For a highly efficient recycling of a wastewater containing a high concentration of MgCl_(2),Al(Ⅲ)and P507 were scheduled to be removed in advance.In this study,the in-situ removal of Al(Ⅲ)and P507 from a high conce...For a highly efficient recycling of a wastewater containing a high concentration of MgCl_(2),Al(Ⅲ)and P507 were scheduled to be removed in advance.In this study,the in-situ removal of Al(Ⅲ)and P507 from a high concentration MgCl_(2)solution at different pH values and Al/P molar ratios was investigated.The results showed that P507 formed organic complexes of Al_(x)(OH)_y^(Z+)-P507 at pH of 2.0-4.0.At pH of 4.0-5.0,Al(Ⅲ)precipitated and transferred into Al(OH)_(3)with a flocculent amorphous morphology.Active sites on the Al(OH)_(3)surface enhanced the removal efficiency of P507.At pH of 6.0-6.5,Al(Ⅲ)and Mg(Ⅱ)formed layered crystalline Al(OH)_(3)and MgAl_(2)(OH)_(8with)small pore channels and fewer active sites,resulting in a reduced removal efficiency of P507.When the Al/P molar ratio exceeded 13 and the pH was between 4.0 and 5.0,the removal rates of both Al(Ⅲ)and P507 were higher than98%,while the concentration loss of Mg(Ⅱ)was only 0.2%-0.9%.展开更多
Behenyl acrylate is a kind of highly efficient pour point depressants. In order to promote theapplication of the pour pint depressant in transportation of crude oils, polybehenyl acrylate was synthesizedby solution po...Behenyl acrylate is a kind of highly efficient pour point depressants. In order to promote theapplication of the pour pint depressant in transportation of crude oils, polybehenyl acrylate was synthesizedby solution polymerization. These conclusions can be drawn from the experimental results that the sequenceof chain transfer constants of four solvents is arranged in the following decreasing order: carbon tetrachloride(6.010-5)>chloroform (2.810-5)>methylbenzene (2.510-5)>tetrachloroethane (1.610-5). The average molecu-lar weight of polybehenyl acrylate mainly depends on the chain transfer constant of the solvents. However, ifthe monomer conversion was higher than 35%, an abnormal phenomenon occurred, resulting in higher aver-age molecular weight of polybehenyl acrylate obtained in methylbenzene solution compared to that obtainedin tetrachloroethane solution. It was attributed to the influence of gelation on the average molecular weight ofpolybehenyl acrylate, which was stronger than the impact of chain transfer in methylbenzene.展开更多
Biodegradable poly (D,L-lactide) (PLA)/carboxyl-functionalized multi-walled carbon nanotubes (c-MWCNTs) composites were achieved via in-situ polymerization. These as-prepared composite materials were characteriz...Biodegradable poly (D,L-lactide) (PLA)/carboxyl-functionalized multi-walled carbon nanotubes (c-MWCNTs) composites were achieved via in-situ polymerization. These as-prepared composite materials were characterized with FT-IR, XRD, TG, DSC, SEM, and high insulation resistance meter. The results demonstrate that the multi-walled carbon nanotube was carboxyl functionalized, which improved the collection between c-MWCNTs and PLA, and further realized the graft copolymerization of c-MWCNTs and PLA. There is a higher glass transition temperature and a lower pyrolysis temperature of PLA/c-MWCNTs composites than pure PLA. The c-MWCNTs gave a better dispersion than unmodified MWCNTs in the PLA matrix, and an even coating of PLA on the surface of c-MWCNTs was obtained, which increased the interfacial interaction. High insulation resistance analysis showed that the addition of c-MWCNTs increased the electric conductivity, and c-MWCNTs performed against the large dielectric coefficient and electrostatic state of PLA. These results demonstrated that c-MWCNTs modified PLA composites were beneficial for potential application in the development of heat-resisting and conductivity plastic engineering.展开更多
The diffusion of nanoparticles immersed in semidilute polymer solutions is investigated by a hybrid mesoscopic multiparticle collision dynamics method. Effects of polymer concentration and hydrodynamic interactions am...The diffusion of nanoparticles immersed in semidilute polymer solutions is investigated by a hybrid mesoscopic multiparticle collision dynamics method. Effects of polymer concentration and hydrodynamic interactions among polymer monomers are focused. Extensive simulations show that the dependence of diffusion coefficient D on the polymer concentration c agrees with Phillies equation D-exp (-αc^δ) with a scaling exponent δ≈0.97 which coincides with the experimental one in literature. For increasing nanoparticle size, the scaling prefactor α increases monotonically while the scaling exponent always keeps fixed. Moreover, we also study the diffusion of nanoparticle without hydrodynamic interactions and find that mobility of the nanoparticle slows down, and the scaling exponent is obviously different from the one in experiments, implying that hydrodynamic interactions play a crucial role in the diffusion of a nanoparticle in semidilute polymer solutions.展开更多
In this paper, a series of experiments, including atomic force microscope (AFM), environmental scanning electron microscope (ESEM), and core displacement tests were conducted to investigate the effect of polymer s...In this paper, a series of experiments, including atomic force microscope (AFM), environmental scanning electron microscope (ESEM), and core displacement tests were conducted to investigate the effect of polymer solution structure on solution properties and oil displacement efficiency. The results show that in the HPAM solution polymer coils were formed and then aggregated into a loose structure, while the HAP2010 solution formed a strong network structure, which would significantly improve the solution viscosity and flow resistance so as to upgrade the capacity of piston-like oil displacement in highly permeable porous media. Meanwhile, the retention of the HAP2010 solution at pore throats were also enhanced, which could reduce water production during subsequent water flooding and enlarge the swept volume during polymer flooding. Therefore, enhancing the interaction among polymer molecules is an effective way to improve the displacement efficiency of polymer solutions in heavy oil reservoirs with high permeability.展开更多
Performance characteristics of partially hydrolyzed polyacrylamide (HPAM) and cross- linked polymer (CLP, Cr^3+ as the cross linker) solutions have been investigated. A Brookfield viscometer, rheometer, dynamic l...Performance characteristics of partially hydrolyzed polyacrylamide (HPAM) and cross- linked polymer (CLP, Cr^3+ as the cross linker) solutions have been investigated. A Brookfield viscometer, rheometer, dynamic light scattering system, and core flow device have been used to measure the viscosity, viscoelasticity, polymer coil dimensions, molecular configuration, flow characteristics, and profile modification. The results show that, under conditions of high salinity and low HPAM and Cr^3+ concentrations, cross-linking mainly occurred between different chains of the same HPAM molecule in the presence of Cr^3+, and a cross-linked polymer (CLP) system with a local network structure was formed. Compared with an HPAM solution of the same concentration, the apparent viscosity of the CLP solution increased slightly or remained almost unchanged, but its viscoelasticity (namely storage modulus, loss modulus, and first normal stress difference) increased, and the resistance coefficient and residual resistance coefficient increased significantly. This indicates that the CLP solution exhibits a strong capability to divert the sequentially injected polymer flood from high-permeability zones to low- permeability zones in a reservoir. Under the same HPAM concentration conditions, the dimensions of polymer coils in the CLP solution increased slightly compared with the dimensions of polymer coils in HPAM solution, which were smaller than the rock pores, indicating that the cross-linked polymer solution was well adapted to reservoir rocks. Core flood experiments show that at the same cost of reagent, the oil recovery by CLP injection (HPAM-1, Cr^3+ as the cross linker) is 3.1% to 5.2% higher than that by HPAM- 2 injection.展开更多
The concentration dependence of the reduced viscosity of dilute polymer solution is interpreted in the light of a new concept of the self-association of polymer chains in dilute solution. The apparent self-association...The concentration dependence of the reduced viscosity of dilute polymer solution is interpreted in the light of a new concept of the self-association of polymer chains in dilute solution. The apparent self-association constant is defined as the molar association constant divided by the molar mass of individual polymer chain and is numerically interconvertible with the Huggins coefficient. The molar association constant is directly proportional to the effective hydrodynamic volume of the polymer chain in solution and is irrespective of the chain architecture. The effective hydrodynamic volume accounts for the non-spherical conformation of a short polymer chain in solution and is a product of a shape factor and hydrodynamic volume. The observed enhancement of Huggins coefficient for short chain and branched polymer is satisfactorily interpreted by the concept of self-association. The concept of self-association allows us to predict the existence of a boundary concentration C-s(dynamic contact concentration) which divides the dilute polymer solution into two regions.展开更多
Polyethylene oxide(PEO)-based solid polymer electrolytes(SPEs)with good electrochemical stability and excellent Li salt solubility are considered as one of the most promising SPEs for solid-state lithium metal batteri...Polyethylene oxide(PEO)-based solid polymer electrolytes(SPEs)with good electrochemical stability and excellent Li salt solubility are considered as one of the most promising SPEs for solid-state lithium metal batteries(SSLMBs).However,PEO-based SPEs suffer from low ionic conductivity at room temperature and high interfacial resistance with the electrodes due to poor interfacial contact,seriously hindering their practical applications.As an emerging technology,in-situ polymerization process has been widely used in PEO-based SPEs because it can effectively increase Li-ion transport at the interface and improve the interfacial contact between the electrolyte and electrodes.Herein,we review recent advances in design and fabrication of in-situ polymerized PEO-based SPEs to realize enhanced performance in LMBs.The merits and current challenges of various SPEs,as well as their stabilizing strategies are presented.Furthermore,various in-situ polymerization methods(such as free radical polymerization,cationic polymerization,anionic polymerization)for the preparation of PEO-based SPEs are summarized.In addition,the application of in-situ polymerization technology in PEO-based SPEs for adjustment of the functional units and addition of different functional filler materials was systematically discussed to explore the design concepts,methods and working mechanisms.Finally,the challenges and future prospects of in-situ polymerized PEO-based SPEs for SSLMBs are also proposed.展开更多
The influence of dissolved oxygen content on the oxidative stability of a linked polymer solution (LPS) was studied by micro-filtration, dynamic light scattering and viscosity measurements. The results showed that at ...The influence of dissolved oxygen content on the oxidative stability of a linked polymer solution (LPS) was studied by micro-filtration, dynamic light scattering and viscosity measurements. The results showed that at the same temperature, the degree of the oxidative degradation of the LPS increased and the rapidity of the oxidative degradation was accelerated with the increase of the dissolved oxygen content. Consequently, the size of linked polymer coils (LPCs) of the LPS became small, and the plugging capability of the LPS decreased. At a fixed content of dissolved oxygen, with increasing degradation temperature, almost the same results were observed, namely, an increased degree of oxidative degradation, accelerated rapidity of the oxidative degradation and decreased plugging capacity, with decreased oxidative stability of LPS. At 90 °C, in the presence of oxygen, LPS lost its plugging capability after having been degraded for a period of time. But at 40 °C, LPS with low dissolved oxygen content could be stable for a long time. The decreased plugging ability of LPS after oxidative degradation is mainly caused by the decreased size and number of the LPCs due to the breaking of hydrolyzed polyacrylamide (HPAM) molecule segments and the structural changing of HPAM molecules.展开更多
Careful measurements of the dilute solution viscosities of polyethylene glycol and polyvinyl alcohol in water were carried out. The reduced viscosities of both polymer solutions plot upward curves at extremely dilute ...Careful measurements of the dilute solution viscosities of polyethylene glycol and polyvinyl alcohol in water were carried out. The reduced viscosities of both polymer solutions plot upward curves at extremely dilute concentration levels similar to the phenomena observed for many polymer solutions in the early 1950's. Upon observation of the changes of the flow times of pure water in and the wall surface wettability of the viscometer after measuring solution viscosity, a view was formed that the observed viscosity abnormality at extremely dilute concentration regions is solely due to the effect of adsorption of polymer chains onto the wall surface of viscometer. A theory of adsorption effect based on the Langmuir isotherms was proposed and a mathematical; analysis for data treatment was performed. The theory could adequately describe the existing viscosity data. It seems necessary to correct the viscosity result of dilute polymer solutions measured by glass capillary viscometer by taking into account the effect of adsorption in all cases.展开更多
Based on the molecular theory of non-linear viscoelasticity with constrained entanglements in polymer melts, the material functions in simple shear flow were formulated, the theoretical relations between. eta((gamma) ...Based on the molecular theory of non-linear viscoelasticity with constrained entanglements in polymer melts, the material functions in simple shear flow were formulated, the theoretical relations between. eta((gamma) over dot), psi (10)((gamma) over dot) and shear rate ((gamma) over dot), and topologically constrained dimension number n ' and a were derived. Linear viscoelastic parameters (eta (0) and G(N)(0)) and topologically constrained dimension number (n ' a and <(<upsilon>)over bar>) as a function of the primary molecular weight (M-n), molecular weight between entanglements (M-C) and the entanglement sites sequence distribution in polymer chain were determined. A new method for determination of viscoelastic parameters (eta (0), psi (10), G(N)(0) and J(e)(0)), topologically constrained dimension number (n ', a and v) and molecular weight (M-n, M-c and M-e) from the shear flow measurements was proposed. It was used to determine those parameters and structures of HDPE, making a good agreement between these values and those obtained by other methods. The agreement affords a quantitative verification for the molecular theory of nonlinear viscoelasticity with constrained entanglement in polymer melts.展开更多
To extend the PSRK (predictive Soave-Redlich-Kwong equation of state) model to vapor-liquid equilibria of polymer solutions, a new EOS-gE mixing rule is applied in which the term ∑ xi ln(b/bi) in the PSRK mixing rule...To extend the PSRK (predictive Soave-Redlich-Kwong equation of state) model to vapor-liquid equilibria of polymer solutions, a new EOS-gE mixing rule is applied in which the term ∑ xi ln(b/bi) in the PSRK mixing rule for the parameter a, and the combinatorial part in the original universal functional activity coefficient (UNIFAC) model are cancelled. To take into account the free volume contribution to the excess Gibbs energy in polymer solution, a quadratic mixing rule for the cross co-volume bij with an exponent equals to 1/2 is applied[bij1/2= 1/2(bi1/2+bj1/2)]. The literature reported Soave-Redlich-Kwong equation of state (SRK EOS) parameters ofpure polymer are employed. The PSRK model with the modified mixing rule is used to predict the vapor-liquid equilibrium (VLE) of 37 solvent-polymer systems over a large range of temperature and pressure with satisfactory results.展开更多
An approach of stochastically statistical mechanics and a unified molecular theory of nonlinear viscoelasticity with constraints of Nagai chain entanglement for polymer melts have been proposed. A multimode model stru...An approach of stochastically statistical mechanics and a unified molecular theory of nonlinear viscoelasticity with constraints of Nagai chain entanglement for polymer melts have been proposed. A multimode model structure for a single polymer chain with n tail segments and N reversible entanglement sites on the test polymer chain is developed. Based on the above model structure and the mechanism of molecular flow by the dynamical reorganization of entanglement sites, the probability distribution function of the end-to-end vectr for a single polymer chain at entangled state and the viscoelastic free energy of deformation for polymer melts are calculated by using the method of the stochastically statistical mechanics. The four types of stress-strain relation and the memory function are derived from this thery. The above theoretical relations are verified by the experimentaf data for various polymer melts. These relations are found to be in good agreement with the experimental results展开更多
According to the behavior that the polymer solution has both the characteristics of viscosity and elastic properties, the transient flow mathe- matical model considered the viscoelasticity of the polymer solution has ...According to the behavior that the polymer solution has both the characteristics of viscosity and elastic properties, the transient flow mathe- matical model considered the viscoelasticity of the polymer solution has been established. The model, in which the variation of the rheological parameters during the seepage flow has been also taken into consideration, has been solved using finite-difference method. The type curves have been plotted. The influence of some properties of polymer solution including the viscocity, the elastic properties and the rheological parameters has been analyzed. Compared with the curves of the power-law fluid, it is shown that the pressure derivative curve considering the elasticity of the polymer solution upwarps less at the radial flow regime. Besides, it will come down as the variation of the rheological parameters, which is quite different from the case regarding them as constants. Therefore, in well test analysis on pressure of polymer solution, it’s necessary to consider the elasticity and the variation of the rheological parameters.展开更多
In this paper,the polymer chain of rotator(PCOR) equation of state(EOS) was used together with an EOS/G^E mixing rule(MHV1) and the Wilson's equation as an excess-Gibbs-energy model in the proposed approach to ext...In this paper,the polymer chain of rotator(PCOR) equation of state(EOS) was used together with an EOS/G^E mixing rule(MHV1) and the Wilson's equation as an excess-Gibbs-energy model in the proposed approach to extend the capability and improve the accuracy of the PCOR EOS for predicting the Henry's constant of solutions containing polymers.The results of the proposed method compared with two equation of state(van der Waals and GC-Flory) and three activity coefficient models(UNIFAC,UNIFAC-FV and Entropic-FV) indicated that the PCOR EOS/Wilson's equation provided more accurate results.The interaction parameters of Wilson's equation were fitted with Henry's constant experimental data and the property parameters of PCOR,a and b,were fitted with experimental volume data(Tait equation).As a result,the present work provided a simple and useful model for prediction of Henry's constant for polymer solutions.展开更多
The UNIQUAC excess Gibbs energy model of Abrams and Prausnitz(1975)is extended to represent thevapor-liquid equilibria of polymer solution with only two adjustable parameters.Discussions on the application ofthe Stave...The UNIQUAC excess Gibbs energy model of Abrams and Prausnitz(1975)is extended to represent thevapor-liquid equilibria of polymer solution with only two adjustable parameters.Discussions on the application ofthe Staverman-Guggenheim and the Flory-Huggins combinatorial contribution in the UNIQUAC model are givenin this paper.The UNIQUAC model with either Staverman-Guggenheim or Flory-Huggins combinatorial expres-sion presents results with about the same accuracy for polymer solutions.Comparisons between the UNIQUAC model and the Flory equation show that theUNIQUAC model can give some better results than the Flory equa-tion in general.展开更多
Thiol-ene click reaction is an intriguing strategy for preparing polymer electrolytes due to its high activity,atom economy and less side reaction.However,the explosive reaction rate and the use of non-electrolytic am...Thiol-ene click reaction is an intriguing strategy for preparing polymer electrolytes due to its high activity,atom economy and less side reaction.However,the explosive reaction rate and the use of non-electrolytic amine catalyst hamper its application in in-situ batteries.Herein,a nitrogen-containing eutectic solution is designed as both the catalyst of the thiol-ene reaction and the plasticizer to in-situ synthesize the gel polymer electrolytes,realizing a mild in-situ gelation process and the preparation of high-performance gel electrolytes.The obtained gel polymer electrolytes exhibit a high ionic conductivity of 4×10^(−4)S cm^(−1)and lithium-ion transference number(t_(Li)^(+))of 0.51 at 60°C.The as-assembled Li/LiFePO_(4)(LFP)cell delivers a high initial discharge capacity of 155.9 mAh g^(-1),and a favorable cycling stability with the capacity retention of 82%after 800 cycles at 1 C is also obtained.In addition,this eutectic solution significantly improves the rate performance of the LFP cell with high specific capacity of 141.5 and 126.8 mAh g^(-1)at 5 C and 10 C,respectively,and the cell can steadily work at various charge–discharge rate for 200 cycles.This powerful and efficient strategy may provide a novel way for in-situ preparing gel polymer electrolytes with desirable comprehensive performances.展开更多
Polypropylene/montmorillonite (PP/MMT)nanocomposites were prepared by in-situ polymerization using aMMT/MgCl_2/TiCl_4-EB Ziegler-Natta catalyst activated by triethylaluminum(TEA). The enlarged layer spacing of MMT was...Polypropylene/montmorillonite (PP/MMT)nanocomposites were prepared by in-situ polymerization using aMMT/MgCl_2/TiCl_4-EB Ziegler-Natta catalyst activated by triethylaluminum(TEA). The enlarged layer spacing of MMT wasconfirmed by X-ray wide angle diffraction (WAXD), demonstrating that MMT were intercalated by the catalyst components.X-ray photoelectron spectrometry (XPS) analysis proved that TiCl_4 was mainly supported on MgCl_2 instead of on the surfaceof MMT The exfoliated structure of MMT layers in the PP matrix of PP/MMT composites was demonstrated by WAXDpatterns and transmission electron microscopy (TEM) observation. The higher glass transition temperature and higher storage modulus of the PP/MMT composites in comparison with pure PP were revealed by dynamic mechanical analysis (DMA).展开更多
Polysulfonamide/zinc oxide(PSA/ZnO) nanocomposite films with w(ZnO)=0.5% were prepared by in-situ polymerization based on 4,4′-diaminodiphenylsulfone and terephthaloyl chloride in the common solvent N,N-Dimethylaceta...Polysulfonamide/zinc oxide(PSA/ZnO) nanocomposite films with w(ZnO)=0.5% were prepared by in-situ polymerization based on 4,4′-diaminodiphenylsulfone and terephthaloyl chloride in the common solvent N,N-Dimethylacetamide(DMAc). Atomic force microscopy (AFM) was employed to observe the microstructure of the composite film. The thermal property was investigated by TGA and mechanical property was characterized by DXLL-1000 electromechanical material testing machine. The results showed that the breaking strength of the film containing 0.5% ZnO was great enhanced. The average size of ZnO particles was below 100 nm. The introduction of ZnO as nano filler in PSA react as UV shield effect and make the composite mechanical property improved.展开更多
基金financial supports from the National Key Research and Development Program of China(No.2022YFB3504501)the National Natural Science Foundation of China(Nos.52274355,91962211)the Gansu Province Science and Technology Major Special Project,China(No.22ZD6GD061)。
文摘For a highly efficient recycling of a wastewater containing a high concentration of MgCl_(2),Al(Ⅲ)and P507 were scheduled to be removed in advance.In this study,the in-situ removal of Al(Ⅲ)and P507 from a high concentration MgCl_(2)solution at different pH values and Al/P molar ratios was investigated.The results showed that P507 formed organic complexes of Al_(x)(OH)_y^(Z+)-P507 at pH of 2.0-4.0.At pH of 4.0-5.0,Al(Ⅲ)precipitated and transferred into Al(OH)_(3)with a flocculent amorphous morphology.Active sites on the Al(OH)_(3)surface enhanced the removal efficiency of P507.At pH of 6.0-6.5,Al(Ⅲ)and Mg(Ⅱ)formed layered crystalline Al(OH)_(3)and MgAl_(2)(OH)_(8with)small pore channels and fewer active sites,resulting in a reduced removal efficiency of P507.When the Al/P molar ratio exceeded 13 and the pH was between 4.0 and 5.0,the removal rates of both Al(Ⅲ)and P507 were higher than98%,while the concentration loss of Mg(Ⅱ)was only 0.2%-0.9%.
文摘Behenyl acrylate is a kind of highly efficient pour point depressants. In order to promote theapplication of the pour pint depressant in transportation of crude oils, polybehenyl acrylate was synthesizedby solution polymerization. These conclusions can be drawn from the experimental results that the sequenceof chain transfer constants of four solvents is arranged in the following decreasing order: carbon tetrachloride(6.010-5)>chloroform (2.810-5)>methylbenzene (2.510-5)>tetrachloroethane (1.610-5). The average molecu-lar weight of polybehenyl acrylate mainly depends on the chain transfer constant of the solvents. However, ifthe monomer conversion was higher than 35%, an abnormal phenomenon occurred, resulting in higher aver-age molecular weight of polybehenyl acrylate obtained in methylbenzene solution compared to that obtainedin tetrachloroethane solution. It was attributed to the influence of gelation on the average molecular weight ofpolybehenyl acrylate, which was stronger than the impact of chain transfer in methylbenzene.
基金Projects(21107032,51073072)supported by the National Natural Science Foundation of ChinaProjects(Y406469,Y4110555,Y4100745)supported by Natural Science Foundation of Zhejiang Province,ChinaProjects(2011AY1048-5,2011AY1030)supported by the Science Foundation of Jiaxing Science and Technology Bureau,China
文摘Biodegradable poly (D,L-lactide) (PLA)/carboxyl-functionalized multi-walled carbon nanotubes (c-MWCNTs) composites were achieved via in-situ polymerization. These as-prepared composite materials were characterized with FT-IR, XRD, TG, DSC, SEM, and high insulation resistance meter. The results demonstrate that the multi-walled carbon nanotube was carboxyl functionalized, which improved the collection between c-MWCNTs and PLA, and further realized the graft copolymerization of c-MWCNTs and PLA. There is a higher glass transition temperature and a lower pyrolysis temperature of PLA/c-MWCNTs composites than pure PLA. The c-MWCNTs gave a better dispersion than unmodified MWCNTs in the PLA matrix, and an even coating of PLA on the surface of c-MWCNTs was obtained, which increased the interfacial interaction. High insulation resistance analysis showed that the addition of c-MWCNTs increased the electric conductivity, and c-MWCNTs performed against the large dielectric coefficient and electrostatic state of PLA. These results demonstrated that c-MWCNTs modified PLA composites were beneficial for potential application in the development of heat-resisting and conductivity plastic engineering.
文摘The diffusion of nanoparticles immersed in semidilute polymer solutions is investigated by a hybrid mesoscopic multiparticle collision dynamics method. Effects of polymer concentration and hydrodynamic interactions among polymer monomers are focused. Extensive simulations show that the dependence of diffusion coefficient D on the polymer concentration c agrees with Phillies equation D-exp (-αc^δ) with a scaling exponent δ≈0.97 which coincides with the experimental one in literature. For increasing nanoparticle size, the scaling prefactor α increases monotonically while the scaling exponent always keeps fixed. Moreover, we also study the diffusion of nanoparticle without hydrodynamic interactions and find that mobility of the nanoparticle slows down, and the scaling exponent is obviously different from the one in experiments, implying that hydrodynamic interactions play a crucial role in the diffusion of a nanoparticle in semidilute polymer solutions.
基金supported by the National Science and Technology Major Project (2011ZX05024-004)National High Technology Research and Development Program of China (863 Program: 2007AA090701-3)
文摘In this paper, a series of experiments, including atomic force microscope (AFM), environmental scanning electron microscope (ESEM), and core displacement tests were conducted to investigate the effect of polymer solution structure on solution properties and oil displacement efficiency. The results show that in the HPAM solution polymer coils were formed and then aggregated into a loose structure, while the HAP2010 solution formed a strong network structure, which would significantly improve the solution viscosity and flow resistance so as to upgrade the capacity of piston-like oil displacement in highly permeable porous media. Meanwhile, the retention of the HAP2010 solution at pore throats were also enhanced, which could reduce water production during subsequent water flooding and enlarge the swept volume during polymer flooding. Therefore, enhancing the interaction among polymer molecules is an effective way to improve the displacement efficiency of polymer solutions in heavy oil reservoirs with high permeability.
基金financial support from the National Key Technology R&D Program in the 12th Five Year Plan of PetroChina (No: 2011ZX05010-003-02)the National Key Technology R&D Program in the 12th Five Year Plan of CNOOC (No: 2011ZX05024-04-05-03)
文摘Performance characteristics of partially hydrolyzed polyacrylamide (HPAM) and cross- linked polymer (CLP, Cr^3+ as the cross linker) solutions have been investigated. A Brookfield viscometer, rheometer, dynamic light scattering system, and core flow device have been used to measure the viscosity, viscoelasticity, polymer coil dimensions, molecular configuration, flow characteristics, and profile modification. The results show that, under conditions of high salinity and low HPAM and Cr^3+ concentrations, cross-linking mainly occurred between different chains of the same HPAM molecule in the presence of Cr^3+, and a cross-linked polymer (CLP) system with a local network structure was formed. Compared with an HPAM solution of the same concentration, the apparent viscosity of the CLP solution increased slightly or remained almost unchanged, but its viscoelasticity (namely storage modulus, loss modulus, and first normal stress difference) increased, and the resistance coefficient and residual resistance coefficient increased significantly. This indicates that the CLP solution exhibits a strong capability to divert the sequentially injected polymer flood from high-permeability zones to low- permeability zones in a reservoir. Under the same HPAM concentration conditions, the dimensions of polymer coils in the CLP solution increased slightly compared with the dimensions of polymer coils in HPAM solution, which were smaller than the rock pores, indicating that the cross-linked polymer solution was well adapted to reservoir rocks. Core flood experiments show that at the same cost of reagent, the oil recovery by CLP injection (HPAM-1, Cr^3+ as the cross linker) is 3.1% to 5.2% higher than that by HPAM- 2 injection.
基金This work was supported by the Chinese National Basic Research Project "Macromolecular Condensed State" and National Natural Science Foundation of China
文摘The concentration dependence of the reduced viscosity of dilute polymer solution is interpreted in the light of a new concept of the self-association of polymer chains in dilute solution. The apparent self-association constant is defined as the molar association constant divided by the molar mass of individual polymer chain and is numerically interconvertible with the Huggins coefficient. The molar association constant is directly proportional to the effective hydrodynamic volume of the polymer chain in solution and is irrespective of the chain architecture. The effective hydrodynamic volume accounts for the non-spherical conformation of a short polymer chain in solution and is a product of a shape factor and hydrodynamic volume. The observed enhancement of Huggins coefficient for short chain and branched polymer is satisfactorily interpreted by the concept of self-association. The concept of self-association allows us to predict the existence of a boundary concentration C-s(dynamic contact concentration) which divides the dilute polymer solution into two regions.
基金This work was supported by the Major Science and Technology Projects of Henan Province(221100230200)the National Key Research and Development Program of China(2020YFB1713500)Open Fund of State Key Laboratory of Advanced Refractories(No.SKLAR202210).
文摘Polyethylene oxide(PEO)-based solid polymer electrolytes(SPEs)with good electrochemical stability and excellent Li salt solubility are considered as one of the most promising SPEs for solid-state lithium metal batteries(SSLMBs).However,PEO-based SPEs suffer from low ionic conductivity at room temperature and high interfacial resistance with the electrodes due to poor interfacial contact,seriously hindering their practical applications.As an emerging technology,in-situ polymerization process has been widely used in PEO-based SPEs because it can effectively increase Li-ion transport at the interface and improve the interfacial contact between the electrolyte and electrodes.Herein,we review recent advances in design and fabrication of in-situ polymerized PEO-based SPEs to realize enhanced performance in LMBs.The merits and current challenges of various SPEs,as well as their stabilizing strategies are presented.Furthermore,various in-situ polymerization methods(such as free radical polymerization,cationic polymerization,anionic polymerization)for the preparation of PEO-based SPEs are summarized.In addition,the application of in-situ polymerization technology in PEO-based SPEs for adjustment of the functional units and addition of different functional filler materials was systematically discussed to explore the design concepts,methods and working mechanisms.Finally,the challenges and future prospects of in-situ polymerized PEO-based SPEs for SSLMBs are also proposed.
文摘The influence of dissolved oxygen content on the oxidative stability of a linked polymer solution (LPS) was studied by micro-filtration, dynamic light scattering and viscosity measurements. The results showed that at the same temperature, the degree of the oxidative degradation of the LPS increased and the rapidity of the oxidative degradation was accelerated with the increase of the dissolved oxygen content. Consequently, the size of linked polymer coils (LPCs) of the LPS became small, and the plugging capability of the LPS decreased. At a fixed content of dissolved oxygen, with increasing degradation temperature, almost the same results were observed, namely, an increased degree of oxidative degradation, accelerated rapidity of the oxidative degradation and decreased plugging capacity, with decreased oxidative stability of LPS. At 90 °C, in the presence of oxygen, LPS lost its plugging capability after having been degraded for a period of time. But at 40 °C, LPS with low dissolved oxygen content could be stable for a long time. The decreased plugging ability of LPS after oxidative degradation is mainly caused by the decreased size and number of the LPCs due to the breaking of hydrolyzed polyacrylamide (HPAM) molecule segments and the structural changing of HPAM molecules.
基金This work was supported by the National Basic Research Project-Macromolecular Condensed State,and the National Natural Science Foundationof China
文摘Careful measurements of the dilute solution viscosities of polyethylene glycol and polyvinyl alcohol in water were carried out. The reduced viscosities of both polymer solutions plot upward curves at extremely dilute concentration levels similar to the phenomena observed for many polymer solutions in the early 1950's. Upon observation of the changes of the flow times of pure water in and the wall surface wettability of the viscometer after measuring solution viscosity, a view was formed that the observed viscosity abnormality at extremely dilute concentration regions is solely due to the effect of adsorption of polymer chains onto the wall surface of viscometer. A theory of adsorption effect based on the Langmuir isotherms was proposed and a mathematical; analysis for data treatment was performed. The theory could adequately describe the existing viscosity data. It seems necessary to correct the viscosity result of dilute polymer solutions measured by glass capillary viscometer by taking into account the effect of adsorption in all cases.
基金The authors gratefully a.cknowledge financial supportfrom th6 Natiol-al Natural Science Foundatiol- of CI-h-a. The number of
文摘Based on the molecular theory of non-linear viscoelasticity with constrained entanglements in polymer melts, the material functions in simple shear flow were formulated, the theoretical relations between. eta((gamma) over dot), psi (10)((gamma) over dot) and shear rate ((gamma) over dot), and topologically constrained dimension number n ' and a were derived. Linear viscoelastic parameters (eta (0) and G(N)(0)) and topologically constrained dimension number (n ' a and <(<upsilon>)over bar>) as a function of the primary molecular weight (M-n), molecular weight between entanglements (M-C) and the entanglement sites sequence distribution in polymer chain were determined. A new method for determination of viscoelastic parameters (eta (0), psi (10), G(N)(0) and J(e)(0)), topologically constrained dimension number (n ', a and v) and molecular weight (M-n, M-c and M-e) from the shear flow measurements was proposed. It was used to determine those parameters and structures of HDPE, making a good agreement between these values and those obtained by other methods. The agreement affords a quantitative verification for the molecular theory of nonlinear viscoelasticity with constrained entanglement in polymer melts.
文摘To extend the PSRK (predictive Soave-Redlich-Kwong equation of state) model to vapor-liquid equilibria of polymer solutions, a new EOS-gE mixing rule is applied in which the term ∑ xi ln(b/bi) in the PSRK mixing rule for the parameter a, and the combinatorial part in the original universal functional activity coefficient (UNIFAC) model are cancelled. To take into account the free volume contribution to the excess Gibbs energy in polymer solution, a quadratic mixing rule for the cross co-volume bij with an exponent equals to 1/2 is applied[bij1/2= 1/2(bi1/2+bj1/2)]. The literature reported Soave-Redlich-Kwong equation of state (SRK EOS) parameters ofpure polymer are employed. The PSRK model with the modified mixing rule is used to predict the vapor-liquid equilibrium (VLE) of 37 solvent-polymer systems over a large range of temperature and pressure with satisfactory results.
文摘An approach of stochastically statistical mechanics and a unified molecular theory of nonlinear viscoelasticity with constraints of Nagai chain entanglement for polymer melts have been proposed. A multimode model structure for a single polymer chain with n tail segments and N reversible entanglement sites on the test polymer chain is developed. Based on the above model structure and the mechanism of molecular flow by the dynamical reorganization of entanglement sites, the probability distribution function of the end-to-end vectr for a single polymer chain at entangled state and the viscoelastic free energy of deformation for polymer melts are calculated by using the method of the stochastically statistical mechanics. The four types of stress-strain relation and the memory function are derived from this thery. The above theoretical relations are verified by the experimentaf data for various polymer melts. These relations are found to be in good agreement with the experimental results
文摘According to the behavior that the polymer solution has both the characteristics of viscosity and elastic properties, the transient flow mathe- matical model considered the viscoelasticity of the polymer solution has been established. The model, in which the variation of the rheological parameters during the seepage flow has been also taken into consideration, has been solved using finite-difference method. The type curves have been plotted. The influence of some properties of polymer solution including the viscocity, the elastic properties and the rheological parameters has been analyzed. Compared with the curves of the power-law fluid, it is shown that the pressure derivative curve considering the elasticity of the polymer solution upwarps less at the radial flow regime. Besides, it will come down as the variation of the rheological parameters, which is quite different from the case regarding them as constants. Therefore, in well test analysis on pressure of polymer solution, it’s necessary to consider the elasticity and the variation of the rheological parameters.
基金financial support provided by Islamic Azad University of Mahshahr Branch,Iran
文摘In this paper,the polymer chain of rotator(PCOR) equation of state(EOS) was used together with an EOS/G^E mixing rule(MHV1) and the Wilson's equation as an excess-Gibbs-energy model in the proposed approach to extend the capability and improve the accuracy of the PCOR EOS for predicting the Henry's constant of solutions containing polymers.The results of the proposed method compared with two equation of state(van der Waals and GC-Flory) and three activity coefficient models(UNIFAC,UNIFAC-FV and Entropic-FV) indicated that the PCOR EOS/Wilson's equation provided more accurate results.The interaction parameters of Wilson's equation were fitted with Henry's constant experimental data and the property parameters of PCOR,a and b,were fitted with experimental volume data(Tait equation).As a result,the present work provided a simple and useful model for prediction of Henry's constant for polymer solutions.
文摘The UNIQUAC excess Gibbs energy model of Abrams and Prausnitz(1975)is extended to represent thevapor-liquid equilibria of polymer solution with only two adjustable parameters.Discussions on the application ofthe Staverman-Guggenheim and the Flory-Huggins combinatorial contribution in the UNIQUAC model are givenin this paper.The UNIQUAC model with either Staverman-Guggenheim or Flory-Huggins combinatorial expres-sion presents results with about the same accuracy for polymer solutions.Comparisons between the UNIQUAC model and the Flory equation show that theUNIQUAC model can give some better results than the Flory equa-tion in general.
基金the National Natural Science Foundation of China(Grant no.51973073)the Fel owship of China Postdoctoral Science Foundation(2021M701303)the analytical and testing assistance from the Analysis and Testing Center of HUST for support of this work
文摘Thiol-ene click reaction is an intriguing strategy for preparing polymer electrolytes due to its high activity,atom economy and less side reaction.However,the explosive reaction rate and the use of non-electrolytic amine catalyst hamper its application in in-situ batteries.Herein,a nitrogen-containing eutectic solution is designed as both the catalyst of the thiol-ene reaction and the plasticizer to in-situ synthesize the gel polymer electrolytes,realizing a mild in-situ gelation process and the preparation of high-performance gel electrolytes.The obtained gel polymer electrolytes exhibit a high ionic conductivity of 4×10^(−4)S cm^(−1)and lithium-ion transference number(t_(Li)^(+))of 0.51 at 60°C.The as-assembled Li/LiFePO_(4)(LFP)cell delivers a high initial discharge capacity of 155.9 mAh g^(-1),and a favorable cycling stability with the capacity retention of 82%after 800 cycles at 1 C is also obtained.In addition,this eutectic solution significantly improves the rate performance of the LFP cell with high specific capacity of 141.5 and 126.8 mAh g^(-1)at 5 C and 10 C,respectively,and the cell can steadily work at various charge–discharge rate for 200 cycles.This powerful and efficient strategy may provide a novel way for in-situ preparing gel polymer electrolytes with desirable comprehensive performances.
文摘Polypropylene/montmorillonite (PP/MMT)nanocomposites were prepared by in-situ polymerization using aMMT/MgCl_2/TiCl_4-EB Ziegler-Natta catalyst activated by triethylaluminum(TEA). The enlarged layer spacing of MMT wasconfirmed by X-ray wide angle diffraction (WAXD), demonstrating that MMT were intercalated by the catalyst components.X-ray photoelectron spectrometry (XPS) analysis proved that TiCl_4 was mainly supported on MgCl_2 instead of on the surfaceof MMT The exfoliated structure of MMT layers in the PP matrix of PP/MMT composites was demonstrated by WAXDpatterns and transmission electron microscopy (TEM) observation. The higher glass transition temperature and higher storage modulus of the PP/MMT composites in comparison with pure PP were revealed by dynamic mechanical analysis (DMA).
基金Education Commission of Shanghai (No04AB19)Science and Technology Commission of Shanghai Municipal Government(Nano Founds No 0452NM051)
文摘Polysulfonamide/zinc oxide(PSA/ZnO) nanocomposite films with w(ZnO)=0.5% were prepared by in-situ polymerization based on 4,4′-diaminodiphenylsulfone and terephthaloyl chloride in the common solvent N,N-Dimethylacetamide(DMAc). Atomic force microscopy (AFM) was employed to observe the microstructure of the composite film. The thermal property was investigated by TGA and mechanical property was characterized by DXLL-1000 electromechanical material testing machine. The results showed that the breaking strength of the film containing 0.5% ZnO was great enhanced. The average size of ZnO particles was below 100 nm. The introduction of ZnO as nano filler in PSA react as UV shield effect and make the composite mechanical property improved.