CN105779982A - Chrome-free metal surface conversion liquid and conversion coating preparation method - Google Patents
Chrome-free metal surface conversion liquid and conversion coating preparation method Download PDFInfo
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- CN105779982A CN105779982A CN201610325236.1A CN201610325236A CN105779982A CN 105779982 A CN105779982 A CN 105779982A CN 201610325236 A CN201610325236 A CN 201610325236A CN 105779982 A CN105779982 A CN 105779982A
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 58
- 239000002184 metal Substances 0.000 title claims abstract description 58
- 239000007788 liquid Substances 0.000 title claims abstract description 30
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 13
- 238000002360 preparation method Methods 0.000 title abstract description 13
- 238000007739 conversion coating Methods 0.000 title abstract 2
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 39
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims abstract description 26
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims abstract description 26
- 150000003608 titanium Chemical class 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000011775 sodium fluoride Substances 0.000 claims abstract description 13
- 235000013024 sodium fluoride Nutrition 0.000 claims abstract description 13
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims abstract description 12
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910001424 calcium ion Inorganic materials 0.000 claims abstract description 12
- 239000003513 alkali Substances 0.000 claims abstract description 7
- 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 abstract description 6
- 235000002906 tartaric acid Nutrition 0.000 claims abstract description 6
- 239000011975 tartaric acid Substances 0.000 claims abstract description 6
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims abstract description 5
- 150000003863 ammonium salts Chemical class 0.000 claims abstract description 5
- 159000000007 calcium salts Chemical class 0.000 claims abstract description 5
- 235000015165 citric acid Nutrition 0.000 claims abstract description 5
- 150000003751 zinc Chemical class 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 24
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 15
- PPSSQRUPSRPZON-UHFFFAOYSA-N nitrobenzene;sodium Chemical compound [Na].[O-][N+](=O)C1=CC=CC=C1 PPSSQRUPSRPZON-UHFFFAOYSA-N 0.000 claims description 11
- 239000003921 oil Substances 0.000 claims description 11
- 239000002351 wastewater Substances 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 238000005554 pickling Methods 0.000 claims description 9
- 239000000377 silicon dioxide Substances 0.000 claims description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 6
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 239000003995 emulsifying agent Substances 0.000 claims description 2
- 239000012046 mixed solvent Substances 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 239000001117 sulphuric acid Substances 0.000 claims description 2
- 235000011149 sulphuric acid Nutrition 0.000 claims description 2
- -1 ammonium ions Chemical class 0.000 abstract description 3
- LJRGBERXYNQPJI-UHFFFAOYSA-M sodium;3-nitrobenzenesulfonate Chemical compound [Na+].[O-][N+](=O)C1=CC=CC(S([O-])(=O)=O)=C1 LJRGBERXYNQPJI-UHFFFAOYSA-M 0.000 abstract 2
- 229910000831 Steel Inorganic materials 0.000 description 10
- 239000010959 steel Substances 0.000 description 10
- 229910019142 PO4 Inorganic materials 0.000 description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 8
- 239000010452 phosphate Substances 0.000 description 8
- 238000005260 corrosion Methods 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 230000007797 corrosion Effects 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 238000002161 passivation Methods 0.000 description 6
- 238000007789 sealing Methods 0.000 description 6
- 238000010586 diagram Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000012752 auxiliary agent Substances 0.000 description 2
- 150000001845 chromium compounds Chemical class 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 239000003755 preservative agent Substances 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- TUSDEZXZIZRFGC-UHFFFAOYSA-N 1-O-galloyl-3,6-(R)-HHDP-beta-D-glucose Natural products OC1C(O2)COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC1C(O)C2OC(=O)C1=CC(O)=C(O)C(O)=C1 TUSDEZXZIZRFGC-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 239000001263 FEMA 3042 Substances 0.000 description 1
- IMQLKJBTEOYOSI-GPIVLXJGSA-N Inositol-hexakisphosphate Chemical compound OP(O)(=O)O[C@H]1[C@H](OP(O)(O)=O)[C@@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@@H]1OP(O)(O)=O IMQLKJBTEOYOSI-GPIVLXJGSA-N 0.000 description 1
- LRBQNJMCXXYXIU-PPKXGCFTSA-N Penta-digallate-beta-D-glucose Natural products OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-PPKXGCFTSA-N 0.000 description 1
- IMQLKJBTEOYOSI-UHFFFAOYSA-N Phytic acid Natural products OP(O)(=O)OC1C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C1OP(O)(O)=O IMQLKJBTEOYOSI-UHFFFAOYSA-N 0.000 description 1
- 239000004111 Potassium silicate Substances 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- BFGKITSFLPAWGI-UHFFFAOYSA-N chromium(3+) Chemical class [Cr+3] BFGKITSFLPAWGI-UHFFFAOYSA-N 0.000 description 1
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 1
- 230000001473 noxious effect Effects 0.000 description 1
- 150000001282 organosilanes Chemical class 0.000 description 1
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 description 1
- 235000002949 phytic acid Nutrition 0.000 description 1
- 239000000467 phytic acid Substances 0.000 description 1
- 229940068041 phytic acid Drugs 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 description 1
- 229910052913 potassium silicate Inorganic materials 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical group [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- LRBQNJMCXXYXIU-NRMVVENXSA-N tannic acid Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-NRMVVENXSA-N 0.000 description 1
- 229940033123 tannic acid Drugs 0.000 description 1
- 235000015523 tannic acid Nutrition 0.000 description 1
- 229920002258 tannic acid Polymers 0.000 description 1
- 229910000349 titanium oxysulfate Inorganic materials 0.000 description 1
- 229910000348 titanium sulfate Inorganic materials 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 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
- C23C22/07—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
-
- 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
- C23C22/82—After-treatment
-
- 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
-
- 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
- C23G1/081—Iron or steel solutions containing H2SO4
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 chrome-free metal surface conversion liquid and a conversion coating preparation method. The chrome-free metal surface conversion liquid comprises phosphating liquid and silicon salt confining liquid. The phosphating liquid comprises calcium salt, zinc salt, ammonium salt, titanium salt, tartaric acid, sodium fluoride, citric acid, sodium 3-nitrobenzene sulfonate and water. The silicon salt confining liquid comprises silicon salt, thiourea and alkali. In the phosphating liquid, the concentration of calcium ions ranges from 2 g/L to 20 g/L, the concentration of zinc ions ranges from 5 g/L to 40 g/L, the concentration of ammonium ions ranges from 0.5 g/L to 5 g/L, the concentration of titanium salt ranges from 0.1 g/L to 2 g/L, the concentration of tartaric acid ranges from 0.5 g/L to 5 g/L, the concentration of sodium fluoride ranges from 0.1 g/L to 1 g/L, the concentration of citric acid ranges from 5 g/L to 50 g/L, and the concentration of sodium 3-nitrobenzene sulfonate ranges from 5 g/L to 50 g/L; the total acidity of chrome-free metal surface conversion liquid is 30-90, and the free acidity of the chrome-free metal surface conversion liquid is 5-30; and in the silicon salt confining liquid, the concentration of silicon salt ranges from 2 g/L to 20 g/L, the concentration of thiourea ranges from 1 g/L to 10 g/L, and the concentration of alkali ranges from 0.1 g/L to 10 g/L.
Description
Technical field
The present invention relates to metal material surface preservative treatment technology field, be specifically related to a kind of chromium-free metal surface conversional solution and conversion film preparation method.
Background technology
In order to slow down the corrosion of metal material, application is means of defence the most economic, convenient.Before application, parkerized chromium passivating technique is as a kind of main anti-corrosion of metal technology, is widely used in different industrial circles, such as automobile, aircraft and shipping industry etc..But the toxicity of hexavalent chromium contained in chromium compounds and carcinogenecity seriously hinder the use of this technique.Along with people's reinforcement to environmental consciousness in recent years, the research and development of the substitute (or claiming " green preservatives ") of chromium compound are just in the ascendant.
Metal current surface chromium-free (VI) passivating technique is totally divided into: inorganic matter passivation, Organic substance passivation and the compound passivation of inorganic-organic thing, relating to trivalent chromium (III) salt, molybdate, tungstates, silicate, rare earth metal salt, titanium salt and organic species (such as tannic acid, phytic acid) etc., and modified Portland passivation, rare earth metal salt passivation, organosilane passivating and inorganic) Organic substance compound passivation progress of research is bigger.But these methods still have the shortcoming using toxic heavy metal or noxious substance, Treatment of Metal Surface effect to be difficult to meet industrial requirement.
Therefore, still need to seek the chromium-free metal surface passivating technique of a kind of environment-friendly and green.
Summary of the invention
It is an object of the invention to overcome the deficiencies in the prior art, it is provided that a kind of chromium-free metal surface conversional solution, described conversional solution has good phosphatization effect, is applied in Treatment of Metal Surface and can reduce the volume of phosphate crystal, increases the compactness of phosphate coating.
Another object of the present invention is to the method that above-mentioned chromium-free metal surface conversional solution prepares conversion film.
For achieving the above object, the present invention adopts the following technical scheme that
A kind of chromium-free metal surface conversional solution, described chromium-free metal surface conversional solution includes Phosphating Solution and silicon salt confining liquid, and described Phosphating Solution comprises calcium salt, zinc salt, ammonium salt, titanium salt, tartaric acid, sodium fluoride, citric acid, m-nitrobenzene sodium sulfonate and water；Described silicon salt confining liquid comprises silicon salt, thiourea and alkali；
In Phosphating Solution, the concentration range of described calcium ion is 2～20g/L, the concentration range of described zinc ion is 5～40g/L, the concentration range of described ammonium ion is 0.5～5g/L, the concentration range of described titanium salt is 0.1～2g/L, and described tartaric concentration range is 0.5～5g/L, and the concentration range of described sodium fluoride is 0.1～1g/L, the concentration range of described citric acid is 5～50g/L, and the concentration range of described m-nitrobenzene sodium sulfonate is 5～50g/L；The total acidity of described chromium-free metal surface conversional solution is 30～90 points, and free acidity is 5～30 points；
In silicon salt confining liquid, the concentration of described silicon salt is 2～20g/L, and the concentration of described thiourea is 1～10g/L, and described paper mill wastewater is 0.1～10g/L.
Preferably, described chromium-free metal surface conversional solution includes Phosphating Solution and silicon salt confining liquid, and described Phosphating Solution comprises calcium salt, zinc salt, ammonium salt, titanium salt, tartaric acid, sodium fluoride, citric acid, m-nitrobenzene sodium sulfonate and water；Described silicon salt confining liquid comprises silicon salt, thiourea and alkali；
In Phosphating Solution, the concentration range of described calcium ion is 3～18g/L, the concentration range of described zinc ion is 7～36g/L, the concentration range of described ammonium ion is 0.9～4.5g/L, the concentration range of described titanium salt is 0.1～1.5g/L, and described tartaric concentration range is 0.8～4.5g/L, and the concentration range of described sodium fluoride is 0.1～0.8g/L, the concentration range of described citric acid is 6～45g/L, and the concentration range of described m-nitrobenzene sodium sulfonate is 6～45g/L；The total acidity of described chromium-free metal surface conversional solution is 30～80 points, and free acidity is 6～25 points；
In silicon salt confining liquid, the concentration of described silicon salt is 4～16g/L, and the concentration of described thiourea is 2～9g/L, and described paper mill wastewater is 0.1～8g/L.Preferably, described calcium ion is the calcium ion being dissolvable in water chromium-free metal surface conversional solution.
Preferably, described zinc ion is the zinc ion being dissolvable in water chromium-free metal surface conversional solution.
Preferably, described alkali is sodium hydroxide or potassium hydroxide.
Preferably, described titanium salt is inorganic soluble titanium salt, it is further preferable that described titanium salt is one or more in titanium sulfate, titanyl sulfate or titanium tetrachloride.
Preferably, described silicon salt is soluble silicate, it is further preferable that described silicon salt is sodium silicate and/or potassium silicate.
The method that above-mentioned chromium-free metal surface conversional solution prepares conversion film, uses Phosphating Solution and silicon salt confining liquid that metal surface carries out phosphatization and silica-based closing respectively；The technique of described conversion film step successively is: washing, oil removing, hot water wash, pickling, washing, phosphatization, washing, silica-based closing, dry.
Preferably, adopt sodium carbonate, sodium hydroxide, OP emulsifying agent mixture solution carry out oil removal treatment.
Preferably, adopt sulphuric acid, the mixed solvent of slow releasing agent carries out pickling.
Preferably, the temperature of described oil removing is 50～100 DEG C, and the oil removing time is 0.5～20min；The temperature of described hot water wash is 50～100 DEG C, and the time is 0.5～20min；The time of described pickling is 0.5～20min；The time of described phosphatization is 2～60min；The time of described silica-based closing is 2～60min；The described dry time is 0.5～1000min.
Compared with prior art, there is advantages that
Present invention optimizes the formula of Phosphating Solution and preparing process, provide formula and the technique of the metal surface conversion film of one " green ", and in conjunction with silicon salt sealing treatment technology, after Phosphating Solution provided by the invention and silicon salt confining liquid are applied in Treatment of Metal Surface, there is good phosphatization effect, the volume of phosphate crystal can be reduced when being applied in Treatment of Metal Surface, increase the compactness of phosphate coating.Phosphating Solution provided by the invention has good stability, has abandoned the heavy metal in original formulation, decreases consumption of raw materials and have compressed production cost, has bigger application value.
Accompanying drawing explanation
Fig. 1 is that the present invention carries out Treatment of Metal Surface pattern comparison diagram；
Fig. 2 is that the present invention carries out linear polarisation curves comparison diagram after Treatment of Metal Surface；
Fig. 3 is that the present invention carries out impedance curve comparison diagram after Treatment of Metal Surface.
Detailed description of the invention
The present invention is further illustrated below in conjunction with specific embodiment.The experimental technique used in following embodiment if no special instructions, is conventional method: used raw material, auxiliary agent etc., if no special instructions, is the raw material and auxiliary agent that can obtain from commercial sources such as conventional market purchases.
Embodiment 1
(1) preparation of Phosphating Solution:
The concentration range of calcium ion is 10g/L, the concentration range of described zinc ion is 10g/L, the concentration range of described ammonium ion is 2g/L, the concentration range of described titanium salt is 0.5g/L, described tartaric concentration range is 2g/L, the concentration range of described sodium fluoride is 0.2g/L, and the concentration range of described citric acid is 10g/L, and the concentration range of described m-nitrobenzene sodium sulfonate is 10g/L；The total acidity of described chromium-free metal surface conversional solution is 60 points, and free acidity is 15 points.
(2) preparation of silicon salt confining liquid
The concentration of described silicon salt is 3g/L, and the concentration of described thiourea is 2g/L, and described paper mill wastewater is 0.5g/L.
(3) metal surface zero waste water discharge preparation technology
Technique: washing---oil removing (90 DEG C, 2 minutes)---------(5 minutes)--silica-based closing (30 minutes) dry (15 minutes) is washed in washing---phosphatization (30 minutes)---to hot water wash (90 DEG C, 2 minutes) in pickling
Embodiment 2
(1) preparation of Phosphating Solution:
The concentration range of calcium ion is 15g/L, the concentration range of described zinc ion is 15g/L, the concentration range of described ammonium ion is 3g/L, the concentration range of described titanium salt is 1g/L, described tartaric concentration range is 3g/L, the concentration range of described sodium fluoride is 0.3g/L, and the concentration range of described citric acid is 20g/L, and the concentration range of described m-nitrobenzene sodium sulfonate is 20g/L；The total acidity of described chromium-free metal surface conversional solution is 80 points, and free acidity is 20 points.
(2) preparation of silicon salt confining liquid
The concentration of described silicon salt is 5g/L, and the concentration of described thiourea is 3g/L, and described paper mill wastewater is 0.2g/L.
(3) metal surface zero waste water discharge preparation technology
Technique: washing---oil removing (80 DEG C, 2 minutes)---------(2 minutes)--silica-based closing (20 minutes) dry (25 minutes) is washed in washing---phosphatization (20 minutes)---to hot water wash (80 DEG C, 2 minutes) in pickling.
Embodiment 3
(1) preparation of Phosphating Solution:
The concentration range of calcium ion is 20g/L, the concentration range of described zinc ion is 20g/L, the concentration range of described ammonium ion is 4g/L, the concentration range of described titanium salt is 0.1g/L, described tartaric concentration range is 5g/L, the concentration range of described sodium fluoride is 0.6g/L, and the concentration range of described citric acid is 15g/L, and the concentration range of described m-nitrobenzene sodium sulfonate is 15g/L；The total acidity of described chromium-free metal surface conversional solution is 65 points, and free acidity is 17 points.
(2) preparation of silicon salt confining liquid
The concentration of described silicon salt is 6g/L, and the concentration of described thiourea is 3g/L, and described paper mill wastewater is 0.2g/L.
(3) metal surface zero waste water discharge preparation technology
Technique: washing---oil removing (70 DEG C, 2 minutes)---------(2 minutes)--silica-based closing (20 minutes) dry (15 minutes) is washed in washing---phosphatization (20 minutes)---to hot water wash (70 DEG C, 2 minutes) in pickling
Metal surface after embodiment 1 is processed adopts Stereo microscope to carry out morphology analysis, Fig. 1 is exaggerated the shape appearance figure of 375 times, in Fig. 1, the picture left above is the shape appearance figure of X70 steel, top right plot is the X70 steel shape appearance figure through conventional phosphatizing, lower-left figure is the shape appearance figure of the X70 steel of alramenting, and bottom-right graph is the shape appearance figure of the X70 steel of silicate sealant.As it is shown in figure 1, the Phosphating Solution provided through the embodiment of the present invention 1 and silicon salt confining liquid process after the surface of X70 steel define that one layer of arrangement be closely knit, the phosphate coating of homogeneous grain size；After silicon salt sealing treatment, phosphate coating intercrystalline pore reduces in a large number, has better sealing effect；And conventional phosphatizing in top right plot process after the crystal grain on X70 steel surface is big, crystal grain with crystal grain gap greatly, and area does not form phosphate coating on a large scale.
To embodiment 2 process after metal carry out linear polarization test, Fig. 2 utilize the present invention to carry out Treatment of Metal Surface after linear polarisation curves comparison diagram.The phosphating process that thered is provided by the embodiment of the present invention 2, silicon salt closing process process after the linear polarisation curves of X70 steel it can be seen that slightly decline relative to corrosion current, by 55 μ A/cm2Reduce to 36 μ A/cm2, it is-613mV that corrosion potential is raised by-726mV, is indicated above the corrosion resistance of metal after bonderizing and slightly improves.By the linear polarisation curves of the X70 steel after silicon salt sealing treatment it can be seen that the corrosion current of X70 steel after silicon salt sealing treatment drops to 43nA/cm2, relatively not close sample etches electric current and drop below 1/1000, be indicated above after bonderizing, re-closed, the corrosion resistance of metal has very big raising.
Metal after embodiment 3 is processed carries out testing impedance, and Fig. 3 is the impedance contrast figure after utilizing the present invention to carry out Treatment of Metal Surface.The size of the low frequency range impedance in impedance diagram is relevant to the resistance of metal surface rete.Although from the figure 3, it may be seen that the surface of the X70 steel after being processed by the embodiment of the present invention 3 has phosphate coating to occur, but there is substantial amounts of hole between crystal grain, resistance value improves inconspicuous.After silicon salt sealing treatment, low frequency range resistance value has had very big raising, about 200 Ω be increased to 200K about Ω, and being indicated above the metal surface phosphating layer after bonderizing is re-closed has fabulous barriering effect.
Claims (10)
1. a chromium-free metal surface conversional solution, it is characterized in that, described chromium-free metal surface conversional solution includes Phosphating Solution and silicon salt confining liquid, and described Phosphating Solution comprises calcium salt, zinc salt, ammonium salt, titanium salt, tartaric acid, sodium fluoride, citric acid, m-nitrobenzene sodium sulfonate and water；Described silicon salt confining liquid comprises silicon salt, thiourea and alkali；
Wherein in Phosphating Solution, the concentration range of described calcium ion is 2～20g/L, the concentration range of described zinc ion is 5～40g/L, the concentration range of described ammonium ion is 0.5～5g/L, the concentration range of described titanium salt is 0.1～2g/L, and described tartaric concentration range is 0.5～5g/L, and the concentration range of described sodium fluoride is 0.1～1g/L, the concentration range of described citric acid is 5～50g/L, and the concentration range of described m-nitrobenzene sodium sulfonate is 5～50g/L；The total acidity of described chromium-free metal surface conversional solution is 30～90 points, and free acidity is 5～30 points；
In silicon salt confining liquid, the concentration of described silicon salt is 2～20g/L, and the concentration of described thiourea is 1～10g/L, and described paper mill wastewater is 0.1～10g/L.
2. chromium-free metal surface conversional solution according to claim 1, it is characterized in that, described chromium-free metal surface conversional solution includes Phosphating Solution and silicon salt confining liquid, and described Phosphating Solution comprises calcium salt, zinc salt, ammonium salt, titanium salt, tartaric acid, sodium fluoride, citric acid, m-nitrobenzene sodium sulfonate and water；Described silicon salt confining liquid comprises silicon salt, thiourea and alkali；
In Phosphating Solution, the concentration range of described calcium ion is 3～18g/L, the concentration range of described zinc ion is 7～36g/L, the concentration range of described ammonium ion is 0.9～4.5g/L, the concentration range of described titanium salt is 0.1～1.5g/L, and described tartaric concentration range is 0.8～4.5g/L, and the concentration range of described sodium fluoride is 0.1～0.8g/L, the concentration range of described citric acid is 6～45g/L, and the concentration range of described m-nitrobenzene sodium sulfonate is 6～45g/L；The total acidity of described chromium-free metal surface conversional solution is 30～80 points, and free acidity is 6～25 points；
In silicon salt confining liquid, the concentration of described silicon salt is 4～16g/L, and the concentration of described thiourea is 2～9g/L, and described paper mill wastewater is 0.1～8g/L.
3. chromium-free metal surface conversional solution according to claim 1, it is characterised in that described calcium ion is the calcium ion being dissolvable in water chromium-free metal surface conversional solution.
4. chromium-free metal surface conversional solution according to claim 1, it is characterised in that described zinc ion is the zinc ion being dissolvable in water chromium-free metal surface conversional solution.
5. chromium-free metal surface conversional solution according to claim 1, it is characterised in that described titanium salt is inorganic soluble titanium salt.
6. chromium-free metal surface conversional solution according to claim 1, it is characterised in that described silicon salt is soluble silicate.
7. one kind utilizes the method that chromium-free metal surface conversional solution described in claim 1～6 prepares conversion film, it is characterised in that use Phosphating Solution and silicon salt confining liquid that metal surface carries out phosphatization and silica-based closing respectively；The technique of described conversion film step successively is: washing, oil removing, hot water wash, pickling, washing, phosphatization, washing, silica-based closing, dry.
8. method according to claim 7, it is characterised in that adopt sodium carbonate, sodium hydroxide, OP emulsifying agent mixture solution carry out oil removal treatment.
9. method according to claim 7, it is characterised in that adopt sulphuric acid, the mixed solvent of slow releasing agent carries out pickling.
10. method according to claim 7, it is characterised in that the temperature of described oil removing is 50～100 DEG C, and the oil removing time is 0.5～20min；The temperature of described hot water wash is 50～100 DEG C, and the time is 0.5～20min；The time of described pickling is 0.5～20min；The time of described phosphatization is 2～60min；The time of described silica-based closing is 2～60min；The described dry time is 0.5～1000min.
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| CN110042384A (en) * | 2019-04-18 | 2019-07-23 | 江苏理工学院 | A kind of steel iron phosphatising film confining liquid and preparation method thereof and application method |
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| CN1066689A (en) * | 1992-06-05 | 1992-12-02 | 伍泽涌 | Zinc-calcium phosphide solution used for no washing before painting under normal temp |
| WO2009112480A1 (en) * | 2008-03-11 | 2009-09-17 | Chemetall Gmbh | Process for coating metallic surfaces with a passivating agent, the passivating agent and its use |
| CN103849866A (en) * | 2014-02-14 | 2014-06-11 | 浙江工业大学 | Grey protective layer for surface of titanium-zinc plate and preparation method |
| CN104018162A (en) * | 2014-06-12 | 2014-09-03 | 广东海洋大学 | Preparation method of cathode protection coating on aluminum alloy surface |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1066689A (en) * | 1992-06-05 | 1992-12-02 | 伍泽涌 | Zinc-calcium phosphide solution used for no washing before painting under normal temp |
| WO2009112480A1 (en) * | 2008-03-11 | 2009-09-17 | Chemetall Gmbh | Process for coating metallic surfaces with a passivating agent, the passivating agent and its use |
| CN103849866A (en) * | 2014-02-14 | 2014-06-11 | 浙江工业大学 | Grey protective layer for surface of titanium-zinc plate and preparation method |
| CN104018162A (en) * | 2014-06-12 | 2014-09-03 | 广东海洋大学 | Preparation method of cathode protection coating on aluminum alloy surface |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110042384A (en) * | 2019-04-18 | 2019-07-23 | 江苏理工学院 | A kind of steel iron phosphatising film confining liquid and preparation method thereof and application method |
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