CN112342478B - Preparation method of nano-porous titanium alloy film - Google Patents
Preparation method of nano-porous titanium alloy film Download PDFInfo
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
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- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
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Abstract
The invention discloses a preparation method of a nano-porous titanium alloy film, which comprises the following steps: firstly, carrying out vacuum heat treatment on an aluminum-titanium-containing alloy foil; secondly, sequentially carrying out surface pickling and purification; thirdly, performing electrochemical dealloying treatment, and cleaning and drying to obtain a porous titanium alloy membrane crude product; and fourthly, carrying out vacuum heat treatment to enlarge the hole to obtain the nano porous titanium alloy film. The invention utilizes the difference of electrochemical potentials of aluminum and titanium in an alkaline solution to selectively dissolve aluminum elements in an aluminum-titanium-containing alloy foil through electrochemical dealloying treatment, so that through pores are formed at the original position of the dissolved and dealloyed aluminum, the size and the depth of the pores are controlled by combining a heat treatment reaming process, and the nano porous titanium alloy membrane with uniform pore distribution and uniform pore diameter is obtained, thereby meeting the high-precision application requirements in the fields of micro-flow control, filtration separation, gas sensors, electrodes of supercapacitors, high-catalytic activity systems, biomedical implant materials and the like.
Description
Technical Field
The invention belongs to the technical field of preparation of porous titanium alloy films, and particularly relates to a preparation method of a nano porous titanium alloy film.
Background
The metal porous titanium alloy foil (membrane) material not only has the characteristics of metal, but also has the functional characteristics of a porous material, so that the metal porous titanium alloy foil (membrane) material has great potential application value in the fields of micro-flow control, filtration and separation of nano-fluid, gas sensors, electrodes of supercapacitors, high catalytic activity systems (serving as current collectors of PEM fuel cells and SPE water electrolysis devices), biomedical implant materials and the like.
The preparation method of the porous titanium alloy foil (film) mainly comprises a loose sintering method, a powder rolling method and an isostatic pressing method. Wherein, the powder rolling method can produce a porous titanium alloy plate with the thickness of 0.2 mm-4 mm, and the porous titanium alloy foil with the thickness of less than 0.2mm can be seriously cracked when being rolled; the porosity of the porous titanium alloy plate prepared by the isostatic pressing method is only 30%, and the thickness of the porous titanium alloy plate is more than 1 mm. The porous titanium alloy foil with the thickness less than 0.02mm is difficult to prepare by the methods.
The patent application No. 201410608980.3 discloses a method for preparing a porous foil by powder metallurgy, the porous metal foil obtained by the method has a wide pore size distribution and an average pore size of 0.05 μm to 100 μm.
Based on the current higher-precision filtration requirement and the technical development requirements of high-activity electrode materials, porous current collectors and the like, the porous titanium alloy foil (membrane) with the pore size of nanometer and the thickness of less than 0.02mm can meet the requirements of miniaturization, light weight, integration and high efficiency of filtration devices, energy sources, electrolysis devices and the like in the application field.
Disclosure of Invention
The technical problem to be solved by the present invention is to provide a method for preparing a nano-porous titanium alloy film, aiming at the defects of the prior art. The method utilizes the difference of electrochemical potentials of aluminum and titanium in an alkaline solution to selectively dissolve aluminum elements in an aluminum-titanium-containing alloy foil through electrochemical dealloying treatment, so that through pores are formed at the original position of dissolved and dealloyed aluminum, and the size and the depth of the pores are controlled by combining a heat treatment reaming process to obtain the nano porous titanium alloy film with uniform pore distribution and uniform pore diameter.
In order to solve the technical problems, the invention adopts the technical scheme that: a preparation method of a nano-porous titanium alloy film is characterized by comprising the following steps:
step one, carrying out vacuum heat treatment on an aluminum-titanium-containing alloy foil; the vacuum degree of the heat treatment is 10-2Pa～10- 3Pa, the temperature is 700-1000 ℃, and the time is 60-240 min;
step two, sequentially carrying out surface acid washing and purification on the aluminum-titanium-containing alloy foil subjected to vacuum heat treatment in the step one;
step three, performing electrochemical dealloying treatment on the aluminum-titanium-containing alloy foil purified in the step two, and then sequentially cleaning and drying to obtain a porous titanium alloy membrane crude product; the electrochemical dealloying process comprises the following steps: soaking the purified aluminum-titanium-containing alloy foil serving as a working electrode into alkaline electrolyte to serve as an anode, and performing electrochemical dealloying by taking a platinum electrode as a cathode and Ag/AgCl as a reference electrode;
step four, carrying out vacuum heat treatment on the porous titanium alloy film crude product obtained in the step three to expand the pores, so as to obtain a nano porous titanium alloy film; the vacuum degree of the vacuum heat treatment is 10-2Pa-10-3Pa, the temperature is 200-500 ℃, and the time is 30-180 min.
The surface of the aluminum-titanium-containing alloy foil is cleaned and purified, then electrochemical dealloying treatment is carried out, the aluminum element in the aluminum-titanium-containing alloy foil is selectively dissolved by utilizing the difference of electrochemical potentials of aluminum and titanium in an alkaline solution, and the titanium is not dissolved, so that a pore is formed at the original position of the dissolved and deallocated aluminum; after the aluminum-containing titanium alloy foil is subjected to vacuum heat treatment, aluminum elements are uniformly distributed in the titanium alloy, and the sizes of all aluminum atoms or aluminum clusters are the same, so that through holes which are uniformly distributed and have uniform apertures are formed in the aluminum-containing titanium alloy foil subjected to electrochemical dealloying treatment, and the nano porous titanium alloy film is obtained after vacuum heat treatment and hole expansion. Because the content, distribution and grain size of aluminum in the aluminum-titanium-containing alloy foil have important influence on the finally obtained nano-porous titanium alloy film, the uniformity of each component is improved, the stress is eliminated and the nano-porous structure of the nano-porous titanium alloy film is ensured by controlling the process conditions of the heat treatment of the aluminum-titanium-containing alloy foil; in addition, because the size of the pores in the crude product of the porous titanium alloy film is smaller, the size of the pores is effectively enlarged by controlling the technological parameters of vacuum heat treatment, and the nano porous titanium alloy film suitable for application is obtained.
The preparation method of the nano-porous titanium alloy film is characterized in that the mass content of the aluminum element in the aluminum-containing titanium alloy foil in the step one is 2-8%. The optimal mass content of the aluminum element in the aluminum-titanium alloy foil is proper, so that a porous titanium alloy film with nano-sized pores can be obtained, and the problems that the processing brittleness of the aluminum-titanium alloy foil is increased and a large number of defects occur in the prepared nano-porous titanium alloy film due to the large amount of TiAl intermetallic compounds caused by the overhigh content of the aluminum element are avoided.
The preparation method of the nano-porous titanium alloy film is characterized in that the components of the aluminum-containing titanium alloy foil are Ti-6Al-4V titanium alloy, Ti-6Al-7Nb titanium alloy, Ti-3Al-2.5V titanium alloy, Ti-2Al-2.5Zr titanium alloy or Ti-8Al-1Mo-1V titanium alloy. The aluminum-containing titanium alloy foil with the optimized components covers the titanium alloy types commonly used in the industry at present, and the practical value of the invention is improved.
The preparation method of the nano-porous titanium alloy film is characterized in that the aluminum-containing titanium alloy foil in the step one is prepared by adopting a smelting and rolling method, and the thickness of the aluminum-containing titanium alloy foil is 20-200 mu m. The thickness of the nano porous titanium alloy film prepared by the preferred aluminum-containing titanium alloy foil is lower, and the requirements of high precision and miniaturization filtration can be met.
The preparation method of the nano-porous titanium alloy film is characterized in that the surface pickling and purifying processes in the step two are as follows: immersing the aluminum-titanium-containing alloy foil subjected to vacuum heat treatment into a mixed acid solution for cleaning for 5s, then sequentially placing the aluminum-titanium-containing alloy foil into deionized water, acetone and absolute ethyl alcohol for ultrasonic cleaning for 60min respectively, taking out the aluminum-titanium-containing alloy foil and purifying the aluminum-titanium-containing alloy foil for 20min to 60min under a nitrogen atmosphere of 0.6Pa to 1.0 Pa; the mixed acid solution consists of HF solution with the mass concentration of 38 percent and HNO with the mass concentration of 65 percent3The acid pickling solution is prepared by mixing the solution and water according to the volume ratio of 1:5:4, and the temperature of the mixed acid solution in the acid pickling process is 40 ℃. Impurities such as surface oxide skin of the aluminum-titanium alloy-containing foil subjected to vacuum heat treatment and the like are effectively removed through the acid washing and purifying process, and the subsequent electrochemical dealloying treatment is facilitated.
The preparation method of the nano-porous titanium alloy film is characterized in that the cleaning in the third step is ultrasonic cleaning by using absolute ethyl alcohol as a solvent, the ultrasonic cleaning time is 60min, and after the ultrasonic cleaning, deionized water is used for boiling, washing and soaking treatment until the pH value is neutral; the drying is vacuum drying, the temperature of the vacuum drying is 60-100 ℃, and the time is 5-10 h. The alkaline electrolyte remained in the pores of the aluminum-titanium alloy foil after the electrochemical dealloying treatment is effectively removed by the optimized process.
The preparation method of the nano-porous titanium alloy membrane is characterized in that the pore diameter of the crude product of the porous titanium alloy membrane in the third step is not more than 10 nm.
The preparation method of the nano-porous titanium alloy film is characterized in that the alkaline electrolyte in the third step contains NaOH and H2O2、C8H4K2O12Sb2、(CH2OH)2And Na2SiO3The mass content of NaOH in the alkaline electrolyte is 1-10%, and H2O21 to 5 percent of C8H4K2O12Sb2(CH) 1-2% by mass2OH)2The mass content of (1-4%) and Na2SiO3The mass content of (A) is 1-3%; the voltage of the electrochemical dealloying treatment is 1V-5V, the time is 60 min-360 min, and the temperature is 40-60 ℃. Through the change of the composition and concentration of the optimized alkaline electrolyte and the technological parameters of the electrochemical dealloying treatment, the effective control of the pore size in the crude product of the porous titanium alloy membrane is realized, so that the pore diameter of the product nano-porous titanium alloy membrane is controlled, and the requirements of different application occasions are met.
The preparation method of the nano-porous titanium alloy film is characterized in that the pore diameter of the nano-porous titanium alloy film in the fourth step is 20 nm-100 nm. The nano porous titanium alloy membrane with the aperture has wide application range and meets the high-precision filtration requirement.
Compared with the prior art, the invention has the following advantages:
1. the method utilizes the difference of electrochemical potentials of aluminum and titanium in an alkaline solution to selectively dissolve aluminum elements in the aluminum-titanium-containing alloy foil through electrochemical dealloying treatment, so that through pores are formed at the original position of dissolved and dealloyed aluminum, and the size and the depth of the pores are controlled by combining a heat treatment reaming process to obtain the nano porous titanium alloy film with uniform pore distribution and uniform pore diameter.
2. According to the invention, by controlling the process conditions of the vacuum heat treatment of the aluminum-titanium alloy-containing foil, the aluminum content distribution and the uniformity of the grain size are improved, the stress is eliminated, and the pore distribution uniformity and the pore diameter uniformity of the nano porous titanium alloy film are improved.
3. The method effectively controls the pore size, the depth and the distribution of the nano porous titanium alloy membrane by controlling the conditions of the electrochemical dealloying treatment, and has the advantages of short preparation flow, high preparation efficiency and lower cost.
4. Compared with the bent hole prepared by a powder metallurgy method, the method provided by the invention has the advantages that the straight-through parallel hole is obtained by dissolving aluminum through electrochemical dealloying treatment, the filtration resistance of the nano porous titanium alloy membrane is reduced, the permeation flux of the nano porous titanium alloy membrane is improved, the nano hole is not easy to block, and the used nano porous titanium alloy membrane is easy to regenerate.
5. Compared with the porous titanium film, the nano-porous titanium alloy film prepared by the method has the advantages that the existence of other alloy elements such as V, Nb, Zr, Mo and the like improves the corrosion resistance of the nano-porous titanium alloy film, so that the nano-porous titanium alloy film is suitable for filtering liquid, solid, gas and liquid and the like in extreme environments of acid and alkali.
6. The thickness of the prepared nano-porous titanium alloy membrane is 20-200 mu m, the aperture is 20-100 nm, and the high-precision application requirements in the fields of micro-flow control, filtration and separation, gas sensors, electrodes of supercapacitors, high-catalytic-activity systems, biomedical implant materials and the like are met.
The technical solution of the present invention is further described in detail by the accompanying drawings and examples.
Drawings
FIG. 1 is a flow chart of the preparation process of the present invention.
FIG. 2 is an SEM image of a crude porous Ti-6Al-4V titanium alloy film prepared in example 1 of the present invention.
FIG. 3 is an SEM image of a nanoporous Ti-6Al-4V titanium alloy film prepared in example 1 of the present invention.
FIG. 4 is an SEM image of a crude porous Ti-6Al-7Nb titanium alloy film prepared in example 2 of the invention.
FIG. 5 is an SEM image of a nanoporous Ti-6Al-7Nb titanium alloy film prepared in example 2 of the invention.
FIG. 6 is an SEM image of a crude porous Ti-3Al-2.5V titanium alloy film prepared in example 3 of the present invention.
FIG. 7 is an SEM image of a nanoporous Ti-3Al-2.5V titanium alloy film prepared in example 3 of the invention.
Detailed Description
As shown in FIG. 1, the preparation process of the invention comprises the following steps: and carrying out heat treatment on the aluminum-titanium-containing alloy foil, then sequentially carrying out surface pickling and purification, then carrying out electrochemical dealloying treatment, and then carrying out vacuum heat treatment and chambering to obtain the nano porous titanium alloy membrane.
Example 1
The embodiment comprises the following steps:
step one, Ti-6Al-4V titanium alloy foil with the thickness of 20 mu m is processed under the vacuum degree of 10-2Pa～10-3Carrying out vacuum heat treatment for 60min under the conditions of Pa and the temperature of 980 ℃; the Ti-6Al-4V titanium alloy foil is prepared by adopting a smelting and rolling method
Step two, sequentially carrying out surface acid washing and purification on the Ti-6Al-4V titanium alloy foil subjected to vacuum heat treatment in the step one; the surface pickling and purification process comprises the following steps: immersing the Ti-6Al-4V titanium alloy foil subjected to heat treatment into a mixed acid solution for cleaning for 5s, then sequentially placing the Ti-6Al-4V titanium alloy foil into deionized water, acetone and absolute ethyl alcohol for respectively ultrasonically cleaning for 60min, taking out the Ti-6Al-4V titanium alloy foil and purifying for 60min under a nitrogen atmosphere of 0.6 Pa; the mixed acid solution consists of HF solution with the mass concentration of 38 percent and HNO with the mass concentration of 65 percent3The acid cleaning agent is prepared by mixing a solution and water according to a volume ratio of 1:5:4, wherein the temperature of the mixed acid solution in the acid cleaning process is 40 ℃;
step three, soaking the purified Ti-6Al-4V titanium alloy foil serving as a working electrode in alkaline electrolyte to serve as an anode, taking a platinum electrode as a cathode, taking Ag/AgCl as a reference electrode to perform electrochemical dealloying treatment, then ultrasonically cleaning for 60min by taking absolute ethyl alcohol as a solvent, boiling, washing and soaking by using deionized water until the pH value is neutral, and performing vacuum drying for 5h at 100 ℃ to obtain a porous Ti-6Al-4V titanium alloy membrane crude product; the alkaline electrolyte contains NaOH and H2O2、C8H4K2O12Sb2、(CH2OH)2And Na2SiO3The mass content of NaOH in the alkaline electrolyte is 5 percent, and H2O2Is 2% by mass, C8H4K2O12Sb2(CH) 1% by mass2OH)21% by mass of Na2SiO3The mass content of (A) is 1%; the voltage of the electrochemical dealloying treatment is 2.5V, the time is 60min, and the temperature is 40 ℃; the aperture of the porous Ti-6Al-4V titanium alloy membrane crude product is 5 nm-6 nm;
step four, the crude product of the porous Ti-6Al-4V film obtained in the step three is subjected to vacuum degree of 10-2Pa～10-3And carrying out vacuum heat treatment for 60min under the conditions of Pa and the temperature of 300 ℃ to enlarge the pores, thereby obtaining the nano porous Ti-6Al-4V titanium alloy film.
Through detection, the aperture of the nano-porous Ti-6Al-4V titanium alloy membrane prepared by the embodiment is 60 nm-100 nm.
FIG. 2 is an SEM image of the crude porous Ti-6Al-4V titanium alloy film prepared in this example, and it can be seen from FIG. 2 that fine nano-pores are generated in the crude porous Ti-6Al-4V titanium alloy film, and the pore diameter of the nano-pores is 5nm to 6 nm.
Fig. 3 is an SEM image of the nanoporous Ti-6Al-4V titanium alloy film prepared in this example, and it can be seen from fig. 3 that nanopores with diameters of 60nm to 100nm are formed on the nanoporous Ti-6Al-4V titanium alloy film, wherein the nanopores are through and uniformly distributed.
The titanium alloy foil in the first step of this embodiment can be replaced by a Ti-2Al-2.5Zr titanium alloy foil.
Example 2
The embodiment comprises the following steps:
step one, Ti-6Al-7Nb titanium alloy foil with the thickness of 200 mu m is processed in the vacuum degree of 10-2Pa～10-3Carrying out vacuum heat treatment for 240min under the conditions of Pa and 700 ℃;
step two, sequentially carrying out surface acid washing and purification on the Ti-6Al-7Nb titanium alloy foil subjected to vacuum heat treatment in the step one; the surface pickling and purification process comprises the following steps: heat treated Ti-6Al-7Nb titanium alloyImmersing the foil into a mixed acid solution for cleaning for 5s, then sequentially placing the foil into deionized water, acetone and absolute ethyl alcohol for ultrasonic cleaning for 60min respectively, taking out the foil and purifying the foil for 40min in a nitrogen atmosphere of 1.0 Pa; the mixed acid solution consists of HF solution with the mass concentration of 38 percent and HNO with the mass concentration of 65 percent3The acid cleaning agent is prepared by mixing a solution and water according to a volume ratio of 1:5:4, wherein the temperature of the mixed acid solution in the acid cleaning process is 40 ℃;
step three, soaking the Ti-6Al-7Nb titanium alloy foil purified in the step two as a working electrode into an alkaline electrolyte as an anode, taking a platinum electrode as a cathode, taking Ag/AgCl as a reference electrode for electrochemical dealloying treatment, then ultrasonically cleaning for 60min by taking absolute ethyl alcohol as a solvent, boiling, washing and soaking by using deionized water until the pH value is neutral, and performing vacuum drying for 10h at 60 ℃ to obtain a porous Ti-6Al-4V titanium alloy membrane crude product; the alkaline electrolyte contains NaOH and H2O2、C8H4K2O12Sb2、(CH2OH)2And Na2SiO3The mass content of NaOH in the alkaline electrolyte is 10 percent, and H2O2Is 5% by mass, C8H4K2O12Sb2(CH) 2% by mass2OH)2Is 4% by mass, Na2SiO3The mass content of (A) is 3%; the voltage of the electrochemical dealloying treatment is 3V, the time is 240min, and the temperature is 50 ℃; the aperture of the porous Ti-6Al-7Nb titanium alloy membrane crude product is 6 nm-8 nm;
step four, subjecting the porous Ti-6Al-7Nb titanium alloy film crude product obtained in the step three to vacuum degree of 10-2Pa～10-3And carrying out vacuum heat treatment for 30min under the conditions of Pa and the temperature of 500 ℃ to expand the pores, thus obtaining the nano-porous Ti-6Al-7Nb titanium alloy film.
Through detection, the pore diameter of the nano-porous Ti-6Al-7Nb titanium alloy film prepared by the embodiment is 40 nm-60 nm.
Fig. 4 is an SEM image of the crude porous Ti-6Al-7Nb titanium alloy film prepared in this example, and it can be seen from fig. 4 that fine nano-pores are generated in the crude porous Ti-6Al-7Nb titanium alloy film, and the pore diameter of the nano-pores is 6nm to 8 nm.
Fig. 5 is an SEM image of the nanoporous Ti-6Al-7Nb titanium alloy film prepared in this example, and as can be seen from fig. 5, through and uniformly distributed nanopores are generated on the nanoporous Ti-6Al-7Nb titanium alloy film, and the diameter of the nanopores is 40nm to 60 nm.
The titanium alloy foil in the first step of this embodiment can be replaced by a Ti-2Al-2.5Zr titanium alloy foil.
Example 3
The embodiment comprises the following steps:
step one, Ti-3Al-2.5V titanium alloy foil with the thickness of 60 mu m is processed under the vacuum degree of 10-2Pa～10-3Carrying out vacuum heat treatment for 100min at the temperature of 1000 ℃ under Pa;
step two, carrying out surface acid washing and purification on the Ti-3Al-2.5V titanium alloy foil subjected to vacuum heat treatment in the step one in sequence; the surface pickling and purification process comprises the following steps: immersing the Ti-3Al-2.5V foil subjected to heat treatment into a mixed acid solution for cleaning for 5s, then sequentially placing the foil into deionized water, acetone and absolute ethyl alcohol for ultrasonic cleaning for 60min respectively, taking out the foil and purifying the foil for 20min in a nitrogen atmosphere of 0.8 Pa; the mixed acid solution consists of HF solution with the mass concentration of 38 percent and HNO with the mass concentration of 65 percent3The acid cleaning agent is prepared by mixing a solution and water according to a volume ratio of 1:5:4, wherein the temperature of the mixed acid solution in the acid cleaning process is 40 ℃;
step three, soaking the Ti-3Al-2.5V titanium alloy foil purified in the step two as a working electrode into an alkaline electrolyte as an anode, performing electrochemical dealloying treatment by taking a platinum electrode as a cathode and Ag/AgCl as a reference electrode, then ultrasonically cleaning for 60min by taking absolute ethyl alcohol as a solvent, boiling, washing and soaking by using deionized water until the pH value is neutral, and performing vacuum drying for 8h at 80 ℃ to obtain a porous Ti-3Al-2.5V titanium alloy membrane crude product; the alkaline electrolyte contains NaOH and H2O2、C8H4K2O12Sb2、(CH2OH)2And Na2SiO3And a mixed solution ofNaOH content of 1% by mass in the alkaline electrolyte, H2O21% by mass of C8H4K2O12Sb2(CH) 1% by mass2OH)21% by mass of Na2SiO3The mass content of (A) is 1%; the voltage of the electrochemical dealloying treatment is 5V, the time is 120min, and the temperature is 60 ℃; the aperture of the porous Ti-3Al-2.5V titanium alloy membrane crude product is 8 nm-10 nm;
step four, the crude product of the porous Ti-3Al-2.5V titanium alloy film obtained in the step three is processed in a vacuum degree of 10-2Pa～10-3And carrying out vacuum heat treatment for 180min under the conditions of Pa and the temperature of 400 ℃ to enlarge the hole, thereby obtaining the nano porous Ti-3Al-2.5V titanium alloy film.
Through detection, the aperture of the nano-porous Ti-3Al-2.5V titanium alloy membrane prepared by the embodiment is 30 nm-50 nm.
FIG. 6 is an SEM image of the crude porous Ti-3Al-2.5V titanium alloy film prepared in this example, and it can be seen from FIG. 6 that fine nano-pores are generated in the crude porous Ti-3Al-2.5V titanium alloy film, and the pore diameter of the nano-pores is 8nm to 10 nm.
Fig. 7 is an SEM image of the nanoporous Ti-3Al-2.5V titanium alloy film prepared in this example, and it can be seen from fig. 7 that nanopores with diameters of 30nm to 50nm are formed on the nanoporous Ti-3Al-2.5V titanium alloy film, wherein the nanopores are through and uniformly distributed.
The titanium alloy foil in the first step of this embodiment can be replaced by a Ti-2Al-2.5Zr titanium alloy foil.
Example 4
The embodiment comprises the following steps:
step one, Ti-8Al-1Mo-1V titanium alloy foil with the thickness of 80 mu m is processed under the vacuum degree of 10-2Pa～10-3Vacuum heat treatment is carried out for 240min under the condition that the temperature is 1000 ℃ and Pa;
step two, sequentially carrying out surface acid washing and purification on the Ti-8Al-1Mo-1V titanium alloy foil subjected to vacuum heat treatment in the step one; the surface pickling and purification process comprises the following steps: immersing the Ti-8Al-1Mo-1V foil subjected to heat treatment into the mixed acid solutionCleaning in the solution for 5s, then sequentially placing in deionized water, acetone and absolute ethyl alcohol, respectively ultrasonically cleaning for 60min, taking out, and purifying for 40min under the nitrogen atmosphere of 0.8 Pa; the mixed acid solution consists of HF solution with the mass concentration of 38 percent and HNO with the mass concentration of 65 percent3The acid cleaning agent is prepared by mixing a solution and water according to a volume ratio of 1:5:4, wherein the temperature of the mixed acid solution in the acid cleaning process is 40 ℃;
step three, soaking the Ti-8Al-1Mo-1V titanium alloy foil purified in the step two as a working electrode into an alkaline electrolyte as an anode, performing electrochemical dealloying treatment by taking a platinum electrode as a cathode and Ag/AgCl as a reference electrode, then ultrasonically cleaning for 60min by taking absolute ethyl alcohol as a solvent, boiling, washing and soaking by using deionized water until the pH value is neutral, and performing vacuum drying for 8h at 80 ℃ to obtain a porous Ti-8Al-1Mo-1V titanium alloy film crude product; the alkaline electrolyte contains NaOH and H2O2、C8H4K2O12Sb2、(CH2OH)2And Na2SiO3The mass content of NaOH in the alkaline electrolyte is 6 percent, and H2O21.5% by mass of C8H4K2O12Sb2(CH) 2% by mass2OH)2Is 2% by mass of Na2SiO3The mass content of (A) is 2%; the voltage of the electrochemical dealloying treatment is 1V, the time is 360min, and the temperature is 40 ℃; the aperture of the porous Ti-8Al-1Mo-1V titanium alloy film crude product is 8 nm-10 nm;
step four, subjecting the porous Ti-8Al-1Mo-1V titanium alloy film crude product obtained in the step three to vacuum degree of 10-2Pa～10-3And carrying out vacuum heat treatment for 120min at the temperature of 200 ℃ under Pa to enlarge the hole, thereby obtaining the nano-porous Ti-8Al-1Mo-1V titanium alloy film.
Through detection, the aperture of the nano-porous Ti-8Al-1Mo-1V titanium alloy membrane prepared by the embodiment is 60 nm-80 nm.
The titanium alloy foil in the first step of this embodiment can be replaced by a Ti-2Al-2.5Zr titanium alloy foil.
The above description is only for the preferred embodiment of the present invention, and is not intended to limit the present invention in any way. Any simple modification, change and equivalent changes of the above embodiments according to the technical essence of the invention are still within the protection scope of the technical solution of the invention.
Claims (6)
1. A preparation method of a nano-porous titanium alloy film is characterized by comprising the following steps:
step one, carrying out vacuum heat treatment on an aluminum-titanium-containing alloy foil; the vacuum degree of the heat treatment is 10-2Pa～10-3Pa, the temperature is 700-1000 ℃, and the time is 60-240 min;
step two, sequentially carrying out surface acid washing and purification on the aluminum-titanium-containing alloy foil subjected to vacuum heat treatment in the step one;
step three, performing electrochemical dealloying treatment on the aluminum-titanium-containing alloy foil purified in the step two, and then sequentially cleaning and drying to obtain a porous titanium alloy membrane crude product; the electrochemical dealloying process comprises the following steps: soaking the purified aluminum-titanium-containing alloy foil serving as a working electrode into alkaline electrolyte to serve as an anode, and performing electrochemical dealloying by taking a platinum electrode as a cathode and Ag/AgCl as a reference electrode; the aperture of the porous titanium alloy membrane crude product is not more than 10 nm;
the alkaline electrolyte contains NaOH and H2O2、C8H4K2O12Sb2、(CH2OH)2And Na2SiO3The mass content of NaOH in the alkaline electrolyte is 1-10%, and H2O21 to 5 percent of C8H4K2O12Sb2(CH) 1-2% by mass2OH)2The mass content of (1-4%) and Na2SiO3The mass content of (A) is 1-3%; the voltage of the electrochemical dealloying treatment is 1V-5V, the time is 60 min-360 min, and the temperature is 40-60 DEG C
Step four, aligning the porous titanium alloy obtained in the step threeCarrying out vacuum heat treatment on the membrane crude product to expand the pores, so as to obtain a nano porous titanium alloy membrane; the vacuum degree of the vacuum heat treatment is 10-2Pa-10-3Pa, the temperature is 200-500 ℃, and the time is 30-180 min; the aperture of the nano-porous titanium alloy membrane is 20 nm-100 nm.
2. The method for preparing a nano-porous titanium alloy film according to claim 1, wherein the mass content of the aluminum element in the aluminum-containing titanium alloy foil in the first step is 2-8%.
3. The method of claim 2, wherein the aluminum-containing titanium alloy foil comprises the following components of Ti-6Al-4V titanium alloy, Ti-6Al-7Nb titanium alloy, Ti-3Al-2.5V titanium alloy, Ti-2Al-2.5Zr titanium alloy, or Ti-8Al-1Mo-1V titanium alloy.
4. The preparation method of the nano-porous titanium alloy film according to claim 1, wherein the aluminum-containing titanium alloy foil in the first step is prepared by a smelting and rolling method, and the thickness of the aluminum-containing titanium alloy foil is 20 μm to 200 μm.
5. The method for preparing a nano-porous titanium alloy film according to claim 1, wherein the surface pickling and purifying process in the second step is as follows: immersing the aluminum-titanium-containing alloy foil subjected to vacuum heat treatment into a mixed acid solution for cleaning for 5s, then sequentially placing the aluminum-titanium-containing alloy foil into deionized water, acetone and absolute ethyl alcohol for ultrasonic cleaning for 60min respectively, taking out the aluminum-titanium-containing alloy foil and purifying the aluminum-titanium-containing alloy foil for 20min to 60min under a nitrogen atmosphere of 0.6Pa to 1.0 Pa; the mixed acid solution consists of HF solution with the mass concentration of 38 percent and HNO with the mass concentration of 65 percent3The acid pickling solution is prepared by mixing the solution and water according to the volume ratio of 1:5:4, and the temperature of the mixed acid solution in the acid pickling process is 40 ℃.
6. The method for preparing a nano-porous titanium alloy film according to claim 1, wherein the cleaning in step three is ultrasonic cleaning with absolute ethyl alcohol as a solvent for 60min, and the ultrasonic cleaning is followed by boiling, rinsing and soaking with deionized water until the pH value is neutral; the drying is vacuum drying, the temperature of the vacuum drying is 60-100 ℃, and the time is 5-10 h.
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