CN107012453B - A kind of method that green low temperature quickly prepares phosphating coat - Google Patents
A kind of method that green low temperature quickly prepares phosphating coat Download PDFInfo
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- CN107012453B CN107012453B CN201710206943.3A CN201710206943A CN107012453B CN 107012453 B CN107012453 B CN 107012453B CN 201710206943 A CN201710206943 A CN 201710206943A CN 107012453 B CN107012453 B CN 107012453B
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- phosphating
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- graphene oxide
- phosphating coat
- low temperature
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000002360 preparation method Methods 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 238000005530 etching Methods 0.000 claims abstract description 14
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 13
- 239000010959 steel Substances 0.000 claims abstract description 13
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 12
- NBIIXXVUZAFLBC-UHFFFAOYSA-K [O-]P([O-])([O-])=O Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 8
- 239000010452 phosphate Substances 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 7
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 6
- NHNBFGGVMKEFGY-UHFFFAOYSA-N nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000003381 stabilizer Substances 0.000 claims abstract description 5
- 238000010792 warming Methods 0.000 claims abstract description 4
- 239000006174 pH buffer Substances 0.000 claims abstract description 3
- 150000003839 salts Chemical class 0.000 claims description 10
- 239000011780 sodium chloride Substances 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 229910052748 manganese Inorganic materials 0.000 claims description 5
- 239000011572 manganese Substances 0.000 claims description 5
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 5
- MFXMOUUKFMDYLM-UHFFFAOYSA-L zinc;dihydrogen phosphate Chemical compound [Zn+2].OP(O)([O-])=O.OP(O)([O-])=O MFXMOUUKFMDYLM-UHFFFAOYSA-L 0.000 claims description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-M dihydrogenphosphate Chemical compound OP(O)([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-M 0.000 claims description 4
- 239000003995 emulsifying agent Substances 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- 241000048284 Potato virus P Species 0.000 claims description 3
- 229910000389 calcium phosphate Inorganic materials 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 3
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 3
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 3
- 229940062672 CALCIUM DIHYDROGEN PHOSPHATE Drugs 0.000 claims description 2
- YYRMJZQKEFZXMX-UHFFFAOYSA-L calcium bis(dihydrogenphosphate) Chemical compound [Ca+2].OP(O)([O-])=O.OP(O)([O-])=O YYRMJZQKEFZXMX-UHFFFAOYSA-L 0.000 claims description 2
- ICSSIKVYVJQJND-UHFFFAOYSA-N calcium nitrate tetrahydrate Chemical compound O.O.O.O.[Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ICSSIKVYVJQJND-UHFFFAOYSA-N 0.000 claims description 2
- BZDIAFGKSAYYFC-UHFFFAOYSA-N manganese;hydrate Chemical compound O.[Mn] BZDIAFGKSAYYFC-UHFFFAOYSA-N 0.000 claims description 2
- 238000010907 mechanical stirring Methods 0.000 claims description 2
- 235000019691 monocalcium phosphate Nutrition 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 239000011574 phosphorus Substances 0.000 claims description 2
- JGPSMWXKRPZZRG-UHFFFAOYSA-N zinc;dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O JGPSMWXKRPZZRG-UHFFFAOYSA-N 0.000 claims description 2
- SEGLCEQVOFDUPX-UHFFFAOYSA-N Di-(2-ethylhexyl)phosphoric acid Chemical compound CCCCC(CC)COP(O)(=O)OCC(CC)CCCC SEGLCEQVOFDUPX-UHFFFAOYSA-N 0.000 claims 1
- 229910052739 hydrogen Inorganic materials 0.000 claims 1
- 239000001257 hydrogen Substances 0.000 claims 1
- 238000005260 corrosion Methods 0.000 abstract description 16
- 239000000853 adhesive Substances 0.000 abstract description 2
- 230000001070 adhesive Effects 0.000 abstract description 2
- 238000002425 crystallisation Methods 0.000 abstract description 2
- 230000005712 crystallization Effects 0.000 abstract description 2
- 239000003973 paint Substances 0.000 abstract description 2
- 238000003756 stirring Methods 0.000 abstract description 2
- 229910052799 carbon Inorganic materials 0.000 abstract 1
- 230000003000 nontoxic Effects 0.000 abstract 1
- 231100000252 nontoxic Toxicity 0.000 abstract 1
- 238000000034 method Methods 0.000 description 10
- 230000001264 neutralization Effects 0.000 description 9
- 239000007921 spray Substances 0.000 description 9
- LPXPTNMVRIOKMN-UHFFFAOYSA-M Sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 8
- ONDPHDOFVYQSGI-UHFFFAOYSA-N Zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 4
- 235000010288 sodium nitrite Nutrition 0.000 description 4
- 238000005265 energy consumption Methods 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N oxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 2
- XTEGARKTQYYJKE-UHFFFAOYSA-M chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000007306 functionalization reaction Methods 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000010422 painting Methods 0.000 description 2
- 235000013024 sodium fluoride Nutrition 0.000 description 2
- 239000011775 sodium fluoride Substances 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- -1 Calcium zinc-manganese Chemical compound 0.000 description 1
- 229910000975 Carbon steel Inorganic materials 0.000 description 1
- 208000003351 Melanosis Diseases 0.000 description 1
- 210000004940 Nucleus Anatomy 0.000 description 1
- 231100000614 Poison Toxicity 0.000 description 1
- YZHUMGUJCQRKBT-UHFFFAOYSA-M Sodium chlorate Chemical compound [Na+].[O-]Cl(=O)=O YZHUMGUJCQRKBT-UHFFFAOYSA-M 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H Tricalcium phosphate Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229960001714 calcium phosphate Drugs 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 239000010962 carbon steel Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000001627 detrimental Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001962 electrophoresis Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 230000002708 enhancing Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 238000005755 formation reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- TWXTWZIUMCFMSG-UHFFFAOYSA-N nitride(3-) Chemical compound [N-3] TWXTWZIUMCFMSG-UHFFFAOYSA-N 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 230000001737 promoting Effects 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000009938 salting Methods 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 229940080281 sodium chlorate Drugs 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002588 toxic Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- HHIMNFJHTNVXBJ-UHFFFAOYSA-L zinc;dinitrite Chemical compound [Zn+2].[O-]N=O.[O-]N=O HHIMNFJHTNVXBJ-UHFFFAOYSA-L 0.000 description 1
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
- C23C22/05—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
-
- 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
- C23C22/13—Orthophosphates containing zinc cations containing also nitrate or nitrite anions
-
- 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
- C23C22/18—Orthophosphates containing manganese cations
-
- 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
- C23C22/18—Orthophosphates containing manganese cations
- C23C22/182—Orthophosphates containing manganese cations containing also zinc cations
-
- 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
- C23C22/22—Orthophosphates containing alkaline earth metal cations
Abstract
The invention discloses a kind of methods that green low temperature quickly prepares phosphating coat.This method comprises: 1) in terms of mass fraction, it will be in the raw material components investment reaction kettle of 5~8 parts of dihydric phosphate, 6~9 parts of nitrate, 0.5~3 part of phosphoric acid, 0.05~0.5 part of graphene oxide, 0.1~1 part of stabilizer, 6~10 parts of pH buffer, 100~120 parts of water, 20~40 DEG C are warming up to, stirring 20~go out kettle after sixty minutes；2) etching solution of preparation is put into phosphating pond, parkerized temperature is made to rise to 15~40 DEG C, be then immersed steel test specimen, handled 2~20 minutes, dry, obtain phosphating coat.The phosphatization film outward appearance ash that the present invention obtains is bright, has preferable corrosion resistance, strong with the adhesive force of paint.Method for bonderizing phosphatization speed of the invention is fast, and phosphatization temperature is low, and film layer crystallization is thin, and phosphating solution is stable, sediment is few, nontoxic to human and environment, low in cost.
Description
Technical field
The invention discloses phosphating coats to belong to material more particularly to a kind of method that green low temperature quickly prepares phosphating coat
Material science and field of surface technology.
Background technique
Metal all must carry out conversion processing to its surface before spraying, coating, it is made to generate conversion film.Conversion film includes
Phosphating coat, passivating film, organic film, rare-earth conversion coatings and colloidal sol silane film etc..Wherein phosphatization film preparation is metal parts
It enters containing Zn, Ni, Mn, in the salting liquid based on the specific acid phosphate such as Fe, while various compound additions is added
Agent, by chemical treatment, in the phosphate conversion film that there is the Surface Creation of metal parts certain thickness to be insoluble in water.Phosphatization
Purpose be mainly: give parent metal provide protection, prevent metal to be corroded to a certain extent；For preceding bottoming of painting, mention
The adhesive force and anti-corrosion capability of high paint film layer；Play antifriction lubrication in metal cold processing.
Currently, both at home and abroad phosphorating treatment using it is more be medium temperature, high temperature phosphorization, not only energy consumption is high, the treatment process time
Long and sediment is more, and needs to carry out Seal treatment after phosphatization, complicates phosphorization treatment process, directly affects painting
Quality, yield or cost.
Currently, still having many defects for the parkerized phosphating solution of steel material, the various aspects of performance of phosphating solution still has
It is to be modified.
Traditional phosphating process is quite time-consuming and operation temperature is relatively high.
The Chinese patent application of Publication No. CN101029386A discloses a kind of to be contained for what steel plate and galvanized sheet were handled
Calcium zinc-manganese triple cationic phosphorizing fluid, although the phosphating solution has phosphating coat formation, speed is fast, good with electrophoretic coating matching,
Be the phosphating solution concentration it is big, at high cost, operating temperature is not suitable with the requirement of low temperature phosphor at 40~60 DEG C.
Application No. is the patent applications of CN103469187A to disclose a kind for the treatment of fluid for steel surface phosphatization melanism,
Although the temperature for the treatment of fluid operation is room temperature and treated that steel surface light is corrosion-resistant, film quality is good, should
Phosphating solution phosphatization steel material speed is slow, long the time required to phosphatization.
Traditional promotor such as nitride, though nitrate and chlorate etc. can effectively improve the property of phosphate coating
Can, but it is harmful to human health and environment.
Application No. is the Chinese invention patent applications of CN201610397553.4 to disclose a kind of carbon steel pipe normal-temperature phosphorizing liquid
Formula, although the formula can use toxic in the phosphorating treatment for being carried out workpiece quickly close under room temperature
Harmful sodium nitrite and sodium fluoride are as promotor, and ratio is higher, and the three-protection design difficulty of generation is big, are unsatisfactory for environmental protection
Demand.
Application No. is the Chinese invention patent applications of CN201510387197.3, provide the organic and inorganic compounding of one kind
Zinc phosphating solution promotor contains in used inorganic accelerator though effectively reducing the operating time of parkerizing process
There is the strong go back original reagent of the Strong oxdiatives such as zinc nitrite, sodium chlorate and hydrogen peroxide, has certain corrosion and to people to operation equipment
Body health is harmful, and higher cost, is not suitable for mass production needs.
In order to adapt to fast-developing market competition needs, the quality of phosphating solution is improved, realizes that room temperature quickly forms phosphatization
Film, reduces energy consumption cost, and technical process simplification, functionalization etc. become current development trend.And according to current existing phosphorus
Change in formula of liquid design, is not yet related to promoting the research of the related fields of phosphating coat film forming about graphene oxide.
Summary of the invention
The technical problem to be solved in the present invention is that a kind of method that green low temperature quickly prepares phosphating coat is provided, to solve
The problem of energy consumption is high for certainly existing phosphorating treatment, processing time length, phosphating process complexity etc. lead to phosphatization increased costs, realization is low
Cost prepares anti-corrosion, wear-resisting phosphating coat, and used phosphating solution is free of the metal ions such as harmful sodium nitrite and chromium,
Operation temperature is room temperature, meets energy conservation and environmental protection consumption reduction and requires.
Graphene oxide (graphene oxide, GO) is a kind of important derivative of graphene, also referred to as functionalization
Graphene, oxidation removing graphite is mainly prepared by Hummers method, GO is made.The structure of GO is substantially the same with graphene, only
It is that some oxygen-containing functional groups (such as epoxy group, hydroxyl, carboxyl) is connected on two-dimentional basal plane.It is worth noting that, graphene exists
It is easy to reunite in solution, and since GO contains more oxygen-containing functional group, hydrophily is especially excellent, so that it is easy to
It is distributed in various solvents, greatly extends its application range.The oxygen-containing group on the surface GO can also live as reaction simultaneously
Property site and solution in other ionic reactions or as nucleation adsorption site bear nucleus, therefore to a certain extent promote crystallization
Generate and construct the nanocrystal with certain pattern.The graphite oxide of 0.02-0.5wt% is added in the present invention in phosphating solution
Alkene is allowed to be co-deposited with phosphating coat on the surface of steel, forms nano graphene oxide complex phosphate coating, utilize graphene oxide
With the characteristic of nano material, enhance resistance to corrosion, the wearability of phosphating coat, while reducing preparation time and the reduction of phosphating coat
Reaction temperature.This is a kind of new quick, low temperature and environmental protection phosphatization membrane preparation method.
The object of the invention is to realize by technical solution:
A kind of green low temperature method for quickly preparing phosphating coat, it is characterised in that preparation steps including etching solution and
Phosphorating treatment step:
1) preparation of etching solution: in terms of mass fraction, by 5~8 parts of dihydric phosphate, 6~9 parts of nitrate, phosphoric acid
0.5~3 part, 0.05~0.5 part of graphene oxide, 0.1~1 part of stabilizer, 6~10 parts of pH buffer, 100~120 parts of water
Raw material components are put into reaction kettle, are warming up to 20~40 DEG C, and control mixing speed is at 200~300 revs/min, mechanical stirring 20
~go out kettle after sixty minutes；
2) phosphorating treatment: the etching solution of preparation is put into phosphating pond, and parkerized temperature is made to rise to 15~40
DEG C, then steel test specimen is immersed, is handled the time 2~20 minutes, is washed down and dried with water, obtain phosphating coat.
To further realize the object of the invention, it is preferable that the dihydric phosphate is phosphate dihydrogen manganese, zinc dihydrogen phosphate
It is one or more with calcium dihydrogen phosphate.
Preferably, the nitrate be four nitric hydrate manganese, zinc nitrate hexahydrate and calcium nitrate tetrahydrate one kind or
It is a variety of.
Preferably, the stabilizer be OP-10 emulsifier, PVP, APEO, SE-10 and TX-10 it is one or more.
Preferably, in terms of mass fraction, 0.05~0.5 part of graphene oxide of the dosage refers to graphene oxide
Effective mass；The graphene oxide is 0.1~4.0wt% graphene oxide water solution or graphene oxide powder, oxidation
Graphene is prepared by Hummers method.
Preferably, further include that lye is added in the feed in the preparation of step 1) etching solution, control etching solution
PH value be 2-3.
The present invention tests the Corrosion Protection of phosphating coat using GB6458-86 neutral salt spray test.
The beneficial effects of the present invention are:
The present invention carries out phosphorating treatment to workpiece using the method that green low temperature quickly prepares phosphating coat, has used novel
Graphene oxide has significantly speeded up the generating rate of phosphating coat as promotor, and phosphating time is short (2~20 minutes), phosphatization temperature
Spend low (15~40 DEG C), can be carried out under room temperature, substantially without phosphating dregs in the phosphating pond after phosphatization, illustrate the phosphatization of test specimen at
Power is high, and phosphatization film outward appearance ash is bright, and even film layer is fine and smooth, and corrosion resistance meets GB6458-86 regulation, and does not contain in phosphating solution
The metal ions such as harmful sodium nitrite and chromium are not detrimental to health and destroy ecological ring in use and using rear
Border, it is at low cost, it is easy to use, industrialization demand can be met.
Specific embodiment
For a better understanding of the invention, the present invention is further explained combined with specific embodiments below, but embodiment is not constituted
Restriction to the claims in the present invention protection scope, is based on embodiment, and those skilled in the art are not making creative work
Under the premise of other embodiments obtained, belong to protection scope of the present invention.
Embodiment 1
(1) according to parts by weight, following raw material components: 4 parts of zinc dihydrogen phosphate, 2 parts of phosphate dihydrogen manganese, zinc nitrate are weighed
6 parts, 2 parts of phosphoric acid, 6 parts of 3.5wt% graphene oxide water solution, 0.2 part of PVP, 100 parts of water.
(2) step (1) each component is put into reaction kettle, adjusting pH using lye is 2, then heats to 40 DEG C, stirring
Uniformly.
(3) etching solution of preparation is put into phosphating pond, parkerized temperature is made to rise to 28 DEG C, then by steel
Test specimen is immersed, and is handled the time 5 minutes, is washed down to dry with water parkerized test specimen can be obtained.
Substantially without phosphating dregs in phosphating pond after phosphatization, illustrate that the phosphatization success rate of test specimen is high.
The present invention tests the Corrosion Protection of phosphating coat using GB6458-86 neutral salt spray test.
The phosphatization film outward appearance ash that the present embodiment 1 obtains is bright, and film layer is fine and smooth, film thickness 2g/m2。
Do not corrode within phosphating coat neutral salt spray test 20 hours, meets anti-corrosion standard as defined in GB6458-86.
Compared with 40~60 DEG C of technologies that traditional phosphating process such as Chinese patent CN101029386A are reported, this hair
The bright method for quickly preparing phosphating coat using green low temperature carries out phosphorating treatment to workpiece, can greatly simplify phosphating process, phosphatization
Temperature is low, can carry out under room temperature.
Compared with 30~60 minutes phosphorization treatment process that the prior art such as Chinese patent CN103469187A are reported, this
The method that invention quickly prepares phosphating coat using green low temperature, the processing time is only 5 minutes, and phosphating reaction speed is fast, when phosphatization
Between it is short.
With the prior art such as Chinese patent CN201610397553.4 report using environmentally harmful sodium nitrite and
Sodium fluoride is compared as parkerized promotor, and the present invention is using biodegradable graphene oxide as promotor, nothing
Poison is harmless, composite environmental-friendly requirement.
Embodiment 2
(1) following raw material components: 8 parts of zinc dihydrogen phosphate, 4 parts of zinc nitrate, 3 parts of calcium phosphate, phosphoric acid are taken by weight ratio
2.5 parts, 0.05 part of graphene oxide powder, 0.2 part of APEO, 100 parts of water.
(2) each component is put into reaction kettle, adjusting pH using lye is 3, then heats to 30 DEG C, stirs evenly.
(3) etching solution of preparation is put into phosphating pond, parkerized temperature is made to rise to 30 DEG C, then by steel
Test specimen is immersed, and is handled the time 4 minutes, is washed down to dry with water parkerized test specimen can be obtained.
The present invention tests the Corrosion Protection of phosphating coat using GB6458-86 neutral salt spray test.
The phosphatization film outward appearance ash that the present embodiment 2 obtains is bright, and film layer is fine and smooth, film thickness 1.5g/m2。
Do not corrode within phosphating coat neutral salt spray test 14 hours, meets anti-corrosion standard as defined in GB6458-86.
Embodiment 3
(1) following raw material components: 7 parts of zinc dihydrogen phosphate, 6 parts of zinc nitrate, phosphatase 11 part, 2.2wt% are taken by weight ratio
0.2 part of graphene oxide water solution, 0.2 part of OP-10 emulsifier, 0.3 part of TX-10,120 parts of water
(2) each component is put into reaction kettle, adjusting pH using lye is 3, then heats to 25 DEG C, stirs evenly.
(3) etching solution of preparation is put into phosphating pond, parkerized temperature is made to rise to 20 DEG C, then by steel
Test specimen is immersed, and is handled the time 10 minutes, is washed down to dry with water parkerized test specimen can be obtained.
The present invention tests the Corrosion Protection of phosphating coat using GB6458-86 neutral salt spray test.
The phosphatization film outward appearance ash that the present embodiment 3 obtains is bright, and film layer is fine and smooth, film thickness 3.0g/m2。
Do not corrode within phosphating coat neutral salt spray test 20 hours, meets anti-corrosion standard as defined in GB6458-86.
Embodiment 4
(1) following raw material components: 5 parts of phosphate dihydrogen manganese, 9 parts of zinc nitrate, 3 parts of phosphoric acid, oxidation stone are taken by weight ratio
0.5 part of black alkene powder, 1 part of OP-10 emulsifier, 100 parts of water
(2) each component is put into reaction kettle, is warming up to 30 DEG C, mixing speed is stirred evenly at 300 revs/min.
(3) etching solution of preparation is put into phosphating pond, parkerized temperature is made to rise to 40 DEG C, then by steel
Test specimen is immersed, and is handled the time 2 minutes, is washed down to dry with water parkerized test specimen can be obtained.
The present invention tests the Corrosion Protection of phosphating coat using GB6458-86 neutral salt spray test.
The phosphatization film outward appearance ash that the present embodiment 4 obtains is bright, and film layer is fine and smooth, film thickness 2.2g/m2。
Do not corrode within phosphating coat neutral salt spray test 10 hours, meets anti-corrosion standard as defined in GB6458-86.
The basic principles, main features and advantages of the present invention have been shown and described above.Industry technology people
Member is it should be appreciated that the present invention is not limited to the above embodiments, without departing from the spirit and scope of the present invention, the present invention
It will also have various changes and improvements, these changes and improvements all fall within the protetion scope of the claimed invention.
Claims (6)
1. a kind of method that green low temperature quickly prepares phosphating coat, it is characterised in that preparation steps and phosphorus including etching solution
Change processing step:
1) preparation of etching solution: in terms of mass fraction, by 5~8 parts of dihydric phosphate, 6~9 parts of nitrate, phosphoric acid 0.5~
3 parts, 0.05~0.5 part of graphene oxide, 0.1~1 part of stabilizer, 6~10 parts of pH buffer, the raw material group of 100~120 parts of water
Divide in investment reaction kettle, be warming up to 20~40 DEG C, controls mixing speed at 200~300 revs/min, 20~60 points of mechanical stirring
Go out kettle after clock；
2) phosphorating treatment: the etching solution of preparation is put into phosphating pond, so that parkerized temperature is risen to 15~40 DEG C, so
Steel test specimen is immersed afterwards, is handled 2~20 minutes, is washed down and dried with water, obtain phosphating coat.
2. the method that green low temperature according to claim 1 quickly prepares phosphating coat, which is characterized in that the di(2-ethylhexyl)phosphate
Hydrogen salt is the one or more of phosphate dihydrogen manganese, zinc dihydrogen phosphate and calcium dihydrogen phosphate.
3. the method that green low temperature according to claim 1 quickly prepares phosphating coat, which is characterized in that the nitrate
For the one or more of four nitric hydrate manganese, zinc nitrate hexahydrate and calcium nitrate tetrahydrate.
4. the method that green low temperature according to claim 1 quickly prepares phosphating coat, which is characterized in that the stabilizer
For OP-10 emulsifier, PVP, APEO, SE-10 and TX-10 it is one or more.
5. the method that green low temperature according to claim 1 quickly prepares phosphating coat, which is characterized in that with mass fraction
Meter, 0.05~0.5 part of graphene oxide of the dosage refer to the effective mass of graphene oxide；The graphene oxide
For 0.1~4.0wt% graphene oxide water solution or graphene oxide powder, graphene oxide is prepared by Hummers method.
6. the method that green low temperature according to claim 1 quickly prepares phosphating coat, which is characterized in that at step 1) phosphatization
Managing in the preparation of liquid further includes that lye is added in the feed, and the pH value for controlling etching solution is 2-3.
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| CN107740168A (en) * | 2017-09-30 | 2018-02-27 | 华南理工大学 | A kind of efficient corrosion resisting Zinc phosphating solution and preparation method thereof |
| CN108165969A (en) * | 2017-12-26 | 2018-06-15 | 贵州钢绳股份有限公司 | A kind of preparation method of steel wire room temperature electrolytic phosphating liquid |
| CN110184596A (en) * | 2019-06-20 | 2019-08-30 | 佛山市众之助新材料科技有限公司 | A method of black phosphating film is covered in metal surface |
| CN112391618A (en) * | 2019-08-12 | 2021-02-23 | 东莞市颖兴金属表面处理材料有限公司 | Environment-friendly phosphating solution containing graphene oxide and preparation method thereof |
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| CN102965655B (en) * | 2012-11-23 | 2017-10-31 | 沈阳工业大学 | One kind improves the corrosion proof method of surface of Nd-Fe-B permanent magnet phosphating coat |
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