CN103898496B - A kind of novel silane nanometer trivalent chromium deactivating liquid and preparation method thereof - Google Patents
A kind of novel silane nanometer trivalent chromium deactivating liquid and preparation method thereof Download PDFInfo
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- CN103898496B CN103898496B CN201210577216.5A CN201210577216A CN103898496B CN 103898496 B CN103898496 B CN 103898496B CN 201210577216 A CN201210577216 A CN 201210577216A CN 103898496 B CN103898496 B CN 103898496B
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- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 229910000077 silane Inorganic materials 0.000 title claims abstract description 33
- 239000011651 chromium Substances 0.000 title claims abstract description 30
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 229910052804 chromium Inorganic materials 0.000 title claims abstract description 28
- 239000007788 liquid Substances 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000002253 acid Substances 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000013530 defoamer Substances 0.000 claims abstract description 15
- NZSLBYVEIXCMBT-UHFFFAOYSA-N chloro hypochlorite;zirconium Chemical class [Zr].ClOCl NZSLBYVEIXCMBT-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000004094 surface-active agent Substances 0.000 claims abstract description 13
- PMTRSEDNJGMXLN-UHFFFAOYSA-N titanium zirconium Chemical compound [Ti].[Zr] PMTRSEDNJGMXLN-UHFFFAOYSA-N 0.000 claims abstract description 13
- UVGLBOPDEUYYCS-UHFFFAOYSA-N silicon zirconium Chemical compound [Si].[Zr] UVGLBOPDEUYYCS-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052500 inorganic mineral Inorganic materials 0.000 claims abstract description 7
- 239000011707 mineral Substances 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 238000013329 compounding Methods 0.000 claims abstract 2
- 238000003756 stirring Methods 0.000 claims description 48
- 150000001875 compounds Chemical class 0.000 claims description 16
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 7
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 7
- 239000011737 fluorine Substances 0.000 claims description 7
- 229910052731 fluorine Inorganic materials 0.000 claims description 7
- 241000790917 Dioxys <bee> Species 0.000 claims description 6
- PDPJQWYGJJBYLF-UHFFFAOYSA-J hafnium tetrachloride Chemical compound Cl[Hf](Cl)(Cl)Cl PDPJQWYGJJBYLF-UHFFFAOYSA-J 0.000 claims description 6
- 235000010755 mineral Nutrition 0.000 claims description 6
- -1 silicon Alkane Chemical class 0.000 claims description 6
- 229910052708 sodium Inorganic materials 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 5
- 229910052710 silicon Inorganic materials 0.000 claims description 5
- 239000010703 silicon Substances 0.000 claims description 5
- MPPQGYCZBNURDG-UHFFFAOYSA-N 2-propionyl-6-dimethylaminonaphthalene Chemical compound C1=C(N(C)C)C=CC2=CC(C(=O)CC)=CC=C21 MPPQGYCZBNURDG-UHFFFAOYSA-N 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 4
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- 229910052700 potassium Inorganic materials 0.000 claims description 4
- 239000011591 potassium Substances 0.000 claims description 4
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical group CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 2
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 claims description 2
- BJZIJOLEWHWTJO-UHFFFAOYSA-H dipotassium;hexafluorozirconium(2-) Chemical compound [F-].[F-].[F-].[F-].[F-].[F-].[K+].[K+].[Zr+4] BJZIJOLEWHWTJO-UHFFFAOYSA-H 0.000 claims description 2
- HLJCWGPUCQTHFY-UHFFFAOYSA-H disodium;hexafluorotitanium(2-) Chemical compound [F-].[F-].[Na+].[Na+].F[Ti](F)(F)F HLJCWGPUCQTHFY-UHFFFAOYSA-H 0.000 claims description 2
- DDXLVDQZPFLQMZ-UHFFFAOYSA-M dodecyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)C DDXLVDQZPFLQMZ-UHFFFAOYSA-M 0.000 claims description 2
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 2
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 2
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 claims description 2
- ZDFDJKNMVBIUTI-UHFFFAOYSA-N 1-(2-bromopropan-2-yl)-2-dodecylbenzene Chemical compound CCCCCCCCCCCCC1=CC=CC=C1C(C)(C)Br ZDFDJKNMVBIUTI-UHFFFAOYSA-N 0.000 claims 1
- AGEZXYOZHKGVCM-UHFFFAOYSA-N benzyl bromide Chemical compound BrCC1=CC=CC=C1 AGEZXYOZHKGVCM-UHFFFAOYSA-N 0.000 claims 1
- 239000007822 coupling agent Substances 0.000 claims 1
- JHJUUEHSAZXEEO-UHFFFAOYSA-M sodium;4-dodecylbenzenesulfonate Chemical compound [Na+].CCCCCCCCCCCCC1=CC=C(S([O-])(=O)=O)C=C1 JHJUUEHSAZXEEO-UHFFFAOYSA-M 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 9
- 239000000853 adhesive Substances 0.000 abstract description 5
- 230000001070 adhesive effect Effects 0.000 abstract description 5
- 229910052735 hafnium Inorganic materials 0.000 abstract description 5
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 abstract description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 4
- 238000006243 chemical reaction Methods 0.000 abstract description 4
- 229910000831 Steel Inorganic materials 0.000 abstract description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052782 aluminium Inorganic materials 0.000 abstract description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052742 iron Inorganic materials 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 abstract description 2
- 150000003839 salts Chemical class 0.000 abstract description 2
- 239000010959 steel Substances 0.000 abstract description 2
- 239000011701 zinc Substances 0.000 abstract description 2
- 229910052725 zinc Inorganic materials 0.000 abstract description 2
- 229940126214 compound 3 Drugs 0.000 abstract 1
- PIDFDZJZLOTZTM-KHVQSSSXSA-N ombitasvir Chemical group COC(=O)N[C@@H](C(C)C)C(=O)N1CCC[C@H]1C(=O)NC1=CC=C([C@H]2N([C@@H](CC2)C=2C=CC(NC(=O)[C@H]3N(CCC3)C(=O)[C@@H](NC(=O)OC)C(C)C)=CC=2)C=2C=CC(=CC=2)C(C)(C)C)C=C1 PIDFDZJZLOTZTM-KHVQSSSXSA-N 0.000 abstract 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 7
- 229910017604 nitric acid Inorganic materials 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- 238000005260 corrosion Methods 0.000 description 6
- 230000007797 corrosion Effects 0.000 description 6
- 238000002161 passivation Methods 0.000 description 4
- 229910021564 Chromium(III) fluoride Inorganic materials 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 229940055042 chromic sulfate Drugs 0.000 description 3
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 description 3
- GRWVQDDAKZFPFI-UHFFFAOYSA-H chromium(III) sulfate Chemical compound [Cr+3].[Cr+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GRWVQDDAKZFPFI-UHFFFAOYSA-H 0.000 description 3
- 229910000356 chromium(III) sulfate Inorganic materials 0.000 description 3
- 239000011696 chromium(III) sulphate Substances 0.000 description 3
- 235000015217 chromium(III) sulphate Nutrition 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 description 3
- 239000001117 sulphuric acid Substances 0.000 description 3
- 235000011149 sulphuric acid Nutrition 0.000 description 3
- 231100000419 toxicity Toxicity 0.000 description 3
- 230000001988 toxicity Effects 0.000 description 3
- FTBATIJJKIIOTP-UHFFFAOYSA-K trifluorochromium Chemical compound F[Cr](F)F FTBATIJJKIIOTP-UHFFFAOYSA-K 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 2
- 150000001845 chromium compounds Chemical class 0.000 description 2
- 239000008139 complexing agent Substances 0.000 description 2
- 150000007522 mineralic acids Chemical group 0.000 description 2
- 229920000259 polyoxyethylene lauryl ether Polymers 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 2
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 1
- 229910021556 Chromium(III) chloride Inorganic materials 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004141 Sodium laurylsulphate Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- XHTYLQIVWOTDHP-UHFFFAOYSA-N [Cr].[Si](O)(O)(O)O Chemical compound [Cr].[Si](O)(O)(O)O XHTYLQIVWOTDHP-UHFFFAOYSA-N 0.000 description 1
- FRHOZLBTKXGMDH-UHFFFAOYSA-N [Zr].[F] Chemical compound [Zr].[F] FRHOZLBTKXGMDH-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 229940077388 benzenesulfonate Drugs 0.000 description 1
- KHSLHYAUZSPBIU-UHFFFAOYSA-M benzododecinium bromide Chemical compound [Br-].CCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 KHSLHYAUZSPBIU-UHFFFAOYSA-M 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 229960000359 chromic chloride Drugs 0.000 description 1
- 229910001430 chromium ion Inorganic materials 0.000 description 1
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 239000005543 nano-size silicon particle Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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- Chemical Treatment Of Metals (AREA)
Abstract
Invention formula relating to a kind of novel silane nanometer trivalent chromium deactivating liquid and preparation method thereof, in particular, provides its technique and preparation process.Its formula composition is formed by following raw material is compounding: chromic compound 3 10 parts, titanium zirconium (zirconium silicon) compound 38 parts, two zirconium oxychlorides (hafnium) 02 parts, silane coupler 03 parts, surface active agent 02 parts, mineral acid 15 parts, defoamer 0 0.5 parts, 70 90 parts of water.The nanometer silane trivalent chromium deactivating liquid prepared by this technique, good stability, goes for iron and steel, zinc and aluminum surface and processes, and forms nano-scale oxide conversion film on the workpiece processed, the uniformity of passivating film, fine and closely woven property can be substantially improved, and then improve its decay resistance.After adding silane coupler, film adhesive force, the hardness of passivating film, wear resistance can be improved, and then increase its salt fog time.
Description
Technical field
The present invention relates to the passivating technique of field of metal surface treatment, be specifically related to a kind of novel silane nanometer trivalent chromium blunt
Change formula of liquid and preparation method thereof.
Background technology
Chromate is the main component of common passivating solution in plating and surface process.The most general passivating solution used all selects
By hexavalent chromate, the passivating solution subject matter of the type is that chromic toxicity is big, can be carcinogenic, can produce human body and environment
Life has a strong impact on.Along with the enhancing of people's environmental consciousness, chromic application is the most gradually restricted.Due to chromic toxicity
Only the 1% of Cr VI toxicity, and the trivalent chromium of trace or the metal ion of needed by human, and trivalent chromium cost of material phase
To relatively low, therefore, trivalent chromium replaces Cr VI, will be substantially reduced the passivating solution pollution to environment.Trivalent chromium is as passivating solution
Main component has been applied to produce, and achieves good result.First generation trivalent chromium deactivating liquid complexing agent is mainly fluorine
Compound, its corrosion-resistant, the most gradually it is eliminated.Second filial generation trivalent chromium deactivating liquid complexing agent mainly selects organic complex,
And adding other metal, its corrosion resistance is greatly improved；But the passivation layer surface formed is coarse, there is many micropores lacks
Fall into, affect brightness and its decay resistance of passivation layer.Third generation trivalent chromium deactivating liquid is on the basis of the second filial generation, directly
Add hole sealing agent and further increase the corrosion resistance of film layer, more convergence and actual application.
In prior art, the hole sealing agent that passivating solution is added has acidic silicasol and nano silicon oxide etc..Chinese patent
CN101158038A discloses and adds the diameter acidic silicasol less than 10 nanometers in the formula of a kind of passivating solution, and it is to passivating film
Brightness impact less, the hardness of passivating film can be increased simultaneously.But Ludox may react with trivalent chromium, generate
The silicic acid chromium of indissoluble, may cause the uniformity of passivating film to reduce, affect its corrosion resistance.Master's thesis " the electricity of Zhang Jinsheng
Galvanized sheet Cr3+Passivation and technical study " in add nanoscale silicon close the space in passivating film, but nano oxidized
Silicon is dispersed in passivating solution as heterogeneous, and its surface can be the highest, is susceptible to reunite, therefore can not well be formed uniformly
Passivation layer.
Summary of the invention
The present invention seeks to the shortcoming being to overcome prior art, it is provided that a kind of filming performance is more preferable, and adhesive force is higher, anti-
The method of the rotten more preferable trivalent chromium deactivating liquid of effect.
For reaching above-mentioned purpose, the technical solution used in the present invention is: add filming performance in chromic passivating solution
Preferably silane based compound, it is achieved passivating process film forming is more uniform, and the passivating film corrosion resistance of formation is higher, is simultaneously introduced
Silane coupler film forming after, abrasion resistance properties also can be improved, and can extend the use time of passivating film；Addition zirconium system,
After zirconium titanium sub-group compound, form nm amorphous state ZrO2New conversion film, and between metal surface and painting layer subsequently
Having good adhesive force, the compactness of passivating film is more preferable, fine corrosion resistance.
The nanometer silane type trivalent chromium deactivating liquid that the present invention relates to, is primarily adapted for use in iron and steel, zinc and aluminum surface and processes, at place
Form nano ceramics conversion film on the workpiece of reason, strengthen adhesive force and the decay resistance of application.
Nanometer silane trivalent chromium deactivating liquid component prescription involved in the present invention is: chromic compound 3-10 part, titanium
Zirconium (zirconium silicon system) compound 3-8 part, two zirconium oxychlorides (hafnium) 0-2 part, silane coupler 0-3 part, surface active agent 0-2 part, nothing
Machine acid 1-5 part, defoamer 0-0.5 part, water 70-90 part.
The present invention also provides for the preparation method of a kind of novel silane nanometer trivalent chromium deactivating liquid, comprises the following steps:
One, various raw material is weighed in proportion；
Two, adding titanium zirconium (zirconium silicon) compound weighed in its 2/3 water requirement, stirring is to dissolving；
Three, adding chromic compound in the solution that step 2 prepares, stirring is to dissolving；
Four, adding mineral acid in the solution that step 3 prepares, stirring is to dissolving；
Five, adding two zirconium oxychlorides (hafnium) in the solution that step 4 prepares, stirring is to dissolving；
Six, adding silane coupler in the solution that step 5 prepares, stirring is to dissolving；
Seven, adding surfactant in the solution that step 6 prepares, stirring is to dissolving；
Eight, adding defoamer in the solution that step 7 prepares, stirring is to dissolving；
Nine, adding the remaining water yield in the solution that step 8 prepares, stirring is to being uniformly dissolved.
The present invention compared with prior art has the advantage that
1, the trivalent chromium deactivating liquid of the present invention adds titanium zirconium compounds, the nano-scale oxide conversion film of formation, permissible
The uniformity of passivating film, compactness are substantially improved, and then improve its decay resistance；
2, film adhesive force, the hardness of film, wear resistance can be improved after the silane coupler film forming added in the present invention,
And then increase the passivating solution salt fog time；
3, in passivating solution used by the present invention, containing a small amount of trivalent chromium compound, the chromium ion danger to environment is greatly reduced
Evil.
Detailed description of the invention
A kind of novel silane nanometer trivalent chromium deactivating liquid, its formula consists of: chromic compound 3-10 part, titanium zirconium
(zirconium silicon system) compound 3-8 part, two zirconium oxychlorides (hafnium) 0-2 part, silane coupler 0-3 part, surface active agent 0-2 part is inorganic
Acid 1-5 part, defoamer 0-0.5 part, water 70-90 part.
The optimal composition (mass fraction) of this nanometer silane trivalent chromium deactivating liquid is: chromic compound 3-5 part, titanium zirconium
(zirconium silicon system) compound 3-5 part, two zirconium oxychlorides (titanium) 0-1 part, silane coupler 0-1 part, surface active agent 0-1 part is inorganic
Acid 1-3 part, defoamer 0-0.3 part, water 85-90 part.
Trivalent chromium compound of the present invention can be chromic sulfate, chromic nitrate, chromium trifluoride, chromium trichloride, three oxidations
One or more in two chromium etc.；Described titanium zirconium (zirconium silicon system) compound can be fluorine zirconic acid, fluotitanic acid, hexafluosilicic acid, fluorine zirconium
One in acid ammonium, potassium fluorozirconate, sodium fluozirconate, potassium fluotitanate, titanium sodium fluoride, ammonium fluosilicate, prodan, potassium fluosilicate etc.
Or it is multiple；Described silane coupler can be gamma-aminopropyl-triethoxy-silane KH550, γ-glycidoxypropyl
Trimethoxy silane KH560, γ-methacryloxypropyl trimethoxy silane KH570, acrylic propyl trimethoxy
Silane KBM-5103, VTES KBE-1003 etc. the inside one or more；Described surface active agent
Fatty alcohol-polyoxyethylene ether, Polyethylene Glycol, alkylphenol polyoxyethylene, sodium lauryl sulphate, dodecyl sodium sulfate, 12
One or more in sodium alkyl benzene sulfonate, Dodecyl trimethyl ammonium chloride, dodecyl dimethyl benzyl ammonium bromide etc. etc.
In one or more；Described mineral acid can be in nitric acid, hydrochloric acid, phosphoric acid, sulphuric acid, Fluohydric acid., hydrobromic acid etc.
Plant or multiple；Described defoamer can be in mineral oil defoaming agent, silicon-type defoamer, polyethers defoamer etc.
Plant or multiple.
The method preparing novel nano silane type trivalent chromium deactivating liquid is as follows:
One, various raw material is weighed in proportion；
Two, adding titanium zirconium (zirconium silicon) compound weighed in its 2/3 water requirement, stirring is to dissolving；
Three, adding chromic compound in the solution that step 2 prepares, stirring is to dissolving；
Four, adding mineral acid in the solution that step 3 prepares, stirring is to dissolving；
Five, adding two zirconium oxychlorides (hafnium) in the solution that step 4 prepares, stirring is to dissolving；
Six, adding silane coupler in the solution that step 5 prepares, stirring is to dissolving；
Seven, adding surfactant in the solution that step 6 prepares, stirring is to dissolving；
Eight, adding defoamer in the solution that step 7 prepares, stirring is to dissolving；
Nine, adding the remaining water yield in the solution that step 8 prepares, stirring is to being uniformly dissolved.
For the ease of being familiar with the preparation of such nanometer silane trivalent chromium deactivating liquid, in conjunction with embodiment, the present invention is carried out in detail
Thin description:
Embodiment 1
A kind of preparation method of nanometer silane trivalent chromium deactivating liquid, its step is as follows:
1) chromic sulfate 3 parts is weighed, fluorine zirconic acid 3 parts, sodium fluozirconate 1.5 parts, two zirconium oxychlorides 0.3 part, KH550 0.5 part,
Polyoxyethylene lauryl ether 0.3 part, 2 parts of nitric acid, hydrochloric acid 1 part, organic silicon defoamer 0.1 part, 88.3 parts of water；
2) in 50 parts of water, 3 parts of fluorine zirconic acid stirrings are added to fully dissolving；
3) 1.5 parts of sodium fluozirconate stirrings are added in step 2 to fully dissolving；
4) 3 parts of chromic sulfate stirrings are added in step 3 to fully dissolving；
5) 2 parts of nitric acid, 1 part of hydrochloric acid stirring are added in step 4 to dissolving；
6) 0.3 part of two zirconium oxychloride stirring is added in steps of 5 to fully dissolving；
7) 0.5 part of KH550 stirring is added in step 6 to fully dissolving；
8) the polyoxyethylene lauryl ether stirring of 0.3 part is added in step 7 to dissolving；
9) the organic silicon defoamer stirring of 0.1 part is added in step 8 to dissolving
10) add 38.3 parts of water in step 9 to stir to mix homogeneously.
Embodiment 2
A kind of preparation method of nanometer silane trivalent chromium deactivating liquid, its step is as follows:
1) chromium trifluoride 5 parts is weighed, fluorine zirconic acid 4 parts, ammonium fluosilicate 3 parts, two zirconium oxychlorides 0.5 part, KH560 0.5 part,
1 part of nitric acid, phosphoric acid 0.5 part, 85.5 parts of water；
2) in 50 parts of water, 4 parts of fluorine zirconic acid stirrings are added to fully dissolving；
3) 3 parts of ammonium fluosilicate stirrings are added in step 2 to fully dissolving；
4) 5 parts of chromium trifluoride stirrings are added in step 3 to fully dissolving；
5) 1 part of nitric acid, 0.5 part of phosphoric acid stirring are added in step 4 to dissolving；
6) 0.5 part of two zirconium oxychloride stirring is added in steps of 5 to fully dissolving；
7) 0.5 part of KH560 stirring is added in step 6 to fully dissolving；
8) add 35.5 parts of water in step 7 to stir to mix homogeneously.
Embodiment 3
A kind of preparation method of nanometer silane trivalent chromium deactivating liquid, its step is as follows:
1) chromic nitrate 6 parts, hexafluosilicic acid 2 parts, prodan 3 parts, dioxy hafnium chloride 0.3 part, KH550 1 part, nitric acid 3 are weighed
Part, 1 part of sulphuric acid, Polyethylene Glycol 0.5 part, 83.2 parts of water；
2) in 50 parts of water, 2 parts of hexafluosilicic acid stirrings are added to fully dissolving；
3) 3 parts of prodan stirrings are added in step 2 to fully dissolving；
4) 6 parts of chromic nitrate stirrings are added in step 3 to fully dissolving；
5) 3 parts of nitric acid, 1 part of sulphuric acid stirring are added in step 4 to dissolving；
6) 0.3 part of two zirconium oxychloride stirring is added in steps of 5 to fully dissolving；
7) 1 part of KH550 stirring is added in step 6 to fully dissolving；
8) 0.5 part of Polyethylene Glycol stirring is added in step 7 to fully dissolving
9) add 33.2 parts of water in step 8 to stir to mix homogeneously.
Claims (2)
1. a nanometer silane trivalent chromium deactivating liquid, it is characterised in that according to mass fraction, form including following raw material is compounding:
Chromic compound 3-10 part, titanium zirconium and/or zirconium silicon compound 3-8 part, two zirconium oxychlorides or dioxy hafnium chloride 0-2 part, silicon
Alkane coupling agent 0-3 part, surface active agent 0-2 part, mineral acid 1-5 part, defoamer 0-0.5 part, water 70-90 part；
Wherein, two zirconium oxychlorides or dioxy hafnium chloride, silane coupler, surface active agent, defoamer are not zero；
Described titanium zirconium and/or zirconium silicon compound are fluorine zirconic acid, fluotitanic acid, hexafluosilicic acid, ammonium fluozirconate, potassium fluorozirconate, fluorine zirconic acid
One or more in sodium, potassium fluotitanate, titanium sodium fluoride, ammonium fluosilicate, prodan, potassium fluosilicate；
Described silane coupler is gamma-aminopropyl-triethoxy-silane KH550, γ-glycidoxypropyl trimethoxy
Silane KH560, γ-methacryloxypropyl trimethoxy silane KH570, acrylic propyl trimethoxy silicane KBM-
5103, one or more in VTES KBE-1003；
Described surface active agent is fatty alcohol-polyoxyethylene ether, Polyethylene Glycol, alkylphenol polyoxyethylene, lauryl sulphate acid
Sodium, dodecyl sodium sulfate, dodecylbenzene sodium sulfonate, Dodecyl trimethyl ammonium chloride, dodecyl dimethyl benzyl bromide a-bromotoluene
Change one or more in ammonium.
2. the preparation method of a nanometer silane trivalent chromium deactivating liquid, it is characterised in that comprise the following steps:
One, raw material is weighed by following mass fraction: chromic compound 3-10 part, titanium zirconium and/or zirconium silicon compound 3-8 part,
Two zirconium oxychlorides or dioxy hafnium chloride 0-2 part, silane coupler 0-3 part, surface active agent 0-2 part, mineral acid 1-5 part, froth breaking
Agent 0-0.5 part, water 70-90 part；Wherein, two zirconium oxychlorides or dioxy hafnium chloride, silane coupler, surface active agent, defoamer
It is not zero；
Two, adding the titanium zirconium weighed and/or zirconium silicon compound in its 2/3 water requirement, stirring is to dissolving；
Three, adding chromic compound in the solution that step 2 prepares, stirring is to dissolving；
Four, adding mineral acid in the solution that step 3 prepares, stirring is to dissolving；
Five, adding two zirconium oxychlorides or dioxy hafnium chloride in the solution that step 4 prepares, stirring is to dissolving；
Six, adding silane coupler in the solution that step 5 prepares, stirring is to dissolving；
Seven, adding surfactant in the solution that step 6 prepares, stirring is to dissolving；
Eight, adding defoamer in the solution that step 7 prepares, stirring is to dissolving；
Nine, adding the remaining water yield in the solution that step 8 prepares, stirring is to being uniformly dissolved.
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| CN104233252B (en) * | 2014-09-16 | 2016-08-24 | 南京华锐化工有限公司 | A kind of room temperature non-phosphate film agent |
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| CN106048514A (en) * | 2016-06-27 | 2016-10-26 | 滁州帝邦科技有限公司 | Preparing method for wear-resisting steel used for water-cooling nozzle |
| CN107236948B (en) * | 2017-06-07 | 2019-02-22 | 广州传福化学技术有限公司 | A kind of passivator for inhibiting zinc coating trivalent chromium to be oxidized to Cr VI |
| CN110809634A (en) * | 2017-07-03 | 2020-02-18 | 深圳市宏昌发科技有限公司 | Passivating agent, metal workpiece and surface passivation method thereof |
| CN108004532A (en) * | 2017-12-20 | 2018-05-08 | 苏州禾川化学技术服务有限公司 | A kind of self-styled closed form trivalent chromium bright blue passivator |
| CN108642482A (en) * | 2018-07-03 | 2018-10-12 | 苏州大韩化工有限公司 | A kind of chromium-free passivation liquid and preparation method thereof |
| CN110760832A (en) * | 2019-12-05 | 2020-02-07 | 佛山市南海高益美环保实业有限公司 | Trivalent chromium cobalt-free color passivator with high corrosion resistance for electro-galvanized layer |
| CN112663037B (en) * | 2020-12-04 | 2023-02-03 | 佛山市顺德区美硕金属表面技术有限公司 | Vitrification agent, preparation method and application thereof |
| CN114016692A (en) * | 2021-11-09 | 2022-02-08 | 晋江市新思维环保科技有限公司 | Honeycomb aluminum plate based on hot press molding and preparation process thereof |
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