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1.
The effect of carboxyl and fluorine modified multi-wall carbon nanotubes (MWCNTs) on the curing behavior of diglycidyl ether of bisphenol A (DGEBA) epoxy resin was studied using differential scanning calorimetry (DSC), rheology and infrared spectroscopy (IR). Activation energy (Ea) and rate constants (k) obtained from isothermal DSC were the same for the neat resin and fluorinated MWCNT system (47.7 and 47.5 kJ/mol, respectively) whereas samples containing carboxylated MWCNTs exhibited a higher activation energy (61.7 kJ/mol) and lower rate constant. Comparison of the activation energies, rate constants, gelation behavior and vitrification times for all of the samples suggests that the cure mechanisms of the neat resin and fluorinated sample are similar but different from the carboxylated sample. This can be explained by the difference in how the fluorinated nanotubes react with the epoxy resin compared to the carboxylated nanotubes. Although the two systems have different reaction mechanisms, both systems have similar degrees of conversion as calculated from the infrared spectroscopic data, glass transition temperature (Tg), and predictions based on DSC data. This difference in reaction mechanism may be attributed to differences in nanotube dispersion; the fluorinated MWCNT system is more uniformly dispersed in the matrix whereas the more heterogeneously dispersed carboxylated MWCNTs can hinder mobility of the reactive species and disrupt the reaction stoichiometry on the local scale.  相似文献   

2.
Yonghong Liu  Kangming Nie 《Polymer》2005,46(25):12016-12025
The POSS-containing nanocomposites of epoxy resin were prepared via the co-curing reaction between octa(propylglycidyl ether) polyhedral oligomeric silsesquioxane (OpePOSS) and the precursors of epoxy resin. The curing reactions were started from the initially homogeneous ternary solution of diglycidyl ether of bisphenol A (DGEBA), 4,4′-Diaminodiphenylmethane (DDM) and OpePOSS. The nanocomposites containing up to 40 wt% of POSS were obtained. The homogeneous dispersion of POSS cages in the epoxy matrices was evidenced by scanning electronic microscopy (SEM), transmission electronic microscopy (TEM) and atomic force microscopy (AFM). Differential scanning calorimetry (DSC) and dynamic mechanical analysis (DMA) showed that at the lower POSS concentrations (<30 wt%) the glass transition temperatures (Tgs) of the nanocomposites almost remained invariant whereas the nanocomposites containing POSS more than 40 wt% displayed the lower Tgs than the control epoxy. The DMA results show that the moduli of the nanocomposites in glass and rubbery states are significantly higher than those of the control epoxy, indicating the nanoreinforcement effect of POSS cages. Thermogravimetric analysis (TGA) indicates that the thermal stability of the polymer matrix was not sacrificed by introducing a small amount of POSS, whereas the properties of oxidation resistance of the materials were significantly enhanced. The improved thermal stability could be ascribed to the nanoscaled dispersion of POSS cages and the formation of tether structure of POSS cages with epoxy matrix.  相似文献   

3.
The epoxy resin used as the bonding agent in carbon fiber-reinforced polymer (CFRP) strengthening systems was modified by the infusion of multiwalled carbon nanotubes (MWCNTs). Two types of surfactants, Triton X-100 and C12E8, were used to disperse the nanotubes in the epoxy resin employing ultrasonic mixing. Dynamic mechanical analysis and tensile tests were conducted to study the effect of the surfactant-assisted dispersion of nanotubes on the thermal and mechanical properties of epoxy composites. The morphology of the epoxy composites was interpreted using scanning electron microscopy (SEM). Moreover, the effect of surfactant treatment on the structure of nanotubes was investigated by Fourier transform infrared (FT-IR). Based on the experimental results, the tensile strength and the storage modulus of the epoxy resin were increased by 32% and 26%, respectively, by the addition of MWCNTs. This was attributed to the homogeneous dispersion of nanotubes in the epoxy resin according to the SEM images. Another reason for the enhancement in the tensile properties was the reinforced nanotube/epoxy interaction as a result of the surfactant anchoring effect which was proved by FT-IR. A moderate improvement in the glass transition temperature (T g) was recorded for the composite fabricated using Triton X-100, which was due to the restricted molecular motions in the epoxy matrix. To characterize the temperature-dependent tensile behavior of the modified epoxy composites, tensile tests were conducted at elevated temperatures. It was revealed that the MWCNT modification using surfactant substantially improves the tensile performance of the epoxy adhesive at temperatures above the T g of the neat epoxy.  相似文献   

4.
Supercritical carbon dioxide was employed as the solvent for the functionalization of multi-walled carbon nanotubes (MWCNTs) with an epoxy-capped silane. The silanization protocol was found to be a suitable green alternative to traditional routes that rely on organic solvents for grafting nearly monolayers of silane molecules onto the nanotube surfaces. The addition of silanized MWCNTs to a model epoxy markedly increased its Tg, and measurements of the network cooperativity length scale linked this change to a reduction in polymer segment mobility. Composites filled with low loading levels of both pristine and silanized MWCNTs exhibited significantly higher strain at break and toughness than the neat epoxy, and the greatest improvements were observed at low loading levels. SEM analysis of the composite fracture surfaces revealed that nanotube pullout was the primary failure mechanism in epoxy loaded with pristine MWCNTs while crack bridging predominated in composites containing silanized MWCNTs as the result of strong interfacial bonding with the matrix. The elevated Tg and toughness achieved with small additions of silanized MWCNTs promise to extend the engineering applications of the epoxy resin.  相似文献   

5.
In this work, α-Fe2O3 nanoparticles was synthesized, terminal-epoxide functionalized by using 3-glycidoxypropyltrimethoxysilane (GPS) coupling agent, characterized by FT-IR, X-ray diffraction, TGA and particle size analyzer and used in preparation of nanocomposites with epoxy resin (DGEBA) using different weight fractions (2–11 wt%). TEM and SEM were used to observe particle dispersion in the resin matrix and to investigate the fractured surface of nanocomposites for evidence of extrinsic toughening mechanism. The mechanical and thermo-mechanical properties of nanocomposites prepared from DGEBA and modified epoxide-terminated α-Fe2O3 were compared with the properties of untreated α-Fe2O3/DGEBA nanocomposites and neat DGEBA. The modified α-Fe2O3/DGEBA nanocomposites showed improvement in properties such as glass transition temperature (Tg) and tensile, flexural and impact strength. These improvements are due to better dispersion of epoxide-terminated α-Fe2O3 particles in the resin matrix and enhanced interfacial adhesion between DGEBA and α-Fe2O3 phases.  相似文献   

6.
Novel organoclays were synthesized by several kinds of phosphonium cations to improve the dispersibility in matrix resin of composites and accelerate the curing of matrix resin. The possibility of the application for epoxy/clay nanocomposites and the thermal, mechanical, and adhesive properties were investigated. Furthermore, the structures and morphologies of the epoxy/clay nanocomposites were evaluated by transmission electron microscopy. Consequently, the corporation of organoclays with different types of phosphonium cations into the epoxy matrix led to different morphologies of the organoclay particles, and then the distribution changes of silicate layers in the epoxy resin influenced the physical properties of the nanocomposites. When high‐reactive phosphonium cations with epoxy groups were adopted, the clay particles were well exfoliated and dispersed. The epoxy/clay nanocomposite realized the high glass‐transition temperature (Tg) and low coefficient of thermal expansion (CTE) in comparison with those of neat epoxy resin. On the other hand, in the case of low‐reactive phoshonium cations, the dispersion states of clay particles were intercalated but not exfoliated. The intercalated clay did not influence the Tg and CTE of the nanocomposite. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011  相似文献   

7.
Previous research has shown that the inclusion of the spherical silica (SiO2) nanoparticles into epoxy resin can achieve simultaneous improvement of fracture toughness and modulus. However, the glass transition temperature of the nanocomposite was significantly decreased when loading the nanosilica was higher than 5 wt.%. This perhaps was caused by utilization of the ultrasonication probe in the processing of these materials. In this paper, milder processing procedures were applied to make spherical silica epoxy nanocomposites while investigating if the homogeneous dispersion and morphology of the individual silica nanoparticle dispersed in the epoxy matrix could still be achieved. The results show that even at high loading of the silica nanoparticle, such as 30 wt.% silica, the perfect morphology of the nanocomposite could still be achieved with these milder processing conditions which indicates that ultrasonication is not needed. With the use of milder processing conditions, the glass transition temperature of the nanocomposite of 5 wt.% silica loading did not change, and the drop in the Tg was minimal for silica loading up to 15%, but some effects of self-polymerization of the epoxy were noted on Tg up to 30 wt.% loading of silica. Thermal analysis and flammability testing of the resulting materials suggest that nanosilica has only an inert filler effect (dilution of fuel) on flammability reduction and char yield increase, not a synergistic decrease in heat release as is often observed for clays and carbon nanotubes/nanofibers. So the mild and easy processing procedure only achieved uniform nanoscale morphology with excellent dispersion in the final nanocomposite, but also the effect on the change in the Tg can be minimized as nanosilica loading was increased.  相似文献   

8.
Multi-walled carbon nanotube-epoxy composites are modified with titania nanoparticles in order to obtain multiphase nanocomposites with an enhanced dispersion of carbon nanotubes. The dispersion is monitored using rheological and electrical conductivity measurements. An increase in dispersion quality can be correlated to an increased storage shear modulus of the uncured suspensions and to a decreased electrical conductivity in the bulk nanocomposite. The newly formed microstructure is revealed using transmission electron and optical microscopies. Due to chemical interactions between both types of nanoparticles an attractive potential is generated leading to a significant rearrangement in the particle network structure. Besides an enhanced dispersion, the hybrid structure leads to synergistic effects in terms of the glass transition of the nanocomposites. Although a decrease of the glass transition temperature (Tg) is observed for the nanocomposites containing only one type of filler, the combination of titania and carbon nanotubes into a hybrid structure reduces the decrease of Tg, thus demonstrating the potential of such hybrid structures as fillers for multi-functional epoxy nanocomposites.  相似文献   

9.
Biodegradable poly(butylene succinate)/carbon nanotubes nanocomposites were prepared by melt mixing process, and the influence of carbon nanotubes on the properties of the nanocomposites was investigated. Differential scanning calorimetry showed that crystallization temperature (Tc) increase with increasing carbon nanotube content. Improvement of tensile modulus was observed by the addition of carbon nanotubes compared with pure poly(butylene succinate). Electrical conductivity showed that conductivity of polybutylene succinate/carbon nanotube composites increased with addition of carbon nanotube content. The storage moduli of polybutylene succinate/carbon nanotube composites are higher than the neat polybutylene succinate. The processability of polybutylene succinate/carbon nanotubes composites was improved and more pronounced in higher content of carbon nanotubes. POLYM. COMPOS., 31:1309–1314, 2010. © 2009 Society of Plastics Engineers  相似文献   

10.
A sonochemical technique is used for in situ coating of iron oxide (Fe3O4) nanoparticles on outer surface of MWCNTs. These Fe3O4/MWCNTs were characterized using a high‐resolution transmission electron microscope (HRTEM), X‐ray diffraction, and thermogravimetric analysis. The as‐prepared Fe3O4/MWCNTs composite nanoparticles were further used as reinforcing fillers in epoxy‐based resin (Epon‐828). The nanocomposites of epoxy were prepared by infusion of (0.5 and 1.0 wt %) pristine MWCNTs and Fe3O4/MWCNTs composite nanoparticles. For comparison purposes, the neat epoxy resin was also prepared in the same procedure as the nanocomposites, only without nanoparticles. The thermal, mechanical, and morphological tests were carried out for neat and nanocomposites. The compression test results show that the highest improvements in compressive modulus (38%) and strength (8%) were observed for 0.5 wt % loading of Fe3O4/MWCNTs. HRTEM results show the uniform dispersion of Fe3O4/MWCNTs nanoparticles in epoxy when compared with the dispersion of MWCNTs. These Fe3O4/MWCNTs nanoparticles‐infused epoxy nanocomposite shows an increase in glass transition (Tg) temperature. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010  相似文献   

11.
The effect of three different alkylammonium‐modified montmorillonite on morphological and mechanical properties of glassy epoxy‐amine nanocomposites is reported. Small amounts of clays <10 phr (part per hundred of resin) were used in each system of nanocomposite. The morphology of the prepared nanocomposites was performed by means of X‐ray diffraction and transmission electron microscopy. Differential scanning calorimetry (DSC) was used to investigate the glass transition temperatures (Tg). Mechanical properties were based on tensile characteristics (Young's modulus), impact strength, and fracture toughness. The measured moduli were compared to theoretical predictions. Scanning electron microscopy was used to study the morphological structure of the fracture surfaces of impacted specimens. It was found that at a low content of 2 phr (1.2 wt %) of nanoclays, the impact strength and the fracture toughness were improved by 77 and 90% respectively, comparatively to the neat epoxy, whereas DSC revealed a reduction of the Tg of nanocomposites. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011  相似文献   

12.
The cure kinetics and morphology of diglycidyl ether of bisphenol-A (DGEBA) epoxy resin modified with a poly (ether ether ketone) based on tertiary butyl hydroquinone (PEEK-T) cured with diamino diphenyl sulphone (DDS) were investigated using differential scanning calorimetry (DSC), scanning electron microscopy (SEM) and dynamic mechanical thermal analysis (DMTA). The results obtained from DSC were applied to autocatalytic and diffusion controlled kinetic models. The reaction mechanism broadly showed autocatalytic behaviour regardless of the presence of PEEK-T. At higher PEEK-T concentration, more diffusion controlled mechanism was observed. The rate of curing reaction decreased with increase in thermoplastic content and also with the lowering of curing temperature. The activation energies of the blends are higher than that of the neat resin. The blends showed a phase separated morphology. The dispersed phase showed a homogeneous particle size distribution. The Tg of the neat resin decreased with the decrease in cure temperature. Two Tg's corresponding to the epoxy rich and thermoplastic rich phases were observed in the dynamic mechanical spectrum. The storage modulus of 10 and 20 phr PEEK-T blends are found to be greater than the neat resin.  相似文献   

13.
Jihua Gou 《Polymer International》2006,55(11):1283-1288
A new processing method for the fabrication of single‐walled nanotube (SWNT)‐reinforced nanocomposites was developed to achieve uniform dispersion and high composition of the nanotubes in the nanocomposites. In this method, SWNTs were preformed as bucky paper by multi‐step dispersion and micro‐filtration of a suspension of nanotubes. The nanocomposites were then fabricated by infiltration of diluted epoxy resin through the bucky paper and hot pressing. The wetting of the nanocomposites was examined using scanning electron microscopy and atomic force microscopy. The results showed that the epoxy resin completely penetrated the bucky paper through the nanoporous structures. The results of dynamic mechanical analysis of the nanocomposites showed that the storage moduli of the nanocomposites increased by 200–250%. The tan δ curves indicated that the nanotubes had a strong influence on the damping properties of the nanocomposites. This processing technique is an effective method for fabricating nanocomposites with uniform dispersion and high composition of SWNTs. Copyright © 2006 Society of Chemical Industry  相似文献   

14.
Yong Ni  Kangming Nie 《Polymer》2004,45(16):5557-5568
The organic-inorganic hybrids involving epoxy resin and polyhedral oligomeric silsesquioxanes (POSS) were prepared via in situ polymerization of diglycidyl ether of bisphenol A (DGEBA) and 4,4′-diaminodiphenylmethane (DDM) in the presence of the two structurally similar POSS monomers. The organic groups on silsesquioxane cage are aminophenyl and nitrophenyl groups, respectively. The curing reactions were started from the initially homogeneous mixture of DGEBA, DDM and the POSS cages. The inorganic-organic hybrids containing up to 20 wt% of POSS were obtained. The morphologies of the resulting hybrids were quite dependent on the types of R groups in the POSS monomers. The phase separation induced by polymerization occurred in the hybrids containing octanitrophenyl POSS (OnpPOSS) and the spherical particles of POSS-rich phase (<0.5 μm in diameter) were uniformly dispersed the continuous epoxy matrix as shown by scanning electronic microscopy. In marked contrast to the OnpPOSS-containing hybrids, the octaaminophenyl POSS (OapPOSS)-containing nanocomposites exhibited a homogeneous morphology. Differential scanning calorimetry and dynamic mechanical analysis showed that the glass transition temperatures (Tg) of the POSS-containing hybrids were lower than that of the control epoxy. The moduli of glass states for the hybrids are significantly higher than that of the control epoxy. For the OapPOSS epoxy nanocomposites the storage moduli of the rubbery plateau were higher than that of the control epoxy when the contents of POSS are less than 20 wt%, indicating the nanoreinforcement effect of POSS cages. Thermogravimetric analysis indicates that the thermal stability of the polymer matrix was not much sacrificed by introducing a small amount of POSS, whereas the properties of oxidation resistance of the materials were significantly enhanced. The OapPOSS epoxy nanocomposites displayed more pronounced improvement than the OnpPOSS hybrids, which could be ascribed to the nanoscaled dispersion of POSS cages and the formation of tether structure of POSS cages with epoxy matrix.  相似文献   

15.
Our previous studies showed that herringbone graphitic GNFs surface‐derivatized with reactive linker molecules bearing pendant primary amino functional groups capable of binding covalently to epoxy resins. Of special importance, herringbone GNFs derivatized with 3,4′‐oxydianiline (GNF‐ODA) were found to react with neat butyl glycidyl ether to form mono‐, di‐, tri‐, and tetra‐glycidyl oligomers covalently coupled to the ODA pendant amino group. The resulting reactive GNF‐ODA (butyl glycidyl)n nanofibers, r‐GNF‐ODA, are especially well suited for reactive, covalent incorporation into epoxy resins during thermal curing. Based on these studies, nanocomposites reinforced by the r‐GNF‐ODA nanofibers at nanofiber loadings of 0.15–1.3 wt% were prepared. Flexural property of cured r‐GNF‐ODA/epoxy nanocomposites were measured through three‐point‐bending tests. Thermal properties, including glass transition temperature (Tg) and coefficient of thermal expansion (CTE) for the nanocomposites, were investigated using thermal mechanical analysis. The nanocomposites containing 0.3 wt% of the nanofibers gives the highest mechanical properties. At this 0.3‐wt% fiber loading, the flexural strength, modulus and breaking strain of the particular nanocomposite are increased by about 26, 20, and 30%, respectively, compared to that of pure epoxy matrix. Moreover, the Tg value is the highest for this nanocomposite, 14°C higher than that of pure epoxy. The almost constant change in CTEs before and after Tg, and very close to the change of pure epoxy, is in agreement with our previous study results on a chemical bond existing between the r‐GNF‐ODA nanofibers and epoxy resin in the resulting nanocomposites. POLYM. COMPOS., 28:605–611, 2007. © 2007 Society of Plastics Engineers  相似文献   

16.
This study describes the influence of triethylenetetramine (TETA) grafting of multi‐walled carbon nanotubes (MWCNTs) on the dispersion state, interfacial interaction, and thermal properties of epoxy nanocomposites. MWCNTs were first treated by a 3:1 (v/v) mixture of concentrated H2SO4/HNO3, and then TETA grafting was performed. Chemically grafted MWCNT/bisphenol‐A glycidol ether epoxy resin/2‐ethyl‐4‐methylimidazole nanocomposites were prepared. TETA grafting could establish the connection of MWCNTs to the epoxy matrix and transform the smooth and nonreactive MWCNT surface into a hybrid material that possesses the characteristics of both MWCNTs and TETA, which facilitates homogeneous dispersion of MWCNTs and improves nanotube‐epoxy interfacial interaction. Therefore, the impact property, glass transition temperature, thermal stability, and thermal conductivity of epoxy nanocomposites are enhanced. POLYM. ENG. SCI., 2009. © 2009 Society of Plastics Engineers  相似文献   

17.
In this study, carboxylic acid functionalized carbon nanotubes (CNTs) were used to modify epoxy with intent to develop a nanocomposite matrix for hybrid multiscale composites combining benefits of nanoscale reinforcement with well‐established fibrous composites. CNTs were dispersed in epoxy by using high energy sonication, followed by the fabrication of epoxy/CNTs composites. The processibility of CNTs/epoxy systems was explored with respect to their dispersion state and viscosity. The dependences of viscosity, mechanical and thermomechanical properties of nanocomposite system on CNTs content were investigated. The dispersion quality and reagglomeration behavior of CNTs in epoxy and the capillary infiltration of continuous fiber with the epoxy/CNTs dispersion were characterized using optical microscope and capillary experiment. As compared with neat epoxy sample, the CNTs nanocomposites exhibit flexural strength of 126.5 MPa for 1 wt% CNTs content and impact strength of 28.9 kJ m?2 for 0.1 wt% CNTs content, respectively. A CNTs loading of 0.1 wt% significantly improved the glass transition temperatures, Tg, of the nanocomposites. Scanning electron microscopy (SEM) was used to examine the fracture surface of the failed specimens. It is demonstrated that the properties of CNTs/epoxy system are dispersion‐dominated and interface sensitive. POLYM. ENG. SCI., 2013. © 2012 Society of Plastics Engineers  相似文献   

18.
Tarek Agag  Hajime Tsuchiya 《Polymer》2004,45(23):7903-7910
Novel organic-inorganic hybrids were prepared from polybenzoxazine and titania using sol-gel process by blending titanium isopropoxide as a precursor for titania with a typical benzoxazine monomer, bis(3-phenyl-3,4-dihydro-2H-1,3-benzoxazinyl)isopropane (Ba). Deep red brown and transparent hybrid materials were obtained after thermal cure at 200 °C. DSC indicated that, in the presence of titania precursor, the onset and maximum temperature of the exothermic peak due to the ring opening polymerization of Ba decreased by ca. 30 and 70 °C, respectively. Viscoelastic analyses revealed that the glass transition temperatures (Tg) of the polybenzoxazine-titania hybrids shifted to higher temperature than the neat polybenzoxazine. The storage moduli below Tg for the hybrids increased with the increase of the titania content, and the storage moduli were maintained constant up to higher temperature than the neat resin. TGA results confirmed that the thermal stability and char yield of polybenzoxazine increased by hybridization with titania.  相似文献   

19.
Layered double hydroxides (LDHs)/epoxy nanocomposites were prepared by mixing the amino laurate intercalated LDHs, EPON 828 resin, and Jeffamine D400 as a curing agent. The organo-modified LDHs with hydrophobic property easily disperse in epoxy resin, and the amino laurate intercalated LDHs with large gallery space allow the epoxy molecules and the curing agents to easily diffuse into the LDHs galleries at elevated temperature. After the thermal curing process, the exfoliated LDHs/epoxy nanocomposites were formed. X-ray diffraction was used to detect the formation process of the exfoliated LDHs/epoxy nanocomposites. TEM was used to observe the dispersed behavior of the LDHs nanolayers, and the LDHs nanolayers were exfoliated and well dispersed in these nanocomposites. Owing to the reaction between the amine groups of the intercalated amino laurate and epoxy groups, the adhesion between the LDHs nanolayers and epoxy molecules makes these LDHs/epoxy nanocomposites more compatible. Consequently, the tensile properties from tensile test and the mechanical properties from DMA were enhanced, and the Tg of these nanocomposites from DMA and TMA were increased. Coefficients of thermal expansion (CTEs, below and above Tg) of these nanocomposites from TMA decreased with the LDHs content. The thermal stability of these nanocomposites was enhanced by the well dispersed LDHs nanolayers.  相似文献   

20.
Multiwalled carbon nanotube (MWCNT)/epoxy composites are prepared, and the characteristics and morphological properties are studied. Scanning electron microscopy microphotographs show that MWCNTs are dispersed on the nanoscale in the epoxy resin. The glass‐transition temperature (Tg) of MWCNT/epoxy composites is dramatically increased with the addition of 0.5 wt % MWCNT. The Tg increases from 167°C for neat epoxy to 189°C for 0.5 wt % CNT/epoxy. The surface resistivity and bulk resistivity are decreased when MWCNT is added to the epoxy resins. The surface resistivity of CNT/epoxy composites decreases from 4.92 × 1012 Ω for neat epoxy to 3.03 × 109 Ω for 1 wt % MWCNT/epoxy. The bulk resistivity decreases from 8.21 × 1016 Ω cm for neat epoxy to 6.72 × 108 Ω cm for 1 wt % MWCNT/epoxy. The dielectric constant increases from 3.5 for neat epoxy to 5.5 for 1 wt % MWCNT/epoxy. However, the coefficient of thermal expansion is not affected when the MWCNT content is less than 0.5 wt %. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1272–1278, 2007  相似文献   

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