CN114086189A - Environment-friendly stainless steel pickling passivation solution - Google Patents
Environment-friendly stainless steel pickling passivation solution Download PDFInfo
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- CN114086189A CN114086189A CN202111399909.5A CN202111399909A CN114086189A CN 114086189 A CN114086189 A CN 114086189A CN 202111399909 A CN202111399909 A CN 202111399909A CN 114086189 A CN114086189 A CN 114086189A
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- 229910001220 stainless steel Inorganic materials 0.000 title claims abstract description 68
- 239000010935 stainless steel Substances 0.000 title claims abstract description 68
- 238000002161 passivation Methods 0.000 title claims abstract description 57
- 238000005554 pickling Methods 0.000 title claims abstract description 50
- 239000012621 metal-organic framework Substances 0.000 claims abstract description 55
- 239000002086 nanomaterial Substances 0.000 claims abstract description 55
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims abstract description 54
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 48
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 36
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000003945 anionic surfactant Substances 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 11
- 238000009832 plasma treatment Methods 0.000 claims abstract description 9
- 238000002360 preparation method Methods 0.000 claims description 18
- 239000002253 acid Substances 0.000 claims description 15
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 13
- 239000001301 oxygen Substances 0.000 claims description 13
- 229910052760 oxygen Inorganic materials 0.000 claims description 13
- 239000002904 solvent Substances 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 12
- 150000000703 Cerium Chemical class 0.000 claims description 10
- 125000003118 aryl group Chemical group 0.000 claims description 9
- 239000003446 ligand Substances 0.000 claims description 9
- 238000004729 solvothermal method Methods 0.000 claims description 9
- QURGMSIQFRADOZ-UHFFFAOYSA-N 5-(3,5-dicarboxyphenyl)benzene-1,3-dicarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C=2C=C(C=C(C=2)C(O)=O)C(O)=O)=C1 QURGMSIQFRADOZ-UHFFFAOYSA-N 0.000 claims description 8
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- NEQFBGHQPUXOFH-UHFFFAOYSA-N 4-(4-carboxyphenyl)benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C1=CC=C(C(O)=O)C=C1 NEQFBGHQPUXOFH-UHFFFAOYSA-N 0.000 claims description 4
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 2
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 claims description 2
- OZECDDHOAMNMQI-UHFFFAOYSA-H cerium(3+);trisulfate Chemical compound [Ce+3].[Ce+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O OZECDDHOAMNMQI-UHFFFAOYSA-H 0.000 claims description 2
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 2
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 2
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 230000007797 corrosion Effects 0.000 abstract description 17
- 238000005260 corrosion Methods 0.000 abstract description 17
- 230000000694 effects Effects 0.000 abstract description 12
- 239000000758 substrate Substances 0.000 abstract description 4
- 239000000243 solution Substances 0.000 description 28
- 230000000052 comparative effect Effects 0.000 description 9
- 238000002156 mixing Methods 0.000 description 6
- -1 cerium nitrate-3, 3',5,5' -biphenyltetracarboxylic acid Chemical compound 0.000 description 4
- 239000006104 solid solution Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000005530 etching Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 150000002910 rare earth metals Chemical class 0.000 description 2
- 230000003213 activating effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Classifications
-
- 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
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
- C23G1/08—Iron or steel
- C23G1/088—Iron or steel solutions containing organic acids
-
- 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
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/48—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 not containing phosphates, hexavalent chromium compounds, fluorides or complex fluorides, molybdates, tungstates, vanadates or oxalates
- C23C22/50—Treatment of iron or alloys based thereon
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
Abstract
The invention discloses an environment-friendly stainless steel pickling passivation solution, which comprises the following raw materials in percentage by mass: 3-5% of concentrated sulfuric acid, 2-4% of citric acid, 3-5% of hydrogen peroxide, 0.5-1% of cerium nitrate, 0.02-0.05% of modified Ce-MOFs nano material, 0.03-0.1% of anionic surfactant and the balance of water, wherein the modified Ce-MOFs nano material is obtained by carrying out low-temperature plasma treatment on the Ce-MOFs nano material. The stainless steel pickling passivation solution disclosed by the invention can be used for efficiently and quickly removing oxide skins on the surface of stainless steel, has an excellent passivation corrosion-resistant effect on a stainless steel substrate, is green and environment-friendly, and has low harm to a human body.
Description
Technical Field
The invention relates to the technical field of stainless steel surface treatment, in particular to an environment-friendly stainless steel pickling passivation solution.
Background
The stainless steel is a metal material with good mechanical property and processability and excellent corrosion resistance and wear resistance, and is widely applied to the fields of science and technology, production and living such as aerospace, power equipment, petrochemical industry, building and building materials, automobile transportation, furniture and the like. In the process of processing stainless steel into products such as parts and profiles, complex processing is usually required, so that oxide scale is formed on the surface of the stainless steel, which not only affects the appearance, but also hinders the subsequent coating and other processes. In addition, the stainless steel product is corroded due to the influence of the external environment, so that the attractiveness and the practicability of the stainless steel product are influenced, and particularly, the service life of the stainless steel product is greatly shortened due to the corrosion of the stainless steel product on stainless steel pipes and equipment parts which need to be in special environmental conditions for a long time. Therefore, the method removes the oxide skin on the surface of the stainless steel by the pickling passivation process, passivates the surface of the stainless steel to improve the corrosion resistance of the stainless steel, and becomes a key process in the stainless steel processing. At present, in order to achieve a good passivation effect, stainless steel pickling passivation solution adopted by a pickling passivation process is mainly prepared by compounding high-concentration strong-oxidizing acid solution and additives, so that the surface of stainless steel is greatly damaged, the processing effect is influenced, acid mist is easily volatilized in a workshop environment to form, and the safety coefficient is low. Therefore, how to optimize the formula of the pickling passivation solution, improve the safety coefficient of the pickling passivation solution and keep the excellent passivation effect becomes the current research focus.
Disclosure of Invention
The invention aims to make up the defects of the prior art and provide an environment-friendly stainless steel pickling passivation solution.
The invention is realized by the following technical scheme:
an environment-friendly stainless steel pickling passivation solution comprises the following raw materials in percentage by mass:
3-5% of concentrated sulfuric acid, 2-4% of citric acid, 3-5% of hydrogen peroxide, 0.5-1% of cerium nitrate, 0.02-0.05% of modified Ce-MOFs nano material, 0.03-0.1% of anionic surfactant and the balance of water;
the modified Ce-MOFs nano material is obtained by carrying out low-temperature plasma treatment on the Ce-MOFs nano material.
Preferably, the preparation method of the modified Ce-MOFs nano material comprises the following steps: and (2) placing the Ce-MOFs nano material in a plasma reactor, introducing oxygen, and carrying out low-temperature plasma treatment for 5-20min under the condition that the discharge power is 50-100W.
Preferably, the oxygen flow rate is 80-150 mL/min.
Preferably, the Ce-MOFs nano material is prepared by taking cerium salt and a rigid aromatic polycarboxylic acid ligand as raw materials and carrying out solvothermal reaction.
Preferably, the molar ratio of the cerium salt to the rigid aromatic polycarboxylic acid ligand is 1: (2-4).
Preferably, the preparation method of the Ce-MOFs nano material comprises the following steps: adding cerium salt and rigid aromatic polycarboxylic acid ligand into a solvent, carrying out solvothermal reaction at the temperature of 120-160 ℃ for 20-30h, centrifuging, and washing and drying the obtained solid substance to obtain the cerium-doped cerium oxide.
Preferably, the cerium salt is one or more of cerium nitrate, cerium chloride and cerium sulfate; the rigid aromatic polycarboxylic acid ligand is one or a mixture of 3,3',5,5' -biphenyl tetracarboxylic acid and 4,4' -biphenyl dicarboxylic acid; the solvent is DMF.
Preferably, the ratio of the cerium salt to the solvent is (1-3) g: 100 mL.
Preferably, the anionic surfactant is one or a mixture of sodium dodecyl sulfate and sodium dodecyl benzene sulfonate.
Preferably, the mass fraction of the concentrated sulfuric acid is 95-98%.
Preferably, the mass fraction of the hydrogen peroxide is 20-30%.
The preparation method of the environment-friendly stainless steel pickling passivation solution comprises the following steps: and uniformly mixing concentrated sulfuric acid, citric acid, hydrogen peroxide, cerium nitrate, the modified Ce-MOFs nano material, an anionic surfactant and water in proportion to obtain the modified Ce-MOFs nano material.
The use method of the environment-friendly stainless steel pickling passivation solution comprises the following steps: and immersing the stainless steel into the pickling passivation solution, pickling and passivating for 20-30min at the temperature of 40-60 ℃, taking out the stainless steel, and cleaning.
The invention has the advantages that:
the method comprises the steps of firstly preparing the Ce-MOFs nano material by taking cerium salt and a rigid aromatic polycarboxylic acid ligand as raw materials through a solvothermal synthesis method, then activating the Ce-MOFs nano material by utilizing low-temperature plasma in an oxygen atmosphere under a proper condition, and introducing a large number of oxygen-containing groups with high reaction activity on the surface of the Ce-MOFs nano material, thereby obtaining the modified Ce-MOFs nano material. The modified Ce-MOFs nano material is uniformly mixed with concentrated sulfuric acid, citric acid, hydrogen peroxide, cerium nitrate, a surfactant and water according to a proper proportion, so that the obtained stainless steel pickling passivation solution not only can efficiently and quickly remove oxide skin on the surface of stainless steel, but also can interact with a rare earth conversion film formed on the surface of the stainless steel by the cerium nitrate due to a large number of oxygen-containing active groups on the surface of the modified Ce-MOFs nano material, so that the modified Ce-MOFs nano material is uniformly doped in the rare earth conversion film, a more compact passivation layer with a better corrosion resistance effect is formed on the surface of the stainless steel, and the corrosion resistance of the stainless steel is remarkably improved, and therefore, the corrosion resistance of the treated stainless steel can be greatly improved by the stainless steel pickling passivation solution.
In conclusion, the stainless steel pickling passivation solution disclosed by the invention can be used for efficiently and quickly removing oxide skins on the surface of stainless steel, has an excellent passivation corrosion-resistant effect on a stainless steel substrate, is green and environment-friendly, and is low in harm to human bodies.
Detailed Description
In the following examples, the mass fraction of the hydrogen peroxide is 30% and the mass fraction of the concentrated sulfuric acid is 98%.
Example 1
An environment-friendly stainless steel pickling passivation solution comprises the following raw materials in percentage by mass:
4% of concentrated sulfuric acid, 3% of citric acid, 4% of hydrogen peroxide, 0.8% of cerium nitrate, 0.04% of modified Ce-MOFs nano material, 0.06% of sodium dodecyl sulfate and the balance of water;
the preparation method of the modified Ce-MOFs nano material comprises the following steps: and (2) placing the Ce-MOFs nano material in a plasma reactor, introducing oxygen, and performing low-temperature plasma treatment for 10min under the condition that the discharge power is 80W, wherein the oxygen flow is 100mL/min, thus obtaining the material.
The preparation method of the Ce-MOFs nano material comprises the following steps: adding cerous nitrate and 3,3',5,5' -biphenyltetracarboxylic acid into a solvent DMF, carrying out solvothermal reaction for 25h at 140 ℃, centrifuging, washing and drying the obtained solid matter to obtain the cerium nitrate-3, 3',5,5' -biphenyltetracarboxylic acid solid solution, wherein the molar ratio of the cerous nitrate to the 3,3',5,5' -biphenyltetracarboxylic acid is 1: 2, the ratio of cerium nitrate to DMF solvent is 2 g: 100 mL.
The preparation method of the environment-friendly stainless steel pickling passivation solution comprises the following steps: and uniformly mixing concentrated sulfuric acid, citric acid, hydrogen peroxide, cerium nitrate, the modified Ce-MOFs nano material, an anionic surfactant and water in proportion to obtain the modified Ce-MOFs nano material.
Example 2
The environment-friendly stainless steel pickling passivation solution comprises the following raw materials in percentage by mass:
3% of concentrated sulfuric acid, 4% of citric acid, 5% of hydrogen peroxide, 0.5% of cerium nitrate, 0.02% of modified Ce-MOFs nano material, 0.03% of sodium dodecyl sulfate and the balance of water;
the preparation method of the modified Ce-MOFs nano material comprises the following steps: and (2) placing the Ce-MOFs nano material in a plasma reactor, introducing oxygen, and performing low-temperature plasma treatment for 20min under the condition that the discharge power is 50W, wherein the oxygen flow is 80mL/min, thus obtaining the material.
The preparation method of the Ce-MOFs nano material comprises the following steps: adding cerium nitrate and 4,4' -biphenyldicarboxylic acid into a solvent DMF, carrying out solvothermal reaction for 30h at 120 ℃, centrifuging, washing and drying the obtained solid matter, and thus obtaining the cerium nitrate-4, 4' -biphenyldicarboxylic acid solid solution, wherein the molar ratio of the cerium nitrate to the 4,4' -biphenyldicarboxylic acid is 1: 4, the ratio of the cerium nitrate to the solvent DMF is 1 g: 100 mL.
The preparation method of the environment-friendly stainless steel pickling passivation solution comprises the following steps: and uniformly mixing concentrated sulfuric acid, citric acid, hydrogen peroxide, cerous nitrate, the modified Ce-MOFs nano material, an anionic surfactant and water in proportion to obtain the modified Ce-MOFs nano material.
Example 3
The environment-friendly stainless steel pickling passivation solution comprises the following raw materials in percentage by mass:
5% of concentrated sulfuric acid, 2% of citric acid, 3% of hydrogen peroxide, 1% of cerium nitrate, 0.05% of modified Ce-MOFs nano material, 0.1% of sodium dodecyl sulfate and the balance of water;
the preparation method of the modified Ce-MOFs nano material comprises the following steps: and (2) placing the Ce-MOFs nano material in a plasma reactor, introducing oxygen, and carrying out low-temperature plasma treatment for 5min under the condition that the discharge power is 100W, wherein the oxygen flow is 150m/min, thus obtaining the material.
The preparation method of the Ce-MOFs nano material comprises the following steps: adding cerous nitrate and 3,3',5,5' -biphenyltetracarboxylic acid into a solvent DMF, carrying out solvothermal reaction for 20h at 160 ℃, centrifuging, washing and drying the obtained solid matter to obtain the cerium nitrate-3, 3',5,5' -biphenyltetracarboxylic acid solid solution, wherein the molar ratio of the cerous nitrate to the 3,3',5,5' -biphenyltetracarboxylic acid is 1: 2, the ratio of cerium nitrate to DMF solvent is 3 g: 100 mL.
The preparation method of the environment-friendly stainless steel pickling passivation solution comprises the following steps: and uniformly mixing concentrated sulfuric acid, citric acid, hydrogen peroxide, cerium nitrate, the modified Ce-MOFs nano material, an anionic surfactant and water in proportion to obtain the modified Ce-MOFs nano material.
Comparative example 1
Comparative example 1 differs from example 1 only in that: the modified Ce-MOFs nano material is not added, and the specific steps are as follows:
the environment-friendly stainless steel pickling passivation solution comprises the following raw materials in percentage by mass:
4% of concentrated sulfuric acid, 3% of citric acid, 4% of hydrogen peroxide, 0.8% of cerium nitrate, 0.06% of sodium dodecyl sulfate and the balance of water.
The preparation method of the environment-friendly stainless steel pickling passivation solution comprises the following steps: mixing concentrated sulfuric acid, citric acid, hydrogen peroxide, cerous nitrate, anionic surfactant and water at a certain proportion.
Comparative example 2
Comparative example 2 differs from example 1 only in that: the Ce-MOFs nano material is used for replacing the modified Ce-MOFs nano material, and the specific steps are as follows:
the environment-friendly stainless steel pickling passivation solution comprises the following raw materials in percentage by mass:
4% of concentrated sulfuric acid, 3% of citric acid, 4% of hydrogen peroxide, 0.8% of cerium nitrate, 0.04% of Ce-MOFs nano material, 0.06% of sodium dodecyl sulfate and the balance of water;
the preparation method of the Ce-MOFs nano material comprises the following steps: adding cerous nitrate and 3,3',5,5' -biphenyltetracarboxylic acid into a solvent DMF, carrying out solvothermal reaction for 25h at 140 ℃, centrifuging, washing and drying the obtained solid matter to obtain the cerium nitrate-3, 3',5,5' -biphenyltetracarboxylic acid solid solution, wherein the molar ratio of the cerous nitrate to the 3,3',5,5' -biphenyltetracarboxylic acid is 1: 2, the ratio of cerium nitrate to DMF solvent is 2 g: 100 mL.
The preparation method of the environment-friendly stainless steel pickling passivation solution comprises the following steps: and uniformly mixing concentrated sulfuric acid, citric acid, hydrogen peroxide, cerium nitrate, the Ce-MOFs nano material, an anionic surfactant and water in proportion to obtain the catalyst.
Test examples
The 303 stainless steel test piece is subjected to acid pickling passivation by adopting examples 1-3 and comparative examples 1-2, and the acid pickling passivation method comprises the following steps: and (3) immersing the stainless steel test piece into an acid pickling passivation solution, carrying out acid pickling passivation for 25min at the temperature of 50 ℃, taking out the stainless steel test piece, and cleaning.
Referring to a GB4334.7-1984 stainless steel ferric trichloride corrosion test method, the corrosion test is respectively carried out on the stainless steel test piece after pickling and passivating treatment, the test temperature is 50 +/-1 ℃, and the test time is 24 hours. Calculating the corrosion rate of the test piece, wherein the calculation formula is as follows: the results of the etching rate (weight before test piece etching-weight after test piece etching)/(test piece area × etching time) are shown in table 1.
TABLE 1
As can be seen from Table 1, the pickling passivation solution provided by the invention can significantly improve the corrosion resistance of the treated test piece, and has excellent passivation and corrosion resistance effects.
Comparing the test results of the embodiment 1 and the comparative examples 1-2, it can be seen that the corrosion resistance effect of the comparative example 1 is much lower than that of the embodiment 1, because the modified Ce-MOFs nano material is added into the pickling passivation solution, the passivation layer doped with the modified Ce-MOFs nano material can be formed on the surface of the stainless steel substrate in the pickling passivation process, and the passivation corrosion resistance to the stainless steel can be greatly improved; the corrosion resistance effect of the comparative example 2 is slightly better than that of the comparative example 1, but still far lower than that of the example 1, because the Ce-MOFs nano material which is not subjected to the surface low-temperature plasma treatment is added into the pickling passivation solution, the surface active groups are few, and the Ce-MOFs nano material cannot be fully doped into the passivation layer, so that the improvement effect on the corrosion resistance effect of the stainless steel substrate is limited.
Claims (10)
1. The environment-friendly stainless steel pickling passivation solution is characterized by comprising the following raw materials in percentage by mass:
3-5% of concentrated sulfuric acid, 2-4% of citric acid, 3-5% of hydrogen peroxide, 0.5-1% of cerium nitrate, 0.02-0.05% of modified Ce-MOFs nano material, 0.03-0.1% of anionic surfactant and the balance of water;
the modified Ce-MOFs nano material is obtained by carrying out low-temperature plasma treatment on the Ce-MOFs nano material.
2. The environment-friendly stainless steel pickling passivation solution of claim 1, wherein the preparation method of the modified Ce-MOFs nano material comprises the following steps: and (2) placing the Ce-MOFs nano material in a plasma reactor, introducing oxygen, and carrying out low-temperature plasma treatment for 5-20min under the condition that the discharge power is 50-100W.
3. The environment-friendly stainless steel pickling passivation solution of claim 2, wherein the oxygen flow is 80-150 m/min.
4. The environment-friendly stainless steel pickling passivation solution as claimed in claim 2, wherein the Ce-MOFs nano material is prepared by taking cerium salt and a rigid aromatic polycarboxylic acid ligand as raw materials and performing solvothermal reaction.
5. The environment-friendly stainless steel pickling passivation solution as claimed in claim 4, wherein the molar ratio of the cerium salt to the rigid aromatic polycarboxylic acid ligand is 1: (2-4).
6. The environment-friendly stainless steel pickling passivation solution of claim 2, wherein the preparation method of the Ce-MOFs nano material comprises the following steps: adding cerium salt and rigid aromatic polycarboxylic acid ligand into a solvent, carrying out solvothermal reaction at the temperature of 120-160 ℃ for 20-30h, centrifuging, and washing and drying the obtained solid substance to obtain the cerium-doped cerium oxide.
7. The environment-friendly stainless steel pickling passivation solution of claim 6, wherein the cerium salt is one or a mixture of cerium nitrate, cerium chloride and cerium sulfate; the rigid aromatic polycarboxylic acid ligand is one or a mixture of 3,3',5,5' -biphenyltetracarboxylic acid and 4,4' -biphenyldicarboxylic acid; the solvent is DMF.
8. The environment-friendly stainless steel pickling passivation solution as claimed in claim 1, wherein the anionic surfactant is one or a mixture of sodium dodecyl sulfate and sodium dodecyl benzene sulfonate.
9. A preparation method of the environment-friendly stainless steel pickling passivation solution as claimed in claims 1-8, characterized in that concentrated sulfuric acid, citric acid, hydrogen peroxide, cerium nitrate, modified Ce-MOFs nano material, anionic surfactant and water are mixed uniformly in proportion to obtain the environment-friendly stainless steel pickling passivation solution.
10. A use method of the environment-friendly stainless steel pickling passivation solution as claimed in claims 1-8, characterized in that stainless steel is immersed in the pickling passivation solution, pickled and passivated for 20-30min at 40-60 ℃, and then taken out and cleaned.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100132844A1 (en) * | 2007-03-05 | 2010-06-03 | Poligrat Gmbh | Method for the thermochemical passivation of stainless steel |
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