CN115522191A - Phosphating solution for metal surface treatment and preparation method and application thereof - Google Patents
Phosphating solution for metal surface treatment and preparation method and application thereof Download PDFInfo
- Publication number
- CN115522191A CN115522191A CN202211239151.3A CN202211239151A CN115522191A CN 115522191 A CN115522191 A CN 115522191A CN 202211239151 A CN202211239151 A CN 202211239151A CN 115522191 A CN115522191 A CN 115522191A
- Authority
- CN
- China
- Prior art keywords
- phosphating
- polyvinyl alcohol
- surface treatment
- solution
- phosphating solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 44
- 239000002184 metal Substances 0.000 title claims abstract description 44
- 238000004381 surface treatment Methods 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000000243 solution Substances 0.000 claims abstract description 92
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 53
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 53
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 42
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000000843 powder Substances 0.000 claims abstract description 32
- 238000003756 stirring Methods 0.000 claims abstract description 28
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 21
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 20
- 239000011787 zinc oxide Substances 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000005260 corrosion Methods 0.000 claims abstract description 17
- 230000007797 corrosion Effects 0.000 claims abstract description 17
- 238000010438 heat treatment Methods 0.000 claims abstract description 12
- 239000011259 mixed solution Substances 0.000 claims abstract description 8
- 238000004321 preservation Methods 0.000 claims abstract description 3
- 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
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 11
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 8
- 239000005543 nano-size silicon particle Substances 0.000 claims description 7
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 6
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 6
- 239000011975 tartaric acid Substances 0.000 claims description 6
- 235000002906 tartaric acid Nutrition 0.000 claims description 6
- 235000012239 silicon dioxide Nutrition 0.000 claims description 5
- 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
- 239000004202 carbamide Substances 0.000 claims description 4
- 239000008139 complexing agent Substances 0.000 claims description 4
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 4
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 4
- 239000003112 inhibitor Substances 0.000 claims description 4
- 239000002105 nanoparticle Substances 0.000 claims description 4
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 4
- 239000004094 surface-active agent Substances 0.000 claims description 4
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 3
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims description 3
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 claims description 2
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 2
- 239000011575 calcium Substances 0.000 claims description 2
- 238000003889 chemical engineering Methods 0.000 claims description 2
- 229940124274 edetate disodium Drugs 0.000 claims description 2
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 2
- 239000004312 hexamethylene tetramine Substances 0.000 claims description 2
- 239000011572 manganese Substances 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
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims 1
- 238000010276 construction Methods 0.000 claims 1
- 125000005456 glyceride group Chemical group 0.000 claims 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims 1
- 239000002893 slag Substances 0.000 abstract description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- 229910000976 Electrical steel Inorganic materials 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 6
- 239000011148 porous material Substances 0.000 description 6
- 230000009286 beneficial effect Effects 0.000 description 4
- 238000002161 passivation Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 230000009467 reduction Effects 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000008236 heating water Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000013049 sediment Substances 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011534 incubation Methods 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
- 239000007788 liquid Substances 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
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 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
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Treatment Of Metals (AREA)
Abstract
The invention relates to a phosphating solution for metal surface treatment and a preparation method and application thereof. The phosphating solution comprises the following components in percentage by liter: l liter of water, 41 to 45g of phosphoric acid, 24.5 to 29g of zinc oxide, 20 to 24.5g of nitric acid and 1.5 to 2.2g of polyvinyl alcohol. The preparation method of the phosphating solution for metal surface treatment comprises the following steps: (1) Adding the polyvinyl alcohol powder into the water, continuously stirring for a period of time to swell the polyvinyl alcohol powder, and stirring the obtained mixed solution under a heating condition to fully dissolve the polyvinyl alcohol powder to obtain a polyvinyl alcohol solution for later use. (2) Adding the phosphoric acid, the zinc oxide and the nitric acid under the condition of heat preservation, and uniformly stirring to obtain the phosphating solution. The phosphating solution disclosed by the invention not only can form a more compact phosphating film on the surface of a metal workpiece and improve the corrosion resistance, but also can reduce the generation of phosphating slag.
Description
Technical Field
The invention relates to the technical field of metal surface treatment, in particular to a phosphating solution for metal surface treatment and a preparation method and application thereof.
Background
The information disclosed in this background of the invention is only for enhancement of understanding of the general background of the invention and is not necessarily to be taken as an acknowledgement or any form of suggestion that this information forms the prior art already known to a person skilled in the art.
Phosphating is a common pretreatment technology and is mainly applied to surface phosphating of steel, and one of the purposes of phosphating is to provide protection for base metal and prevent the metal from being corroded to a certain degree. At present, the method of phosphating treatment is mainly to soak a metal workpiece in a phosphoric acid solution containing manganese, iron, zinc and the like to generate a phosphate protective film which is difficult to dissolve in water on the surface of the metal workpiece. However, many phosphating solutions form a phosphating film on the surface of a metal substrate with certain pores, and the pores are important factors influencing the corrosion resistance of the phosphating film, so that the reduction of the porosity of the surface of the phosphating film is beneficial to further improving the corrosion resistance of the material.
At present, the mode adopted for solving the problems is mainly passivation treatment after phosphating, namely, metal workpieces after phosphating are retreated by using passivation solution, so that the complexity of a phosphating process is increased, and the problem of environmental pollution is easily caused if residual passivation solution waste liquid after the passivation treatment is not properly treated. In addition, the traditional phosphating solution is easy to generate more phosphating slag in the metal surface treatment process, the surface is researched, the service life of the phosphating solution can be shortened due to the generation of a large amount of phosphating slag, the phosphating cost is improved, the quality of a phosphating film can be influenced, and even the normal production is influenced, so that the novel phosphating solution capable of overcoming the problems needs to be developed.
Disclosure of Invention
In view of the above, the invention provides a phosphating solution for metal surface treatment, a preparation method and an application thereof, wherein the phosphating solution not only can form a more compact phosphating film on the surface of a metal workpiece and improve the corrosion resistance, but also can reduce the generation of phosphating slag. In order to realize the purpose, the invention discloses the following technical scheme:
in a first aspect, the invention discloses a phosphating solution for metal surface treatment, which comprises the following components in percentage by liter: l liter of water, 41 to 45g of phosphoric acid, 24.5 to 29g of zinc oxide, 20 to 24.5g of nitric acid and 1.5 to 2.2g of polyvinyl alcohol.
In some typical embodiments, the phosphating solution also comprises 0.05-0.2 g/L of complexing agent. Optionally, the complexing agent comprises tartaric acid (C) 4 H 6 O 6 ) Citric acid (C) 6 H 8 O 7 ) And edetate disodium (EDTA-2 Na).
In some typical embodiments, the phosphating solution also comprises 0.005-0.01 g/L of corrosion inhibitor. Optionally, the corrosion inhibitor includes any one of bis-o-toluenethiourea, hexamethylenetetramine, thiourea, urea, and the like.
In some typical embodiments, the phosphating solution also comprises 0.002-0.04 g/L of surfactant. Optionally, the surfactant comprises any one of sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, fatty acid glyceride, and the like.
In some typical embodiments, the phosphating solution also comprises 0.5-0.85 g/L of inorganic nanoparticles. Optionally, the inorganic nanoparticles include any one of nano-silica, nano-titania, nano-silicon nitride, and the like. The inorganic nano-ions are helpful for improving the corrosion resistance of the phosphating film.
In some typical embodiments, the phosphating solution also comprises 0.7-1.1 g/L of an accelerator. Optionally, the metal promoter comprises a metal capable of providing Ni 2+ 、Mn 2+ 、Ca 2+ The at least one metal ion source substance is preferably at least one of nickel nitrate, manganese nitrate, calcium nitrate, and the like. The accelerator helps to promote the generation of the phosphating film and the refinement of the grain of the phosphating film, thereby promoting the compactness of the phosphating film.
In a first aspect, the invention discloses a preparation method of the phosphating solution for metal surface treatment, which comprises the following steps:
(1) Adding the polyvinyl alcohol powder into the water, continuously stirring for a period of time to swell the polyvinyl alcohol powder, and stirring the obtained mixed solution under the heating condition to fully dissolve the polyvinyl alcohol powder to obtain a polyvinyl alcohol solution for later use.
(2) Adding the phosphoric acid, the zinc oxide and the nitric acid under the condition of heat preservation, and uniformly stirring to obtain the phosphating solution.
In some typical embodiments, in step (1), the continuous stirring time is 20 to 35 minutes, so that the polyvinyl alcohol powder is dispersed in water to prevent agglomeration and influence the subsequent dissolution rate in hot water.
In some typical embodiments, in step (1), the heating temperature is 70 to 85 ℃ so that the polyvinyl alcohol powder is sufficiently dissolved.
In some exemplary embodiments, in step (2), the temperature of the incubation is the same as the heating temperature in step (1).
Finally, the invention discloses the application of the phosphating solution for metal surface treatment in the fields of materials, chemical engineering, buildings and the like.
Compared with the prior art, the invention has the following beneficial effects: as mentioned above, some conventional phosphating solutions form a phosphating film on the surface of a metal substrate with certain pores, and the pores are important factors influencing the corrosion resistance of the phosphating film. Therefore, the polyvinyl alcohol is added into the phosphating solution for metal surface treatment, and when the phosphating solution is formed, the lamellar phosphating films can be connected into a whole, so that gaps among phosphating film blocks are eliminated, the phosphating films can be better formed into a whole, a more compact phosphating film can be formed on the surface of a metal workpiece, the corrosion resistance of the phosphating film is improved, and the bonding force between the phosphating film and a metal substrate is stronger. In addition, the polyvinyl alcohol molecule contains a large number of hydroxyl groups, has good reducibility, and can dissolve Fe in the phosphating solution in the phosphating process 3+ Reduction of ions to Fe 2+ Ions, thereby effectively reducing FePO 4 The generation of the sediment can relieve the problem that the traditional phosphating solution is easy to generate the phosphating slag, and the generated Fe 2+ Ions can participate in the formation of the phosphating film, which is beneficial to increasing the thickness of the phosphating film and improving the corrosion resistance of the phosphating film.
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. The invention will now be further illustrated by specific examples.
Example 1
A preparation method of phosphating solution for metal surface treatment comprises the following steps:
(1) Adding polyvinyl alcohol 1788 powder into water, continuously stirring for 30 minutes to swell the polyvinyl alcohol powder, heating the obtained mixed solution in water bath to 80 ℃, stirring for 20 minutes to fully dissolve the polyvinyl alcohol powder to obtain a polyvinyl alcohol solution for later use.
(2) And continuously keeping the polyvinyl alcohol solution at 80 ℃, adding a phosphoric acid solution, zinc oxide and a nitric acid solution, and uniformly stirring to obtain a phosphating solution with the components of 42g/L of phosphoric acid, 26g/L of zinc oxide, 22.5g/L of nitric acid and 1.8g/L of polyvinyl alcohol powder.
Example 2
A preparation method of phosphating solution for metal surface treatment comprises the following steps:
(1) Adding polyvinyl alcohol 17-92 powder into water, continuously stirring for 35 minutes to swell the polyvinyl alcohol powder, heating the obtained mixed solution in water bath to 85 ℃, stirring for 30 minutes to fully dissolve the polyvinyl alcohol powder to obtain a polyvinyl alcohol solution for later use.
(2) And continuously keeping the polyvinyl alcohol solution at 85 ℃, adding a phosphoric acid solution, zinc oxide and a nitric acid solution, and uniformly stirring to obtain a phosphating solution with the components of 45g/L of phosphoric acid, 29g/L of zinc oxide, 24.5g/L of nitric acid and 2.2g/L of polyvinyl alcohol powder.
Example 3
A preparation method of a phosphating solution for metal surface treatment comprises the following steps:
(1) Adding polyvinyl alcohol 1788 powder into water, continuously stirring for 20 minutes to swell the polyvinyl alcohol powder, heating the obtained mixed solution in water bath to 70 ℃, stirring for 35 minutes to fully dissolve the polyvinyl alcohol powder to obtain a polyvinyl alcohol solution for later use.
(2) And continuously keeping the polyvinyl alcohol solution at 70 ℃, adding a phosphoric acid solution, zinc oxide and a nitric acid solution, and uniformly stirring to obtain a phosphating solution with the components of 41g/L of phosphoric acid, 24.5g/L of zinc oxide, 20g/L of nitric acid and 1.5g/L of polyvinyl alcohol powder.
Example 4
A preparation method of a phosphating solution for metal surface treatment comprises the following steps:
(1) Adding polyvinyl alcohol 1788 powder into water, continuously stirring for 30 minutes to swell the polyvinyl alcohol powder, heating the obtained mixed solution in water bath to 80 ℃, stirring for 20 minutes to fully dissolve the polyvinyl alcohol powder to obtain a polyvinyl alcohol solution for later use.
(2) And continuously keeping the polyvinyl alcohol solution at 80 ℃, adding a phosphoric acid solution, zinc oxide, a nitric acid solution, tartaric acid, di-o-toluenethiourea, sodium dodecyl sulfate and nano silicon dioxide, and uniformly stirring to obtain a phosphating solution containing 42g/L of phosphoric acid, 26g/L of zinc oxide, 22.5g/L of nitric acid, 1.8g/L of polyvinyl alcohol powder, 0.2g/L of tartaric acid, 0.01g/L of di-o-toluenethiourea, 0.04g/L of sodium dodecyl sulfate and 0.85g/L of nano silicon dioxide.
Example 5
A preparation method of a phosphating solution for metal surface treatment comprises the following steps:
(1) Adding polyvinyl alcohol 1788 powder into water, continuously stirring for 20 minutes to swell the polyvinyl alcohol powder, heating the obtained mixed solution in water bath to 70 ℃, stirring for 35 minutes to fully dissolve the polyvinyl alcohol powder to obtain a polyvinyl alcohol solution for later use.
(2) And continuously keeping the polyvinyl alcohol solution at 70 ℃, adding a phosphoric acid solution, zinc oxide, a nitric acid solution, citric acid, urea, sodium dodecyl benzene sulfonate and nano titanium dioxide, and uniformly stirring to obtain a phosphating solution containing 41g/L of phosphoric acid, 24.5g/L of zinc oxide, 20g/L of nitric acid, 1.5g/L of polyvinyl alcohol powder, 0.05g/L of citric acid, 0.005g/L of urea, 0.002g/L of sodium dodecyl benzene sulfonate and 0.5g/L of nano titanium dioxide.
Example 6
A preparation method of phosphating solution for metal surface treatment comprises the following steps: heating water to 80 ℃, adding a phosphoric acid solution, zinc oxide and a nitric acid solution, and uniformly stirring to obtain a phosphating solution containing 42g/L of phosphoric acid, 26g/L of zinc oxide and 22.5g/L of nitric acid.
Example 7
A preparation method of a phosphating solution for metal surface treatment comprises the following steps: heating water to 80 ℃, adding a phosphoric acid solution, zinc oxide, a nitric acid solution, tartaric acid, di-o-toluenethiourea, sodium dodecyl sulfate and nano silicon dioxide, and uniformly stirring to obtain a phosphating solution containing 42g/L of phosphoric acid, 26g/L of zinc oxide, 22.5g/L of nitric acid, 1.8g/L of polyvinyl alcohol powder, 0.2g/L of tartaric acid, 0.01g/L of di-o-toluenethiourea, 0.04g/L of sodium dodecyl sulfate and 0.85g/L of nano silicon dioxide.
Performance testing
And (3) immersing the silicon steel sheet into the phosphating solution prepared in the embodiment for 20 minutes, and then testing three performance indexes, namely the corrosion resistance, the adhesive force of a phosphating film and the generation amount of phosphated slag, of the corresponding silicon steel sheet obtained by the treatment of the phosphating solution of each embodiment. Wherein the corrosion resistance is according to standard GBT6807-2001, a phosphatized silicon steel sheet sample is immersed in a 3wt.% NaCl solution at 25 ℃, and the time to rust of the phosphating film is recorded, the results are shown in table 1.
TABLE 1
As can be seen from the test results in table 1, the phosphating solutions prepared in examples 1 to 5 have significantly better effect on the phosphating treatment of silicon steel sheets than those prepared in examples 6 and 7, because polyvinyl alcohol is not added to the phosphating solutions of examples 6 and 7, so that the phosphating solutions form a phosphating film on the surface of the silicon steel sheets with more pores, and the pores affect the corrosion resistance of the phosphating film. And the phosphating solution prepared in the embodiment 1-embodiment 5 is added with polyvinyl alcohol, and when the phosphating solution is formed, the phosphating films in sheet shapes can be connected into a whole, gaps among phosphating film blocks are eliminated, the phosphating films can be better integrated, a more compact phosphating film can be formed on the surface of a metal workpiece, the corrosion resistance of the phosphating film is obviously improved, and the phosphating film and the silicon steel sheet are enabled to be combinedThe bonding force between the two is stronger. In addition, the polyvinyl alcohol molecule contains a large number of hydroxyl groups, has good reducibility, and can dissolve Fe in the phosphating solution in the phosphating process 3+ Reduction of ions to Fe 2+ Ions, thereby effectively reducing FePO 4 The generation of the sediment can relieve the problem that the traditional phosphating solution is easy to generate the phosphating slag, and the generated Fe 2+ Ions can participate in the formation of the phosphating film, which is beneficial to increasing the thickness of the phosphating film and further improving the corrosion resistance of the phosphating film.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made to the present invention by those skilled in the art. 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. The phosphating solution for metal surface treatment is characterized by comprising the following components in percentage by liter: l liter of water, 41 to 45g of phosphoric acid, 24.5 to 29g of zinc oxide, 20 to 24.5g of nitric acid and 1.5 to 2.2g of polyvinyl alcohol.
2. The phosphating solution for metal surface treatment according to claim 1, further comprising 0.05-0.2 g/L of a complexing agent; preferably, the complexing agent comprises any one of tartaric acid, citric acid and edetate disodium.
3. The phosphating solution for metal surface treatment according to claim 1, further comprising 0.005-0.01 g/L of corrosion inhibitor; preferably, the corrosion inhibitor comprises any one of di-o-toluenethiourea, hexamethylenetetramine, thiourea and urea.
4. The phosphating solution for metal surface treatment according to claim 1, further comprising 0.002-0.04 g/L of surfactant; preferably, the surfactant comprises any one of sodium dodecyl sulfate, sodium dodecyl benzene sulfonate and fatty glyceride.
5. The phosphating solution for metal surface treatment according to claim 1, further comprising 0.5-0.85 g/L of inorganic nanoparticles; preferably, the inorganic nanoparticles comprise any one of nano silicon dioxide, nano titanium dioxide and nano silicon nitride.
6. The phosphating solution for metal surface treatment according to any one of claims 1 to 5, further comprising 0.7 to 1.1g/L of an accelerator; preferably, the metal promoter comprises a metal capable of providing Ni 2+ 、Mn 2+ 、Ca 2+ Preferably at least one of nickel nitrate, manganese nitrate and calcium nitrate.
7. A method for preparing a phosphating solution for metal surface treatment according to any one of claims 1 to 6, comprising the steps of:
(1) Adding the polyvinyl alcohol powder into the water, continuously stirring for a period of time to swell the polyvinyl alcohol powder, and stirring the obtained mixed solution under a heating condition to fully dissolve the polyvinyl alcohol powder to obtain a polyvinyl alcohol solution for later use;
(2) Adding the phosphoric acid, the zinc oxide and the nitric acid under the condition of heat preservation, and uniformly stirring to obtain the phosphating solution.
8. The method of producing a phosphating solution for metal surface treatment according to claim 7, wherein in the step (1), the continuous stirring time is 20 to 35 minutes; preferably, in the step (1), the heating temperature is 70 to 85 ℃.
9. The method of claim 7 or 8, wherein the temperature of the heat-retaining in the step (2) is the same as the heating temperature in the step (1).
10. Use of the phosphating solution for metal surface treatment according to any one of claims 1 to 6 or the phosphating solution for metal surface treatment obtained by the preparation method according to any one of claims 7 to 9 in the fields of materials, chemical engineering or construction.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211239151.3A CN115522191B (en) | 2022-10-11 | 2022-10-11 | Phosphating solution for metal surface treatment and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211239151.3A CN115522191B (en) | 2022-10-11 | 2022-10-11 | Phosphating solution for metal surface treatment and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115522191A true CN115522191A (en) | 2022-12-27 |
| CN115522191B CN115522191B (en) | 2024-06-07 |
Family
ID=84702319
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211239151.3A Active CN115522191B (en) | 2022-10-11 | 2022-10-11 | Phosphating solution for metal surface treatment and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115522191B (en) |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB932845A (en) * | 1960-06-23 | 1963-07-31 | Stefan Klinghoffer | Method of phosphate-coating metal workpieces and phosphating solution used therefor |
| US3837928A (en) * | 1971-10-05 | 1974-09-24 | Dulux Australia Ltd | Conversion coating on metal |
| US4233088A (en) * | 1979-03-29 | 1980-11-11 | International Lead Zinc Research Organization, Inc. | Phosphatization of steel surfaces and metal-coated surfaces |
| CN1127800A (en) * | 1995-08-01 | 1996-07-31 | 刘光炳 | Cold black coslettising liquid |
| CN101245458A (en) * | 2007-02-16 | 2008-08-20 | 天津新技术产业园区科茂化学试剂有限公司 | Four-function treating liquid for surface of iron or steel |
| CN102817025A (en) * | 2012-07-28 | 2012-12-12 | 蚌埠市福沃特车轮制造科技有限公司 | Low-temperature phosphating solution containing chromic acid |
| CN102817022A (en) * | 2012-07-28 | 2012-12-12 | 蚌埠市福沃特车轮制造科技有限公司 | Normal-temperature phosphating solution containing sodium thiosulfate |
| CN102817023A (en) * | 2012-07-28 | 2012-12-12 | 蚌埠市福沃特车轮制造科技有限公司 | High-temperature corrosion-resistant phosphating solution |
| CN108018545A (en) * | 2017-11-25 | 2018-05-11 | 蚌埠市福沃特车轮制造科技有限公司 | A kind of preparation method of automotive hub high temperature phosphorization liquid |
| CN112501670A (en) * | 2020-11-26 | 2021-03-16 | 常州市武进信和精密机械有限公司 | Compact electrophoresis coating process |
| CN115537790A (en) * | 2022-09-13 | 2022-12-30 | 首钢集团有限公司 | Phosphating solution and phosphating method for preparing high-alkali-resistance phosphating film on surface of galvanized sheet |
-
2022
- 2022-10-11 CN CN202211239151.3A patent/CN115522191B/en active Active
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB932845A (en) * | 1960-06-23 | 1963-07-31 | Stefan Klinghoffer | Method of phosphate-coating metal workpieces and phosphating solution used therefor |
| US3837928A (en) * | 1971-10-05 | 1974-09-24 | Dulux Australia Ltd | Conversion coating on metal |
| US4233088A (en) * | 1979-03-29 | 1980-11-11 | International Lead Zinc Research Organization, Inc. | Phosphatization of steel surfaces and metal-coated surfaces |
| CN1127800A (en) * | 1995-08-01 | 1996-07-31 | 刘光炳 | Cold black coslettising liquid |
| CN101245458A (en) * | 2007-02-16 | 2008-08-20 | 天津新技术产业园区科茂化学试剂有限公司 | Four-function treating liquid for surface of iron or steel |
| CN102817025A (en) * | 2012-07-28 | 2012-12-12 | 蚌埠市福沃特车轮制造科技有限公司 | Low-temperature phosphating solution containing chromic acid |
| CN102817022A (en) * | 2012-07-28 | 2012-12-12 | 蚌埠市福沃特车轮制造科技有限公司 | Normal-temperature phosphating solution containing sodium thiosulfate |
| CN102817023A (en) * | 2012-07-28 | 2012-12-12 | 蚌埠市福沃特车轮制造科技有限公司 | High-temperature corrosion-resistant phosphating solution |
| CN108018545A (en) * | 2017-11-25 | 2018-05-11 | 蚌埠市福沃特车轮制造科技有限公司 | A kind of preparation method of automotive hub high temperature phosphorization liquid |
| CN112501670A (en) * | 2020-11-26 | 2021-03-16 | 常州市武进信和精密机械有限公司 | Compact electrophoresis coating process |
| CN115537790A (en) * | 2022-09-13 | 2022-12-30 | 首钢集团有限公司 | Phosphating solution and phosphating method for preparing high-alkali-resistance phosphating film on surface of galvanized sheet |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115522191B (en) | 2024-06-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107345297B (en) | Alkaline cleaning solution, phosphating solution and metal surface treatment method | |
| CN102953055B (en) | Black phosphating liquid and use method thereof | |
| CN106148974A (en) | A kind of iron and steel derusting and phosphorating agent | |
| CN109457242B (en) | Chromium-free passivator and preparation method and application thereof | |
| CN100540754C (en) | The method of fading decorative chromium coating through electroanalysis | |
| CN109972186A (en) | A kind of passivation for stainless steel processing method | |
| TW201326459A (en) | Process for manufacturing cold rolled steel sheets excellent in terms of phosphatability and corrosion resistance under paint films | |
| CN108048826B (en) | Rust removal phosphating solution for wire drawing and preparation method thereof | |
| CN115522191A (en) | Phosphating solution for metal surface treatment and preparation method and application thereof | |
| CN112095096A (en) | Zinc-series low-slag phosphating agent and preparation method thereof | |
| CN106222632A (en) | A kind of environment-friendly type is anti-corrosion, the preparation method of wear-resistant magnesium alloy layer | |
| CN101200799B (en) | Medium-low temperature high corrosion resistant black phosphating solution on steel surface | |
| CN115074010B (en) | Wear-resistant austenitic stainless steel belt and preparation method thereof | |
| CN115261837A (en) | Pre-painting treatment process for steel-aluminum mixed base material | |
| CN113265651A (en) | Graphene-enhanced phytate-based passivator, preparation method and application | |
| CN102877069B (en) | Ferro-aluminum composite metal corrosion inhibitor and preparation method thereof | |
| JP2007138211A (en) | Cold-rolled steel sheet superior in chemical conversion treatment property and galling resistance, and manufacturing method therefor | |
| JP2007138216A (en) | Cold-rolled steel sheet superior in chemical conversion treatment property and galling resistance, and manufacturing method therefor | |
| CN115821246A (en) | Three-in-one metal surface treating agent and use method thereof | |
| CN104357818A (en) | Composition for steel phosphating and preparation method thereof | |
| CN111349920A (en) | Environment-friendly phosphating solution containing rare earth composite accelerator and using method | |
| CN114686867B (en) | Novel efficient zinc series surface conditioner and preparation method and application thereof | |
| CN112962089B (en) | Environment-friendly and efficient nickel-free manganese phosphating agent and preparation method and application thereof | |
| TW201042082A (en) | Process for forming corrosion protection layers on metal surfaces | |
| JP2007138213A (en) | Cold-rolled steel sheet superior in chemical conversion treatment property and galling resistance, and manufacturing method therefor |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant |