CN113751294A - Method for preparing titanium-based nano anticorrosive film by taking titanium tetrachloride as titanium source - Google Patents
Method for preparing titanium-based nano anticorrosive film by taking titanium tetrachloride as titanium source Download PDFInfo
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- 239000010936 titanium Substances 0.000 title claims abstract description 108
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 101
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 101
- 238000000034 method Methods 0.000 title claims abstract description 56
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 title claims abstract description 41
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 57
- 239000010959 steel Substances 0.000 claims abstract description 57
- 238000000576 coating method Methods 0.000 claims abstract description 32
- 239000011248 coating agent Substances 0.000 claims abstract description 25
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 238000010438 heat treatment Methods 0.000 claims abstract description 9
- 239000000758 substrate Substances 0.000 claims abstract description 8
- 239000000243 solution Substances 0.000 claims description 68
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 44
- 238000003756 stirring Methods 0.000 claims description 29
- 239000002244 precipitate Substances 0.000 claims description 27
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 22
- 239000000725 suspension Substances 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 13
- 238000005406 washing Methods 0.000 claims description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000010935 stainless steel Substances 0.000 claims description 11
- 229910001220 stainless steel Inorganic materials 0.000 claims description 11
- 238000001354 calcination Methods 0.000 claims description 8
- 238000000975 co-precipitation Methods 0.000 claims description 8
- 238000007598 dipping method Methods 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 7
- 238000009210 therapy by ultrasound Methods 0.000 claims description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 6
- 239000003518 caustics Substances 0.000 claims description 6
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(I) nitrate Inorganic materials [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 6
- 238000002791 soaking Methods 0.000 claims description 6
- 229910000975 Carbon steel Inorganic materials 0.000 claims description 4
- 239000010962 carbon steel Substances 0.000 claims description 4
- 239000007888 film coating Substances 0.000 claims description 3
- 238000009501 film coating Methods 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims 2
- 238000005260 corrosion Methods 0.000 abstract description 19
- 230000007797 corrosion Effects 0.000 abstract description 14
- 238000002360 preparation method Methods 0.000 abstract description 6
- 239000002245 particle Substances 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 230000002035 prolonged effect Effects 0.000 abstract description 4
- 238000003980 solgel method Methods 0.000 abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 27
- 239000008367 deionised water Substances 0.000 description 16
- 229910021641 deionized water Inorganic materials 0.000 description 16
- 229910052751 metal Inorganic materials 0.000 description 10
- 239000002184 metal Substances 0.000 description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 7
- 238000012360 testing method Methods 0.000 description 4
- 101710134784 Agnoprotein Proteins 0.000 description 3
- 238000006056 electrooxidation reaction Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000005536 corrosion prevention Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000003618 dip coating Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000003837 high-temperature calcination Methods 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000036632 reaction speed Effects 0.000 description 2
- 239000010963 304 stainless steel Substances 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910000589 SAE 304 stainless steel Inorganic materials 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000009194 climbing Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000002120 nanofilm Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/36—Successively applying liquids or other fluent materials, e.g. without intermediate treatment
- B05D1/38—Successively applying liquids or other fluent materials, e.g. without intermediate treatment with intermediate treatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/02—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by baking
- B05D3/0254—After-treatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/50—Multilayers
- B05D7/56—Three layers or more
- B05D7/58—No clear coat specified
- B05D7/586—No clear coat specified each layer being cured, at least partially, separately
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- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
- Chemical Treatment Of Metals (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
Abstract
The invention discloses a method for preparing a titanium-based nano anticorrosive film by using titanium tetrachloride as a titanium source, belonging to the technical field of nano titanium-based film preparation. The invention provides a method for preparing a titanium-based nano anti-corrosion film by taking titanium tetrachloride as a titanium source, which aims to reduce the production cost of titanium-based film anti-corrosion and simplify the process, and comprises the following steps: preparing titanium-based hydrosol by using titanium tetrachloride, treating a substrate, coating and thermally treating. According to the invention, titanium tetrachloride with low price is used as a titanium source, a sol-gel method with mild reaction is used for preparing the titanium-based hydrosol with excellent stability, the particle size is about 45nm, the sol is uniformly coated on the surface of a steel product, the thickness of a five-time coating film is less than 1 mu m, the titanium-based hydrosol is converted into a titanium-based film through heat treatment, the corrosion potential is improved, the corrosion current is reduced, the protection efficiency is up to more than 95%, the corrosion resistance of the steel product can be remarkably improved, and the service life of the steel product is prolonged.
Description
Technical Field
The invention belongs to the technical field of titanium-based nano-film preparation, and particularly relates to a method for preparing a titanium-based nano anti-corrosion film by taking titanium tetrachloride as a titanium source.
Background
It is reported that the loss caused by corrosion is about eight billion yuan each year in China, the metal materials scrapped due to corrosion all over the world account for about 10% of the total metal production amount in the year, and steel scrapped due to corrosion in China reaches more than one thousand tons each year, thus seriously hindering the development of society.
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. Because the oxide film of several to dozens of nanometers generated on the surface of the titanium is extremely complete and compact and has the capability of self-repairing in the moment after local damage, the metal titanium and the alloy thereof have very good corrosion resistance, and the titanium-based film also has relevant 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 film preparation methods include a precipitation method, a sol-gel method, a hydrothermal method and the like, although the methods have made certain progress, most of the methods are in a laboratory research stage, 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 titanium tetrachloride as a titanium source is not researched and proposed so far.
Disclosure of Invention
The invention provides a method for preparing a titanium-based nano anticorrosive film by using titanium tetrachloride as a titanium source, which aims to solve the problems in the prior art and comprises the following steps:
preparing titanium-based hydrosol:
A. dripping titanium tetrachloride solution into water to obtain solution A;
B. mixing caustic alkali and water to obtain a solution B;
C. dropwise adding the solution B into the solution A under stirring, stopping adding the solution B when the pH value of the system is 6-7, carrying out coprecipitation reaction to obtain a precipitate, washing the obtained precipitate, and dispersing the precipitate in water to obtain a suspension;
D. dropwise adding hydrogen peroxide into the suspension, stirring until the solution is transparent, adjusting the pH value of the system to 6-7 by using ammonia water, and standing to obtain titanium-based hydrosol;
substrate treatment:
E. if the steel material is stainless steel, the surface of the stainless steel is cleaned by water, and then the stainless steel is put into H2SO4And H2O2Soaking in the mixed solution, washing the surface of the stainless steel with water, and then putting into the water for later use;
if the steel is carbon steel and other steels, the steel is sequentially placed in acetone, absolute ethyl alcohol and water for ultrasonic treatment, and then dried for later use;
film coating:
F. e, coating the steel processed in the step E with 3-5 layers of films, and drying each layer of film and then coating the next layer of film;
and (3) heat treatment:
G. calcining the coated steel at 350-900 ℃, and generating the titanium-based nano anticorrosive film on the surface of the steel after heat treatment.
In the method for preparing the titanium-based nano anticorrosive film by using titanium tetrachloride as a titanium source, in the step A, the titanium concentration of the obtained solution A is 0.2-0.6 mol/L.
In the method for preparing the titanium-based nano anticorrosive film by using titanium tetrachloride as a titanium source, in the step B, the caustic alkali concentration of the obtained solution B is 2-6 mol/L.
In the step C, the solution B is dripped into the solution A at the rotating speed of 200-500 r/min.
In the step C, after the dropwise addition is finished, the stirring is continued for 10-40 min.
Wherein, in the step C, the washing is as follows: washing the precipitate with hot water and anhydrous ethanol alternately until AgNO3No Cl can be detected-Until now.
In the method for preparing the titanium-based nano anticorrosive film by using the titanium tetrachloride as the titanium source, in the step C, the precipitate is dispersed in water and then stirred for 10-30 min.
In the method for preparing the titanium-based nano anticorrosive film by using titanium tetrachloride as a titanium source, in the step C, the titanium concentration of the obtained suspension is 0.1-0.2 mol/L.
In the method for preparing the titanium-based nano anticorrosive film by using titanium tetrachloride as a titanium source, in the step D, the concentration of hydrogen peroxide is not lower than 28%.
In the step D, the hydrogen peroxide is added according to the amount of H in the system2O2With Ti4+Is not less than 4: 1 is the standard.
In the method for preparing the titanium-based nano anticorrosive film by using titanium tetrachloride as a titanium source, in the step D, the stirring time is 30-60 min.
In the method for preparing the titanium-based nano anticorrosive film by using titanium tetrachloride as a titanium source, in the step D, the standing time is 10-18 hours.
Wherein, in the step E, the method for preparing the titanium-based nano anticorrosive film by using the titanium tetrachloride as the titanium source comprises the step H2SO4And H2O2The mixed solution of (A) is H with the mass fraction of 98%2SO4And 30% of H2O2Volume ratio of1-3: 1.
In the method for preparing the titanium-based nano anticorrosive film by using titanium tetrachloride as a titanium source, in the step E, the soaking time is 6-12 hours.
In the method for preparing the titanium-based nano anticorrosive film by using titanium tetrachloride as a titanium source, in the step E, the ultrasonic time is 15-30 min.
In the step E, the drying temperature is 90-110 ℃ and the drying time is 5-10 min.
In the method for preparing the titanium-based nano anticorrosive film by using titanium tetrachloride as a titanium source, in the step F, a dip-coating method or a coating method is adopted for coating; in the dipping and pulling method, the dipping time is controlled to be 2min to 5min, and a pulling machine pulls at the speed of 1cm/min to 2.5 cm/min; in the coating method, coating is performed at 1mm/s to 2.5 mm/s.
In the step F, the drying temperature is 90-110 ℃ and the time is 5-10 min.
In the method for preparing the titanium-based nano anticorrosive film by using titanium tetrachloride as a titanium source, in the step G, the calcining time is 2-4.5 h.
It should be noted that, since chloride ions or some metal ions cause great corrosion to steel, it is ensured that the surface of hydrosol and steel does not contain Cl-And metal ions, it is desirable to use Cl-free in the various stages of the invention (including titanium-based hydrosol preparation and substrate processing)-And water of metal ions, such as deionized water.
The invention has the beneficial effects that:
according to the invention, titanium tetrachloride with low price is used as a titanium source, and compared with an organic titanium source such as n-butyl titanate, the titanium-based hydrosol with excellent stability is prepared by a sol-gel method with mild reaction, the particle size of the titanium-based sol is about 45nm, the sol is uniformly coated on the surface of a steel to be protected, the titanium-based hydrosol is converted into a titanium-based film through heat treatment, the thickness of a five-time coating film is less than 1 mu m, the corrosion potential is improved, the corrosion current is reduced, the protection efficiency is up to more than 95%, the corrosion resistance of the steel can be remarkably improved, and the service life of the steel can be prolonged; in the whole production process, no toxic and harmful substances are generated and left, the sustainable production method can be carried out, and the method is simple, short in flow, suitable for industrial production and widely applicable.
Detailed Description
Specifically, the method for preparing the titanium-based nano anticorrosive film by using titanium tetrachloride as a titanium source comprises the following steps:
preparing titanium-based hydrosol:
A. dripping titanium tetrachloride solution into water to obtain solution A;
B. mixing caustic alkali and water to obtain a solution B;
C. dropwise adding the solution B into the solution A under stirring, stopping adding the solution B when the pH value of the system is 6-7, carrying out coprecipitation reaction to obtain a precipitate, washing the obtained precipitate, and dispersing the precipitate in water to obtain a suspension;
E. dropwise adding hydrogen peroxide into the suspension, stirring until the solution is transparent, adjusting the pH value of the system to 6-7 by using ammonia water, and standing to obtain titanium-based hydrosol;
substrate treatment:
E. if the steel material is stainless steel, the surface of the stainless steel is cleaned by water, and then the stainless steel is put into H2SO4And H2O2Soaking in the mixed solution, washing the surface of the stainless steel with water, and then putting into the water for later use;
if the steel is carbon steel and other steels, the steel is sequentially placed in acetone, absolute ethyl alcohol and water for ultrasonic treatment, and then dried for later use;
film coating:
F. e, coating the steel processed in the step E with 3-5 layers of films, and drying each layer of film and then coating the next layer of film;
and (3) heat treatment:
G. calcining the coated steel at 350-900 ℃, and generating the titanium-based nano anticorrosive film on the surface of the steel after heat treatment.
In the step A of the method, a titanium tetrachloride solution is adopted to realize the controllability of the reaction speed, and the titanium concentration of the solution A is controlled to be 0.2-0.6 mol/L; in the step B, controlling the concentration of caustic alkali (potassium hydroxide or sodium hydroxide) in the solution B to be 2-6 mol/L; by controlling the concentration of the solution A and the solution B, the coprecipitation reaction speed is proper, and the generation of byproducts is avoided; if the concentration is too high, the reaction is too fast, more byproducts are produced, and white precipitate cannot be generated; too low a concentration takes too long an experiment. Wherein, the titanium tetrachloride solution and the potassium hydroxide or the sodium hydroxide are all commercial products.
In the step C of the method, the solution B is dropwise added into the solution A at the rotating speed of 200-500 r/min, so that side reaction is avoided, and a precipitator of potassium hydroxide or sodium hydroxide is fully contacted with titanium tetrachloride; since each TiO is2+Require two OH groups-Reaction, in order to ensure sufficient OH-, through experiments, when the pH value of the system reaches 6-7, the dropwise addition of the solution B is stopped, the precipitation reaction can be fully completed, white precipitate continuously appears in the process, and the reaction is thoroughly performed by subsequently stirring for 10-40 min.
In the step C of the method, after the coprecipitation reaction is completed, the precipitate is sequentially and alternately cleaned by hot water (50-60 ℃) and absolute ethyl alcohol until AgNO3No Cl can be detected-Until the end; and then dispersing the precipitate in water, stirring for 10-30 min to fully disperse the precipitate, and controlling the titanium concentration of the suspension to be 0.1-0.2 mol/L to ensure that hydrosol with proper concentration is formed and improve the protection effect of the hydrosol on steel.
In the step D of the method, not less than 28 percent of hydrogen peroxide is adopted, a commercially available product is generally adopted, the concentration of the hydrogen peroxide is generally 30 percent, and the addition amount of the hydrogen peroxide is equal to the amount of H in the system2O2With Ti4+Is not less than 4: and (1) continuously stirring while dropping hydrogen peroxide for 30-60 min to obtain a dark yellow transparent solution, and standing for 10-18 h to obtain the pale yellow transparent titanium-based hydrosol.
In step E of the process of the present invention, said H2SO4And H2O2The mixed solution of (A) is H with the mass fraction of 98%2SO4And 30% of H2O2The volume ratio of (A) to (B) is 1-3: 1, soaking the steel in the mixed solution for 6-12 hours.
In the step E of the method, the ultrasonic treatment is carried out for 15-30 min, and then the steel is dried for 5-10 min at the temperature of 90-110 ℃.
In the step F of the method, a dip-coating method or a coating method is adopted for coating; in the dipping and pulling method, the dipping time is controlled to be 2min to 5min, and a pulling machine pulls at the speed of 1cm/min to 2.5 cm/min; in the coating method, coating is performed at 1mm/s to 2.5 mm/s. The effect is better when 3-5 layers are plated through tests, and each layer of film is firstly dried for 5-15 min at 80-120 ℃, and then the next layer of film is plated.
In the step G of the method, the coated steel is calcined at 350-900 ℃ for 2-4.5 h, wherein the crystal form of the film obtained by calcining at 350-600 ℃ is mainly anatase type, and the crystal form of the film obtained by calcining at 600-900 ℃ is mainly rutile type; after heat treatment, the titanium-based nano anticorrosive film is generated on the surface of the steel.
The present invention is further illustrated by the following examples, which are not intended to limit the scope of the invention.
Example 1
The method comprises the following steps: a commercially available titanium tetrachloride solution (with a mass concentration of 98%) was dropwise added to deionized water to prepare a solution A with a concentration of 0.4 mol/L.
Step two: dispersing NaOH particles in deionized water, and ultrasonically stirring to prepare a NaOH solution B with the concentration of 4 mol/L.
Step three: stirring the solution A at the rotating speed of 350r/min, dropwise adding the solution B into the solution A to perform coprecipitation reaction, stopping dropwise adding the solution B when the pH value of a system reaches 6.5, and continuously generating white precipitate in the process; stirring for 15min to react completely, filtering the white precipitate, and repeatedly washing with hot deionized water and anhydrous ethanol respectively until AgNO is used3No Cl can be detected-Until the end; and dispersing the obtained white precipitate into deionized water, and stirring for 10min to obtain a suspension with the concentration of 0.15 mol/L.
Step four: will market 30% H2O2Solution (H)2O2：Ti4+The molar ratio is 4: 1) and slowly dropping the solution into the suspension by using a pipette, continuously stirring for 45min until the solution is dark yellow and transparent, then adjusting the pH value of the system to 7 by using ammonia water, and standing for 12h to obtain the pale yellow and transparent titanium-based hydrosol.
Step five: in the embodiment, carbon steel DP590 is used 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 later use.
Step six: titanium-based hydrosol is used for coating the steel at the speed of 1mm/s, and the coating needs to be dried for 5min and then coated for the next time every time, wherein the coating is performed for 3 times in the embodiment.
Step seven: and (3) placing the plated steel in a muffle furnace for high-temperature calcination at 500 ℃ for 4 h.
Step eight: and carrying out electrochemical corrosion test on the coated steel plate, wherein the protection efficiency reaches 97.2%.
Example 2
The method comprises the following steps: a commercially available titanium tetrachloride solution was dropwise added to deionized water to prepare a solution A having a concentration of 0.5 mol/L.
Step two: dispersing NaOH particles in deionized water, and ultrasonically stirring to prepare a NaOH solution B with the concentration of 5 mol/L.
Step three: stirring the solution A at the rotating speed of 400r/min, dropwise adding the solution B into the solution A to perform coprecipitation reaction, stopping dropwise adding the solution B when the pH value of the system reaches 7, and continuously generating white precipitate in the process; stirring for 15min to react completely, filtering the white precipitate, and repeatedly washing with hot deionized water and anhydrous ethanol respectively until AgNO is used3No Cl can be detected-Until the end; and dispersing the obtained white precipitate in deionized water, and stirring for 10min to obtain a suspension with the concentration of 0.2 mol/L.
Step four: will market 30% H2O2Solution (H)2O2：Ti4+The molar ratio is 4: 1) slowly dripping into the suspension with a pipette, stirring for 30min until the solution is dark yellow and transparent,then ammonia water is used for adjusting the pH value of the system to 7, and the mixture is kept stand for 12 hours to obtain the pale yellow transparent titanium-based hydrosol.
Step five: in the embodiment, 5083 aluminum alloy is used as a substrate, the prepared steel is respectively placed in acetone, absolute ethyl alcohol and deionized water for ultrasonic treatment for 15min, and then is dried in a drying oven at 100 ℃ for 10min and then is taken out for later use.
Step six: the titanium-based hydrosol is used for coating the steel by a pulling method at the speed of 2cm/min, and the coating needs to be dried for 5min and then coated for the next time every time, wherein the coating is coated for 3 times in the embodiment.
Step seven: and (3) calcining the plated steel at the high temperature of 450 ℃ in a muffle furnace for 4.5 h.
Step eight: and carrying out electrochemical corrosion test on the coated steel plate, wherein the protection efficiency reaches 97.6%.
Example 3
The method comprises the following steps: a commercially available titanium tetrachloride solution was dropwise added to deionized water to prepare a solution A having a concentration of 0.3 mol/L.
Step two: dispersing NaOH particles in deionized water, and ultrasonically stirring to prepare a NaOH solution B with the concentration of 5 mol/L.
Step three: stirring the solution A at the rotating speed of 450r/min, dropwise adding the solution B into the solution A to perform coprecipitation reaction, stopping dropwise adding the solution B when the pH value of the system reaches 7, and continuously generating white precipitate in the process; stirring for 20min to react completely, filtering the white precipitate, and repeatedly washing with hot deionized water and anhydrous ethanol respectively until AgNO is used3No Cl can be detected-Until the end; and dispersing the obtained white precipitate into a certain amount of deionized water, and stirring for 10min to obtain a suspension with the concentration of 0.2 mol/L.
Step four: will market 30% H2O2Solution (H)2O2：Ti4+The molar ratio is 4: 1) and slowly dropping the solution into the suspension by using a pipette, continuously stirring for 30min until the solution is dark yellow and transparent, then adjusting the pH value of the system to 7 by using ammonia water, and standing for 12h to obtain the pale yellow and transparent titanium-based hydrosol.
Step five: in the embodiment, 304 stainless steel is used 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 later use.
Step six: the titanium-based hydrosol is used for coating the steel by a pulling method at the speed of 2cm/min, and the coating needs to be dried for 5min and then coated for the next time every time, wherein the coating is coated for 4 times in the embodiment.
Step seven: and (3) placing the plated steel in a muffle furnace for high-temperature calcination at 550 ℃ for 3.5 h.
Step eight: and carrying out electrochemical corrosion test on the coated steel plate, wherein the protection efficiency reaches 98.2%.
According to the titanium-based nano anti-corrosion film disclosed by the invention, the protection efficiency can reach more than 95%, the anti-corrosion performance of steel can be obviously improved, the service life of the steel can be prolonged (5-10 years), 830 million tons of iron, 940 million tons of steel and 890 million tons of steel are produced by climbing steel every year according to the service life of common steel being 20 years, the price of each ton of steel is about 4000, and 532 million yuan can be saved after the service life is prolonged by 10 years.
Claims (9)
1. The method for preparing the titanium-based nano anticorrosive film by taking titanium tetrachloride as a titanium source is characterized by comprising the following steps of: the method comprises the following steps:
preparing titanium-based hydrosol:
A. dripping titanium tetrachloride solution into water to obtain solution A;
B. mixing caustic alkali and water to obtain a solution B;
C. dropwise adding the solution B into the solution A under stirring, stopping adding the solution B when the pH value of the system is 6-7, carrying out coprecipitation reaction to obtain a precipitate, washing the obtained precipitate, and dispersing the precipitate in water to obtain a suspension;
D. dropwise adding hydrogen peroxide into the suspension, stirring until the solution is transparent, adjusting the pH value of the system to 6-7 by using ammonia water, and standing to obtain titanium-based hydrosol;
substrate treatment:
E. if the steel material is stainless steel, the surface of the stainless steel is cleaned by water, and then the stainless steel is put into H2SO4And H2O2Soaking in the mixed solution, and washing with water to remove rustPutting the steel surface into water for later use;
if the steel is carbon steel and other steels, the steel is sequentially placed in acetone, absolute ethyl alcohol and water for ultrasonic treatment, and then dried for later use;
film coating:
F. e, coating the steel processed in the step E with 3-5 layers of films, and drying each layer of film and then coating the next layer of film;
and (3) heat treatment:
G. calcining the coated steel at 350-900 ℃, and generating the titanium-based nano anticorrosive film on the surface of the steel after heat treatment.
2. The method for preparing titanium-based nano anticorrosive film using titanium tetrachloride as a titanium source according to claim 1, characterized in that: in the step A, the titanium concentration of the obtained solution A is 0.2-0.6 mol/L.
3. The method for preparing titanium-based nano anticorrosive film using titanium tetrachloride as a titanium source according to claim 1, characterized in that: in the step B, the caustic alkali concentration of the obtained solution B is 2-6 mol/L.
4. The method for preparing titanium-based nano anticorrosive film using titanium tetrachloride as a titanium source according to claim 1, characterized in that: in step C, at least one of the following is satisfied:
dropwise adding the solution B into the solution A at the rotating speed of 200-500 r/min;
after the dropwise adding is finished, continuously stirring for 10-40 min;
the washing is as follows: washing the precipitate with hot water and anhydrous ethanol alternately until AgNO3No Cl can be detected-Until now.
5. The method for preparing titanium-based nano anticorrosive film using titanium tetrachloride as a titanium source according to claim 1, characterized in that: in step C, at least one of the following is satisfied:
dispersing the precipitate in water, and stirring for 10-30 min;
the titanium concentration of the obtained suspension is 0.1-0.2 mol/L.
6. The method for preparing titanium-based nano anticorrosive film using titanium tetrachloride as a titanium source according to claim 1, characterized in that: in step D, at least one of the following is satisfied:
the concentration of the hydrogen peroxide is not lower than 28 percent;
the addition of the hydrogen peroxide is H in the system2O2With Ti4+Is not less than 4: 1 is the standard;
the stirring time is 30-60 min;
the standing time is 10-18 h.
7. The method for preparing titanium-based nano anticorrosive film using titanium tetrachloride as a titanium source according to claim 1, characterized in that: in step E, at least one of the following is satisfied:
said H2SO4And H2O2The mixed solution of (A) is H with the mass fraction of 98%2SO4And 30% of H2O2The volume ratio of (A) to (B) is 1-3: 1;
the soaking time is 6-12 hours;
the ultrasonic time is 15-30 min;
the drying temperature is 90-110 ℃, and the drying time is 5-10 min.
8. The method for preparing titanium-based nano anticorrosive film using titanium tetrachloride as a titanium source according to claim 1, characterized in that: in step F, at least one of the following is satisfied:
coating by adopting a dipping and pulling method or a coating method; in the dipping and pulling method, the dipping time is controlled to be 2min to 5min, and a pulling machine pulls at the speed of 1cm/min to 2.5 cm/min; in the coating method, coating is carried out at 1 mm/s-2.5 mm/s;
the drying temperature is 90-110 ℃, and the drying time is 5-10 min.
9. The method for preparing a titanium-based nano anticorrosive film using titanium tetrachloride as a titanium source according to any one of claims 1 to 8, characterized in that: in the step G, the calcining time is 2-4.5 h.
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