首页 | 本学科首页   官方微博 | 高级检索  
相似文献
 共查询到20条相似文献,搜索用时 31 毫秒
1.
《Ceramics International》2017,43(15):11569-11579
Niobium oxide is known for its biocompatibility; however it lacks on bioactivity. Sodium is one of the essential elements required for the formation and maintenance of bone. In this present study, we focus on improving the bioactivity of niobium oxide by incorporating sodium ions and obtaining nanoporous morphology by adding polyethylene glycol. Sodium niobate was prepared using sol-gel method and dip coated on 316L SS. The coated sample was sintered at the optimised heating rate of 0.5 °C min−1. The surface morphology, chemical composition, phase composition and porosity were analysed using scanning electron microscopy (SEM), energy dispersive X-ray analysis (EDX), X-ray diffraction analysis (XRD) and porosimetry. The BET analysis and AFM studies showed that the coating exhibited pores with the average diameter of 97 and 101 nm. The Vicker's microhardness test showed that sodium niobate coating exhibits three fold higher microhardness compared to 316L SS. In vitro studies show that the coating exhibited good bioactivity. Electrochemical studies confirmed that the coating offers better corrosion resistance to the substrate at pH 5.2 and pH 7.4. The hemolysis percentage of the coating was found to be 1.54% and anticoagulation studies showed that coagulation time of sodium niobate coating was similar to that of the plasma. Better adhesion, proliferation and differentiation of MG-63 cells with significant cell spreading were observed in the coating.  相似文献   

2.
Surgical grade stainless steel (316L SS) is a widely used implant material in orthopedic surgeries. However, the release of metallic ions evidenced from the 316L SS implants in vivo conditions is a big challenge. In order to minimize the release of metallic ions, coating the 316L SS implant with a biocompatible material like hydroxyapatite [HAP, Ca10(PO4)6(OH)2] is one of the suitable methods. In this paper, the hydroxyapatite coating on borate passivated through poly-ortho-phenylenediamine (PoPD)-coated 316L SS by a dip coating method has been reported. The coatings were characterized by electrochemical techniques such as potentiodynamic polarization, electrochemical impedance spectroscopy, and cyclic voltammetry. Surface characterization studies of the coatings such as X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and scanning electron microscopy (SEM) were also carried out. The leach out characteristics of the coatings was determined at the impressed potential. The mechanical property of the coatings was evaluated by Vicker’s microhardness test. The Cr-rich passive film formed underneath the PoPD layer showed a higher protective efficiency. The ability to form apatite on the post-passivated PoPD-coated 316L SS specimen was examined by immersing it in the simulated body fluid. The enhanced corrosion resistivity of the HAP coating on the post-passivated PoPD-coated 316L SS was due to an effective barrier of PoPD followed by the passive film underneath the PoPD.  相似文献   

3.
A simple surface pre-treatment method was attempted to establish a stable passive layer on the surface of surgical grade stainless steel (SS) of type 316L for biomedical applications. Surgical grade type 316L SS specimens were subjected to H3PO4 treatment for 1 h by completely immersing them in the acid solutions to develop a passive barrier film. The effect of various concentrations of phosphoric acid on the localized corrosion resistance behavior of type 316L SS was investigated through electrochemical techniques using cyclic polarization studies and electrochemical impedance spectroscopy (EIS). X-ray photoelectron spectroscopy (XPS) was used to evaluate the nature and composition of the passive films. The surface morphology and relative elemental composition of the untreated and acid treated surfaces subjected to anodic polarization was studied by scanning electron microscopy (SEM) and energy dispersive X-ray analysis (EDAX) techniques, respectively. Compared with untreated (pristine) 316L SS, the 40% acid treated surface formed a stable passive layer that had superior corrosion resistance.  相似文献   

4.
《Ceramics International》2022,48(13):18704-18715
In this study, we have synthesized a new family of bioactive glass (BAG) comprising of SiO2, Na2O, CaO, K2O, P2O5 and MgO via sol-gel route. The composition of these oxides has been selected in such a way that the BAG has a coefficient of thermal expansion close to the 316L stainless steel (SS). In vitro test by soaking the BAG in simulated body fluid (SBF) showed good bioactivity due to ion exchange between alkali ions from the BAG and the ions present in the SBF. The 316L SS substrates were textured using laser before application of BAG using sol-gel dip coating. Pull off test showed that the adhesion strength in case of textured and non-textured surfaces were 4.2 MPa and 2.46 MPa, respectively. This implies that texturing of the surface is helpful in increasing the adhesion strength of the coating. The bioactive glass-coated textured surface of 316L SS substrate showed better corrosion resistance in SBF than the bare substrate for which the respective corrosion current densities were 35 nA/cm2 and 353 nA/cm2, thereby indicating that the single layer sol-gel dip coating of bioactive glass improved the corrosion resistance of the 316L SS implants. The analysis of scanning electron microscopy (SEM) images of the coating after immersion in SBF shows the formation and growth of the apatite layer that will further inhibit the corrosion of the substrate. These results demonstrate the potential of the synthesized BAG as a coating material for 316L SS implants.  相似文献   

5.
Bioactive sodium-substituted titania coating on 316L SS substrate was prepared. XRD patterns exhibited the formation of a mixture of two phases (Na2Ti3O7, Na2Ti6O13) with monoclinic structure. FTIR spectra showed that the set of overlapping peaks in the range of 800–400 cm−1 are related to Ti–O and Ti–O–Ti groups. SEM-EDAX, AFM, and TEM showed the surface morphology of the coated surface to be nanoporous and uniform. The influence of the bioactivity of the coating in a simulated body fluid (SBF) medium was examined. Excellent adhesion of the ceramic composites to the substrate was achieved. The hydrophilic nature of the sodium titanate coating induced the formation of hydroxyapatite layer on the metal surface. The corrosion protection performance of the coatings has been evaluated using potentiodynamic polarization and electrochemical impedance spectroscopy measurements, which proved increased corrosion resistance of nanosodium titanate-coated 316L SS. These results imply that the sodium titanate-coated 316L SS acts as a barrier layer to the metallic substrate.  相似文献   

6.
《Ceramics International》2019,45(11):13747-13760
TiO2-rGO nanocomposite coatings were obtained by electrophoretic deposition (EPD) technique of TiO2 nanoparticles and graphene oxide (GO) on stainless steel substrate. First, GO particles were synthesized using a modified Hummers' method. GO was reduced electrochemically to form a coating in the presence of nano-sized TiO2 particles. The influences of different parameters such as GO concentration, coupling co-electro-deposition parameters (electrophoretic duration and voltage) on thickness, surface morphology and, corrosion behavior of the as-synthesized TiO2-rGO nanocomposite coatings were systematically surveyed. The morphology and microstructure were investigated by field emission scanning electron microscopy (FE-SEM), Raman spectra and X-ray diffraction (XRD) techniques. Atomic force microscopy (AFM) was harnessed to evaluate the topography of the as-prepared GO powder. The bonding characteristics of as-synthesized and as-reduced GO were examined after deposition, by Energy Dispersive Analysis of X-Ray (EDX) and Fourier-transform infrared spectroscopy (FT-IR). Corrosion behavior of coatings and that of the pure TiO2 layer were evaluated by electrochemical impedance spectroscopy (EIS) and polarization techniques (by applying potentiodynamic polarization spectroscopy (PDS)). Detailed SEM studies showed that increasing EPD voltage brings about a coating with increased porosity and microcracks with higher thickness. In addition to that, the presence of rGO reduced corrosion current density (icorr) and shifted corrosion potential (Ecorr) toward more noble values in 3.5% NaCl at room temperature. Also, Analyses revealed that the optimum electrophoretically synthesized coating was obtained at GO concentration of 1 g/L, 30 V and 30 min at room temperature. The corrosion current density of the corresponding coating was remediated up to 0.2 μA cm−2, which means an anti-corrosion ability of about 30 times compared to TiO2-coated and bare 316L stainless steel. The results of impedance spectroscopic studies demonstrated that this coating renders as a barrier layer and resistance increased from 2.95 KΩ cm2 for TiO2-coated layer to 10.49 KΩ cm2 for the optimized layer.  相似文献   

7.
Many methods have been reported on improving the photogenerated cathodic protection of nano-TiO2 coatings for metals. In this work, nano-TiO2 coatings doped with cerium nitrate have been developed by sol–gel method for corrosion protection of 316 L stainless steel. Surface morphology, structure, and properties of the prepared coatings were investigated by X-ray diffraction, X-ray photoelectron spectroscopy, scanning electron microscopy and energy dispersive X-ray spectroscopy. The corrosion protection performance of the prepared coatings was evaluated in 3 wt% NaCl solution by using electrochemical techniques in the presence and absence of simulated sunlight illumination. The results indicated that the 1.2% Ce-TiO2 coating with three layers exhibited an excellent photogenerated cathodic protection under illumination attributed to the higher separation efficiency of electron–hole pairs and higher photoelectric conversion efficiency. The results also showed that after doping with an appropriate concentration of cerium nitrate, the anti-corrosion performance of the TiO2 coating was improved even without irradiation due to the self-healing property of cerium ions.  相似文献   

8.
In this work, new water-soluble polypyrrole–sulfonated melamine formaldehyde nanocomposites (PPy–SMF NCs) were first synthesized by one-step in-situ polymerization of pyrrole with FeCl3 in the presence of various mole ratios of sulfonated melamine formaldehyde (SMF). The characterization of the PPy–SMF NCs was investigated via ultraviolet–visible spectroscopy, Fourier transform infrared spectroscopy, scanning electron microscopy, energy dispersive X-ray, dynamic light scattering, transmission electron microscopy, X-ray diffraction, thermogravimetric analysis, differential scanning calorimetry, and conductivity measurements. The resulting PPy–SMF NCs were proved to improve the solubility, electrical properties, and thermal stability. The anti-corrosion performance of PPy-SMF NCs on 316 L stainless steel (316 L SS) was examined using electrochemical impedance spectroscopy, potentiodynamic polarization, and weight-loss method. The result showed that the PPy–SMF NCs acts as a mixed-type inhibitor, as well as a protective layer to 316 L SS against corrosion in 3.5% NaCl solution. The Langmuir adsorption isotherm was well fitted and suitable to explain the adsorption behavior of the PPy-SMF NCs on 316 L SS surface. The inhibition efficiency of PPy-SMF NCs is 99% by the weight-loss method which could be attributed to the protective layer formed on 316 L SS surface by the adsorption of PPy-SMF NCs.  相似文献   

9.
The usage of conducting polymers as coating materials for bipolar plates to prevent corrosion is the recent trend in Proton Exchange Membrane Fuel Cell (PEMFC) technology. Paraphenylenediamine (pPD) monomer was electropolymerized to poly p-phenylenediamine (PpPD) over 316L SS. The characterization of PpPD, the conducting polymer coating, over 316L SS was done using attenuated total reflectance infra-red (ATR-IR) spectroscopy to confirm the formation of PpPD. The surface morphology and topography were studied by scanning electron microscopy (SEM) and atomic force microscopy (AFM). The corrosion protection performance of the coating was evaluated using open circuit potential (OCP) measurement, electrochemical impedance spectroscopy (EIS) and potentiodynamic polarization studies in PEMFC environment. EIS studies revealed that the charge transfer resistance for the coated substrates has increased by one order of magnitude than the bare substrate. Potentiodynamic polarization studies have registered lower corrosion current density by one order magnitude for the 0.06 M pPD coated substrate than the bare substrate and the polarization resistance values for the coated substrates have increased by two and a half time than the bare substrate. These results showed that PpPD coated substrates exhibited enhanced corrosion resistance in PEMFC environment.  相似文献   

10.
Self-assembled layers of vertically aligned titanium nanotubes were fabricated on a Ti disc by anodization. Pamidronic acids (PDAs) were then immobilized on the nanotube surface to improve osseointegration. Wide-angle X-ray diffraction, X-ray photoelectron microscopy, and scanning electron microscopy were employed to characterize the structure and morphology of the PDA-immobilized TiO2 nanotubes. The in vitro behavior of osteoblast and osteoclast cells cultured on an unmodified and surface-modified Ti disc was examined in terms of cell adhesion, proliferation, and differentiation. Osteoblast adhesion, proliferation, and differentiation were improved substantially by the topography of the TiO2 nanotubes, producing an interlocked cell structure. PDA immobilized on the TiO2 nanotube surface suppressed the viability of the osteoclasts and reduced their bone resorption activity.  相似文献   

11.
Yan Wang 《Electrochimica acta》2007,52(24):6793-6798
Increasing attention is being paid to the use of metallic materials as a replacement for non-porous graphite in bipolar plates (BPs) for polymer exchange membrane (PEM) fuel cells. The main aim of the present study was to investigate how O2 and H2 affect the corrosion behavior of 316L stainless steel in simulated anode and cathode environments of a PEM fuel cell. Open circuit potential (OCP) measurements together with potentiodynamic and potentiostatic tests were performed to investigate the corrosion behavior of SS316L in the O2- and H2-containing environments. Optical microscopy and scanning electron microscopy (SEM) were used to characterize the morphology of the corroded surface and the corrosion products. Inductively coupled plasma optical emission spectrometer (ICP-OES) was used to determine the levels of metal ions in solution after corrosion. The OCP and potentiodynamic tests showed that less corrosion of SS316L took place in a simulated cathode environment because it was easier to passivate SS316L in an O2-containing environment. However, the potentiostatic tests showed that there is less corrosion in a simulated anode environment, because H+ ions are reduced, and the resulting negative current can provide partial cathodic protection to the SS316L.  相似文献   

12.
Ze-Quan Lin 《Electrochimica acta》2010,55(28):8717-8723
Shell-core nanostructured ZnS/CdS quantum dots (QDs) were assembled uniformly on the surface of TiO2 nanotube arrays by sequence chemical bath deposition (CBD) of CdS and ZnS in alcohol solution system. The morphology and chemical composition of the obtained composite thin films were characterized by scanning electron microscopy, transmission electron microscopy and energy dispersive X-ray spectroscopy. The effect of solvent and immersion cycles for the photoanode preparation on the photoelectrochemical activity and photogenerated cathodic protection property was investigated. It is found that the nanostructured CdS QDs (20 cycles) coated on TiO2 nanotube arrays show a remarkably enhanced photoelectrochemical activity. The coating of ZnS QD shells (5 cycles) is able to improve the stability of the CdS@TiO2 photoanode under white-light irradiation. After the irradiation light is turned off, the photogenerated cathodic protection of 403 stainless steel (403SS) can be remained for several hours.  相似文献   

13.
Antimicrobial hydroxyapatite (HAp) nanoparticles with different concentrations (0, 3, and 6 mol%) of zinc were prepared by the ultrasonication process. The prepared nanoparticles and chitosan (CTS) composite were coated on 316L stainless steel implant by spin coating technique. The powder samples were characterised by particle size analyser, X-ray fluorescence, and X-ray diffraction studies. The morphology of the coating was investigated by scanning electron microscopy. The diameter of the particle size decreased with increase in the concentration of zinc in HAp structure. The structure of the coated implant was found to be uniform without any cracks and pores. Antimicrobial activity of the composites against Bacillus subtilis, Staphylococcus aureus, Klebsiella pneumonia, Salmonella typhi and Pseudomonas aeruginosa was analysed. The results showed that the increase in the concentration of zinc enhances the antimicrobial properties of 316L stainless steel implant. The stability of the implant in physiological environment was characterised by electrochemical impedance spectroscopy and polarisation analysis. The higher concentration of the ZnHAp/CTS composite shows higher corrosion resistance than that of the HAp/CTS-coated implant. This study shows that the coating provides corrosion resistance to the stainless steel substrate in simulated body fluid (SBF). The in vitro bioactivity study of the coated samples immersed in SBF solution confirms the formation of bone-like apatite layer on the surface of the implant. Thus, highly biocompatible ZnHAp/CTS-coated materials could be very useful in the long-term stability of the biomedical applications.  相似文献   

14.
In order to improve biological and mechanical properties of hydroxyapatite, the concept of hydroxyapatite-included nanocomposite coatings was introduced. By judiciously choosing constituent ceramics for composites preparation, the biological and mechanical performance of coatings can be tailored in order to meet various clinical requirements. The aim of this work was fabrication, development and characterization of novel hydroxyapatite-forsterite-bioactive glass nanocomposite coatings. The sol-gel technique was used to prepare hydroxyapatite-forsterite-bioactive glass nanocomposite in order to apply coating on 316L stainless steel (SS) by dip coating technique. The X-ray diffraction (XRD), scanning electron microscopy (SEM) and energy dispersive X-ray analysis (EDX) were used to investigate the phase structure, microstructure and morphology of the coating. In order to evaluate the forsterite incorporation influence upon bioactivity, the changes on the surfaces of the prepared composite coatings after the predicted days of contact with simulated body fluid (SBF) were investigated by SEM. Results showed that the suitable calcined temperature for nanocomposite coatings with different amounts of forsterite was 600 °C. At this temperature, the homogenous and crack-free coating could attach to the 316L SS substrate. The crystallite sizes of the prepared coatings were lower than 100 nm. The EDX analysis of hydroxyapatite-forsterite-bioglass, coated 316L SS surface, indicated consisting elements of prepared coatings and the substrate. During immersion in the SBF at pre-determined time intervals, apatite layer was formed and stimulation for apatite formation was increased with increase in forsterite amounts. It seems that hydroxyapatite-forsterite-bioactive glass nanocomposite coatings might be good candidates for biomedical applications.  相似文献   

15.
The development of Hydroxyapatite (HAP)/Titania (TiO2) composite coatings on metallic implants have received a great deal of attention during the recent years owing to their superior advantages in biomedical applications. The present study has focused on the in situ formation of HAP/TiO2 composite powders through aqueous precipitation technique. Five different HAP/TiO2 composite powders of varied HAP to TiO2 ratios has been synthesized in the present study and the results were compared with the stoichiometric HAP, Rutile TiO2 and Anatase TiO2 which also have been synthesized by adapting a similar synthetic procedure. All the synthesized powders have been analyzed using X-ray diffraction (XRD) and X-ray fluorescence (XRF) techniques. Rietveld Refinement technique has been employed to generate quantitative information about the structural characteristics and phase content in all the powder samples. Further, the electrophoretic deposition (EPD) method has been employed to fabricate HAP/TiO2 composite coatings on 316 L SS and the resultant coatings were analyzed for its quantitative structural characteristics. The results from the present investigation has confirmed that concentration of TiO2 in the HAP/TiO2 composites and heat treatment temperatures have played a major role in the degradation of HAP to β-Tricalcium phosphate and also in the conversion of Anatase to Rutile TiO2 phase.  相似文献   

16.
Inorganic/organic heterojunction solar cells (HSCs) have attracted increasing attention as a cost-effective alternative to conventional solar cells. This work presents an HSC by in situ growth of CuInS2(CIS) layer as the photoabsorption material on nanoporous TiO2 film with the use of poly(3-hexylthiophene) (P3HT) as hole-transport material. The in situ growth of CIS nanocrystals has been realized by solvothermally treating nanoporous TiO2 film in ethanol solution containing InCl3 · 4H2O, CuSO4 · 5H2O, and thioacetamide with a constant concentration ratio of 1:1:2. InCl3 concentration plays a significant role in controlling the surface morphology of CIS layer. When InCl3 concentration is 0.1 M, there is a layer of CIS flower-shaped superstructures on TiO2 film, and CIS superstructures are in fact composed of ultrathin nanoplates as ‘petals’ with plenty of nanopores. In addition, the nanopores of TiO2 film are filled by CIS nanocrystals, as confirmed using scanning electron microscopy image and by energy dispersive spectroscopy line scan analysis. Subsequently, HSC with a structure of FTO/TiO2/CIS/P3HT/PEDOT:PSS/Au has been fabricated, and it yields a power conversion efficiency of 1.4%. Further improvement of the efficiency can be expected by the optimization of the morphology and thickness of CIS layer and the device structure.  相似文献   

17.
Poly(vinylcarbazole) (PVK) and PVK‐alumina (Al2O3) nanocomposite coatings were electrochemically coated on 316 L stainless steel (SS) substrates for corrosion protection of 316 L SS in 3.5 weight (wt) % NaCl medium. The formation of PVK and incorporation of nanoalumina particles in PVK‐Al2O3 nanocomposite coatings were confirmed from attenuated total reflectance‐infrared spectroscopy (ATR‐IR). Thermal analysis (TG) results showed enhanced thermal stability for the composites relative to PVK. Incorporation of Al2O3 nanoparticles enhanced the micro hardness of PVK coated 316 L SS. The dispersion of alumina nanoparticles was examined via scanning electron microscope (SEM) and tunneling electron microscopy (TEM) and revealed distinct features. The influence of nanoparticles on the barrier properties of PVK and PVK‐Al2O3 nanocomposites was evaluated in aqueous 3.5 wt % NaCl by potentiodynamic polarization and electrochemical impedance spectroscopy (EIS) studies. The results proved that PVK nanocomposite coatings provided better protection for 316 L SS than PVK coatings. The drastic increase in impedance values is due to the high corrosion resistance offered by the PVK nanocomposite coatings that arises due to the interaction between Al2O3 nanoparticles and PVK. The highest corrosion protection shown by the 2 wt % nano Al2O3 incorporated PVK composite coatings proved enhanced corrosion resistance compared to PVK. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44937.  相似文献   

18.
Sol-gel TiO2-SiO2 films were deposited on 316L stainless steel by dip coating process from a sono-catalysed sol of composition 30TiO2-70SiO2 prepared from a mixture of Ti(OC2H5)4 and Si(OC2H5)4, absolute ethanol C2H5OH and glacial acetic acid CH3COOH as precursors and solvents. The films, densified at 800° C in air for 2 h, are composed of small orthorhombic titania (anatase) crystallites embedded in a SiO2 amorphous matrix as identified by X-ray diffraction. The temperature dependence of the film morphology was observed using scanning electron microscopy (SEM) and the content was determined by FTIR reflection spectroscopy. The corrosion behaviour of 316L stainless steel samples coated with densified 30TiO2-70SiO2 films was studied in 15% H2SO4 by potentiodynamic polarization curves at 25, 40 and 50°C. The measured corrosion rates show a considerable decrease for the protected steel samples in comparison to the bare substrate. The effect of time of heat treatment of the films on the corrosion parameters is also reported.  相似文献   

19.
《Ceramics International》2016,42(16):18443-18452
Highly efficient visible-light-driven heterojunction photocatalysts, spindle-shaped nanoporous TiO2 coupled with graphitic g-C3N4 nanosheets have been synthesized by a facile one-step solvothermal method. The as-prepared photocatalysts were characterized by X-ray diffraction (XRD), energy dispersive spectroscopy (EDS), X-ray photoelectron spectroscopy (XPS), Fourier transform infrared (FTIR), scanning electron microscopy (SEM), transmission electron microscopy (TEM), N2 adsorption-desorption analysis and UV–vis diffuse reflectance spectrometry (DRS), proving a successful modification of TiO2 with g-C3N4. The results showed spindle-shaped nanoporous TiO2 microspheres with a uniform diameter of about 200 nm dispersed uniformly on the surface of graphitic g-C3N4 nanosheets. The g-C3N4/TiO2 hybrid materials exhibited higher photocatalytic activity than either pure g-C3N4 or nanoporous TiO2 towards degradation of typical rhodamine B (RhB), methyl blue (MB) and methyl orange (MO) dyes under visible light (>420 nm), which can be largely ascribed to the increased light absorption, larger BET surface area and higher efficient separation of photogenerated electron–hole pairs due to the formation of heterostructure. In addition, the possible transferred and separated behavior of electron–hole pairs and photocatalytic mechanisms on basis of the experimental results are also proposed in detail.  相似文献   

20.
《Electrochimica acta》2005,50(10):2065-2072
Type 316L SS play a key role in the bone replacement surgery due to its excellent mechanical features, availability at low cost and ease of fabrication. However it fails miserably in vivo conditions due to corrosion-related problems. Hence an alternative method on the development of hydroxyapatite (HAP) coatings has been elucidated to impart corrosion resistance of the base metal and ensure biocompatibility of the ceramic on the metal surface. This also could not match the implant at the host site due to the continuous interaction of hostile environment with the implant and results in the dissolution of both ceramic and metal. An artificially induced passive layer on the metal surface prior to coating may improve the nature of implant on the resistance to corrosion. In the present study, the effect of HNO3 treatments on 316L SS and the coatings on passivated 316L SS is being explored. Electrochemical studies involving cyclic anodic polarization experiments and impedance analysis in Ringer's solution were done to determine the corrosion resistance of the coatings. The leach out characteristics of the coatings was determined at the impressed potential. The results have indicated the efficiency of HAP coatings on HNO3-treated surface.  相似文献   

设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号