CN113089051A - Titanium alloy with ceramic membrane with active adsorption and antibacterial performance and preparation method thereof - Google Patents
Titanium alloy with ceramic membrane with active adsorption and antibacterial performance and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a titanium alloy with ceramic membranes with active adsorption and antibacterial properties and a preparation method thereof, belonging to the field of biological antibacterial materials. According to the preparation method, the antibacterial active ceramic membrane and the ceramic membrane with the active adsorption function are sequentially obtained on the surface of the titanium alloy by utilizing twice micro-arc oxidation, and the obtained ceramic membrane contains copper with two valence states after the micro-arc oxidation is carried out on the aqueous solution containing the copper ammonia complex ions, so that the antibacterial effect is greatly improved; micro-arc oxidation is carried out on the basis of a calcium-phosphorus system aqueous solution, and holes with gradually-increased pores from the inner part to the surface are distributed on the obtained ceramic membrane, so that the ceramic membrane has good adsorption performance; the preparation method of the invention has no special requirements on the material, shape, size and the like of the titanium and the titanium alloy, and the uniform ceramic membrane with adsorption gradient holes can be obtained on the surface of the titanium and the titanium alloy immersed in the electrolyte after micro-arc oxidation treatment, thereby having good universality.
Description
Technical Field
The invention relates to the field of biological antibacterial materials, in particular to a titanium alloy with ceramic membranes having active adsorption and antibacterial properties and a preparation method thereof.
Background
Titanium alloy is an important structural metal developed in the 50 s of the 20 th century, and is widely used in various fields due to its characteristics of high strength, good corrosion resistance, high heat resistance and the like. Among biomedical metal materials, titanium or titanium alloy has become the preferred material for dental implants, bone wound products and artificial joints due to its excellent performance.
The micro-arc oxidation technology is a new technology for growing ceramic membrane on the surface of non-ferrous metal in situ established on the basis of anodic oxidation in recent years, and uses higher voltage in work, during which a plurality of reactions such as thermochemistry, plasma chemistry, electrochemistry and the like occur to form stable TiO with compact inner layer and porous outer layer2The active ceramic layer can obviously improve the bioactivity of the titanium implant material and improve the wear resistance and corrosion resistance of the titanium implant material. The micro-arc oxidation ceramic membrane grows in situ on the surface of titanium metal, has metallurgical bonding property, shows very high bonding strength (close to 30Mp), and is far higher than the bonding strength (about 10Mp) of a coating prepared by a clinically common plasma spraying method. Meanwhile, in the micro-arc oxidation process, electrolyte ions not only participate in the physical and chemical reaction of micro-arc oxidation, but also diffuse into the oxide film through high temperature. Therefore, by controlling the micro-arc oxidation electrical parameters and adjusting the electrolyte components, the chemical composition of the oxide layer can be changed, and the microstructure, the chemical composition and the crystalline phase structure of the ceramic membrane can be adjusted.
Aiming at metal products (such as door handles, ATM keys and the like) in various public places, the metal products have the performance of inhibiting the growth of bacteria attached to the surfaces of the metal products so as to block the way of contacting and transmitting pathogenic bacteria, and the like, and also provide new requirements for bacteriostatic materials and bacteriostatic surface modification methods aiming at the way of transmitting pathogenic bacteria droplets in a closed space.
Disclosure of Invention
The invention aims to overcome the defect of poor antibacterial performance of the surface of the titanium alloy, and provides a ceramic membrane titanium alloy with active adsorption and antibacterial performance and a preparation method thereof.
In order to achieve the purpose, the invention adopts the following technical scheme to realize the purpose:
a preparation method of a titanium alloy with ceramic membranes with active adsorption and antibacterial properties comprises the following steps:
(1) preparing an aqueous solution containing copper ammonia complex ions as a bacteriostatic bottom layer micro-arc oxidation electrolyte;
(2) placing a titanium alloy and a stainless steel plate in a micro-arc oxidation electrolyte of a bacteriostatic bottom layer, taking the titanium alloy as an anode and the stainless steel plate as a cathode, performing micro-arc oxidation, and after the micro-arc oxidation is finished, cleaning and drying the titanium alloy to obtain the titanium alloy with the bacteriostatic performance and the ceramic membrane;
(3) preparing calcium-phosphorus system water solution
4-6 g of calcium glycerophosphate and 15-35 g of calcium acetate are dissolved in every 1L of deionized water and used as an adsorption gradient pore structure layer micro-arc oxidation electrolyte;
(4) and (3) placing the titanium alloy and the stainless steel plate of the ceramic membrane with antibacterial performance in the micro-arc oxidation electrolyte of the adsorption gradient pore structure layer, performing micro-arc oxidation by taking the titanium alloy of the antibacterial ceramic membrane as an anode and the stainless steel plate as a cathode, and after the micro-arc oxidation is finished, cleaning and drying the titanium alloy to obtain the ceramic membrane titanium alloy with active adsorption and antibacterial performance.
Further, in the step (2), the titanium alloy is TA1, TA2 or TC 4.
Further, the micro-arc oxidation process of the step (2) is as follows:
and (3) raising the micro-arc oxidation voltage to 150-300V, continuing for 5-20 min after arcing, then reducing the voltage to zero, and turning off the power supply.
Further, the micro-arc oxidation process in the step (4) comprises the following steps:
and (3) raising the micro-arc oxidation voltage to 300-450V, continuing for 5-20 min after arcing, then reducing the voltage to zero, and turning off the power supply.
Further, the specific operation of the step (1) is as follows: and dropwise adding 8mol/L ammonia water into the copper salt aqueous solution to generate light blue basic copper salt precipitate, and continuously dropwise adding until the precipitate is completely dissolved to obtain the aqueous solution containing copper ammonia complex ions.
Further, the copper salt is one or more of copper sulfate, copper nitrate or copper chloride.
The titanium alloy with the ceramic membrane having the active adsorption and antibacterial properties is prepared by the preparation method.
Furthermore, the composite coating is provided with double coatings, the bottom layer is a ceramic membrane with antibacterial performance, and the upper layer is a ceramic membrane with the pore diameter gradually increasing from the inner layer to the surface.
Further, the ceramic film of the bottom layer contains Cu2O and CuO.
Compared with the prior art, the invention has the following beneficial effects:
according to the preparation method of the titanium alloy with the ceramic membrane having the active adsorption and antibacterial performance, the antibacterial active ceramic membrane and the ceramic membrane having the active adsorption function are sequentially obtained on the surface of the titanium alloy through two-time micro-arc oxidation, and the obtained ceramic membrane contains copper in two valence states after the micro-arc oxidation is carried out on the aqueous solution containing the copper ammonia complex ions, so that the antibacterial effect is greatly improved; micro-arc oxidation is carried out on the basis of a calcium-phosphorus system aqueous solution, and holes with gradually-increased pores from the inner part to the surface are distributed on the obtained ceramic membrane, so that the ceramic membrane has good adsorption performance; the preparation method of the invention has no special requirements on the material, shape, size and the like of the titanium and the titanium alloy, and the uniform ceramic membrane with adsorption gradient holes can be obtained on the surface of the titanium and the titanium alloy immersed in the electrolyte after micro-arc oxidation treatment, thereby having good universality.
The titanium alloy with the ceramic membrane having the active adsorption and antibacterial performance, disclosed by the invention, has a long-acting antibacterial micro-arc oxidation bottom layer, and the membrane layer pore structure is modified through two times of micro-arc oxidation, so that the micro-arc oxidation coating is thickened to generate a gradient pore structure and further generate a capillary condensation effect on aerosol, and the coating has excellent active adsorption performance.
Drawings
FIG. 1 is an XRD pattern of a titanium alloy specimen of example 1;
FIG. 2 is an XPS plot of a titanium alloy sample of example 1;
FIG. 3 is a surface topography SEM image of a titanium alloy specimen of example 1;
FIG. 4 is a cross-sectional SEM image of a titanium alloy coupon of example 1;
FIG. 5 is an adsorption curve of a titanium alloy specimen of example 1;
FIG. 6 is a diagram showing the growth morphology of bacteria after inoculation of bacteria on a conventional micro-arc oxidation sample;
FIG. 7 is a graph of the bacteria growth topography of the titanium alloy test samples of example 1 after inoculation with bacteria;
FIG. 8 is a bar graph of bacterial absorbances obtained by performing bacteriostasis tests on the titanium alloy samples of examples 1, 2, 3 and 4;
FIG. 9 is a bar graph of the bacteriostatic ratio of the titanium alloy samples of examples 1, 2, 3 and 4.
Detailed Description
In order to make the technical solutions of the present invention better understood, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
It should be noted that the terms "first," "second," and the like in the description and claims of the present invention and in the drawings described above are used for distinguishing between similar elements and not necessarily for describing a particular sequential or chronological order. It is to be understood that the data so used is interchangeable under appropriate circumstances such that the embodiments of the invention described herein are capable of operation in sequences other than those illustrated or described herein. Furthermore, the terms "comprises," "comprising," and "having," and any variations thereof, are intended to cover a non-exclusive inclusion, such that a process, method, system, article, or apparatus that comprises a list of steps or elements is not necessarily limited to those steps or elements expressly listed, but may include other steps or elements not expressly listed or inherent to such process, method, article, or apparatus.
The active adsorption and bacteriostasis activation of the titanium, and the modified titanium and titanium alloy treatment has the capability of adsorbing aerosol in the air environment close to the surface of the titanium and blocking the aerosol transmission of virus and bacteria. The adsorption effect on the aerosol is mainly the capillary condensation effect on the aerosol generated by the gradient pore structure of the coating; the bacteriostatic ability mainly depends on the addition of bacteriostatic elements such as Cu, Zn, Ag and the like, and the addition of Cu is the main action factor of the bacteriostatic ability in the coating. The combination of the porous structure outside the coating and the bacteriostatic compact layer at the bottom layer realizes the effective combination of the adsorption and the antibacterial performance of the aerosol. The external structure layer protects the bacteriostatic bottom layer from being damaged, avoids the loss of bacteriostatic elements in the service process, and prolongs the overall service life of the coating. The new technology prepares a long-acting lasting high-antibacterial activity ceramic film layer capable of actively adsorbing aerosol in a certain range on the surface of a workpiece on the surface of a titanium alloy, and can greatly promote the practical popularization and application of the micro-arc oxidation technology in the application aspect of the field of public health and safety.
The invention is described in further detail below with reference to the accompanying drawings:
example 1
(1) Pretreating the surface of a titanium alloy sample
Grinding and polishing until no scratch is left on the surface of a TA1 titanium alloy sample, then removing oil and washing with alkali, and naturally drying for later use;
(2) dropwise adding 8mol/L ammonia water into 1mol/L copper sulfate aqueous solution to generate light blue basic copper salt precipitate, and continuously dropwise adding until the precipitate is completely dissolved to obtain aqueous solution containing copper ammonia complex ions, wherein the aqueous solution is used as a bacteriostatic bottom layer micro-arc oxidation electrolyte;
(3) at normal temperature, placing a titanium alloy sample and a stainless steel plate in an electrolyte, taking the titanium alloy sample as an anode and the stainless steel plate as a cathode, adjusting the pulse frequency to be 300Hz and the duty ratio to be 5 percent, boosting the voltage to 300V, treating for 5min, reducing the voltage to zero, turning off a power supply, cleaning the titanium alloy sample by using deionized water, and drying at room temperature for later use to obtain the titanium alloy with the ceramic membrane containing the antibacterial active component;
(4) preparing calcium-phosphorus system water solution
Dissolving 5g of calcium glycerophosphate and 15g of calcium acetate in 1L of deionized water to serve as an adsorption gradient pore structure layer micro-arc oxidation electrolyte;
(5) placing a titanium alloy with a ceramic membrane containing antibacterial active ingredients and a stainless steel plate in an adsorption gradient pore structure layer micro-arc oxidation electrolyte, taking a titanium alloy sample as an anode and the stainless steel plate as a cathode, and performing micro-arc oxidation;
and (3) raising the micro-arc oxidation voltage to 300V, reacting for 20min after arc striking, reducing the voltage to zero, turning off a power supply, cleaning the surface of the sample by using deionized water, and drying at room temperature to obtain the ceramic membrane with the antibacterial active component at the bottom layer and the titanium alloy with the ceramic membrane with the pore diameter gradually increased from inside to outside at the surface layer.
The test sample of the example 1 is detected, viable bacteria count is carried out according to JC/T897-2014 antibacterial ceramic product antibacterial performance and GB 4789.2 method, the bacteriostasis rate is calculated under the effective condition of the test, and the measurement result is as follows: the bacteriostasis rate is 92 percent.
Referring to FIG. 1, FIG. 1 shows the XRD results of the titanium alloy sample after the micro-arc oxidation treatment in example 1, and it can be seen that Cu is synthesized in situ in example 12TiO of O2And micro-arc oxidation ceramic layer.
Referring to fig. 2, fig. 2 is an XPS result of the titanium alloy sample after the micro-arc oxidation treatment in example 1, and it can be seen that the micro-arc oxidation ceramic layer contains two Cu oxides, namely monovalent Cu and divalent Cu, and the Cu element with rich valence and various existing forms makes the adsorption coating have excellent bacterial performance.
Referring to fig. 3, fig. 3(a) and (b) are SEM images of the titanium alloy after the micro-arc oxidation treatment of example 1 with different magnifications, respectively, and it can be seen that the outer pore diameter of the reaction channel of the ceramic layer is large.
Referring to fig. 4, fig. 4(a) is a cross-sectional SEM image of the micro-arc oxidized underlayer ceramic layer of example 1, which shows that the pore size of the tighter bacteriostatic underlayer is smaller; FIG. 4(b) is a SEM image of the cross section of the ceramic layer of the micro-arc oxidized product of example 1, and it is clear that the outer pore diameters of the two ceramic layers are larger and are uniformly distributed.
Referring to fig. 5, fig. 5 is an adsorption curve of the titanium alloy sample after micro-arc oxidation treatment in example 1, the total area ratio of the holes with the diameters ranging from 5 nm to 10nm is large, and according to a Kelvin equation of capillary condensation theory, when gas washes over the surface of the sample at a certain speed, the porous micro-arc oxidation layer can generate capillary condensation on aerosol, so that the aerosol is adsorbed. It can be seen from the figure that the sample obtained by the preparation method has excellent adsorption performance.
Referring to fig. 6, fig. 6(a), fig. 6(b), and fig. 6(c) are respectively a graph showing the growth topography of bacteria at different times after the titanium alloy sample is inoculated with the bacteria after the conventional micro-arc oxidation treatment, and fig. 6(a), fig. 6(b), fig. 6(c) correspond to the inoculated bacteria 10h, 24h, and 48h, respectively, it can be seen that the bacterial community rapidly proliferates over time, and it is obvious that the micro-arc oxidation ceramic layer has no bacteriostatic property.
Referring to fig. 7, fig. 7(a), 7(b), and 7(c) are respectively a graph of the growth topography of the titanium alloy sample after the micro-arc oxidation treatment of example 1, after being inoculated with bacteria, at different times, and fig. 7(a), 7(b), and 7(c) correspond to the inoculated bacteria for 10h, 24h, and 48h, respectively, it can be seen that the concentration of the flora is reduced and the number of bacteria is sharply reduced within a short time after the inoculation, and it is obvious that the micro-arc oxidation ceramic layer shows excellent bacteriostatic performance.
Example 2
(1) Pretreating the surface of a titanium alloy sample
Grinding and polishing until no scratch is left on the surface of a TA2 titanium alloy sample, then removing oil and washing with alkali, and naturally drying for later use;
(2) dropwise adding 8mol/L ammonia water into 1mol/L copper nitrate aqueous solution to generate light blue basic copper salt precipitate, and continuously dropwise adding until the precipitate is completely dissolved to obtain aqueous solution containing copper ammonia complex ions, wherein the aqueous solution is used as a bacteriostatic bottom layer micro-arc oxidation electrolyte;
(3) at normal temperature, placing a titanium alloy sample and a stainless steel plate in an electrolyte, taking the titanium alloy sample as an anode and the stainless steel plate as a cathode, adjusting the pulse frequency to be 500Hz and the duty ratio to be 30%, boosting the voltage to 200V, treating for 10min, reducing the voltage to zero, turning off a power supply, cleaning the titanium alloy sample by using deionized water, and drying at room temperature for later use to obtain the titanium alloy with the ceramic membrane containing the antibacterial active component;
(4) preparing calcium-phosphorus system water solution
Dissolving 4g of calcium glycerophosphate and 20g of calcium acetate in 1L of deionized water to serve as an adsorption gradient pore structure layer micro-arc oxidation electrolyte;
(5) placing a titanium alloy with a ceramic membrane containing antibacterial active ingredients and a stainless steel plate in an adsorption gradient pore structure layer micro-arc oxidation electrolyte, taking a titanium alloy sample as an anode and the stainless steel plate as a cathode, and performing micro-arc oxidation;
and (3) raising the micro-arc oxidation voltage to 350V, reacting for 15min after arc striking, reducing the voltage to zero, turning off a power supply, cleaning the surface of the sample by using deionized water, and drying at room temperature to obtain the ceramic membrane with the antibacterial active component at the bottom layer and the titanium alloy with the ceramic membrane with the pore diameter gradually increased from inside to outside at the surface layer.
The results of the measurement of the bacteriostatic rate were as follows: the bacteriostasis rate is 85 percent.
Example 3
(1) Pretreating the surface of a titanium alloy sample
Grinding and polishing until no scratch is formed on the surface of a TC4 titanium alloy sample, then removing oil and washing with alkali, and naturally drying for later use;
(2) preparing an aqueous solution containing copper ammonia complex ions as a bacteriostatic bottom layer micro-arc oxidation electrolyte;
dropwise adding 8mol/L ammonia water into 2mol/L copper chloride aqueous solution to generate light blue basic copper salt precipitate, and continuously dropwise adding until the precipitate is completely dissolved to obtain aqueous solution containing copper-ammonia complex ions;
(3) at normal temperature, placing a titanium alloy sample and a stainless steel plate in an electrolyte, taking the titanium alloy sample as an anode and the stainless steel plate as a cathode, adjusting the pulse frequency to be 1000Hz and the duty ratio to be 30%, boosting the voltage to 300V, treating for 5min, reducing the voltage to zero, turning off a power supply, cleaning the titanium alloy sample by using deionized water, and drying at room temperature for later use to obtain the titanium alloy with the ceramic membrane containing the antibacterial active component;
(4) preparing calcium-phosphorus system water solution
Dissolving 6g of calcium glycerophosphate and 35g of calcium acetate in 1L of deionized water to serve as an adsorption gradient pore structure layer micro-arc oxidation electrolyte;
(5) placing a titanium alloy with a ceramic membrane containing antibacterial active ingredients and a stainless steel plate in an adsorption gradient pore structure layer micro-arc oxidation electrolyte, taking a titanium alloy sample as an anode and the stainless steel plate as a cathode, and performing micro-arc oxidation;
and (3) raising the micro-arc oxidation voltage to 450V, reacting for 5min after arc striking, reducing the voltage to zero, turning off a power supply, cleaning the surface of the sample by using deionized water, and drying at room temperature to obtain the ceramic membrane with the antibacterial active component at the bottom layer and the titanium alloy with the ceramic membrane with the pore diameter gradually increased from inside to outside at the surface layer.
The results of the measurement of the bacteriostatic rate were as follows: the bacteriostasis rate is 79 percent.
Example 4
The other preparation conditions of this example were the same as in example 1 except that: the calcium-phosphorus system water solution is as follows: 4g of calcium glycerophosphate, 20g of calcium acetate and 1L of deionized water.
The results of the measurement of the bacteriostatic rate were as follows: the bacteriostasis rate is 83 percent.
Referring to fig. 8, fig. 8 is a bar graph of bacterial absorbance obtained by bacteriostatic tests of the titanium alloy samples after the micro-arc oxidation treatment of examples 1, 2, 3 and 4, and it can be seen from the bar graph that the number of bacteria is reduced in examples 1 to 4.
Referring to fig. 9, fig. 9 is a bar graph of the bacteriostatic rate obtained by bacteriostatic tests on the titanium alloy samples after the micro-arc oxidation treatment of examples 1, 2, 3 and 4, wherein the bacteriostatic rate is equal to or greater than 75%, and the titanium alloy samples have a significant bacteriostatic effect.
Example 5
The other preparation conditions of this example were the same as in example 1 except that: calcium glycerophosphate in the aqueous calcium-phosphorus system solution was 5g, calcium acetate was 20g, and 1L in deionized water.
The results of the measurement of the bacteriostatic rate were as follows: the bacteriostasis rate is 84 percent.
Example 6
The other preparation conditions of this example were the same as in example 1 except that: calcium glycerophosphate in the aqueous calcium-phosphorus system solution was 6g, calcium acetate was 20g, and 1L in deionized water.
The results of the measurement of the bacteriostatic rate were as follows: the bacteriostasis rate is 87 percent.
The above-mentioned contents are only for illustrating the technical idea of the present invention, and the protection scope of the present invention is not limited thereby, and any modification made on the basis of the technical idea of the present invention falls within the protection scope of the claims of the present invention.
Claims (9)
1. A preparation method of a titanium alloy with ceramic membranes having active adsorption and antibacterial properties is characterized by comprising the following steps:
(1) preparing an aqueous solution containing copper ammonia complex ions as a bacteriostatic bottom layer micro-arc oxidation electrolyte;
(2) placing a titanium alloy and a stainless steel plate in a micro-arc oxidation electrolyte of a bacteriostatic bottom layer, taking the titanium alloy as an anode and the stainless steel plate as a cathode, performing micro-arc oxidation, and after the micro-arc oxidation is finished, cleaning and drying the titanium alloy to obtain the titanium alloy with the bacteriostatic performance and the ceramic membrane;
(3) preparing calcium-phosphorus system water solution
4-6 g of calcium glycerophosphate and 15-35 g of calcium acetate are dissolved in every 1L of deionized water and used as an adsorption gradient pore structure layer micro-arc oxidation electrolyte;
(4) and (3) placing the titanium alloy and the stainless steel plate of the ceramic membrane with antibacterial performance in the micro-arc oxidation electrolyte of the adsorption gradient pore structure layer, performing micro-arc oxidation by taking the titanium alloy of the antibacterial ceramic membrane as an anode and the stainless steel plate as a cathode, and after the micro-arc oxidation is finished, cleaning and drying the titanium alloy to obtain the ceramic membrane titanium alloy with active adsorption and antibacterial performance.
2. The method for preparing a titanium alloy for a ceramic membrane with active adsorption and antibacterial properties as claimed in claim 1, wherein the titanium alloy in step (2) is TA1, TA2 or TC 4.
3. The method for preparing a ceramic membrane titanium alloy with active adsorption and antibacterial properties according to claim 1, wherein the micro-arc oxidation process in step (2) is as follows:
and (3) raising the micro-arc oxidation voltage to 150-300V, continuing for 5-20 min after arcing, then reducing the voltage to zero, and turning off the power supply.
4. The method for preparing a ceramic membrane titanium alloy with active adsorption and antibacterial properties according to claim 1, wherein the micro-arc oxidation process in step (4) comprises:
and (3) raising the micro-arc oxidation voltage to 300-450V, continuing for 5-20 min after arcing, then reducing the voltage to zero, and turning off the power supply.
5. The method for preparing titanium alloy for ceramic membrane with active adsorption and antibacterial property as claimed in claim 1, wherein the specific operation of step (1) is: and dropwise adding 8mol/L ammonia water into the copper salt aqueous solution to generate light blue basic copper salt precipitate, and continuously dropwise adding until the precipitate is completely dissolved to obtain the aqueous solution containing copper ammonia complex ions.
6. The method of claim 5, wherein the copper salt is one or more of copper sulfate, copper nitrate or copper chloride.
7. Titanium alloy for ceramic membranes with active adsorption and bacteriostatic properties, characterized in that it is prepared according to the preparation method of any one of claims 1 to 6.
8. The titanium alloy having an actively adsorbing bacteriostatic ability of ceramic membrane according to claim 7, wherein said titanium alloy has a double-layer coating, the bottom layer is a ceramic membrane having bacteriostatic ability, and the upper layer is a ceramic membrane having a pore size gradually increasing from the inner layer to the surface.
9. The titanium alloy for ceramic membranes with active adsorption and bacteriostatic properties as claimed in claim 8, wherein said bottom ceramic membrane contains Cu2O and CuO.
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