CN115110074A - Nano zirconate conversion coating process for rusted plate - Google Patents
Nano zirconate conversion coating process for rusted plate Download PDFInfo
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- CN115110074A CN115110074A CN202210833971.9A CN202210833971A CN115110074A CN 115110074 A CN115110074 A CN 115110074A CN 202210833971 A CN202210833971 A CN 202210833971A CN 115110074 A CN115110074 A CN 115110074A
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- 238000000034 method Methods 0.000 title claims abstract description 70
- 238000007739 conversion coating Methods 0.000 title claims abstract description 22
- 238000004017 vitrification Methods 0.000 claims abstract description 108
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims abstract description 88
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 69
- 239000002253 acid Substances 0.000 claims abstract description 50
- 238000005260 corrosion Methods 0.000 claims abstract description 43
- 230000007797 corrosion Effects 0.000 claims abstract description 42
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 38
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 38
- 239000010703 silicon Substances 0.000 claims abstract description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 38
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 34
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims abstract description 34
- 238000005238 degreasing Methods 0.000 claims abstract description 28
- 229920005989 resin Polymers 0.000 claims abstract description 26
- 239000011347 resin Substances 0.000 claims abstract description 26
- 230000005764 inhibitory process Effects 0.000 claims abstract description 25
- 229920005749 polyurethane resin Polymers 0.000 claims abstract description 19
- 239000002994 raw material Substances 0.000 claims abstract description 19
- 239000007788 liquid Substances 0.000 claims abstract description 16
- 238000002791 soaking Methods 0.000 claims abstract description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 21
- 230000000149 penetrating effect Effects 0.000 claims description 16
- 238000005406 washing Methods 0.000 claims description 16
- 239000000919 ceramic Substances 0.000 claims description 14
- 239000002270 dispersing agent Substances 0.000 claims description 14
- 239000004094 surface-active agent Substances 0.000 claims description 13
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 12
- 239000000080 wetting agent Substances 0.000 claims description 11
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- 238000005516 engineering process Methods 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 239000011248 coating agent Substances 0.000 claims description 6
- 238000000576 coating method Methods 0.000 claims description 6
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- 238000006243 chemical reaction Methods 0.000 abstract description 12
- 239000000463 material Substances 0.000 abstract description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 34
- 229910052742 iron Inorganic materials 0.000 description 17
- 239000002585 base Substances 0.000 description 13
- 230000000694 effects Effects 0.000 description 7
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- 239000002245 particle Substances 0.000 description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
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- 239000003513 alkali Substances 0.000 description 2
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- 239000000084 colloidal system Substances 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
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- 239000012752 auxiliary agent Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000000875 corresponding effect Effects 0.000 description 1
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- 238000009396 hybridization Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
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- 239000002893 slag Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- 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
- C23C22/78—Pretreatment of the material to be coated
-
- 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
- C23C22/34—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 fluorides or complex fluorides
-
- 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
- C23G1/04—Cleaning or pickling metallic material with solutions or molten salts with acid solutions using inhibitors
- C23G1/06—Cleaning or pickling metallic material with solutions or molten salts with acid solutions using inhibitors organic inhibitors
- C23G1/061—Cleaning or pickling metallic material with solutions or molten salts with acid solutions using inhibitors organic inhibitors nitrogen-containing compounds
-
- 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
-
- 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
- C23G1/086—Iron or steel solutions containing HF
-
- 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
- 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
- C23G1/14—Cleaning or pickling metallic material with solutions or molten salts with alkaline solutions
- C23G1/19—Iron or steel
Abstract
The invention discloses a nano zirconate conversion coating process for a rusted plate, and relates to the technical field of vitrification processes. The operation flow of the nano zirconate conversion film process sequentially comprises degreasing treatment, derusting treatment, film removing treatment and vitrification treatment; derusting treatment: immersing the degreased rusted plate into a rust remover, forming a corrosion inhibition film on the surface of a non-rusted area of the rusted plate, and forming a corrosion inhibition film on the surface of a rusted area after the rust remover dissolves rust in the rusted area of the rusted plate; the raw materials of the rust remover comprise acid and organic silicon modified polyurethane resin, and the vitrification treatment comprises the following steps: soaking the rusted plate with a clean film removed in a vitrification liquid to form a vitrification film on the surface of the plate; the vitrification liquid consists of vitrification agent and water, and the vitrification agent has material including fluorozirconic acid, zirconium dioxide sol and organosilicon resin. The nano zirconate conversion coating process for the rusted plate can generate a vitrified film on the surface of the rusted plate, and successfully applies the vitrified film to the rusted plate.
Description
Technical Field
The invention relates to the technical field of vitrification processes, in particular to a process for preparing a nano zirconate conversion coating for a rusted plate.
Background
In the hardware coating industry, before the metal surface is sprayed with paint, the metal coating pretreatment is generally required to improve the adhesive force and corrosion resistance of a coating film on the surface of a metal material, at present, the coating pretreatment process of a metal plate mainly adopts a phosphating process and a vitrification process (also called as a nano zirconate conversion film process), the cost of the phosphating process is low, but a large amount of phosphating slag, waste acid, oxynitride and heavy metal ions are generated in the phosphating process, and the serious influence is caused on a human body and the environment; although the production cost of the vitrification process is higher than that of the phosphating process, the vitrification agent used in the vitrification process does not contain heavy metal, phosphate and any organic volatile component, and almost no sediment is generated in the film forming reaction process, so that the vitrification process is environment-friendly and does not harm human bodies, and therefore, the existing vitrification process gradually replaces the phosphating process.
Although the vitrification process is environment-friendly and does not harm human bodies, the vitrification process has difficulty in the application of cold-rolled sheets, particularly difficult to realize vitrification in rusty sheets (referred to as cold-rolled sheets) made of iron materials, because rust removal is needed before the rust plate is subjected to the process, the iron on the surface of the rust plate is dissolved after rust removal, impurities are enriched on the surface, and the impurities are carbon, silicon, manganese, copper and other elements, these elements are not dissolved in the range of the optimal film-forming pH value (pH is about 5) for vitrification, and cannot cause the pH value to rise in a micro area enriched with impurities, so that the fluozirconic acid cannot be hydrolyzed to form zirconium dioxide to be deposited on the plate, and a compact zirconium dioxide film (namely a conversion film) cannot be formed, so that the existing common vitrification process cannot be applied to rusted plates, and the existing pretreatment of the rusted plates mainly adopts a phosphorization process.
Disclosure of Invention
Aiming at the problems brought forward by the background technology, the invention aims to provide a nano zirconate conversion film process for a rusted plate, which can generate a vitrification film on the surface of the rusted plate, successfully apply the vitrification process to the rusted plate and solve the problem that the existing vitrification process is difficult to form a zirconium dioxide film on a rusted plate.
In order to achieve the purpose, the invention adopts the following technical scheme:
a nano zirconate conversion coating process for a rusted plate comprises the operation processes of degreasing treatment, derusting treatment, film stripping treatment and vitrification treatment in sequence;
the operation method of the rust removal treatment comprises the steps of immersing the degreased rusty plate into a rust remover, forming a corrosion inhibition film on the surface of a non-rusty area of the rusty plate, and forming a corrosion inhibition film on the surface of a rusty area after the rust remover dissolves iron rust in the rusty area of the rusty plate;
the raw materials of the rust remover comprise acid and organic silicon modified polyurethane resin, wherein the acid is any one or combination of more of hydrochloric acid, hydrofluoric acid and citric acid;
the operation method of the ceramic treatment comprises the steps of soaking a rusty plate with a clean film removing function in a ceramic solution to form a ceramic film on the surface of the plate; the vitrification liquid consists of a vitrification agent and water, and the vitrification agent comprises fluozirconic acid, zirconium dioxide sol and organic silicon resin.
Further, the vitrification agent comprises, by mass, 0.5-1.5% of fluorozirconic acid, 1-2% of zirconium dioxide sol, 5-7% of organic silicon resin and the balance of water;
the mass concentration of the fluozirconic acid is 45 percent.
Further, the preparation method of the vitrification agent comprises the following steps: according to the formula, fluozirconic acid is added into water, zirconium dioxide sol is added after the mixture is uniformly stirred, after the mixture reacts for 5 to 30 minutes, organic silicon resin is added under the stirring state, the mixture reacts for 10 to 30 minutes, and the balance of water is supplemented to obtain the vitrification agent.
Further, the mass concentration of the vitrification agent in the vitrification liquid is 2%.
Furthermore, the raw materials of the rust remover comprise, by mass, 0.3-20% of acid, 0.5-1% of organosilicon modified polyurethane resin and the balance of water.
Further, the operation method of the film removing treatment is to soak the rust plate after rust removal in a film removing agent, or to spray the film removing agent on the surface of the rust plate after rust removal.
Further, the film stripping agent comprises, by mass, 5-10% of a strong base, 1-5% of a surfactant, 0.5-2% of a penetrating agent, 0.5-2% of a wetting agent, 2-5% of a dispersing agent, and the balance of water.
Further, the strong base is any one or combination of sodium hydroxide and potassium hydroxide;
the surfactant is selected from surfactants with the model number of S603G of Shenzhen Henshengxi technology Limited;
the penetrating agent is penetrating agent OEP-98, and the wetting agent is penetrating agent Q-12;
the dispersant is selected from the dispersant with model number FS-01 of Shenzhen Henshengxian science and technology Limited.
Further, after the degreasing treatment, the rust removal treatment, the film removal treatment and the vitrification treatment are completed, washing with water is performed for a plurality of times, respectively.
The technical scheme has the following beneficial effects:
1. the technical scheme is used for a nano zirconate conversion film process of a rusted plate, a rust-free area is well protected by using organic silicon modified polyurethane resin during rust removal treatment, impurity enrichment caused by excessive dissolution of iron is prevented, and meanwhile, in vitrification treatment, a rusted part is protected by using the characteristic that organic silicon resin in a vitrification agent is easy to adsorb to form a film, so that a vitrification film is generated on the surface of the rusted plate.
2. The vitrification agent comprises fluozirconic acid, zirconium dioxide sol and organic silicon resin, wherein in the vitrification treatment process, the fluozirconic acid is decomposed to form zirconium dioxide deposited on the surface of a rusted plate, and meanwhile, the zirconium dioxide colloid can promote effective zirconium elements in the vitrification agent to strengthen the compactness of a formed film; in addition, the organic silicon resin is added, so that gaps among the zirconium dioxide deposited particles can be filled, and the organic silicon resin can be directly adsorbed in a substrate area where the zirconium dioxide deposited film cannot be formed due to corrosion, so that the corrosion resistance of the bare film of the integral film layer is enhanced, the rust return before spraying is prevented, and the vitrification treatment of a rusted iron piece is further completed.
Drawings
FIG. 1 is a graph showing the effect of degreasing the nano-zirconate conversion coating process for rusting a plate according to example 1;
FIG. 2 is a graph showing the effect of the nano-zirconate conversion coating process of example 1 on the rust removal treatment;
FIG. 3 is a graph of the effects of the nano-zirconate conversion coating process of example 1 after stripping;
FIG. 4 is a graph showing the effect of the vitrification process of the nano-zirconate conversion coating process of example 1;
Detailed Description
The technical solution of the present invention will be further described with reference to the following embodiments.
A nano zirconate conversion coating process for a rusted plate comprises the operation processes of degreasing treatment, derusting treatment, film stripping treatment and vitrification treatment in sequence;
the operation method of the rust removal treatment comprises the steps of immersing the degreased rusty plate into a rust remover, forming a corrosion inhibition film on the surface of a non-rusty area of the rusty plate, and forming a corrosion inhibition film on the surface of a rusty area after the rust remover dissolves rust in the rusty area of the rusty plate;
the raw materials of the rust remover comprise acid and organic silicon modified polyurethane resin, wherein the acid is any one or combination of more of hydrochloric acid, hydrofluoric acid and citric acid;
the operation method of the ceramic treatment comprises the steps of soaking a rusty plate with a clean film removing function in a ceramic solution to form a ceramic film on the surface of the plate; the vitrification liquid consists of a vitrification agent and water, and the vitrification agent comprises fluozirconic acid, zirconium dioxide sol and organic silicon resin.
The existing common vitrification process can not be applied to rusty plates, and the prior pretreatment of the rusty plates mainly adopts a phosphorization process.
It is worth explaining that the technical scheme is used for the nano zirconate conversion film process of the rusted plate, when the rust removing process is carried out, an organic silicon modified polyurethane resin is utilized to protect a rust-free area, so that impurity enrichment caused by excessive dissolution of iron is prevented, meanwhile, in the vitrification process, the organic silicon resin in a vitrification agent is utilized to protect a rusted part by utilizing the characteristic of extremely easy adsorption film forming, so that a vitrification film is generated on the surface of the rusted plate, and the vitrification film is an inorganic-organic hybridization film and has better naked film corrosion resistance than a common vitrification film, so that the rusted plate is ensured not to have a rust return state before being sprayed with the rust coating.
Specifically, the nano zirconate conversion coating process for the rusted plate in the technical scheme is firstly subjected to degreasing treatment, so that degreasing can be guaranteed to be clean, and the subsequent process can be conveniently implemented; the rust removal treatment can remove rust efficiently under the condition of not damaging or extremely damaging a rust-free area; the corrosion inhibition film generated on the surface of the base material in the rust removal treatment can be efficiently removed through the film removing treatment, so that the vitrification is facilitated; and (3) performing vitrification treatment, namely forming a vitrification film with high corrosion resistance on the surface of the base material after rust removal, fully washing the workpiece after vitrification treatment, and drying to spray powder paint or spray paint.
The rust remover is used for carrying out rust removal treatment, because acid and the organic silicon modified polyurethane resin are contained in the rust remover, the organic silicon modified polyurethane resin can be adsorbed on the surface of an iron material, and the acid can corrode rust; in a rusty area of the rusty plate, the organosilicon modified polyurethane resin cannot be adsorbed with iron rust, the iron rust is directly contacted with acid to be subjected to a dissolution reaction, the iron rust is removed, after the iron rust is completely removed, and when the iron below the iron rust is exposed, the organosilicon modified polyurethane resin in the rust remover can be adsorbed, so that a corrosion inhibition film is quickly formed, further corrosion of the acid is isolated, the phenomenon that the iron is excessively dissolved to cause impurity enrichment, so that a compact zirconium dioxide film cannot be formed on the surface of the base material is prevented, a bright base material surface is formed after rust removal treatment, and the later-stage vitrification can be favorably carried out.
Further, the raw materials of the vitrification agent in the technical scheme comprise fluozirconic acid, zirconium dioxide sol and organic silicon resin, in the vitrification treatment process, the fluozirconic acid is decomposed to form zirconium dioxide deposited on the surface of a rusted plate, and meanwhile, the effective zirconium element in the vitrification agent can be improved through zirconium dioxide colloid, so that the compactness of a formed film is enhanced; in addition, the organic silicon resin is added, so that gaps among the zirconium dioxide deposited particles can be filled, and the organic silicon resin can be directly adsorbed in a substrate area where the zirconium dioxide deposited film cannot be formed due to corrosion, so that the corrosion resistance of the bare film of the integral film layer is enhanced, the rust return before spraying is prevented, and the vitrification treatment of a rusted iron piece is further completed.
Specifically, the degreasing treatment in the technical scheme can be performed by adopting the conventional degreasing product, and only the degreasing requirement is met, so that the subsequent process is convenient to perform.
Further, the raw materials of the vitrification agent comprise, by mass, 0.5-1.5% of fluozirconic acid, 1-2% of zirconium dioxide sol, 5-7% of organic silicon resin and the balance of water;
the mass concentration of the fluozirconic acid is 45 percent.
It is worth to be noted that, in the technical scheme, the mass percentage of the fluozirconic acid is 0.5-1.5%, the range can ensure that the vitrification liquid is in the required fluozirconic acid content within the optimal film forming pH range, if the fluozirconic acid content is too high or too low, the pH value of the vitrification liquid is lower or higher, and exceeds the optimal pH range (4.4-5.4) for film forming of the vitrification film, the vitrification film is difficult to form; according to the technical scheme, 1-2% of zirconium dioxide sol is added into a vitrification agent, effective zirconium element in the vitrification agent can be improved, the compactness of a formed film is strengthened, the content of the zirconium dioxide sol is set to be 1-2%, the optimal pH value of the formed film can be balanced, and if the content of the zirconium dioxide sol is too high or too low, the pH value is not in the optimal film forming range. According to the technical scheme, 5-7% of organic silicon resin is added into a vitrification agent, the organic silicon resin is organic film-forming resin, can be filled in gaps among zirconium dioxide deposited particles and can be directly adsorbed in a substrate area where a zirconium dioxide deposited film (namely a vitrified film) cannot be formed due to corrosion, the corrosion resistance of a naked film of an integral film layer can be enhanced, rust returning before spraying is prevented, and further the vitrification treatment of a corroded iron piece is completed, and if the content of the organic silicon resin is too low, the gaps among the zirconium dioxide particles cannot be effectively filled; if the content of the organic silicon resin is too high, the film forming advantage is greater than the deposition of zirconium dioxide, so that the thickness of a vitrified film is reduced, the corrosion resistance is reduced to a certain extent, and the cost is higher.
Further, the preparation method of the vitrification agent is as follows: according to the formula, fluorozirconic acid is added into water, zirconium dioxide sol is added after the mixture is uniformly stirred, after the mixture reacts for 5 to 30 minutes, organic silicon resin is added under the stirring state, the reaction lasts for 10 to 30 minutes, and the balance of water is supplemented to obtain the vitrification agent.
Further, the mass concentration of the vitrification agent in the vitrification liquid is 2%.
Further, the raw materials of the rust remover comprise, by mass, 0.3-20% of acid, 0.5-1% of organosilicon modified polyurethane resin and the balance of water.
Specifically, when the content of the acid in the rust remover needs to be selected according to the severe condition of a rusted plate, if the content of the acid in the rust remover exceeds 20%, the corrosion effect of the acid is strong, excessive corrosion is easy to occur, and if the content of the acid is less than 0.3%, rust is difficult to remove. When the content of the organic silicon modified polyurethane resin is 0.5-1%, a corrosion inhibition film can be well formed, and if the content of the organic silicon modified polyurethane resin is lower than 0.5%, the formed corrosion inhibition film is thin and is difficult to protect a rusted plate.
It is worth to say that sulfuric acid cannot be selected as the acid of the rust remover, because the sulfuric acid can reduce the adsorption strength of the organosilicon modified polyurethane resin in the rust remover on the surface of the base material, and weaken the over-corrosion protection of the base material.
Further, the operation method of the film removing treatment is to soak the rusty plate after rust removal in a film removing agent, or to spray a film removing agent on the surface of the rusty plate after rust removal.
And dissolving the corrosion inhibition film in the rust removal treatment by film removal treatment to obtain a clean substrate surface to be treated, so that the ceramic treatment is convenient, and the ceramic film is formed on the surface of the rusted plate.
Further, the film stripping agent comprises, by mass, 5-10% of a strong base, 1-5% of a surfactant, 0.5-2% of a penetrating agent, 0.5-2% of a wetting agent, 2-5% of a dispersing agent, and the balance of water.
The effect is as follows: it is worth explaining that the film removing agent of the technical scheme has a large destructive effect on a corrosion inhibition film, and can dissolve the corrosion inhibition film, so that a clean substrate surface to be treated is obtained, and the ceramic treatment at the later stage is facilitated.
By further illustration, the strong base is any one or a combination of two of sodium hydroxide and potassium hydroxide;
the surfactant is selected from surfactant with model number S603G of Shenzhen Hengyuxiang technology Limited;
the penetrating agent is a penetrating agent OEP-98, and the wetting agent is Q-12;
the OEP-98 is a general brand; q-12 was from Chuangen chemical technology, Inc., Guangzhou.
The dispersant is selected from a dispersant with model number FS-01 of Shenzhen Henshengxian science and technology Limited.
It is worth pointing out that the strong base in the stripping agent of the technical scheme is any one or the combination of two of sodium hydroxide and potassium hydroxide, the sodium hydroxide and the potassium hydroxide can better destroy the adsorption effect of the special groups of the organic silicon modified polyurethane on the base material under the synergistic action of various active agents (wetting agent, penetrating agent and dispersing agent), and the protective resin is eluted from the base material, so that the corrosion inhibition film is destroyed, thereby being beneficial to the subsequent ceramic treatment, and meanwhile, the two strong bases of the sodium hydroxide and the potassium hydroxide are difficult to react with iron at normal temperature, therefore, the corrosion to the plate material is avoided.
Specifically, the surfactant, the penetrating agent, the wetting agent and the dispersing agent used in the technical scheme have strong alkali resistance, so that the auxiliary agents can still exert corresponding effects in strong alkali.
Further, after the degreasing treatment, the rust removal treatment, the film removal treatment, and the vitrification treatment are completed, it is necessary to perform water washing a plurality of times, respectively.
Specifically, after each step is finished, the next step can be better performed by performing multiple water washes to remove impurities on the surface of the processed plate.
The technical scheme of the invention is further illustrated by combining specific examples and comparative examples.
Example 1
The operation flow of the nano zirconate conversion film process for the corrosion plate sequentially comprises degreasing treatment, derusting treatment, film removing treatment and vitrification treatment;
degreasing treatment: degreasing by using the conventional degreasing product, and washing for 2 times after degreasing is finished;
derusting treatment: immersing the degreased rusty plate into a rust remover, forming a corrosion inhibition film on the surface of a non-rusty area of the rusty plate, dissolving rust in a rusty area of the rusty plate by using the rust remover, forming the corrosion inhibition film on the surface of the rusty area, and washing for 2 times after rust removal; the raw materials of the rust remover consist of 10 percent of acid (hydrofluoric acid), 0.5 percent of organic silicon modified polyurethane resin and the balance of water;
film removing treatment: soaking the rust plate subjected to rust removal in a film removing agent to remove a corrosion inhibition film, and washing for 2 times after the film removing treatment is finished; the raw materials of the film removing agent comprise 7 percent of sodium hydroxide, 3 percent of surfactant (Hengfixianxiang S603G), 0.5 percent of penetrating agent (OEP-98), 0.5 percent of wetting agent (Q-12), 5 percent of dispersing agent (Hengfixianxiang FS-01) and the balance of water;
carrying out vitrification treatment: soaking the rusted plate with a clean film removed in a vitrification liquid to form a vitrification film on the surface of the plate, and washing the plate with water for 2 times after vitrification is finished; the vitrification liquid consists of 2 percent of vitrification agent and water, and the raw materials of the vitrification agent consist of 1 percent of fluozirconic acid, 2 percent of zirconium dioxide sol, 5 percent of organic silicon resin and the balance of water; wherein the mass concentration of the fluozirconic acid is 45 percent.
Example 2
The operation flow of the nano zirconate conversion film process for the corrosion plate sequentially comprises degreasing treatment, derusting treatment, film removing treatment and vitrification treatment;
degreasing treatment: degreasing by using the conventional degreasing product, and washing for 2 times after degreasing;
derusting treatment: immersing the degreased rusted plate into a rust remover, forming a corrosion inhibition film on the surface of a non-rusted area of the rusted plate, dissolving rust in a rusted area of the rusted plate by the rust remover, forming the corrosion inhibition film on the surface of the rusted area, and washing for 2 times after rust removal is finished; the raw materials of the rust remover consist of 0.3 percent of acid (citric acid), 1 percent of organic silicon modified polyurethane resin and the balance of water;
film removing treatment: soaking the rust plate subjected to rust removal in a film removing agent to remove a corrosion inhibition film, and washing for 2 times after the film removing treatment is finished; the raw materials of the film removing agent comprise 5% of sodium hydroxide, 1% of surfactant (Hengfixianxiang S603G), 1% of penetrating agent (OEP-98), 1% of wetting agent (Q-12), 2% of dispersing agent (Hengfixianxiang FS-01) and the balance of water;
carrying out ceramic treatment: soaking the rusted plate with a clean film removed in a vitrification liquid to form a vitrification film on the surface of the plate, and washing the plate with water for 2 times after vitrification is finished; the vitrification liquid consists of 2 percent of vitrification agent and water, and the raw materials of the vitrification agent consist of 1.5 percent of fluozirconic acid, 1 percent of zirconium dioxide sol, 5 percent of organic silicon resin and the balance of water; wherein the mass concentration of the fluozirconic acid is 45 percent.
Example 3
The operation flow of the nano zirconate conversion film process for the corrosion plate sequentially comprises degreasing treatment, derusting treatment, film removing treatment and vitrification treatment;
degreasing treatment: degreasing by using the conventional degreasing product, and washing for 2 times after degreasing is finished;
derusting treatment: immersing the degreased rusted plate into a rust remover, forming a corrosion inhibition film on the surface of a non-rusted area of the rusted plate, dissolving rust in a rusted area of the rusted plate by the rust remover, forming the corrosion inhibition film on the surface of the rusted area, and washing for 2 times after rust removal is finished; the raw materials of the rust remover consist of 20 percent of acid (hydrochloric acid), 0.5 percent of organic silicon modified polyurethane resin and the balance of water;
film removing treatment: soaking the rust plate subjected to rust removal in a film removing agent to remove a corrosion inhibition film, and washing for 2 times after the film removing treatment is finished; the raw materials of the film removing agent comprise 10% of potassium hydroxide, 5% of surfactant (Hengfixianxiang S603G), 2% of penetrating agent (OEP-98), 2% of wetting agent (Q-12), 5% of dispersing agent (Hengfixianxiang FS-01) and the balance of water;
carrying out vitrification treatment: soaking the rusted plate with a clean film removed in a vitrification liquid to form a vitrification film on the surface of the plate, and washing the plate with water for 2 times after vitrification is finished; the vitrification liquid consists of 2 percent of vitrification agent and water, and the vitrification agent is prepared from 0.5 percent of fluozirconic acid, 2 percent of zirconium dioxide sol, 7 percent of organic silicon resin and the balance of water; wherein the mass concentration of the fluozirconic acid is 45 percent.
Specifically, fig. 1-4 are operation process diagrams of the nano zirconate conversion coating process for rusting a plate in example 1, and it can be seen from fig. 2 that the rust remover of the present embodiment can effectively remove rust without excessively corroding the plate, and it can be seen from fig. 4 that a vitrified film can be formed on the surface of the corroded plate after the vitrification.
The technical principle of the present invention is described above in connection with specific embodiments. The description is made for the purpose of illustrating the principles of the invention and should not be construed in any way as limiting the scope of the invention. Based on the explanations herein, those skilled in the art will be able to conceive of other embodiments of the present invention without inventive effort, which would fall within the scope of the present invention.
Claims (9)
1. The nano zirconate conversion coating process for the rusted plate is characterized by sequentially comprising the steps of degreasing treatment, derusting treatment, coating stripping treatment and vitrification treatment;
the operation method of the rust removal treatment comprises the steps of immersing the degreased rusty plate into a rust remover, forming a corrosion inhibition film on the surface of a non-rusty area of the rusty plate, and forming a corrosion inhibition film on the surface of a rusty area after the rust remover dissolves rust in the rusty area of the rusty plate;
the raw materials of the rust remover comprise acid and organic silicon modified polyurethane resin, wherein the acid is any one or combination of more of hydrochloric acid, hydrofluoric acid and citric acid;
the operation method of the ceramic treatment comprises the steps of soaking a rusty plate with a clean film removing function in a ceramic solution to form a ceramic film on the surface of the plate; the vitrification liquid consists of a vitrification agent and water, and the vitrification agent comprises fluozirconic acid, zirconium dioxide sol and organic silicon resin.
2. The nano zirconate conversion coating process for the rusted plate according to claim 1, wherein the raw materials of the vitrification agent consist of, by mass, 0.5-1.5% of fluorozirconic acid, 1-2% of zirconium dioxide sol, 5-7% of silicone resin and the balance of water;
the mass concentration of the fluozirconic acid is 45 percent.
3. The nano zirconate conversion coating process for rusting a plate according to claim 2, wherein the preparation method of the vitrification agent is as follows: according to the formula, fluozirconic acid is added into water, zirconium dioxide sol is added after the mixture is uniformly stirred, after the mixture reacts for 5 to 30 minutes, organic silicon resin is added under the stirring state, the mixture reacts for 10 to 30 minutes, and the balance of water is supplemented to obtain the vitrification agent.
4. The nano zirconate conversion coating process for rusting a plate according to claim 3, wherein the mass concentration of the vitrification agent in the vitrification liquid is 2%.
5. The nano zirconate conversion coating process for the rusted plate according to claim 1, wherein the raw material of the rust remover consists of 0.3-20% of acid, 0.5-1% of organosilicon modified polyurethane resin and the balance of water by mass percent.
6. The nano zirconate conversion coating process for the rusted plate according to claim 1, wherein the operation method of the film removing treatment is to soak the rusted plate subjected to rust removal in a film removing agent, or to spray the film removing agent on the surface of the rusted plate subjected to rust removal.
7. The nano zirconate conversion coating process for the rusted plate according to claim 6, wherein the raw materials of the stripping agent comprise, by mass, 5-10% of strong base, 1-5% of surfactant, 0.5-2% of penetrating agent, 0.5-2% of wetting agent, 2-5% of dispersing agent and the balance of water.
8. The nano zirconate conversion coating process for rusting a sheet according to claim 7, wherein the strong base is any one or a combination of two of sodium hydroxide and potassium hydroxide;
the surfactant is selected from surfactant with model number S603G of Shenzhen Hengyuxiang technology Limited;
the penetrating agent is penetrating agent OEP-98, and the wetting agent is penetrating agent Q-12;
the dispersant is selected from the dispersant with model number FS-01 of Shenzhen Henshengxian science and technology Limited.
9. The nano zirconate conversion coating process for rusting a plate according to claim 1, wherein after the degreasing treatment, the derusting treatment, the film removing treatment and the vitrification treatment are completed, water washing is respectively required to be performed for a plurality of times.
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