(TEOS)was catalyzed by HCl and NH3.H2O,respectively.The ionic conductivity,the contact angle and the morphology of inorganic particles in the CPEs were investigated by AC impedance spectra,contact angle method and TEM.The conductivities of acid-catalyzed CPE and alkali-catalyzed CPE are 2.2×10-5and 1.1×10-5S/cm respectively at 30℃.The results imply that the catalyst plays an important role in the structure of in-situ preparation of SiO2,and influences the surface energy and conductivity of CPE films directly.Meanwhile,the ionic conductivity is related to the surface energy.展开更多
PEO-LiClO4-TiO2 composite polymer electrolyte films were prepared. TiO2 was formed directly in matrix by hydrolysis and condensation reaction of tetrabutyl titanate. The crystallinity, morphology and ionic conductivit...PEO-LiClO4-TiO2 composite polymer electrolyte films were prepared. TiO2 was formed directly in matrix by hydrolysis and condensation reaction of tetrabutyl titanate. The crystallinity, morphology and ionic conductivity of composite polymer electrolyte films were examined by differential scanning calorimetry, scanning electron microscopy, atom force microscopy and alternating current impedance spectroscopy, respectively. The glass transition temperature and the crystallinity of composite polymer electrolytes are decreased compared with those of PEO-LiClO4 polymer electrolyte film. The results show that TiO2 particles are uniformly dispersed in PEO-LiClO4-5%TiO2 composite polymer electrolyte film. The maximal conductivity of 5.5×10、5 Scm at 20 ℃ of PEO-LiClO4-TiO2 film is obtained at 5% mass fraction of TiO2.展开更多
The reduced ability of fatty acids to dissolve and disperse at low temperatures limits their effectiveness in winter applications.In this study,a green and environment-friendly reagent,polyethylene glycol 2000(PEG-200...The reduced ability of fatty acids to dissolve and disperse at low temperatures limits their effectiveness in winter applications.In this study,a green and environment-friendly reagent,polyethylene glycol 2000(PEG-2000),was used to evaluate its effect on the collecting performance of sodium oleate during scheelite flotation at low temperatures.The effect of PEG-2000 on the flotation of scheelite with the collector sodium oleate(NaOL)was studied by flotation tests,surface tension tests,infrared spectral analysis,and zeta potential measurements.Flotation tests showed that adding PEG-2000 can enhance the collecting ability of NaOL on scheelite at low temperature(5℃).The recovery of scheelite with the mixed collector of PEG-200 and NaOL is 4.39%higher than that with NaOL only.The surface tension tests,infrared spectral analysis and zeta potential measurements revealed that PEG-2000 and OL^(−)are co-adsorbed on the scheelite surface at low temperatures.The presence of PEG-2000 promoted the increase of the adsorption concentration of oleate ions(OL^(−))on the scheelite surface.The reason was that PEG-2000 has a shielding effect on the electrostatic repulsion between the OL^(−)groups,which changes the micellar configuration of OL^(−)in the solution system and makes the OL^(−)gather more tightly on the surface of scheelite,leading to the enhancement of its hydrophobicity.This discovery provides a reference for the development of collecting reagents for efficient flotation recovery of scheelite under low temperature environment.展开更多
The influence of temperature and mass fraction of Pluonic F127 on the rheological properties of polyvinyl butyric （PVB）/Pluronic F127/polyethylene glycol （PEG） 200 blend systems was investigated by a rotational rh...The influence of temperature and mass fraction of Pluonic F127 on the rheological properties of polyvinyl butyric （PVB）/Pluronic F127/polyethylene glycol （PEG） 200 blend systems was investigated by a rotational rheometer with parallel plates. The results show that the blend systems approach homogeneous state at 140, 150 and 160℃while the rheological properties of the blend systems significantly deviate from the homogeneous systems at 120℃. Shear thinning behavior is observed for all the blend systems at different temperatures and is enhanced by increasing Pluronic F127 content. The complex viscosity, storage modulus, loss modulus, zero-shear activation energy and flow recovery of the blend systems increase with the increase of Pluronic F127 content. There is a crossing point for the loss modulus and the storage modulus of each sample at high frequency, which is called specified frequency （SF）. The loss modulus is larger than the storage modulus when the frequency is less than the SF, and when frequency is more than SF, the loss modulus is smaller than the storage modulus.展开更多
α-Diimide catalysts have attracted widespread attention due to their unique chain walking characteristics.A series ofα-diimide nickel/palladium catalysts with different electronic effects and steric hindrances were ...α-Diimide catalysts have attracted widespread attention due to their unique chain walking characteristics.A series ofα-diimide nickel/palladium catalysts with different electronic effects and steric hindrances were designed and synthesized for olefin polymerization.In this work,we synthesized a series of asymmetricα-diimide nickel complexes with different steric hindrances and used them for ethylene polymerization.These nickel catalysts have high ethylene polymerization activity,up to 6.51×10^(6)g·mol^(−1)·h^(−1),and the prepared polyethylene has a moderate melting point and high molecular weight(up to 38.2×10^(4)g·mol^(−1)),with a branching density distribution between 7 and 94 branches per 1000 carbons.More importantly,the polyethylene prepared by these catalysts exhibits excellent tensile properties,with strain and stress reaching 800%and 30 MPa,respectively.展开更多
In this study, we investigated the performance improvement caused by the addition of copper(Cu)nanoparticles to high-density polyethylene(HDPE) matrix material. Composite materials, with filler percentages of 0.0, 2.0...In this study, we investigated the performance improvement caused by the addition of copper(Cu)nanoparticles to high-density polyethylene(HDPE) matrix material. Composite materials, with filler percentages of 0.0, 2.0, 4.0, 6.0, 8.0, and 10.0 wt% were synthesized through the material extrusion(MEX)3D printing technique. The synthesized nanocomposite filaments were utilized for the manufacturing of specimens suitable for the experimental procedure that followed. Hence, we were able to systematically investigate their tensile, flexural, impact, and microhardness properties through various mechanical tests that were conducted according to the corresponding standards. Broadband Dielectric Spectroscopy was used to investigate the electrical/dielectric properties of the composites. Moreover, by employing means of Raman spectroscopy and thermogravimetric analysis(TGA) we were also able to further investigate their vibrational, structural, and thermal properties. Concomitantly, means of scanning electron microscopy(SEM), as well as atomic force microscopy(AFM), were used for the examination of the morphological and structural characteristics of the synthesized specimens, while energy-dispersive Xray spectroscopy(EDS) was also performed in order to receive a more detailed picture on the structural characteristics of the various synthesized composites. The corresponding nanomaterials were also assessed for their antibacterial properties regarding Staphylococcus aureus(S. aureus) and Escherichia coli(E. coli) with the assistance of a method named screening agar well diffusion. The results showed that the mechanical properties of HDPE benefited from the utilization of Cu as a filler, as they showed a notable improvement. The specimen of HDPE/Cu 4.0 wt% was the one that presented the highest levels of reinforcement in four out of the seven tested mechanical properties(for example, it exhibited a 36.7%improvement in the flexural strength, compared to the pure matrix). At the same time, the nanocomposites were efficient against the S. aureus bacterium and less efficient against the E. coli bacterium.The use of such multi-functional, robust nanocomposites in MEX 3D printing is positively impacting applications in various fields, most notably in the defense and security sectors. The latter becomes increasingly important if one takes into account that most firearms encompass various polymeric parts that require robustness and improved mechanical properties, while at the same time keeping the risk of spreading various infectious microorganisms at a bare minimum.展开更多
文摘With the aim to effectively depolymerize polyethylene terephthalate(PET)under mild reaction conditions,PET methanolysis and dimethyl terephthalate(DMT)hydrolysis are integrated in a catalyst system.Firstly,methanolysis of PET to DMT is achieved over Cu-Mg-Al oxide catalyst.Next,terephthalic acid(TPA)is prepared by DMT hydrolysis.It is found that hydrolysis of DMT to TPA can be promoted by introducing trace amount of water in this catalyst system.CuO-MgO-4.5Al_2O_(3)catalyst demonstrates the excellent catalytic performance for the depolymerization of PET with high conversion rate and TPA yield(100%and 99.5%,respectively)after reaction at 160℃for 6 h,which provides a new idea for the depolymerization of PET.
基金supported by the National Natural Science Foundation of China(22308006,22278001)the Natural Science Foundation of Anhui Provincial Education Department(KJ2021A0407).
文摘This work proposed a strategy to improve the caking index of polyethylene terephthalate(PET)waste,in which low-temperature pyrolysis treatment(LTPT)was used to depolymerize PET waste.The mechanism of G modification was revealed combining thermogravimetric(TG)analysis,Fourier transform infrared spectroscopy,pyrolysis-gas chromatography with mass spectrometric detection,and solid-state 13C nuclear magnetic resonance spectroscopy.Furthermore,crucible coking experiments were also conducted using industrial coal mixture and treated PET with the optimum G(PET300)or raw PET to evaluate the applicability of PET waste in coal-blending coking.According to characterization results of coke reactivity(CR),coke strength after reaction(CSR)indices,TG-related curves,pore volumes,and Raman spectra of the resultant cokes,LTPT could greatly increase the G of PET,and the optimum temperature was 300℃.Specifically,compared with the coke obtained from the blend with PET,the CR of the coke produced from the blend with PET300 decreased by 4.9%,whereas the CSR of the increased by 7.4%,suggesting that LTPT could increase the proportion of PET used for coal-blending coking.The improvement in G is attributed to the changes in C-O/C=O ratio,aliphatic H and aromaticity caused by LTPT.
基金Project(2016TP1007)supported by the Hunan Provincial Science and Technology Plan,China
文摘In this work,a novel alcohol alkali hydrolysis method was explored for the preparation of terephthalic acid(TPA)from waste polyethylene terephthalate(PET).First,a series of single factor experiments on the depolymerization rate of waste PET bottles and the yield of TPA were conducted to determine the optimized experimental conditions,in terms of reaction time,reaction temperature,dosage of ethylene glycol and sodium bicarbonate,amount of distilled water and stirring rate.Then IR spectra and elemental analysis were carried out for the characterization of obtained product.Under optimal experimental conditions,over 98%PET can be depolymerized into the target product(TPA)and the purity and yield of TPA are over 97%and 94%,respectively.Both the experimental and analytical results support a feasible process for the preparation of TPA from waste PET.It is expected that this alcohol alkali hydrolysis method can promise an effective way for the sustainable recycling of waste PET.
文摘The rheological behavior of fumed silica suspensions in polyethylene glycol(PEG) was studied at steady and oscillatory shear stress using AR 2000 stress controlled rheometer. The systems show reversible shear thickening behavior and the shear-thickening behavior can be explained by the clustering mechanism. The viscosity and the degree of shear-thickening of the systems strongly depend on the mass fraction of the silica, the molecular weigh of PEG and the frequency used in the rheological measurement. The silica volume fraction of the systems is 1.16% 3.62%, corresponding to the mass fraction of 4%9%. The shear-thickening taking place in the low volume fraction may contribute to the fractal nature of the silica. At oscillatory shear stress, when the shear stress is less than the critical stress, the storage modulus decreases significantly, meanwhile the loss modulus and the complex viscosity almost remain unchanged; when the shear stress is larger than the critical stress, the storage modulus, the loss modulus and the complex viscosity increase with the increase of shear stress. The loss modulus is larger than the storage modulus in the range of stress studied and both moduli depend on frequency.
基金Project(20050335050) supported by the Special Foundation of Education Ministry of ChinaProject(10472105) supported by the National Natural Science Foundation of China
文摘The experimental observations about remarkable influence of the substrates on the isothermal crystallization rate of a high density polyethylene(HDPE) were presented.Two methods were used to characterize the crystallization rate:the change of turbidity of the HDPE specimen and the changes of the complex viscosity and storage modulus measured by a rotational rheometer,which gave consistent results showing that the isothermal crystallization rate decreased in sequence as the specimen contacted with aluminum,brass and stainless steel plates,respectively.As to the dominant influence factor,the chemical composition of the substrates can be excluded via insulating the plate by an aluminum foil.Instead,we propose the plate's ability of removing the latent heat of crystallization from the specimen.Rheological measurement is sensitive to the crystallization process.The colloid like model proposed by BOUTAHAR et al for the crystallization of HDPE gives reasonable predictions of the crystallized fraction from the measured storage modulus.
文摘Mesoporous polyethylene glycol-resorcinol and formaldehyde（PEG-RF） carbon xerogels were prepared by a new polymer blend method in which PEG-RF mixed organic xerogels were synthesized by blending thermally unstable polyethylene glycol with organic monomers, resorcinol and formaldehyde and then subjected to pyrolization at 1 000 ℃. The influences of mass ratio of PEG to the theoretical yield of RF xerogel, m（PEG）/m（RF） and the （relative） molecular mass of PEG on the pore structure and electric double layer capacitance（EDLC） performance of PEG-RF carbon xerogels were investigated. The results show that PEG under different conditions leads to the difference of phase separation structure of the polymer blend and thus the change of pore structure of PEG-RF carbon xerogels. Specific surface area and capacity of PEG-RF carbon xerogels in 30% H2SO4 solution can reach （755 m2/g） and 150 F/g, respectively. Their surface can be fully utilized to form electric double layer. However, the pore structure differences of PEG-RF carbon xerogels result in their different EDLC performances. The distributed capacitance effect increases with decreasing the pore size of PEG-RF carbon xerogels.
基金Project(20574020) supported by the National Natural Science Foundation of ChinaProject(20061001) supported by the Opening Project of the Key Laboratory of Polymer Processing Engineering, Ministry of Education, ChinaProject (20060106-2) supported by Guangdong Key Projects
文摘Metal hydroxides （MAH） consisting of magnesium hydroxide and aluminum hydroxide with a mass ratio of 1：2 were surface-modified by y-diethoxyphosphorous ester propyldiethoxymethylsilane, boric acid and diphenylsilanediol in xylene under dibutyl tin dilaurate catalyst at 140 ℃. Phosphorus, silicon and boron elements covalently bonded to metal hydroxide particles were detected by X-ray photoelectron spectroscopy. The degradation behavior of the surface-modified MAH was characterized by thermogravimetric analysis. The results show that linear low density polyethylene （LLDPE） composite, filled with 50% （mass fraction） of MAH modified by 5.0% （mass fraction） of modifiers, passes the V-0 rating of UL-94 test and shows the limited oxygen index of 34%, and its heat release rate and average effective heat combustion in a cone calorimeter measurement decrease obviously; The mechanical properties of MAH can be improved by surface-modification. The uniform dispersion of particles and strong interfacial bonding between particles and matrix are obtained.
文摘In order to explore the mechanism of improving the surface wettability of low-energy polytetrafluoroethylene(PTFE)by new extended surfactants,five kinds of extended anionic surfactants with different numbers of oxypropylene(PO)and oxyethylene(EO),octadecyl-(PO)_(m)-(EO)_(n)-sodium carboxylate(C_(18)PO_(m)EO_(n)C,m=5,10,15,n=5,10,15),were studied.The surface tension and contact angle of C_(18)PO_(m)EO_(n)C solution with different concentrations were measured,and the adhesion tension,PTFE-water interfacial tension,and adhesion work were calculated.It was found that the extended surfactant molecules adsorb on the surface of the solution and the PTFE-liquid interface simultaneously when the concentration is lower than the critical micelle concentration(cmc),and there was a linear relationship between surface tension and adhesion tension.The adsorption amount of C_(18)PO_(m)EO_(n)C at the PTFE-water interface was significantly lower than that on the surface of the solution.As the concentration increases above cmc,semi-micelle aggregates on the surface of PTFE are formed by C_(18)PO_(m)EO_(n)C molecules through hydrophobic interaction,and the hydrophilic group faces the solution to modify the surface of PTFE with high efficiency.
文摘A nanomicelle(denoted as TPGS/Ppa)was fabricated via the coassembly of the amphiphilic D-α-tocopheryl polyethylene glycol 1000 succinate(TPGS)and the hydrophobic photosensitizer pyropheophorbide a(Ppa)for photodynamic therapy(PDT).The obtained nanomicelle possessed a spherical structure with a diameter of(18.0±2.2)nm and a zeta potential of approximately -18 mV.Besides,the nanomicelle exhibited excellent photostability,biocompatibility,and phototoxicity,and could effectively reach the tumor region via the enhanced permeability and retention effect.Additionally,it could be found that the TPGS/Ppa nanomicelle exhibited higher phototoxicity against 4T1 murine mammary cancer cells than free Ppa.In the 4T1 tumor-bearing mouse model,the nanomicelle showed an excellent antitumor therapeutic effect.This study develops a new type of photodynamic nanomicelle TPGS/Ppa,which can increase the accumulation of drugs and prolong their tumor retention time,providing a feasible strategy for realizing the delivery of small-molecule hydrophobic drugs and tumor PDT.
基金Project(20704011) supported by the National Natural Science Foundation of ChinaProject(09JJ3027) supported by the Natural Science Foundation of Hunan Province,ChinaProject(50725825) supported by the National Science Foundation for Distinguished Young Scholars
文摘A new multifunctional mPEG-b-PAA-grafted chitosan copolymer possessing amino and carboxyl groups,mPEG-b-PAA-g-CHI(compound 6) ,was designed for a potential application in gene/drug delivery and synthesized by the methods of reversible addition-fragmentation chain transfer(RAFT) polymerization of acrylic acid(AA) and grafting reaction of a biodegradable chitosan(CHI) derivative.Completion of the reactions and characterization of the resulting compounds were demonstrated by 1 H NMR,FTIR and gel permeation chtomatography(GPC) studies.The results show that the molar ratio of amino groups to carboxyl groups in the copolymer(compound 6) is 0.41-0.59.
文摘Composite polymer electrolytes based on polyethylene oxide(PEO) were prepared by using LiClO4 as doping salt and silane-modified SiO2 as filler. SiO2 was formed in-situ in (PEO)8LiClO4 matrix by the hydrolysis and condensation reaction of Si(OC4H9)4. The crystallinity,morphology and ionic conductivity of composite polymer electrolyte films were examined by differential scanning calorimetry,scanning electron microscopy,atom force microscopy and alternating current impedance spectroscopy,respectively. Compared with the crystallinity of the unmodified SiO2 as inert filler,that of composite polymer electrolytes is decreased. The results show that silane-modified SiO2 particles are uniformly dispersed in (PEO)8LiClO4 composite polymer electrolyte film and the addition of silane-modified SiO2 increases the ionic conductivity of the (PEO)8LiClO4 more noticeably. When the mass fraction of SiO2 is about 10%,the conductivity of (PEO)8LiClO4-modified SiO2 attains a maximum value of 4.8×10-5 S·cm-1.
基金supported in part by the National Natural Science Foundation of China(No.22075146)。
文摘Nitrocellulose,or cellulose nitrate,has received considerable interest due to its various applications,such as propellants,coating agents and gas generators.However,its high mechanical sensitivity caused many accidents during its storage and usage in ammunition.In this work,two kinds of insensitive step ladderstructured nitrocellulose(LNC)with different nitrogen contents were synthesized.The products were characterized by FT-IR,Raman,XRD,SEM,elemental analysis,TGA,DSC,accelerating rate calorimeter analysis(ARC),and drop weight test to study their molecular structure,thermal characteristics and desensitization performance.Compared with raw nitrocellulose,LNC has a sharper exothermic peak in the DSC and ARC curves.The H50values of the two kinds of LNC increased from 25.76 to 30.01 cm for low nitrogen content and from 18.02 to 21.84 cm for high nitrogen content,respectively.The results show that the ladder-structure of LNC which provides regular molecular arrangement and a soft buffer made with polyethylene glycol could affect the energy releasing process of LNC and reduce the sensitivity of LNC.Insensitive LNC provides an alternative to be used as a binder in insensitive propellants formulation.
文摘(PEO)8LiClO4-SiO2 composite polymer electrolytes(CPEs)were prepared by in-situ reaction,in which ethyl-orthosilicate(TEOS)was catalyzed by HCl and NH3.H2O,respectively.The ionic conductivity,the contact angle and the morphology of inorganic particles in the CPEs were investigated by AC impedance spectra,contact angle method and TEM.The conductivities of acid-catalyzed CPE and alkali-catalyzed CPE are 2.2×10-5and 1.1×10-5S/cm respectively at 30℃.The results imply that the catalyst plays an important role in the structure of in-situ preparation of SiO2,and influences the surface energy and conductivity of CPE films directly.Meanwhile,the ionic conductivity is related to the surface energy.
文摘PEO-LiClO4-TiO2 composite polymer electrolyte films were prepared. TiO2 was formed directly in matrix by hydrolysis and condensation reaction of tetrabutyl titanate. The crystallinity, morphology and ionic conductivity of composite polymer electrolyte films were examined by differential scanning calorimetry, scanning electron microscopy, atom force microscopy and alternating current impedance spectroscopy, respectively. The glass transition temperature and the crystallinity of composite polymer electrolytes are decreased compared with those of PEO-LiClO4 polymer electrolyte film. The results show that TiO2 particles are uniformly dispersed in PEO-LiClO4-5%TiO2 composite polymer electrolyte film. The maximal conductivity of 5.5×10、5 Scm at 20 ℃ of PEO-LiClO4-TiO2 film is obtained at 5% mass fraction of TiO2.
基金Project(2023JJ10070)supported by the Hunan Provincial Outstanding Youth Fund,ChinaProjects(51974364,52074355,52304316)supported by the National Natural Science Foundation of China。
文摘The reduced ability of fatty acids to dissolve and disperse at low temperatures limits their effectiveness in winter applications.In this study,a green and environment-friendly reagent,polyethylene glycol 2000(PEG-2000),was used to evaluate its effect on the collecting performance of sodium oleate during scheelite flotation at low temperatures.The effect of PEG-2000 on the flotation of scheelite with the collector sodium oleate(NaOL)was studied by flotation tests,surface tension tests,infrared spectral analysis,and zeta potential measurements.Flotation tests showed that adding PEG-2000 can enhance the collecting ability of NaOL on scheelite at low temperature(5℃).The recovery of scheelite with the mixed collector of PEG-200 and NaOL is 4.39%higher than that with NaOL only.The surface tension tests,infrared spectral analysis and zeta potential measurements revealed that PEG-2000 and OL^(−)are co-adsorbed on the scheelite surface at low temperatures.The presence of PEG-2000 promoted the increase of the adsorption concentration of oleate ions(OL^(−))on the scheelite surface.The reason was that PEG-2000 has a shielding effect on the electrostatic repulsion between the OL^(−)groups,which changes the micellar configuration of OL^(−)in the solution system and makes the OL^(−)gather more tightly on the surface of scheelite,leading to the enhancement of its hydrophobicity.This discovery provides a reference for the development of collecting reagents for efficient flotation recovery of scheelite under low temperature environment.
基金Project(20776161) supported by the National Natural Science Foundation of China
文摘The influence of temperature and mass fraction of Pluonic F127 on the rheological properties of polyvinyl butyric （PVB）/Pluronic F127/polyethylene glycol （PEG） 200 blend systems was investigated by a rotational rheometer with parallel plates. The results show that the blend systems approach homogeneous state at 140, 150 and 160℃while the rheological properties of the blend systems significantly deviate from the homogeneous systems at 120℃. Shear thinning behavior is observed for all the blend systems at different temperatures and is enhanced by increasing Pluronic F127 content. The complex viscosity, storage modulus, loss modulus, zero-shear activation energy and flow recovery of the blend systems increase with the increase of Pluronic F127 content. There is a crossing point for the loss modulus and the storage modulus of each sample at high frequency, which is called specified frequency （SF）. The loss modulus is larger than the storage modulus when the frequency is less than the SF, and when frequency is more than SF, the loss modulus is smaller than the storage modulus.
基金supported by the National Natural Science Foundation of China(52203016)the USTC Research Funds of the Double First-Class Initiative(YD9990002018)+3 种基金the Overseas Students Innovation and Entrepreneurship Support Program Project of Anhui Province(2021LCX022)the Key R&D Projects in Anhui Province(2022i01020012)the Natural Science Foundation of Hefei(2022039)the Excellent Research and Innovation Team Project of Anhui Province(2022AH010001).
文摘α-Diimide catalysts have attracted widespread attention due to their unique chain walking characteristics.A series ofα-diimide nickel/palladium catalysts with different electronic effects and steric hindrances were designed and synthesized for olefin polymerization.In this work,we synthesized a series of asymmetricα-diimide nickel complexes with different steric hindrances and used them for ethylene polymerization.These nickel catalysts have high ethylene polymerization activity,up to 6.51×10^(6)g·mol^(−1)·h^(−1),and the prepared polyethylene has a moderate melting point and high molecular weight(up to 38.2×10^(4)g·mol^(−1)),with a branching density distribution between 7 and 94 branches per 1000 carbons.More importantly,the polyethylene prepared by these catalysts exhibits excellent tensile properties,with strain and stress reaching 800%and 30 MPa,respectively.
文摘In this study, we investigated the performance improvement caused by the addition of copper(Cu)nanoparticles to high-density polyethylene(HDPE) matrix material. Composite materials, with filler percentages of 0.0, 2.0, 4.0, 6.0, 8.0, and 10.0 wt% were synthesized through the material extrusion(MEX)3D printing technique. The synthesized nanocomposite filaments were utilized for the manufacturing of specimens suitable for the experimental procedure that followed. Hence, we were able to systematically investigate their tensile, flexural, impact, and microhardness properties through various mechanical tests that were conducted according to the corresponding standards. Broadband Dielectric Spectroscopy was used to investigate the electrical/dielectric properties of the composites. Moreover, by employing means of Raman spectroscopy and thermogravimetric analysis(TGA) we were also able to further investigate their vibrational, structural, and thermal properties. Concomitantly, means of scanning electron microscopy(SEM), as well as atomic force microscopy(AFM), were used for the examination of the morphological and structural characteristics of the synthesized specimens, while energy-dispersive Xray spectroscopy(EDS) was also performed in order to receive a more detailed picture on the structural characteristics of the various synthesized composites. The corresponding nanomaterials were also assessed for their antibacterial properties regarding Staphylococcus aureus(S. aureus) and Escherichia coli(E. coli) with the assistance of a method named screening agar well diffusion. The results showed that the mechanical properties of HDPE benefited from the utilization of Cu as a filler, as they showed a notable improvement. The specimen of HDPE/Cu 4.0 wt% was the one that presented the highest levels of reinforcement in four out of the seven tested mechanical properties(for example, it exhibited a 36.7%improvement in the flexural strength, compared to the pure matrix). At the same time, the nanocomposites were efficient against the S. aureus bacterium and less efficient against the E. coli bacterium.The use of such multi-functional, robust nanocomposites in MEX 3D printing is positively impacting applications in various fields, most notably in the defense and security sectors. The latter becomes increasingly important if one takes into account that most firearms encompass various polymeric parts that require robustness and improved mechanical properties, while at the same time keeping the risk of spreading various infectious microorganisms at a bare minimum.
