CN114836741A - Steel substrate surface film forming solution based on organic-inorganic chelating compounding and preparation and application thereof - Google Patents
Steel substrate surface film forming solution based on organic-inorganic chelating compounding and preparation and application thereof Download PDFInfo
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- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 46
- 239000010959 steel Substances 0.000 title claims abstract description 46
- 239000000758 substrate Substances 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 238000013329 compounding Methods 0.000 title abstract description 3
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 36
- 238000005260 corrosion Methods 0.000 claims abstract description 34
- 230000007797 corrosion Effects 0.000 claims abstract description 33
- 239000003112 inhibitor Substances 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000002738 chelating agent Substances 0.000 claims abstract description 15
- 230000003472 neutralizing effect Effects 0.000 claims abstract description 14
- 239000008235 industrial water Substances 0.000 claims abstract description 8
- 229910052751 metal Inorganic materials 0.000 claims abstract description 8
- 239000002184 metal Substances 0.000 claims abstract description 8
- 238000004381 surface treatment Methods 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 56
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 13
- 150000004697 chelate complex Chemical class 0.000 claims description 12
- IMQLKJBTEOYOSI-GPIVLXJGSA-N Inositol-hexakisphosphate Chemical compound OP(O)(=O)O[C@H]1[C@H](OP(O)(O)=O)[C@@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@@H]1OP(O)(O)=O IMQLKJBTEOYOSI-GPIVLXJGSA-N 0.000 claims description 11
- IMQLKJBTEOYOSI-UHFFFAOYSA-N Phytic acid Natural products OP(O)(=O)OC1C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C1OP(O)(O)=O IMQLKJBTEOYOSI-UHFFFAOYSA-N 0.000 claims description 11
- 229940068041 phytic acid Drugs 0.000 claims description 11
- 235000002949 phytic acid Nutrition 0.000 claims description 11
- 239000000467 phytic acid Substances 0.000 claims description 11
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 8
- 239000012964 benzotriazole Substances 0.000 claims description 7
- 238000009472 formulation Methods 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 6
- 238000005238 degreasing Methods 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- FDGBQHCDMSYZRC-UHFFFAOYSA-N 2-hydroxy-2-oxo-1,3,2$l^{5}-dioxaphosphinan-4-amine Chemical compound NC1CCOP(O)(=O)O1 FDGBQHCDMSYZRC-UHFFFAOYSA-N 0.000 claims description 4
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- DDAQLPYLBPPPRV-UHFFFAOYSA-N [4-(hydroxymethyl)-2-oxo-1,3,2lambda5-dioxaphosphetan-2-yl] dihydrogen phosphate Chemical compound OCC1OP(=O)(OP(O)(O)=O)O1 DDAQLPYLBPPPRV-UHFFFAOYSA-N 0.000 claims description 4
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims description 4
- 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 description 4
- 229960001484 edetic acid Drugs 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 239000011258 core-shell material Substances 0.000 claims description 3
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 3
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 3
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 claims description 3
- 235000019982 sodium hexametaphosphate Nutrition 0.000 claims description 3
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Polymers [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 claims description 3
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 2
- 239000003895 organic fertilizer Substances 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 230000008021 deposition Effects 0.000 claims 9
- 238000006243 chemical reaction Methods 0.000 abstract description 10
- 239000002994 raw material Substances 0.000 abstract description 8
- 239000007788 liquid Substances 0.000 abstract description 6
- 230000007547 defect Effects 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract 2
- 229910021645 metal ion Inorganic materials 0.000 abstract 1
- 239000005416 organic matter Substances 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 11
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 8
- 229910000365 copper sulfate Inorganic materials 0.000 description 7
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 7
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 4
- 239000003973 paint Substances 0.000 description 4
- 239000011780 sodium chloride Substances 0.000 description 4
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 3
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 3
- 229910001385 heavy metal Inorganic materials 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 229940098458 powder spray Drugs 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229910021432 inorganic complex Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 239000008399 tap water Substances 0.000 description 2
- 235000020679 tap water Nutrition 0.000 description 2
- 229910000861 Mg alloy Inorganic materials 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 1
- 241000220317 Rosa Species 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- YDONNITUKPKTIG-UHFFFAOYSA-N [Nitrilotris(methylene)]trisphosphonic acid Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CP(O)(O)=O YDONNITUKPKTIG-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000003354 benzotriazolyl group Chemical group N1N=NC2=C1C=CC=C2* 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- 238000007739 conversion coating Methods 0.000 description 1
- 238000005536 corrosion prevention Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hcl hcl Chemical compound Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Images
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
- 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
- C23C22/07—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 containing phosphates
- C23C22/08—Orthophosphates
- C23C22/12—Orthophosphates containing zinc cations
- C23C22/17—Orthophosphates containing zinc cations containing also 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
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
- C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
- C23F11/14—Nitrogen-containing compounds
- C23F11/149—Heterocyclic compounds containing nitrogen as hetero atom
Abstract
The invention belongs to the field of metal surface treatment, and relates to an organic-inorganic chelating and compounding based steel substrate surface film forming solution, and preparation and application thereof. The raw material components and the mass percentage of 100 percent are as follows: 0.3-3% of film-forming agent, 0.05-0.5% of chelating agent, 0.1-5% of slow-release agent, 0.1-5% of neutralizing agent and the balance of water (industrial water). The invention has the advantages that the corrosion inhibitor is wrapped in the film forming liquid, the corrosion inhibitor is slowly released in a corrosion medium to achieve the effect of self-enhancement of the conversion film, the metal ions of the complex organic matter are added, and the defects of poor stability and incapability of self-enhancement of corrosion resistance of the organic conversion liquid are improved. The invention can not only improve the corrosion resistance of the film, but also reduce the production cost and simplify the production steps, and meanwhile, the treatment area of the treatment solution is large and the treatment solution is suitable for large-scale application.
Description
Technical Field
The invention belongs to the technical field of metal surface treatment, and mainly relates to a preparation method and application of a steel anti-corrosion film forming solution on a steel surface.
Background
The information in this background section is only for enhancement of understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art that is already known to a person of ordinary skill in the art.
In the metal surface pretreatment process, the phosphating process is the most commonly used process in the prior art, has been used for hundreds of years since the invention day by day, and has the advantages of stronger corrosion resistance, good paint film performance, wide workpiece treatment range and the like, so that the phosphating process is widely applied to various fields of metal surface pretreatment once the invention is invented. But with the higher and higher requirements of the society on environmental protection nowadays, the defects of the phosphating technology are undoubtedly exposed, the sediments are more after the phosphating treatment, the content of heavy metal ions is high, the waste liquid discharge pollution is serious, and the harm to the environment is increasingly serious.
Based on the background, the research and development of novel environment-friendly pretreatment film-forming solution is urgent in the metal surface pretreatment industry. A mainstream environment-friendly product in the current market is as follows: an organic phosphonic acid conversion film. The organic phosphating solution product has the advantages that: (1) the operation can be completed in low concentration and short time; (2) the conversion treatment liquid does not contain pollutants such as heavy metal nickel, nitrite, chromate and the like, and does not need surface adjustment, so that the burden of wastewater treatment can be reduced; (3) the solution is convenient to maintain, the solution is used at normal temperature, the pH value is controlled to be 4.5-5.5, the treatment time is 30-200s, and the film thickness is 20-120 nm; (4) the corrosion resistance of the conversion coating is equivalent to the adhesion of the coating film in phosphating treatment; (5) self-repairing performance exists in a corrosive environment; (6) it is suitable for the pre-coating treatment (dipping or spraying) of various metal materials (such as steel, aluminum, zinc, magnesium alloy and the like).
However, the inventor finds that: the organic phosphating solution products also have the defects of poor stability of the treatment solution, large side effect of other impurity ions in the treatment solution, necessity of adopting pure water, high requirements on the process flow, high requirements on the surface treatment of the treatable base material and the like.
Disclosure of Invention
In order to solve the problems, the invention provides an improved organic-inorganic film-forming solution which is based on corrosion resistance of the steel surface, has excellent adhesive force performance and self-reinforcing performance in a corrosive medium, can adopt industrial water to prepare a solution, can treat steel base materials with poor surface conditions, greatly reduces the cost and can realize large-scale industrial application.
In order to achieve the technical purpose, the invention adopts the following technical scheme:
in a first aspect of the invention, there is provided a steel substrate surface film-forming solution based on organic-inorganic chelate complex formulation, comprising: the corrosion inhibitor is encapsulated in the film forming agent to form a core-shell structure;
the film-forming agent is one or more of hydroxyethylidene diphosphate, aminotrimethylene phosphate, phytic acid and ethylene diamine tetraacetic acid, and the mass fraction of the film-forming agent is 0.3-3%;
The corrosion inhibitor is one or more of benzotriazole, sodium dodecyl benzene sulfonate, sodium hexametaphosphate and polyacrylate, and the mass fraction of the corrosion inhibitor is 0.1-5%.
The second aspect of the invention provides a preparation method of a steel substrate surface film-forming solution based on organic-inorganic chelate complex formulation, which comprises the following steps:
adding a film forming agent into water, uniformly mixing, adding a corrosion inhibitor, uniformly mixing, adding a neutralizing agent, and adjusting the pH value to 3.5-4.5 to obtain a mixed solution;
and heating the mixed solution to 90-100 ℃, adding a chelating agent after heating for 20-30 minutes, and stirring until the chelating agent is dissolved to obtain the water-soluble organic fertilizer.
The invention has the beneficial effects that:
(1) the research finds that: BTA is a micromolecular corrosion inhibitor, and phytic acid can be agglomerated to form colloidal particles with the particle size of hundred nanometers in the heating process. The phytic acid colloid has negative charges, the BTA has positive charges, and the BTA can be wrapped in the phytic acid colloid due to the attraction of the positive charges and the negative charges, so that the corrosion inhibitor is packaged in the film forming agent to form a core-shell structure, and the corrosion inhibitor can be released from the film forming agent in a corrosive environment, thereby achieving the effect of self-enhancement of corrosion prevention. Improves the defect of weak corrosion resistance compared with the traditional organic phosphating film. The protection time of the conversion film is greatly prolonged;
(2) The invention adopts the chelating agent to chelate with the film forming agent, thus greatly enhancing the corrosion resistance of the conversion film;
(3) the invention adopts industrial water as raw material, improves the defect that the traditional phosphating solution needs to use pure water, and greatly reduces the cost of raw material;
(4) the performance of the film on the surface of the steel is not obviously reduced compared with that of the traditional phosphating film, the steel can still meet the bare film test, the paint film test and the like, and all indexes can meet the international standard;
(5) the film-forming solution of the invention has no pollution, no heavy metal ions and no damage to the environment;
(6) the conversion film of the invention can maintain performance for a long time in a corrosive environment.
(7) The operation method is simple, low in cost, universal and easy for large-scale production.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate exemplary embodiments of the invention and together with the description serve to explain the invention and not to limit the invention.
FIG. 1 is a graph showing the soaking resistance results of example 1.
Detailed Description
It is to be understood that the following detailed description is exemplary and is intended to provide further explanation of the invention as claimed. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
Interpretation of terms
In the present application, "industrial water" is "laboratory tap water".
An organic-inorganic film forming solution for improving the surface of steel, which comprises the following raw material components in percentage by mass 100 percent: 0.3-3% of film-forming agent, 0.05-0.5% of chelating agent, 0.1-5% of slow-release agent, 0.1-5% of neutralizing agent and the balance of water.
Compared with the phosphine film-forming solution researched by numerous scholars, the film-forming solution disclosed by the invention has the advantages that the starting point is to improve the corrosion resistance time of a conversion film, so that the service life of metal is prolonged, the dilemma that the corrosion resistance time of the existing phosphine film-forming solution is short is solved, and the requirements of the new national era on environmental protection are met.
The preferable organic-inorganic film-forming solution for improving the surface of the steel consists of a film-forming agent, a corrosion inhibitor and a chelating agent
According to the invention, the preferable film forming agent comprises one or more of hydroxyethylidene diphosphate, aminotrimethylene phosphate, phytic acid and ethylene diamine tetraacetic acid. More preferably, the film-forming agent is phytic acid or aminotrimethylene phosphonic acid.
Compared with the organic-inorganic complex system researched by the prior paper, the invention researches a wider system such as hydroxyethylidene diphosphate, aminotrimethylene phosphate, phytic acid and ethylene diamine tetraacetic acid, can adopt industrial water, does not need pure water, reduces the cost, and can meet the requirements of various raw materials and treatment liquid on industrial application.
According to the invention, the corrosion inhibitor preferably comprises one or more of benzotriazole, sodium dodecyl benzene sulfonate, sodium hexametaphosphate and polyacrylate; more preferably, the corrosion inhibitor is benzotriazole to improve the rust prevention time of the metal.
Preferred chelating agents according to the invention include one or more of zinc nitrate, manganese nitrate, calcium nitrate, cerium nitrate. More preferably the chelating agent is zinc nitrate.
According to the invention, the neutralizing agent preferably comprises one or more of sodium hydroxide, sodium carbonate, potassium hydroxide and ammonia water. More preferably, the neutralizing agent is sodium hydroxide to adjust the pH of the film-forming solution and improve the film-forming property.
The preparation method of the improved organic-inorganic chelating film-forming agent comprises the following steps:
(1) gradually adding the film forming agent into the industrial water, and stirring;
(2) adding the corrosion inhibitor, stirring and dissolving;
(3) adding a neutralizing agent, and adjusting the pH to about 4.0;
(4) heating the mixed solution to 90 ℃ for 20 minutes;
(5) adding a chelating agent into the solution in a heating state, and stirring to dissolve.
The application process of the improved organic-inorganic film forming agent in the steel surface treatment comprises the following steps:
(1) degreasing the surface of steel to be treated, and washing the surface of the steel with tap water after oil stains on the surface of the steel are completely removed;
(2) Soaking the steel in the film forming liquid for 1-5 min;
(3) and then taking out, washing with water, and airing or drying in a natural environment to obtain a layer of corrosion-resistant film on the surface, wherein the film is light blue.
The present invention is described in further detail below with reference to specific examples, which are intended to be illustrative of the invention and not limiting.
In the following examples, the modified organic-inorganic chelating film formers were prepared as follows:
(1) gradually adding the film forming agent into the industrial water, and stirring;
(2) adding the corrosion inhibitor, stirring and dissolving;
(3) adding a neutralizing agent, and adjusting the pH to about 4.0;
(4) heating the mixed solution to 90 ℃ for 20 minutes;
(5) adding a chelating agent into the solution in a heating state, and stirring to dissolve.
Example 1
An organic-inorganic complex film-forming solution for improving the surface of steel, which comprises the following raw materials in mass: 1% of phytic acid, 0.2% of benzotriazole, 0.15% of zinc nitrate hexahydrate, 0.5% of sodium hydroxide and the balance of water.
Sequentially adding solvents according to the method described above to prepare a treatment solution, and adjusting the pH value of the treatment solution to 4.0 by using a neutralizing agent sodium hydroxide; then treating the surface of steel by using the prepared improved organic phosphonic acid film forming solution, wherein the steps are as follows;
(1) Degreasing, washing and then washing the steel surface;
(2) placing the steel plate treated in the step (1) in the film-forming solution with the pH value of 4.0 adjusted for 3 minutes at 90 ℃;
(3) and (3) washing the steel surface treated in the step (2) with water, and naturally airing or drying to finish the film forming process. The panels were then subjected to a copper sulfate drop test and an epoxy dry powder spray salt spray test, respectively.
Example 2
An organic-inorganic chelating film-forming solution for improving the surface of steel, which comprises the following raw materials in percentage by mass: 1% of phytic acid, 0.2% of benzotriazole, 0.18% of zinc nitrate hexahydrate, 0.5% of sodium hydroxide and the balance of water.
Sequentially adding solvents according to the method described above to prepare a treatment solution, and adjusting the pH value of the treatment solution to 4.0 by using a neutralizing agent sodium hydroxide; then the prepared improved organic-inorganic chelating film-forming solution is used for treating the surface of the steel, and the steps are as follows:
(1) degreasing, washing and then washing the steel surface;
(2) placing the steel plate treated in the step (1) in the film-forming solution with the pH value of 4.0 adjusted at 90 ℃ for 3 minutes;
(3) and (3) washing the steel surface treated in the step (2) with water, and naturally airing or drying to finish the film forming process. The panels were then subjected to a copper sulfate drop test and an epoxy dry powder spray salt spray test, respectively.
Example 3
An organic-inorganic chelating film-forming solution for improving the surface of steel, which comprises the following raw materials in percentage by mass: 1% of phytic acid, 0.2% of benzotriazole, 0.18% of zinc nitrate hexahydrate, 0.5% of sodium hydroxide and the balance of water.
Sequentially adding solvents according to the method described above to prepare a treatment solution, and adjusting the pH value of the treatment solution to 4.0 by using a neutralizing agent sodium hydroxide; then the prepared improved organic phosphonic acid film forming solution is used for processing the surface of steel, and the steps are as follows:
(1) degreasing, washing and then washing the steel surface;
(2) placing the steel plate treated in the step (1) in the film-forming solution with the pH value of 4.0 adjusted for 3 minutes at 90 ℃;
(3) and (3) washing the steel surface treated in the step (2) with water, and naturally airing or drying to finish the film forming process. The panels were then subjected to a copper sulfate drop test and an epoxy dry powder spray salt spray test, respectively.
The experimental results are as follows:
1) appearance of the product
2) Copper sulfate point and sodium chloride immersion experiment
Referring to QB/T3824-1999, 40mL of 0.5mol/L copper sulfate (CuSO) 4 ·5H 2 O) solution, 20mL of 10% sodium chloride (NaCl) solution and 0.8mL of 0.1mol/L hydrochloric acid (HCl) are mixed to prepare a required solution, and the time is counted from the time when the copper sulfate is dripped to the surface of the sample until the rose color spots appear on the surface of the sample, namely the copper sulfate corrosion resistant time of the sample.
The results of the examples demonstrate that: the density and the corrosion resistance of the improved organic-inorganic chelating conversion film prepared by the invention are greatly improved.
3) Electrochemical testing
The polarization curve measurement was performed using the electrochemical workstation of CHI660E, with the sample as the working electrode, the saturated calomel electrode as the reference electrode, and the platinum electrode as the auxiliary electrode. Taking the preparation surface as a working surface, and packaging and insulating the rest by 704 silica gel; room temperature; the solution was 3.5 wt.% NaCl in deionized water.
Impedance curve:
open circuit time: 1200s
Scanning frequency: 1000kHz-0.1mHz
As can be seen from FIG. 1, the impedance value of the improved organic-inorganic chelating film is far higher than that of the blank bare iron, and the corrosion resistance is obviously improved.
Paint film test results
The paint film test result shows that: the improved organic-inorganic chelating conversion film has excellent performance and large-scale application potential.
It should be noted that the above-mentioned embodiments are only preferred embodiments of the present invention, and the present invention is not limited thereto, and although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that modifications and equivalents can be made in the technical solutions described in the foregoing embodiments, or equivalents thereof. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A steel substrate surface film-forming solution based on organic-inorganic chelate complex formulation is characterized by comprising: the corrosion inhibitor is encapsulated in the film forming agent to form a core-shell structure;
the film-forming agent is one or more of hydroxyethylidene diphosphate, aminotrimethylene phosphate, phytic acid and ethylene diamine tetraacetic acid, and the mass fraction of the film-forming agent is 0.3-3%;
the corrosion inhibitor is one or more of benzotriazole, sodium dodecyl benzene sulfonate, sodium hexametaphosphate and polyacrylate, and the mass fraction of the corrosion inhibitor is 0.1-5%.
2. The organic-inorganic chelate complex-based steel substrate surface deposition solution according to claim 1, wherein the deposition solution further comprises: a neutralizing agent and a chelating agent.
3. The steel substrate surface deposition solution based on organic-inorganic chelate complex formulation according to claim 2, wherein the neutralizing agent is one or more of sodium hydroxide, sodium carbonate, potassium hydroxide and ammonia water.
4. The organic-inorganic chelate complex-based steel substrate surface deposition solution according to claim 2, wherein the mass fraction of the neutralizing agent is 0.1-5%.
5. The steel substrate surface deposition solution based on organic-inorganic chelate complex formulation according to claim 2, wherein the chelating agent is one or more of zinc nitrate, manganese nitrate, calcium nitrate and cerium nitrate.
6. The organic-inorganic chelate complex-based steel substrate surface deposition solution according to claim 2, wherein the mass fraction of the chelating agent is 0.05-0.5%.
7. The organic-inorganic chelate complex-based steel substrate surface deposition solution according to claim 1, wherein the water is industrial water.
8. The organic-inorganic chelate complex-based steel substrate surface deposition solution according to claim 1, wherein the specific steps of the deposition solution for metal surface treatment are as follows:
degreasing the surface of steel to be treated, and washing;
placing the treated steel in the film forming solution to be soaked for 1-5 minutes; then taking out, washing with water, and drying to obtain a layer of corrosion-resistant film.
9. A preparation method of a steel substrate surface film-forming solution based on organic-inorganic chelate complex formulation is characterized by comprising the following steps:
adding a film forming agent into water, uniformly mixing, adding a corrosion inhibitor, uniformly mixing, adding a neutralizing agent, and adjusting the pH value to 3.5-4.5 to obtain a mixed solution;
and heating the mixed solution to 90-100 ℃, adding a chelating agent after heating for 20-30 minutes, and stirring until the chelating agent is dissolved to obtain the water-soluble organic fertilizer.
10. The method for preparing the surface film-forming solution based on the organic-inorganic chelate complex formulation steel substrate according to claim 9, wherein the pH is adjusted to 4.0.
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