CN105779982B - A kind of chromium-free metal surface conversion fluid and conversion membrane preparation method - Google Patents
A kind of chromium-free metal surface conversion fluid and conversion membrane preparation method Download PDFInfo
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- CN105779982B CN105779982B CN201610325236.1A CN201610325236A CN105779982B CN 105779982 B CN105779982 B CN 105779982B CN 201610325236 A CN201610325236 A CN 201610325236A CN 105779982 B CN105779982 B CN 105779982B
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 57
- 239000002184 metal Substances 0.000 title claims abstract description 57
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 42
- 239000012530 fluid Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title abstract description 13
- 239000012528 membrane Substances 0.000 title abstract description 4
- 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
- 239000007788 liquid Substances 0.000 claims abstract description 24
- 150000003608 titanium Chemical class 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000003513 alkali Substances 0.000 claims abstract description 14
- 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
- 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 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
- 235000002906 tartaric acid Nutrition 0.000 claims abstract description 12
- 239000011975 tartaric acid Substances 0.000 claims abstract description 12
- PPSSQRUPSRPZON-UHFFFAOYSA-N nitrobenzene;sodium Chemical compound [Na].[O-][N+](=O)C1=CC=CC=C1 PPSSQRUPSRPZON-UHFFFAOYSA-N 0.000 claims abstract description 11
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 8
- 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
- 150000003376 silicon Chemical class 0.000 claims description 39
- 238000000034 method Methods 0.000 claims description 20
- 239000003921 oil Substances 0.000 claims description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 229910052710 silicon Inorganic materials 0.000 claims description 9
- 239000010703 silicon Substances 0.000 claims description 9
- 239000000758 substrate Substances 0.000 claims description 9
- 238000005260 corrosion Methods 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 230000007797 corrosion Effects 0.000 claims description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000005554 pickling 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
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 3
- 238000001035 drying Methods 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
- AIRRELHUAAZTTL-UHFFFAOYSA-N 3-nitrobenzenesulfonic acid;sodium Chemical compound [Na].OS(=O)(=O)C1=CC=CC([N+]([O-])=O)=C1 AIRRELHUAAZTTL-UHFFFAOYSA-N 0.000 claims 1
- LIBWRRJGKWQFSD-UHFFFAOYSA-M sodium;2-nitrobenzenesulfonate Chemical compound [Na+].[O-][N+](=O)C1=CC=CC=C1S([O-])(=O)=O LIBWRRJGKWQFSD-UHFFFAOYSA-M 0.000 claims 1
- 229910000831 Steel Inorganic materials 0.000 description 10
- 239000010959 steel Substances 0.000 description 10
- 229910019142 PO4 Inorganic materials 0.000 description 8
- 239000010452 phosphate Substances 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 7
- 238000012545 processing Methods 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 238000010586 diagram Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000002161 passivation Methods 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
- 239000002351 wastewater 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
- 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
- -1 rare earth metal salt Chemical class 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
- 206010007269 Carcinogenicity Diseases 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
- 239000002253 acid Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 231100000260 carcinogenicity Toxicity 0.000 description 1
- 230000007670 carcinogenicity Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 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
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 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
- 239000005416 organic matter Substances 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
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 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
- 238000007789 sealing Methods 0.000 description 1
- 235000019795 sodium metasilicate Nutrition 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
- 238000004381 surface treatment Methods 0.000 description 1
- 238000013268 sustained release Methods 0.000 description 1
- 239000012730 sustained-release form Substances 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 present invention relates to a kind of chromium-free metal surface conversion fluid and conversion membrane preparation method, the chromium-free metal surface conversion fluid includes phosphating solution and silicon salt confining liquid, and the phosphating solution includes calcium salt, zinc salt, ammonium salt, titanium salt, tartaric acid, sodium fluoride, citric acid, m-nitrobenzene sodium sulfonate and water；The silicon salt confining liquid includes silicon salt, thiocarbamide and alkali；Wherein in phosphating solution, the concentration range of the calcium ion is 2~20g/L, the concentration range of the zinc ion is 5~40g/L, the concentration range of the ammonium ion is 0.5~5g/L, the concentration range of the titanium salt is 0.1~2g/L, and the concentration range of the tartaric acid is 0.5~5g/L, and the concentration range of the sodium fluoride is 0.1~1g/L, the concentration range of the citric acid is 5~50g/L, and the concentration range of the m-nitrobenzene sodium sulfonate is 5~50g/L；The total acidity of the chromium-free metal surface conversion fluid is 30~90 points, and free acidity is 5~30 points；In silicon salt confining liquid, the concentration of the silicon salt is 2~20g/L, and the concentration of the thiocarbamide is 1~10g/L, and the concentration of the alkali is 0.1~10g/L.
Description
Technical field
The present invention relates to metal material surface preservative treatment technology field, and in particular to a kind of chromium-free metal surface conversion fluid
And conversion membrane preparation method.
Background technology
In order to slow down the corrosion of metal material, application is the most economic, convenient means of defence.It is parkerized before application
Chromium passivating technique is widely used in different industrial circles, such as automobile, aircraft and ship as a kind of main anti-corrosion of metal technology
Oceangoing ship industry etc..But the toxicity and carcinogenicity of hexavalent chromium contained in chromium compounds seriously hinder the use of the technique.With
Reinforcement of the people to environmental consciousness in recent years, the research and development of the substitute (or " green preservatives ") of chromium compound are square
Xing Weiai.
Metal surface Chrome-free (VI) passivating technique is totally divided at present：Inorganic matter passivation, organic matter passivation and inorganic-organic
The compound passivation of thing, it is related to trivalent chromium (III) salt, molybdate, tungstates, silicate, rare earth metal salt, titanium salt and organic thing
Matter (such as tannic acid, phytic acid), and modified Portland passivation, rare earth metal salt are passivated, are organosilane passivating and inorganic) organic
The compound passivation progress of research of thing is larger.But still have in these methods using toxic heavy metal or noxious material, metal watch
The shortcomings that face treatment effect is difficult to meet industrial requirement.
Therefore, still need to seek a kind of chromium-free metal surface passivating technique of environment-friendly and green.
The content of the invention
It is an object of the invention to overcome the deficiencies of the prior art and provide a kind of chromium-free metal surface conversion fluid, described turn
Changing liquid has preferable phosphatization effect, applies the volume that phosphate crystal can be reduced in Treatment of Metal Surface, increases phosphate coating
Compactness.
Another object of the present invention is to the method that above-mentioned chromium-free metal surface conversion fluid prepares conversion film.
To achieve the above object, the present invention adopts the following technical scheme that：
A kind of chromium-free metal surface conversion fluid, the chromium-free metal surface conversion fluid include phosphating solution and silicon salt confining liquid,
The phosphating solution includes calcium salt, zinc salt, ammonium salt, titanium salt, tartaric acid, sodium fluoride, citric acid, m-nitrobenzene sodium sulfonate and water；Institute
State silicon salt confining liquid and include silicon salt, thiocarbamide and alkali；
In phosphating solution, the concentration range of the calcium ion is 2~20g/L, and the concentration range of the zinc ion is 5~40g/
L, the concentration range of the ammonium ion is 0.5~5g/L, and the concentration range of the titanium salt is 0.1~2g/L, the tartaric acid
Concentration range is 0.5~5g/L, and the concentration range of the sodium fluoride is 0.1~1g/L, the concentration range of the citric acid for 5~
50g/L, the concentration range of the m-nitrobenzene sodium sulfonate is 5~50g/L；The total acidity of the chromium-free metal surface conversion fluid is
30~90 points, free acidity is 5~30 points；
In silicon salt confining liquid, the concentration of the silicon salt is 2~20g/L, and the concentration of the thiocarbamide is 1~10g/L, the alkali
Concentration be 0.1~10g/L.
Preferably, the chromium-free metal surface conversion fluid includes phosphating solution and silicon salt confining liquid, and the phosphating solution includes calcium
Salt, zinc salt, ammonium salt, titanium salt, tartaric acid, sodium fluoride, citric acid, m-nitrobenzene sodium sulfonate and water；The silicon salt confining liquid includes
Silicon salt, thiocarbamide and alkali；
In phosphating solution, the concentration range of the calcium ion is 3~18g/L, and the concentration range of the zinc ion is 7~36g/
L, the concentration range of the ammonium ion are 0.9~4.5g/L, and the concentration range of the titanium salt is 0.1~1.5g/L, the winestone
The concentration range of acid is 0.8~4.5g/L, and the concentration range of the sodium fluoride is 0.1~0.8g/L, the concentration of the citric acid
Scope is 6~45g/L, and the concentration range of the m-nitrobenzene sodium sulfonate is 6~45g/L；The chromium-free metal surface conversion fluid
Total acidity be 30~80 points, free acidity be 6~25 points；
In silicon salt confining liquid, the concentration of the silicon salt is 4~16g/L, and the concentration of the thiocarbamide is 2~9g/L, the alkali
Concentration be 0.1~8g/L.Preferably, the calcium ion is the calcium ion for being dissolvable in water chromium-free metal surface conversion fluid.
Preferably, the zinc ion is the zinc ion for being dissolvable in water chromium-free metal surface conversion fluid.
Preferably, the alkali is sodium hydroxide or potassium hydroxide.
Preferably, the titanium salt is inorganic soluble titanium salt, it is further preferable that the titanium salt be titanium sulfate, titanyl sulfate or
One or more in titanium tetrachloride.
Preferably, the silicon salt is soluble silicate, it is further preferable that the silicon salt is sodium metasilicate and/or potassium silicate.
The method that above-mentioned chromium-free metal surface conversion fluid prepares conversion film, respectively using phosphating solution and silicon salt confining liquid to gold
Metal surface carries out phosphatization and silicon substrate closing；Step is the technique of the conversion film successively：Washing, oil removing, hot water wash, pickling, water
Wash, phosphatization, washing, silicon substrate closing, dry.
Preferably, oil removal treatment is carried out using the mixture solution of sodium carbonate, sodium hydroxide, OP emulsifying agents.
Preferably, pickling is carried out using the mixed solvent of sulfuric acid, sustained release agent.
Preferably, the temperature of the oil removing is 50~100 DEG C, and the oil removing time is 0.5~20min；The temperature of the hot water wash
Spend for 50~100 DEG C, the time is 0.5~20min；The time of the pickling is 0.5~20min；The time of the phosphatization be 2~
60min；The time of the silicon substrate closing is 2~60min；The time of the drying is 0.5~1000min.
Compared with prior art, the present invention has the advantages that：
Present invention optimizes the formula of phosphating solution and preparing process, there is provided the metal surface conversion film of a kind of " green "
Formula and technique, and silicon salt Seal treatment technology is combined, phosphating solution provided by the invention and silicon salt confining liquid are applied in metal
After surface treatment, there is preferable phosphatization effect, applied the volume that phosphate crystal can be reduced in Treatment of Metal Surface,
Increase the compactness of phosphate coating.Phosphating solution provided by the invention has preferable stability, has abandoned the heavy metal in original formulation,
Reduce consumption of raw materials and have compressed production cost, there is larger application value.
Brief description of the drawings
Fig. 1 carries out Treatment of Metal Surface pattern comparison diagram for the present invention；
Fig. 2 is linear polarisation curves comparison diagram after present invention progress Treatment of Metal Surface；
Fig. 3 is impedance curve comparison diagram after present invention progress Treatment of Metal Surface.
Embodiment
The present invention is further illustrated with reference to specific embodiment.Experimental method used in following embodiments is such as without spy
Different explanation, is conventional method：Used raw material, auxiliary agent etc., unless otherwise specified, being can be from business such as conventional market purchases
The raw material and auxiliary agent that approach obtains.
Embodiment 1
（1）The preparation of phosphating solution：
The concentration range of calcium ion is 10g/L, and the concentration range of the zinc ion is 10g/L, the concentration of the ammonium ion
Scope is 2g/L, and the concentration range of the titanium salt is 0.5g/L, and the concentration range of the tartaric acid is 2g/L, the sodium fluoride
Concentration range is 0.2g/L, and the concentration range of the citric acid is 10g/L, and the concentration range of the m-nitrobenzene sodium sulfonate is
10g/L；The total acidity of the chromium-free metal surface conversion fluid is 60 points, and free acidity is 15 points.
（2）The preparation of silicon salt confining liquid
The concentration of the silicon salt is 3g/L, and the concentration of the thiocarbamide is 2g/L, and the concentration of the alkali is 0.5g/L.
(3) metal surface zero waste water discharge preparation technology
Technique：Washing-- oil removing (90 DEG C, 2 minutes)-- hot water wash (90 DEG C, 2 minutes)-- pickling-- (5 points
Clock) -- washing-- phosphatization (30 minutes)-- washing --- silicon substrate is closed（30 minutes）--- dry（15 minutes）
Embodiment 2
（1）The preparation of phosphating solution：
The concentration range of calcium ion is 15g/L, and the concentration range of the zinc ion is 15g/L, the concentration of the ammonium ion
Scope is 3g/L, and the concentration range of the titanium salt is 1g/L, and the concentration range of the tartaric acid is 3g/L, the sodium fluoride it is dense
Degree scope is 0.3g/L, and the concentration range of the citric acid is 20g/L, and the concentration range of the m-nitrobenzene sodium sulfonate is 20g/
L；The total acidity of the chromium-free metal surface conversion fluid is 80 points, and free acidity is 20 points.
（2）The preparation of silicon salt confining liquid
The concentration of the silicon salt is 5g/L, and the concentration of the thiocarbamide is 3g/L, and the concentration of the alkali is 0.2g/L.
(3) metal surface zero waste water discharge preparation technology
Technique：Washing-- oil removing (80 DEG C, 2 minutes)-- hot water wash (80 DEG C, 2 minutes)-- pickling-- (2 points
Clock) -- washing-- phosphatization (20 minutes)-- washing --- silicon substrate is closed（20 minutes）--- dry（25 minutes）.
Embodiment 3
（1）The preparation of phosphating solution：
The concentration range of calcium ion is 20g/L, and the concentration range of the zinc ion is 20g/L, the concentration of the ammonium ion
Scope is 4g/L, and the concentration range of the titanium salt is 0.1g/L, and the concentration range of the tartaric acid is 5g/L, the sodium fluoride
Concentration range is 0.6g/L, and the concentration range of the citric acid is 15g/L, and the concentration range of the m-nitrobenzene sodium sulfonate is
15g/L；The total acidity of the chromium-free metal surface conversion fluid is 65 points, and free acidity is 17 points.
（2）The preparation of silicon salt confining liquid
The concentration of the silicon salt is 6g/L, and the concentration of the thiocarbamide is 3g/L, and the concentration of the alkali is 0.2g/L.
(3) metal surface zero waste water discharge preparation technology
Technique：Washing-- oil removing (70 DEG C, 2 minutes)-- hot water wash (70 DEG C, 2 minutes)-- pickling-- (2 points
Clock) -- washing-- phosphatization (20 minutes)-- washing --- silicon substrate is closed（20 minutes）--- dry（15 minutes）
Morphology analysis is carried out using Stereo microscope to the metal surface after the processing of embodiment 1, Fig. 1 is to be exaggerated 375 times
Shape appearance figure, the picture left above is the shape appearance figure of X70 steel in Fig. 1, and top right plot is shape appearance figure of the X70 steel through conventional phosphatizing, and lower-left figure is
The shape appearance figure of the X70 steel of alramenting, bottom-right graph are the shape appearance figure of the X70 steel of silicate sealant.As shown in figure 1, through the present invention
The surface of X70 steel after phosphating solution and silicon salt the confining liquid processing that embodiment 1 provides forms one layer of closely knit, grain size of arrangement
Uniform phosphate coating；After silicon salt Seal treatment, phosphate coating intercrystalline pore is largely reduced, and has more preferable sealing effect；It is and right
The crystal grain of the X70 steel surfaces after conventional phosphatizing processing in upper figure is big, crystal grain and crystal grain gap are big, and a wide range of area is not formed
Phosphate coating.
Linear polarization test is carried out to the metal after the processing of embodiment 2, after Fig. 2 carries out Treatment of Metal Surface using the present invention
Linear polarisation curves comparison diagram.X70 steel after the phosphating process that is provided by the embodiment of the present invention 2, the processing of silicon salt closing process
Linear polarisation curves understand, be declined slightly relative to corrosion current, by 55 μ A/cm2It is reduced to 36 μ A/cm2, corrosion potential by-
726 mV rises are -613 mV, and the corrosion resistance for being indicated above the metal after phosphorating treatment slightly improves.By silicon salt Seal treatment
The linear polarisation curves of X70 steel afterwards understand that the corrosion current of the X70 steel after silicon salt Seal treatment drops to 43 nA/cm2, phase
1/1000 is dropped below to unclosed sample etches electric current, is indicated above after phosphorating treatment, is re-closed, metal it is resistance to
Corrosion is greatly improved.
Testing impedance is carried out to the metal after the processing of embodiment 3, Fig. 3 is after carrying out Treatment of Metal Surface using the present invention
Impedance contrast figure.The size of low frequency range impedance in impedance diagram is related to the resistance of metal surface film layer.From the figure 3, it may be seen that by this
Although there is phosphate coating appearance on the surface of X70 steel after the processing of inventive embodiments 3, but substantial amounts of hole between crystal grain be present, hinders
Anti- value improves unobvious.After silicon salt Seal treatment, low frequency range impedance value, which has, to be greatly improved, and is increased to by 200 Ω or so
200K Ω or so, being indicated above the metal surface phosphating layer after phosphorating treatment is re-closed has fabulous barriering effect.
Claims (10)
1. a kind of chromium-free metal surface conversion fluid, it is characterised in that the chromium-free metal surface conversion fluid includes phosphating solution and silicon
Salt confining liquid, the phosphating solution include calcium salt, zinc salt, ammonium salt, titanium salt, tartaric acid, sodium fluoride, citric acid, m-nitrobenzene sulfonic acid
Sodium and water；The silicon salt confining liquid includes silicon salt, thiocarbamide and alkali；
Wherein in phosphating solution, the concentration range of calcium ion is 2~20g/L, and the concentration range of zinc ion is 5~40g/L, ammonium ion
Concentration range be 0.5~5g/L, the concentration range of the titanium salt is 0.1~2g/L, and the concentration range of the tartaric acid is 0.5
~5g/L, the concentration range of the sodium fluoride is 0.1~1g/L, and the concentration range of the citric acid is 5~50g/L, between described
The concentration range of nitrobenzene sodium sulfonate is 5~50g/L；The total acidity of the chromium-free metal surface conversion fluid is 30~90 points, trip
It it is 5~30 points from acidity；
In silicon salt confining liquid, the concentration of the silicon salt is 2~20g/L, and the concentration of the thiocarbamide is 1~10g/L, the alkali it is dense
Spend for 0.1~10g/L.
2. chromium-free metal surface conversion fluid according to claim 1, it is characterised in that the chromium-free metal surface conversion fluid bag
Include phosphating solution and silicon salt confining liquid, the phosphating solution include calcium salt, zinc salt, ammonium salt, titanium salt, tartaric acid, sodium fluoride, citric acid,
M-nitrobenzene sodium sulfonate and water；The silicon salt confining liquid includes silicon salt, thiocarbamide and alkali；
In phosphating solution, the concentration range of the calcium ion is 3~18g/L, and the concentration range of the zinc ion is 7~36g/L, institute
The concentration range for stating ammonium ion is 0.9~4.5g/L, and the concentration range of the titanium salt is 0.1~1.5g/L, the tartaric acid
Concentration range is 0.8~4.5g/L, and the concentration range of the sodium fluoride is 0.1~0.8g/L, the concentration range of the citric acid
For 6~45g/L, the concentration range of the m-nitrobenzene sodium sulfonate is 6~45g/L；The chromium-free metal surface conversion fluid it is total
Acidity is 30~80 points, and free acidity is 6~25 points；
In silicon salt confining liquid, the concentration of the silicon salt is 4~16g/L, and the concentration of the thiocarbamide is 2~9g/L, the alkali it is dense
Spend for 0.1~8g/L.
3. chromium-free metal surface conversion fluid according to claim 1, it is characterised in that the calcium ion is to be dissolvable in water Chrome-free
The calcium ion of metal surface conversion fluid.
4. chromium-free metal surface conversion fluid according to claim 1, it is characterised in that the zinc ion is to be dissolvable in water Chrome-free
The zinc ion of metal surface conversion fluid.
5. chromium-free metal surface conversion fluid according to claim 1, it is characterised in that the titanium salt is inorganic soluble titanium salt.
6. chromium-free metal surface conversion fluid according to claim 1, it is characterised in that the silicon salt is soluble silicate.
7. a kind of utilize the method that chromium-free metal surface conversion fluid prepares conversion film claim 1~6 described, it is characterised in that
Phosphatization is carried out to metal surface using phosphating solution and silicon salt confining liquid respectively and silicon substrate is closed；The technique of the conversion film walks successively
Suddenly it is：Washing, oil removing, hot water wash, pickling, washing, phosphatization, washing, silicon substrate are closed, dried.
8. method according to claim 7, it is characterised in that the mixture using sodium carbonate, sodium hydroxide, OP emulsifying agents is molten
Liquid carries out oil removal treatment.
9. method according to claim 7, it is characterised in that pickling is carried out using the mixed solvent of sulfuric acid, corrosion inhibiter.
10. method according to claim 7, it is characterised in that the temperature of the oil removing is 50~100 DEG C, and the oil removing time is
0.5~20min；The temperature of the hot water wash is 50~100 DEG C, and the time is 0.5~20min；The time of the pickling be 0.5~
20min；The time of the phosphatization is 2~60min；The time of the silicon substrate closing is 2~60min；The time of the drying is
0.5~1000min.
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