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1.
The purpose of this study is to overcome the poor dimensional stability of poly(vinylidene fluoride) (PVDF)-based electrospun membranes for polymer electrolytes, a new type of composite fibrous membranes based on PVDF/poly(2-acrylamido-2-methylpropanesulfonic acid lithium) (PAMPSLi) blend systems with different blend ratios were fabricated by electrospinning method. Morphology of the composite fibrous membranes was evaluated by scanning electron microscopy. Average diameters of the membranes were less than 250 nm, which were far less than that of pure PVDF fibrous membrane (400 nm). Fourier transform infrared spectroscopy and Raman scattering were used to characterize the interactions of two polymers. Wide-angle X-ray diffraction and differential scanning calorimetry techniques were applied to investigate the crystal structure of composite fibrous membranes. Owning to the good miscibility between PVDF and PAMPSLi, no phase-separated microstructure was observed in composite fibrous membranes. The membranes possessed a good wettability by liquid electrolytes and exhibited an excellent dimensional stability even at high loading of electrolytes. The polymer electrolyte showed the ionic conductivity of 3.45 × 10?3 S/cm at room temperature and electrochemical stability up to 5.4 V for the blend ratio of 5/1. PVDF/PAMPSLi (5/1)-based polymer electrolyte was observed much more suitable than polymer electrolytes with other ratios of PVDF/PAMPSLi for application in high-performance lithium rechargeable batteries.  相似文献   

2.
In this study, solvent‐free nanofibrous electrolytes were fabricated through an electrospinning method. Polyethylene oxide (PEO), lithium perchlorate and ethylene carbonate were used as polymer matrix, salt and plasticizer respectively in the electrolyte structures. Keggin‐type hetero polyoxometalate (Cu‐POM@Ru‐rGO, Ni‐POM@Ru‐rGO and Co‐POM@Ru‐rGO (POM, polyoxometalate; rGO, reduced graphene oxide)) nanoparticles were synthesized and inserted into the PEO‐based nanofibrous electrolytes. TEM and SEM analyses were carried out for further evaluation of the synthesized filler structures and the electrospun nanofibre morphologies. The fractions of free ions and crystalline phases of the as‐spun electrolytes were estimated by obtaining Fourier transform infrared and XRD spectra, respectively. The results showed a significant improvement in the ionic conductivity of the nanofibrous electrolytes by increasing filler concentrations. The highest ionic conductivity of 0.28 mS cm?1 was obtained by the introduction of 0.49 wt% Co‐POM@Ru‐rGO into the electrospun electrolyte at ambient temperature. Compared with solution‐cast polymeric electrolytes, the electrospun electrolytes present superior ionic conductivity. Moreover, the cycle stability of the as‐spun electrolytes was clearly improved by the addition of fillers. Furthermore, the mechanical strength was enhanced with the insertion of 0.07 wt% fillers to the electrospun electrolytes. The results implied that the prepared nanofibres are good candidates as solvent‐free electrolytes for lithium ion batteries. © 2020 Society of Chemical Industry  相似文献   

3.
Achievement of high conductivity and electrochemical window at ambient temperature for an all‐solid polymer electrolyte used in lithium ion batteries is a challenge. Here, we report the synthesis and characterization of a novel solid‐state single‐ion electrolytes based on comb‐like siloxane copolymer with pendant lithium 4‐styrenesulfonyl (perfluorobutylsulfonyl) imide and poly(ethylene glycol). The highly delocalized anionic charges of ? SO2? N(–)? C4F9 have a weak association with lithium ions, resulting in the increase of mobile lithium ions number. The designed polymer electrolytes possess ultra‐low glass transition temperature in the range from ?73 to ?54 °C due to the special flexible polysiloxane. Promising electrochemical properties have been obtained, including a remarkably high conductivity of 3.7 × 10?5 S/cm and electrochemical window of 5.2 V (vs. Li+/Li) at room temperature. A high lithium ion transference number of 0.80, and good compatibility with anode were also observed. These prominent characteristics endow the polymer electrolyte a potential for the application in high safety lithium ion batteries. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45848.  相似文献   

4.
BACKGROUND: Much interest has recently been shown in improving the performance of lithium‐ion polymer batteries with gel polymer electrolytes (GPEs) due to a rapid expansion in industrial demand. Novel GPEs based on poly(vinylidene fluoride)‐graft‐poly(tert‐butyl acrylate) (PVDF‐gtBA) microporous mats are suggested in this study. RESULTS: Microfibrous polymer electrolytes were prepared using electrospinning and characterized for extent of grafting, morphology, crystallinity, electrochemical stability, ionic conductivity, interfacial resistance and cell cycleability. The degree of crystallinity was lower for tBA‐grafted PVDF mats than that of neat PVDF. The PVDF‐gtBA showed an improvement in the ionic conductivity, electrochemical stability, interfacial resistance and cyclic performance. CONCLUSION: The tBA‐grafted PVDF microporous electrolytes are promising candidates for enhancing the performance of lithium‐ion polymer batteries. Copyright © 2008 Society of Chemical Industry  相似文献   

5.
Modified carbon nanotubes (m‐CNTs) were successfully prepared by the interactions between nitric and sulfuric acids and CNTs, which was confirmed using Fourier transform infrared spectroscopy. Poly[(vinylidene fluoride)‐co‐hexafluoropropylene]‐based composite polymer electrolyte (CPE) membranes doped with various amounts of m‐CNTs were prepared by phase inversion method. The desired CPEs were obtained by soaking the liquid electrolytes for 30 min. The physicochemical and electrochemical properties of the CPE membranes were investigated using scanning electron microscopy, X‐ray diffraction, thermogravimetry, electrochemical impedance spectroscopy and linear sweep voltammetry. The results show that the CPE membranes doped with 2.2 wt% m‐CNTs possess the smoothest surface and the highest decomposition temperature about 450 °C. Obviously, adding an appropriate amount of m‐CNTs into the polymer matrix can decrease the crystallinity and enhance the ionic conductivity; the temperature dependence of ionic conductivity follows the Arrhenius relation and the ionic conductivity at room temperature is up to 4.9 mS cm?1. The interfacial resistance can reach a stable value of about 415 Ω cm?2 after 10 days storage. The excellent rate and cycle performances with an electrochemical working window up to 5.4 V ensure that the CPEs doped with 2.2 wt% m‐CNTs can be considered as potential candidates as polymer electrolyte for lithium ion batteries. © 2013 Society of Chemical Industry  相似文献   

6.
Poly(2‐acrylamido glycolic acid‐co‐2‐acrylamido‐2‐methyl‐1‐propane sulfonic acid) [P(AGA‐co‐APSA)] was synthesized by radical polymerization in an aqueous solution. The water‐soluble polymer, containing secondary amide, hydroxyl, carboxylic, and sulfonic acid groups, was investigated, in view of their metal‐ion‐binding properties, as a polychelatogen with the liquid‐phase polymer‐based retention technique under different experimental conditions. The investigated metal ions were Ag+, Co2+, Ni2+, Cu2+, Zn2+, Cd2+, Pb2+, and Cr3+, and these were studied at pHs 3, 5, and 7. P(AGA‐co‐APSA) showed efficient retention of all metal ions at the pHs studied, with a minimum of 60% for Co(II) at pH 3 and a maximum close to 100% at pH 7 for all metal ions. The maximum retention capacity (n metal ion/n polymer) ranged from 0.22 for Cd2+ to 0.34 for Ag+. The antibacterial activity of Ag+, Cu2+, Zn2+, and Cd2+ polymer–metal complexes was studied, and P(AGA‐co‐APSA)–Cd2+ presented selective antibacterial activity for Staphylococcus aureus with a minimum inhibitory concentration of 2 μg/mL. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009  相似文献   

7.
Two oxetane‐derived monomers 3‐(2‐cyanoethoxy)methyl‐ and 3‐(methoxy(triethylenoxy)) methyl‐3′‐methyloxetane were prepared from the reaction of 3‐methyl‐3′‐hydroxymethyloxetane with acrylonitrile and triethylene glycol monomethyl ether, respectively. Their homo‐ and copolyethers were synthesized with BF3· Et2O/1,4‐butanediol and trifluoromethane sulfonic acid as initiator through cationic ring‐opening polymerization. The structure of the polymers was characterized by FTIR and1H NMR. The ratio of two repeating units incorporated into the copolymers is well consistent with the feed ratio. Regarding glass transition temperature (Tg), the DSC data imply that the resulting copolymers have a lower Tg than pure poly(ethylene oxide). Moreover, the TGA measurements reveal that they possess in general a high heat decomposition temperature. The ion conductivity of a sample (P‐AN 20) is 1.07 × 10?5 S cm?1 at room temperature and 2.79 × 10?4 S cm?1 at 80 °C, thus presenting the potential to meet the practical requirement of lithium ion batteries for polymer electrolytes. Copyright © 2005 Society of Chemical Industry  相似文献   

8.
Summary: Two distinct types of polymer electrolyte membranes for conducting protons and lithium ions have been prepared by a radiation‐induced grafting method. The polymer electrolyte precursor (PVDF‐g‐PS) is obtained by the simultaneous grafting of styrene onto poly(vinylidene fluoride) (PVDF) followed by one of two specific treatments. This includes sulfonation with a chlorosulfonic acid/dichloromethane mixture to obtain proton (H+)‐conducting membranes, or activation with LiPF6/EC/DC liquid electrolyte to obtain lithium ion (Li+)‐conducting membranes. The chemical structure of the obtained electrolyte membranes is verified by FT‐IR spectroscopy. Differential scanning calorimetry is used to examine the changes in the crystallinity and the thermal properties of both electrolyte membranes during the preparation process. The thermal stability of both electrolyte membranes is also evaluated using thermal gravimetrical analysis. The obtained polymer electrolyte membranes achieve superior conductivity values: 1.61 × 10?3 S · cm?1 for Li+ and 5.95 × 10?2 S · cm?1 for H+ at room temperature at a polystyrene content of 50%. The results of this work suggest that high quality H+‐ and Li+‐conducting membranes can be obtained using a single radiation‐induced grafting method.

Schematic representation of the single root for preparation of Li+‐ and H+‐conducting membranes started by radiation‐induced grafting of styrene onto a PVDF film followed by chemical treatment.  相似文献   


9.
A special “pore/bead” membrane was prepared with a mesoporous inorganic filler (MCM‐41) and a P(VDF‐HFP) binder. The special “pore/bead” structure of the MCM‐41 filler not only enhanced the puncture strength of the membrane but also improved its ionic conductivity. The puncture strength of the dried “pore/bead” membrane (MCM‐41 : P(VDF‐HFP) = 1 : 1.5) was 18 N, and showed a slight decrease (16 N) after the membrane was wetted by liquid electrolyte. Additionally, the composite membrane showed excellent thermal dimensional stability. The composite membrane could be activated by adding 1M LiClO4‐EC/DMC (1 : 1 by volume). The activated membrane displayed a high ionic conductivity about 3.4 × 10?3 S cm?1 at room temperature. Its electrochemical stability window was up to 5.3 V vs. Li/Li+, indicating that it was very suitable for lithium‐ion battery application. The battery assembled using the composite electrolyte also showed reasonably good high‐rate performance. The approach of preparing a “pore/bead” membrane provides a new avenue for improving both the conductivity and the mechanical strength of polymer electrolytes for lithium batteries. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013  相似文献   

10.
Cation exchange membranes (CEMs) hold promise for efficient and environment‐friendly lithium extraction from salt‐lake brine. However, development and practical application of CEMs are significantly hindered by the low Li+ permeation and permselectivity. Herein, novel hybrid CEMs are developed by dispersing lithium ion‐sieves (LMO) into sulfonated poly(ether ether ketone) matrix. Two kinds of LMOs are synthesized including acidified LMO (HMO) and its sulfonation compound (HMO‐S). The physicochemical property and separation performance of hybrid membranes are systematically investigated. The uniformly dispersed HMO and HMO‐S enhance the thermal, mechanical stability, and swelling resistance of hybrid membranes. Furthermore, these fillers obviously reduce the area resistance from 8.0 to less than 6.0 Ω cm?2. Importantly, the unique Li+ transfer channels in HMO/HMO‐S efficiently elevate the Li+ permeation by up to 66%. While the “ion‐sieve effect” of the channels weakens the migration of Mg2+ and K+, thus notably rising Li+/Mg2+ and Li+/K+ permselectivities by ≈5 times, which is difficult to realize with conventional fillers. Comparing with HMO, HMO‐S shows higher improvement for permselectivity because of the reduced area resistance of the resultant hybrid membrane. This study paves a way to design and development of selective Li+ exchange membranes for transport and separation applications.  相似文献   

11.
Nanofibrous solid polymer electrolytes were prepared using the electrospinning method. These nanofibres were constructed from poly(ethylene oxide), lithium perchlorate and ethylene carbonate, which were incorporated with multi‐walled carbon nanotube (MWCNT) and graphene oxide (GO). The morphological properties of the as‐prepared electrolytes and the interaction between the components of the composites were characterized using scanning electron microscopy and Fourier transform infrared spectroscopy, respectively. X‐ray spectra and differential scanning calorimetry indicated an increase in amorphous regions of the nanofibrous electrolytes on addition of the fillers. However, the crystalline regions were increased on incorporation of fillers into polymeric film electrolytes. The conductivity values of the nanofibrous electrolytes reached 0.048 and 0.057 mS cm?1 when 0.35 wt% MWCNT and 0.21 wt % GO were introduced into the nanofibrous structures, respectively. The capacity and cycling stability of the nanofibrous electrolytes were improved by incorporation of MWCNT filler. Furthermore, stress and elongation modulus were improved at low MWCNT and GO filler contents. Results revealed that the nanofibrous structures could be promising candidates as solvent‐free electrolytes applicable in lithium ion batteries. © 2019 Society of Chemical Industry  相似文献   

12.
A cross‐linked copolymer of acrylamide (AM) with 2‐acrylamido‐2‐methylpropanesulfonic acid (AMPS) was prepared by solution polymerization. In this reaction, potassium persulfate (PPS) and N,N′‐methylenebisacrylamide (NMBA) were used as initiator and cross‐linker, respectively. This copolymer, poly(acrylamide‐co‐2‐acrylamido‐2‐methylpropanesulfonic acid) (PAMA), can absorb up to 1749 g/g of dry polymer in distilled water and 87 g/g of dry polymer in 0.9 wt % NaCl aqueous solution at room temperature. The PAMA also has excellent performance in absorbing pure alcohols. Its absorbencies in methanol and glycol are about 310 g/g and 660 g/g, respectively. The effects of various salt solutions on the swelling properties were studied systematically, and the relationship between the absorbency and the concentrations of the different salt solutions can be expressed as Q = kcn. Experimental results indicate that the absorbencies were stable at different water temperatures. The swelling rates of the copolymer in distilled water and a water/ethanol mixture (Vwater:Valcohol = 1:1) were also investigated, and the results showed that PAMA could absorb 992 g of distilled water per gram of dry polymer and 739 g of water/ethanol mixture per gram of dry polymer in five minutes. The PAMA has such good water retention at higher temperatures that the swollen gel can retain 71.6 and 49.5% of the maximum absorbency after being heated for 9 hours at 60 and 80 °C, respectively. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 3481–3487, 2003  相似文献   

13.
《Polymer Composites》2017,38(4):629-636
In this study, poly(vinylidene fluoride) (PVDF)/polyhedral oligomeric silsesquioxanes (POSS) nanofibrous membranes are prepared through electrospun process. Field emission scanning electron microscope images clearly show that PVDF/POSS membranes have interconnected multi fibrous layers with ultrafine porous structures. The average fiber diameter and crystallinity of PVDF/POSS membranes are lesser than that of pure PVDF membrane. Thermal stability and electrolyte uptake of blend membranes increase with increasing POSS content. Finally, PVDF/POSS membranes are soaked in a liquid electrolyte to form the polymer electrolytes and are assembled in coin cells to test their electrochemical properties such as ionic conductivity, interfacial characteristics, and electrochemical stability windows. The ionic conductivity improves with increasing POSS content and the highest ionic conductivity reaches 2.91 × 10−3 S/cm at room temperature. It is also worth mention that the composite polymer electrolytes show low interfacial resistance and high electrochemical stability window of 5.6 V (vs. Li+ /Li) with storage time. POLYM. COMPOS., 38:629–636, 2017. © 2015 Society of Plastics Engineers  相似文献   

14.
Polymer electrolyte based lithium ion batteries represent a revolution in the battery community due to their intrinsic enhanced safety, and as a result polymer electrolytes have been proposed as a replacement for conventional liquid electrolytes. Herein, the preparation of a family of crosslinked network polymers as electrolytes via the ‘click‐chemistry’ technique involving thiol‐ene or thiol‐epoxy is reported. These network polymer electrolytes comprise bifunctional poly(ethylene glycol) as the lithium ion solvating polymer, pentaerythritol tetrakis (3‐mercaptopropionate) as the crosslinker and lithium bis(trifluoromethane)sulfonimide as the lithium salt. The crosslinked network polymer electrolytes obtained show low Tg, high ionic conductivity and a good lithium ion transference number (ca 0.56). In addition, the membrane demonstrated sterling mechanical robustness and high thermal stability. The advantages of the network polymer electrolytes in this study are their harmonious characteristics as solid electrolytes and the potential adaptability to improve performance by combining with inorganic fillers, ionic liquids or other materials. In addition, the simple formation of the network structures without high temperatures or light irradiation has enabled the practical large‐area fabrication and in situ fabrication on cathode electrodes. As a preliminary study, the prepared crosslinked network polymer materials were used as solid electrolytes in the elaboration of all‐solid‐state lithium metal battery prototypes with moderate charge–discharge profiles at different current densities leaving a good platform for further improvement. © 2018 Society of Chemical Industry  相似文献   

15.
Poly(vinyl alcohol)/sulfosuccinic acid (PVA/SSA) membranes in the hydrogen form were converted to monovalent metal ion forms Li+, Na+, and K+. The effect of exchange with metal ions was investigated by measuring the swelling of water–ethanol (10/90) mixtures at 30 °C and by the pervaporative dehydration performance test for aqueous ethanol solutions with various ethanol concentrations at 30, 40, and 50 °C. In addition, electron spectroscopy for chemical analysis (ESCA) analysis was carried out to study the quantity of metal ions in membranes. From the ESCA analysis, the lithium ion quantity in the resulting membranes is greater than that of any other metal ions in question because of the easy diffusion of a smaller metal ion into the membrane matrix. The swelling ratio was in the following order: PVA/SSA‐Li+ > PVA/SSA‐Na+ > PVA/SSA‐K+ membranes. For pervaporation, the PVA/SSA‐Na+ membrane showed the lowest flux and highest separation factor for all aqueous ethanol solutions. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 1867–1873, 2002  相似文献   

16.
Nanostructured block copolymer electrolytes (BCEs) based on poly(ethylene oxide) (PEO) are considered as promising candidates for solid‐state electrolytes in high energy density lithium metal batteries (LMBs). Because of their self‐assembly properties, they confer on electrolytes both high mechanical strength and sufficient ionic conductivity, which linear PEO cannot provide. Two types of PEO‐based BCEs are commonly known. There are the traditional ones, also called dual‐ion conducting BCEs, which are a mixture of block copolymer chains and lithium salts. In these systems, the cations and anions participate in the conduction, inducing a concentration polarization in the electrolyte, thus leading to poor performances of LMBs. The second family of BCEs are single‐lithium‐ion conducting BCEs (SIC‐BCEs), which consist of anions being covalently grafted to the polymer backbone, therefore involving conduction by lithium ions only. SIC‐BCEs have marked advantages over dual‐ion conducting BCEs due to a high lithium ion transference number, absence of anion concentration gradients as well as low rate of lithium dendrite growth. This review focuses on the recent developments in BCEs for applications in LMBs with particular emphasis on the physicochemical and electrochemical properties of these materials. © 2018 Society of Chemical Industry  相似文献   

17.
We report the synthesis of all‐solid‐state polymeric electrolytes based on electrospun nanofibers. These nanofibers are composed of polyethylene oxide (PEO) as the matrix, lithium perchlorate (LiClO4) as the lithium salt and propylene carbonate (PC) as the plasticizer. The effects of the PEO, LiClO4 and PC ratios on the morphological, mechanical and electrochemical characteristics were investigated using the response surface method (RSM) and analysis of variance test. The prepared nanofibrous electrolytes were characterized using SEM, Fourier transform infrared, XRD and DSC analyses. Conductivity measurements and tensile tests were conducted on the prepared electrolytes. The results show that the average diameter of the nanofibers decreased on reduction of the PEO concentration and addition of PC and LiClO4. Fourier transport infrared analysis confirmed the complexation between PEO and the additives. The highest conductivity was 0.05 mS cm?1 at room temperature for the nanofibrous electrolyte with the lowest PEO concentration and the highest ratio of LiClO4. The optimum nanofibrous electrolyte showed stable cycling over 30 cycles. The conductivity of a polymer film electrolyte was 29 times lower than that of the prepared nanofibrous electrolyte with similar chemical composition. Furthermore, significant fading in mechanical properties was observed on addition of the PC plasticizer. The results obtained imply that further optimization might lead to practical uses of nanofibrous electrolytes in lithium ion batteries. © 2019 Society of Chemical Industry  相似文献   

18.
The transport properties of lithiated perfluorinated ionomers imbibed with nonaqueous solvents and solvent mixtures were studied. Polymeric ion‐exchange membranes have potential use in the next generation single‐ion secondary lithium polymer batteries, where the lithiated form of the membrane is used as a polymer electrolyte. The novelty of the approach for lithium battery applications lies in the advantage offered by a transference number of unity, no additional salt (e.g., LiPF6) is needed, and the excellent physical and chemical stability of the fluoropolymers. Ion‐exchange membranes were converted to the Li+ salt form and analyzed for total conversion using FT‐IR. Nonaqueous solvents and solvent mixtures were imbibed into the membranes in a glove box, and the uptake was measured over time. A four‐point probe was used to determine the ionic conductivity based on impedance measurements performed over a frequency range of 10 to 35,000 Hz. Conductivities exceeding 10?4 S/cm with transference numbers of unity were achieved making these ionomeric membranes potentially useful in rechargeable lithium polymer batteries.  相似文献   

19.
Superabsorbent copolymer hydrogels were prepared by gamma irradiation of aqueous solutions of 2‐acrylamido‐2‐methylpropanesulfonic acid (AMPS) and 2‐dimethyaminoethyl methacrylate (DEMA) monomers mixtures. The thermal stability of hydrogels was evaluated by thermogravimetric analysis. The ability to adsorb Cu2+ ions and dyes by the prepared hydrogels from aqueous solutions was investigated. The swelling study, in water, showed that the hydrogels based on pure AMPS monomer and AMPS/DEMA copolymers reached the equilibrium state after 6 h. However, the hydrogel based on pure AMPS monomer showed higher swelling than the copolymer hydrogels based on AMPS/DEMA. It was found that the copolymer hydrogels based on different compositions showed affinity to absorb Cu2+ metal ions as well as basic and acid dyes; however, this affinity was found to decrease with increasing the ratio of DEMA in the initial feeding solutions. POLYM. COMPOS., 2011. © 2011 Society of Plastics Engineers  相似文献   

20.
Highly porous poly(vinylidene fluoride‐co‐hexafluoropropylene) (PVdF–HFP)‐based polymer membranes filled with fumed silica (SiO2) were prepared by a phase‐inversion technique, and films were also cast by a conventional casting method for comparison. N‐Methyl‐2‐pyrrolidone as a solvent was used to dissolve the polymer and to make the slurry with SiO2. Phase inversion occurred just after the impregnation of the applied slurry on a glass plate into flowing water as a nonsolvent, and then a highly porous structure developed by mutual diffusion between the solvent and nonsolvent components. The PVdF–HFP/SiO2 cast films and phase‐inversion membranes were then characterized by an examination of the morphology, thermal and crystalline properties, absorption ability of an electrolyte solution, ionic conductivity, electrochemical stability, and interfacial resistance with a lithium electrode. LiPF6 (1M) dissolved in a liquid mixture of ethylene carbonate and dimethyl carbonate (1:1 w/w) was used as the electrolyte solution. Through these characterizations, the phase‐inversion polymer electrolytes were proved to be superior to the cast‐film electrolytes for application to rechargeable lithium batteries. In particular, phase‐inversion PVdF–HFP/SiO2 (30–40 wt %) electrolytes could be recommended to have optimum properties for the application. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 140–148, 2006  相似文献   

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