CN113913795A - Method for preparing iron element doped titanium-based nano corrosion-resistant film - Google Patents

Method for preparing iron element doped titanium-based nano corrosion-resistant film Download PDF

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CN113913795A
CN113913795A CN202111181793.8A CN202111181793A CN113913795A CN 113913795 A CN113913795 A CN 113913795A CN 202111181793 A CN202111181793 A CN 202111181793A CN 113913795 A CN113913795 A CN 113913795A
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doped titanium
resistant film
coating
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李文靓
彭穗
辛亚男
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Chengdu Advanced Metal Materials Industry Technology Research Institute Co Ltd
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Chengdu Advanced Metal Materials Industry Technology Research Institute Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
    • C23C18/1208—Oxides, e.g. ceramics
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/125—Process of deposition of the inorganic material
    • C23C18/1254—Sol or sol-gel processing
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/125—Process of deposition of the inorganic material
    • C23C18/1295—Process of deposition of the inorganic material with after-treatment of the deposited inorganic material

Abstract

The invention relates to the field of preparation of nano titanium-based films, in particular to a method for preparing an iron element doped titanium-based nano corrosion-resistant film, which has the advantages of relatively low product price, good performance, simple production process and environmental friendliness, and comprises the following steps: a. preparing iron element doped titanium-based hydrosol; b. treatment of the substrate: the substrate is stainless steel or carbon steel or aluminum alloy, is polished by water sand paper and then is respectively treated by ultrasonic treatment in acetone, absolute ethyl alcohol and deionized water, and then is dried by a drying oven; c. film coating: coating a film on the substrate for 2-4 times by using the iron element doped titanium-based hydrosol, wherein the next film coating is carried out after drying treatment of each coated film; d. and (3) heat treatment: and (3) placing the plated steel in a furnace for high-temperature calcination at the temperature of 300-900 ℃, and then finishing the preparation. The invention is especially suitable for the preparation process of the iron element doped titanium-based nano corrosion-resistant film.

Description

Method for preparing iron element doped titanium-based nano corrosion-resistant film
Technical Field
The invention relates to the field of preparation of nano titanium-based films, in particular to a method for preparing an iron element doped titanium-based nano corrosion-resistant film.
Background
The metal Ti is a silver gray transition metal, and has high melting point (1675 deg.C), high hardness, strong plasticity, and low density (4.51 g/cm)3) And the like. The oxide film of several to tens of nanometers generated on the surface of the titanium is extremely completeThe titanium-based film has the advantages that the titanium-based film has the capacity of self-repairing in an instant after local damage, so that the metal titanium and the alloy thereof have very good corrosion resistance, and the titanium-based film also has related characteristics. Research shows that TiO2The film having a cathodic protective action on the metal, i.e. TiO2The film is used as a photo-anode and provides enough electrons for the protected metal under illumination, so that the potential of the protected metal is reduced from a corrosion area to a stable area, and the electrochemical protection of the metal is realized. As metal corrosion protection coatings (passivation layer, paint, self-sacrificial coating), TiO2The film has the advantages of compact film formation, long service life and the like, and has the double anticorrosion function of preventing the contact corrosion of metal and corrosive medium and performing cathode protection on the metal. Reported TiO2The preparation methods of the film comprise a precipitation method, a sol-gel method, a hydrothermal method and the like, and although the methods have made certain progress, most of the methods are in the research stage of a laboratory, and the preparation procedures are complex, the experimental conditions are severe, the raw materials are expensive, and relevant reports of titanium-based film preparation industrialization are not found at present. At the same time, most of TiO2The film is mainly used in the field of photocatalysis, and a great deal of research and application are lacked in the field of corrosion prevention, and particularly, the titanium-based nano corrosion prevention film prepared by using cheap titanyl sulfate as a titanium source is not researched and proposed so far. Meanwhile, Fe element is adopted to dope the film, the forbidden bandwidth of the titanium-based film is reduced, the light absorption range of the titanium-based film is expanded from ultraviolet light to visible light, the better corrosion resistance of the film can be maintained under a dark state condition, a good photoproduction cathode protection effect is achieved, and the method has responsiveness to different light sources, so that the method has potential application prospect.
Disclosure of Invention
The invention aims to solve the technical problem of providing a method for preparing the iron element doped titanium-based nano corrosion-resistant film, which has the advantages of relatively low product price, good performance, simple production process and environmental friendliness.
The technical scheme adopted by the invention for solving the technical problems is as follows: the method for preparing the iron element doped titanium-based nano corrosion-resistant film is characterized by comprising the following steps of:
a. iron element doped titanium-based hydrosolPreparation: firstly TiOSO4Dispersing the solid in deionized water to obtain solution, and adding urea, NaOH or NaCO3Or decomposing ammonia water into deionized water to obtain 2.5-5.5mol/L precipitant solution, and adding Fe (NO) nitrate3)3Fe (NO) in a ratio of 0.1 to 0.2mol/l3)3The solution is prepared by the following specific steps: stirring TiOSO at the rotating speed of 350-4Solution, dropwise addition of precipitant solution to TiOSO4Coprecipitation reaction occurs in the solution, white precipitate appears when the pH value is adjusted to 6-7, the white precipitate is filtered and washed by absolute ethyl alcohol and deionized water respectively until BaCl is used2No SO can be detected in the solution4 2-Dispersing the obtained white precipitate in deionized water to obtain a suspension solution with the concentration of 0.2-0.4mol/l, stirring, adding dilute nitric acid as a complexing agent into the suspension solution, continuously stirring, heating to 80-100 ℃ at room temperature, maintaining for 2-4 h, and adding 0.1-0.2mol/l Fe (NO)3)3The solution is added into the suspension solution to form a solution with the mass fraction range of 1-3%, and then standing and aging reaction are carried out to finally obtain the iron element doped titanium-based hydrosol;
b. treatment of the substrate: the substrate is stainless steel or carbon steel or aluminum alloy, is polished by water sand paper and then is respectively treated by ultrasonic treatment in acetone, absolute ethyl alcohol and deionized water, and then is dried by a drying oven;
c. film coating: coating a film on the substrate for 2-4 times by using the iron element doped titanium-based hydrosol, wherein the next film coating is carried out after drying treatment of each coated film;
d. and (3) heat treatment: and (3) placing the plated steel in a furnace for high-temperature calcination at the temperature of 300-900 ℃, and then finishing the preparation.
Further, in step a, TiOSO4The solution concentration of the solution prepared by dispersing the solid in deionized water is 0.2 mol/L.
Further, in step a, BaCl2The mass fraction of the solution was 4%.
Furthermore, in the step a, 25% ammonia water is selected to be decomposed into deionized water to prepare 2.5-5.5mol/L precipitator solution for later use.
Further, in the step a, after white precipitation appears when the pH value is adjusted to 6-7, stirring is continued for 30min until the reaction is complete.
Further, in the step a, dilute nitric acid is used as a complexing agent and added into the suspension solution, and the stirring time is continuously 30 min.
Further, in the step a, the standing aging reaction time is 12 hours.
Furthermore, in the step c, the coating mode is a dip-coating method of dipping first and then coating.
Furthermore, in the step c, in the step of pulling by the dip-pulling method, the steel material is subjected to a film-pulling coating at a speed of 1-2 mm/s.
Further, the plated steel is placed in a muffle furnace for high-temperature calcination.
The invention has the beneficial effects that: the method has the following advantages: firstly, the product has relatively low price and good performance: because vanadyl sulfate is used as a titanium source, the prepared product has lower price and is more environment-friendly compared with other products using organic titanium sources such as tetrabutyl titanate. The grain diameter of the prepared iron-doped titanium-based sol is less than 50nm, the thickness of the five-time coating is less than 1 mu m, the film is compact and uniform, the corrosion potential is improved, the corrosion current is reduced, and the protection efficiency is up to 99%. And secondly, the production process is simple. The invention provides a method for preparing an iron element doped titanium-based nano anticorrosive film by taking titanyl sulfate as a titanium source. Compared with other methods for preparing the film, the method is simple, short in flow, capable of realizing industrial production and avoiding complex preparation processes. Thirdly, the environment is friendly, and no toxic and harmful substances are generated and left: in the whole preparation and production process, no toxic and harmful substances are generated and left, and sustainable production can be carried out. The invention is especially suitable for the preparation process of the iron element doped titanium-based nano corrosion-resistant film.
Detailed Description
The method for preparing the iron element doped titanium-based nano corrosion-resistant film comprises the following steps: a. preparing iron element doped titanium-based hydrosol: firstly TiOSO4Dispersing the solid in deionized water to obtain solution, and adding urea, NaOH or NaCO3Or decomposing ammonia water into deionized water to obtain 2.5-5.5mol/L precipitant solution, and adding Fe (NO) nitrate3)3Fe (NO) in a ratio of 0.1 to 0.2mol/l3)3The solution is prepared by the following specific steps: stirring TiOSO at the rotating speed of 350-4Solution, dropwise addition of precipitant solution to TiOSO4Coprecipitation reaction occurs in the solution, white precipitate appears when the pH value is adjusted to 6-7, the white precipitate is filtered and washed by absolute ethyl alcohol and deionized water respectively until BaCl is used2No SO can be detected in the solution4 2-Dispersing the obtained white precipitate in deionized water to obtain a suspension solution with the concentration of 0.2-0.4mol/l, stirring, adding dilute nitric acid as a complexing agent into the suspension solution, continuously stirring, heating to 80-100 ℃ at room temperature, maintaining for 2-4 h, and adding 0.1-0.2mol/l Fe (NO)3)3The solution is added into the suspension solution to form a solution with the mass fraction range of 1-3%, and then standing and aging reaction are carried out to finally obtain the iron element doped titanium-based hydrosol; b. treatment of the substrate: the substrate is stainless steel or carbon steel or aluminum alloy, is polished by water sand paper and then is respectively treated by ultrasonic treatment in acetone, absolute ethyl alcohol and deionized water, and then is dried by a drying oven; c. film coating: coating a film on the substrate for 2-4 times by using the iron element doped titanium-based hydrosol, wherein the next film coating is carried out after drying treatment of each coated film; d. and (3) heat treatment: and (3) placing the plated steel in a furnace for high-temperature calcination at the temperature of 300-900 ℃, and then finishing the preparation. Wherein the crystal form of the film calcined at the temperature of 300-500 ℃ is mainly anatase type, the crystal form of the film calcined at the temperature of 550-600 ℃ is a mixture of anatase and rutile, and the crystal form of the film calcined at the temperature of 600-900 ℃ is mainly rutile type. After heat treatment, the nano-scale iron element doped titanium-based film is generated on the surface of the steel.
Using cheap titanyl sulfate as a titanium source, preparing titanium-based hydrosol with excellent stability and uniform state by a sol-gel method with mild reaction, introducing a certain amount of iron element in the process, uniformly coating the sol prepared in the early stage on the surface of steel to be protected by a pulling method in the later stage, and converting the hydrosol into the iron element doped titanium-based nano corrosion-resistant film by heat treatment. The invention defines the preparation means of the iron element doped nanometer titanium-based film, and prepares the iron element doped nanometer titanium-based corrosion-resistant film by utilizing the photoproduction cathodic protection and the photoresponse mechanism to form the controllable synthesis process technology of the iron element-containing nanometer uniform corrosion-resistant titanium-based film. The iron element doped titanium-based nano corrosion-resistant film is used as a permanent corrosion-resistant coating, the service life of the iron element doped titanium-based nano corrosion-resistant film is far longer than that of other corrosion-resistant technologies, the titanium-based film is low in price and relatively simple in preparation process, the iron element doped film plays a good role in photoproduction cathode protection, the corrosion resistance of the iron element doped titanium-based nano corrosion-resistant film is improved, and the iron element doped titanium-based nano corrosion-resistant film has responsiveness to different light sources.
In order to obtain better and more precise process control and thus better product, it is preferred that in step a, TiOSO4The solution concentration of the solution prepared by dispersing the solid in deionized water is 0.2 mol/L; preferably, in step a, BaCl2The mass fraction of the solution is 4 percent; preferably, in the step a, 25% ammonia water is selected to be decomposed into deionized water to prepare 2.5-5.5mol/L precipitant solution for standby.
In order to ensure the reaction to be complete, in step a, after white precipitation appears when the pH value is adjusted to 6-7, stirring is continued for 30min to ensure that the reaction is complete. In the step a, dilute nitric acid is used as a complexing agent and added into the suspension solution, and the continuous stirring time is 30 min. In step a, in order to ensure sufficient standing and aging effect, the standing and aging reaction time is preferably 12 hours.
In the step c, the preferable coating method is a dip-coating method in which dipping is performed first and then coating is performed. Wherein, in order to ensure the quality of the coating film, the steel is preferably subjected to the pulling coating film at the speed of 1-2mm/s in the pulling step of the dip-coating method in the step c. The plated steel is preferably calcined in a muffle furnace at high temperature.
Examples
Example 1
The method comprises the following steps: adding a certain amount of TiOSO4The solid is dispersed in deionized water to prepare a solution A with the concentration of 0.2 mol/L.
Step two: a solution B of 2.5mol/L was prepared by dispersing a predetermined amount of urea in ionized water and stirring for 15 min.
Step three: stirring the solution A at the rotating speed of 350r/min, dropwise adding the solution B into the solution A, carrying out coprecipitation reaction, and adjusting the pH value to 6, wherein white precipitate continuously appears in the process. Stirring for 30min to react completely, filtering the white precipitate, and washing with anhydrous ethanol and deionized water respectively until 4% BaCl is used2No SO was detected4 2-Until now. Then, the obtained white precipitate was dispersed in a certain amount of deionized water (concentration: 0.2mol/L) to obtain solution C, and stirred for 15 min.
Step four: slowly dripping a certain amount of commercially available dilute nitric acid solution into the solution C by a pipette, continuously stirring for 30min, heating to a certain temperature of 90 deg.C in room temperature water bath for 2h to obtain a beige transparent solution, and simultaneously adding Fe (NO) with a molar fraction of 0.1mol/l3)3Adding the solution into the suspension (the mass fraction range is 1.5%), standing and aging for 12h to finally obtain light blue transparent iron-doped titanium-based hydrosol D.
Step five: the scheme is that a 304 stainless steel plate is used as a substrate, prepared steel is placed in acetone, absolute ethyl alcohol and deionized water for ultrasonic treatment for 15min respectively, a drying oven is used for drying at 100 ℃, and the steel is taken out for standby after 10 min.
Step six: iron element doped titanium-based hydrosol D is used for coating the steel at the speed of 1.5mm/s, and the steel is coated for the next time after being dried for 5min at the temperature of 90 ℃ every time, and the scheme is used for 2 times.
Step seven: and (3) placing the plated steel in a muffle furnace for high-temperature calcination at 450 ℃ for 3 h.
Step eight: and packaging the coated steel plate as an electrode, performing an electrochemical corrosion test, wherein the protection efficiency reaches 94%, and the size of the compact single particle with uniform film appearance is about 18nm under a scanning electron microscope.
Example 2
The method comprises the following steps: adding a certain amount of TiOSO4The solid is dispersed in deionized water to prepare a solution A with the concentration of 0.2 mol/L.
Step two: a solution B of 3.5mol/L was prepared by dispersing a predetermined amount of urea in ionized water and stirring for 15 min.
Step three: stirring the solution A at the rotating speed of 400r/min, dropwise adding the solution B into the solution A, carrying out coprecipitation reaction, adjusting the pH value to 6, subsequently stirring for 15min till the reaction is complete, filtering the white precipitate, and respectively cleaning the white precipitate with absolute ethyl alcohol and deionized water until the white precipitate is washed with BaCl with the mass fraction of 4%2No SO was detected4 2-Until now. Then, the obtained white precipitate was dispersed in a certain amount of deionized water (concentration: 0.2mol/L) to obtain solution C, and stirred for 15 min.
Step four: slowly dripping a certain amount of commercially available dilute nitric acid solution into the solution C by a pipette, continuously stirring for 30min, heating to a certain temperature of 100 deg.C in a room temperature water bath for 2h until the solution is light blue and transparent, and simultaneously adding Fe (NO) with a molar fraction of 0.2mol/l3)3The solution is added into the suspension (the mass fraction is 2 percent), and then the mixture is kept stand and aged for 12 hours to finally obtain light blue transparent silver-containing titanium-based hydrosol D.
Step five: the scheme is that aluminum alloy 5083 is used as a substrate, prepared steel is placed in acetone, absolute ethyl alcohol and deionized water for ultrasonic treatment for 15min respectively, and the steel is dried in a drying oven at 100 ℃ for 10min and then taken out for later use.
Step six: the steel was coated with silver-containing titanium-based hydrosol D at a rate of 1.5mm/s, this protocol being 4 times.
Step seven: and (3) placing the plated steel in a muffle furnace for high-temperature calcination at 500 ℃ for 3 h.
Step eight: the coated steel plate is packaged into an electrode and subjected to electrochemical corrosion test, the protection efficiency reaches 97.1%, and the size of a single compact particle with uniform film appearance is about 20nm under the observation of a scanning electron microscope.
Example 3
The method comprises the following steps: adding a certain amount of TiOSO4The solid is dispersed in deionized water to prepare a solution A with the concentration of 0.2 mol/L.
Step two: ionic water was added to a predetermined amount of urea and the mixture was stirred for 5 minutes to prepare a solution B of 5.5 mol/L.
Step three: stirring the solution A at the rotating speed of 500r/min, dropwise adding the solution B into the solution A, carrying out coprecipitation reaction, adjusting the pH value to 6, subsequently stirring for 10min till the reaction is complete, filtering the white precipitate, and respectively cleaning with absolute ethyl alcohol and deionized water until the BaCl with the mass fraction of 4% is used2No SO was detected4 2-Until now. Then, the obtained white precipitate was dispersed in a certain amount of deionized water (concentration: 0.4mol/L) to obtain a solution C, and stirred for 10 min.
Step four: slowly dripping a certain amount of commercially available dilute nitric acid solution into the solution C by a pipette, continuously stirring for 30min, heating to a certain temperature of 90 deg.C in a room temperature water bath for 3h until the solution is light blue and transparent, and simultaneously adding Fe (NO) with a molar fraction of 0.1mol/l3)3Adding the solution into the suspension (the mass fraction is 1.5%), standing and aging for 12h to finally obtain light blue transparent iron-doped titanium-based hydrosol D.
Step five: the scheme uses carbon steel as a substrate, the prepared steel is respectively placed in acetone, absolute ethyl alcohol and deionized water for ultrasonic treatment for 15min, and the steel is dried in a drying oven at 100 ℃ for 10min and then taken out for standby.
Step six: the steel was coated with titanium-based hydrosol D at a rate of 2mm/s, this protocol was 3 times.
Step seven: and (3) placing the plated steel in a muffle furnace for high-temperature calcination at 500 ℃ for 3 h.
Step eight: the coated steel plate is packaged into an electrode and subjected to electrochemical corrosion test, the protection efficiency reaches 99.3%, and the size of a single compact particle with uniform film appearance is about 22nm under the observation of a scanning electron microscope.
The technical scheme of the invention has obvious advantages and wide market popularization prospect.

Claims (10)

1. The method for preparing the iron element doped titanium-based nano corrosion-resistant film is characterized by comprising the following steps of:
a. preparing iron element doped titanium-based hydrosol: firstly TiOSO4Dispersing the solid in deionized water to prepare solutionBy mixing urea or NaOH or NaCO3Or decomposing ammonia water into deionized water to obtain 2.5-5.5mol/L precipitant solution, and adding Fe (NO) nitrate3)3Fe (NO) in a ratio of 0.1 to 0.2mol/l3)3The solution is prepared by the following specific steps: stirring TiOSO at the rotating speed of 350-4Solution, dropwise addition of precipitant solution to TiOSO4Coprecipitation reaction occurs in the solution, white precipitate appears when the pH value is adjusted to 6-7, the white precipitate is filtered and washed by absolute ethyl alcohol and deionized water respectively until BaCl is used2No SO can be detected in the solution4 2-Dispersing the obtained white precipitate in deionized water to obtain a suspension solution with the concentration of 0.2-0.4mol/l, stirring, adding dilute nitric acid as a complexing agent into the suspension solution, continuously stirring, heating to 80-100 ℃ at room temperature, maintaining for 2-4 h, and adding 0.1-0.2mol/l Fe (NO)3)3The solution is added into the suspension solution to form a solution with the mass fraction range of 1-3%, and then standing and aging reaction are carried out to finally obtain the iron element doped titanium-based hydrosol;
b. treatment of the substrate: the substrate is stainless steel or carbon steel or aluminum alloy, is polished by water sand paper and then is respectively treated by ultrasonic treatment in acetone, absolute ethyl alcohol and deionized water, and then is dried by a drying oven;
c. film coating: coating a film on the substrate for 2-4 times by using the iron element doped titanium-based hydrosol, wherein the next film coating is carried out after drying treatment of each coated film;
d. and (3) heat treatment: and (3) placing the plated steel in a furnace for high-temperature calcination at the temperature of 300-900 ℃, and then finishing the preparation.
2. The method for preparing the iron-doped titanium-based nano corrosion-resistant film according to claim 1, wherein the method comprises the following steps: in step a, TiOSO4The solution concentration of the solution prepared by dispersing the solid in deionized water is 0.2 mol/L.
3. The method of claim 1, wherein the iron-doped titanium-based nanoparticles are prepared byA method of etching a film, characterized by: in step a, BaCl2The mass fraction of the solution was 4%.
4. The method for preparing the iron-doped titanium-based nano corrosion-resistant film according to claim 1, wherein the method comprises the following steps: in the step a, 25% ammonia water is selected to be decomposed into deionized water to prepare 2.5-5.5mol/L precipitator solution for standby.
5. The method for preparing the Fe-doped Ti-based nano corrosion-resistant film according to claim 1, 2, 3 or 4, wherein: in the step a, after white precipitation appears when the pH value is adjusted to 6-7, stirring is continued for 30min until the reaction is complete.
6. The method for preparing the Fe-doped Ti-based nano corrosion-resistant film according to claim 1, 2, 3 or 4, wherein: in the step a, dilute nitric acid is used as a complexing agent and added into the suspension solution, and the continuous stirring time is 30 min.
7. The method for preparing the Fe-doped Ti-based nano corrosion-resistant film according to claim 1, 2, 3 or 4, wherein: in the step a, the standing and aging reaction time is 12 hours.
8. The method for preparing the Fe-doped Ti-based nano corrosion-resistant film according to claim 1, 2, 3 or 4, wherein: in the step c, the coating mode is a dip-coating method of dipping first and then coating.
9. The method for preparing the Fe-doped Ti-based nano corrosion-resistant film according to claim 1, 2, 3 or 4, wherein: and c, in the step of pulling by the dip-pulling method, the steel is subjected to pull coating at the speed of 1-2 mm/s.
10. The method for preparing the Fe-doped Ti-based nano corrosion-resistant film according to claim 1, 2, 3 or 4, wherein: and (4) placing the plated steel in a muffle furnace for high-temperature calcination.
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Publication number Priority date Publication date Assignee Title
CN1899686A (en) * 2006-07-24 2007-01-24 同济大学 Process for preparing iron blended TiO2/active carbon composite visible light catalyst
CN101376112A (en) * 2008-09-27 2009-03-04 东华大学 Method for preparing anatase titanic oxide sol
CN102407105A (en) * 2011-10-27 2012-04-11 济南大学 Nanometer titanium dioxide modified film and gradient doping modification method of nanometer titanium dioxide film

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