CN102899653A - Stainless steel passivation water solution and preparation method thereof - Google Patents
Stainless steel passivation water solution and preparation method thereof Download PDFInfo
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- CN102899653A CN102899653A CN201110212948XA CN201110212948A CN102899653A CN 102899653 A CN102899653 A CN 102899653A CN 201110212948X A CN201110212948X A CN 201110212948XA CN 201110212948 A CN201110212948 A CN 201110212948A CN 102899653 A CN102899653 A CN 102899653A
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- stainless steel
- passivation
- aqueous solution
- molybdate
- acid
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- 229910001220 stainless steel Inorganic materials 0.000 title claims abstract description 94
- 239000010935 stainless steel Substances 0.000 title claims abstract description 93
- 238000002161 passivation Methods 0.000 title claims abstract description 84
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 40
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000012964 benzotriazole Substances 0.000 claims abstract description 22
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000001509 sodium citrate Substances 0.000 claims abstract description 22
- BRWIZMBXBAOCCF-UHFFFAOYSA-N hydrazinecarbothioamide Chemical compound NNC(N)=S BRWIZMBXBAOCCF-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 20
- 239000000243 solution Substances 0.000 claims description 68
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 claims description 21
- 229940038773 trisodium citrate Drugs 0.000 claims description 21
- 239000007864 aqueous solution Substances 0.000 claims description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 17
- 239000002253 acid Substances 0.000 claims description 16
- IIACRCGMVDHOTQ-UHFFFAOYSA-M sulfamate Chemical compound NS([O-])(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-M 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 11
- 230000003750 conditioning effect Effects 0.000 claims description 11
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 10
- 229910052700 potassium Inorganic materials 0.000 claims description 10
- 239000011591 potassium Substances 0.000 claims description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- VPTUPAVOBUEXMZ-UHFFFAOYSA-N (1-hydroxy-2-phosphonoethyl)phosphonic acid Chemical compound OP(=O)(O)C(O)CP(O)(O)=O VPTUPAVOBUEXMZ-UHFFFAOYSA-N 0.000 claims description 8
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 7
- 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 6
- 229910052708 sodium Inorganic materials 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 6
- -1 hydroxy butylidene Chemical group 0.000 claims description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- 239000011609 ammonium molybdate Substances 0.000 claims description 4
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 4
- 229940010552 ammonium molybdate Drugs 0.000 claims description 4
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- JJJOZVFVARQUJV-UHFFFAOYSA-N 2-ethylhexylphosphonic acid Chemical compound CCCCC(CC)CP(O)(O)=O JJJOZVFVARQUJV-UHFFFAOYSA-N 0.000 claims description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 2
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 claims description 2
- 230000007797 corrosion Effects 0.000 abstract description 27
- 238000005260 corrosion Methods 0.000 abstract description 27
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 abstract description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 abstract description 5
- 229910017604 nitric acid Inorganic materials 0.000 abstract description 5
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 abstract description 5
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 abstract 1
- 239000003002 pH adjusting agent Substances 0.000 abstract 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 abstract 1
- 150000003839 salts Chemical class 0.000 description 19
- 230000007935 neutral effect Effects 0.000 description 18
- 238000007747 plating Methods 0.000 description 18
- 239000007921 spray Substances 0.000 description 18
- 239000000126 substance Substances 0.000 description 18
- 238000012360 testing method Methods 0.000 description 18
- 239000007788 liquid Substances 0.000 description 16
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 15
- 229910052802 copper Inorganic materials 0.000 description 15
- 239000010949 copper Substances 0.000 description 15
- 229910000906 Bronze Inorganic materials 0.000 description 14
- 239000010974 bronze Substances 0.000 description 14
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 14
- 239000004033 plastic Substances 0.000 description 13
- 229920003023 plastic Polymers 0.000 description 13
- 238000002474 experimental method Methods 0.000 description 10
- 241001163841 Albugo ipomoeae-panduratae Species 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 238000011056 performance test Methods 0.000 description 9
- 239000002994 raw material Substances 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- 238000004321 preservation Methods 0.000 description 8
- 230000001105 regulatory effect Effects 0.000 description 7
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 239000012528 membrane Substances 0.000 description 6
- 230000001681 protective effect Effects 0.000 description 6
- 238000007772 electroless plating Methods 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000009713 electroplating Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 102000004160 Phosphoric Monoester Hydrolases Human genes 0.000 description 3
- 108090000608 Phosphoric Monoester Hydrolases Proteins 0.000 description 3
- 238000000280 densification Methods 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 239000012756 surface treatment agent Substances 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- AFWGHYJWBLURRI-UHFFFAOYSA-N aminothiourea azane Chemical compound NNC(=S)N.N AFWGHYJWBLURRI-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 229960004424 carbon dioxide Drugs 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006388 chemical passivation reaction Methods 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 235000011389 fruit/vegetable juice Nutrition 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- 201000004792 malaria Diseases 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000008261 resistance mechanism Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
Landscapes
- Preventing Corrosion Or Incrustation Of Metals (AREA)
- Chemical Treatment Of Metals (AREA)
Abstract
The invention provides a stainless steel passivation water solution. The solution comprises the components of: molybdate, sulfamic acid, organic phosphoric acid, sodium citrate, benzotriazole, thiosemicarbazide, and a pH adjusting agent. The invention also provides a preparation method of the stainless steel passivation water solution. The stainless steel passivation water solution provided by the invention does not contain harmful components of nitric acid, hydrofluoric acid, and potassium dichromate. The solution is an environment-friendly novel alkaline passivation solution. A stainless steel passivation layer processed by the passivation of the passivation solution is compact and has good corrosion resistance.
Description
Technical field
The invention belongs to metal finishing and aseptic technic field, be specifically related to a kind of passivation for stainless steel aqueous solution and preparation method thereof.
Background technology
Stainless steel is because its superior solidity to corrosion is widely used in the every field of modern society.Yet in many corrosive atmosphere media, stainless corrosion still often occurs, especially easily the larger local corrosion of Occurrence.Further investigation stainless steel corrosion resistance mechanism, for instructing, the development corrosion proof stainless steel novel material of superelevation and surface modification new technology are significant.
Stainless steel be one deck of forming by its surface as thin as a wafer and firm fine and closely woven stable rich chromium oxide film (protective film) prevents that the continuation of Sauerstoffatom from infiltrating, continues oxidation, and obtain corrosion protection ability.Once this film has suffered constantly isolating of iron atom in the continuous infiltration of Sauerstoffatom or metal because of certain reason, easily forms loose ferric oxide, metallic surface also just is subject to constantly corrosion.The form that this oxide film is damaged is a lot, and common in daily life have following four kinds:
1. stainless steel surface is stockpiling the dust that contains other metallic elements or the dirt settling of disparate metals particle, in malaria, and the water of condensation between dirt settling and stainless steel, the two is linked to be to a microbattery, caused electrochemical reaction, protective membrane is damaged, and is referred to as galvanic corrosion;
2. stainless steel surface adheres to organism juice, is having in water oxygen situation, forms organic acid, and organic acid produces corrosion to metallic surface for a long time;
3. stainless steel surface adheres to and contains acid, alkali, salts substances (as buck, the liming splash of finishing wall), causes local corrosion;
4. in the air of pollution is arranged (as the atmosphere that contains a large amount of sulfide, carbonoxide, nitrogen oxide), meet water of condensation, forms sulfuric acid, nitric acid, acetate solution point, causes chemical corrosion.
Breaking and transmission that the generating process of spot corrosion has comprised electronics and ion of stainless steel surface passive film, the transmission of electric charge occurs under electric field driven, and electric field is subject to the impact of passive film electronic structure.Therefore, passive film solidity to corrosion and its semi-conductor electricity sub-feature are closely related.There are some researches show, stainless solidity to corrosion depends on composition, structure and the thickness etc. of its surface passivated membrane to a great extent.The development of the science and technology by recent years, the process for treating surface that has developed many advanced persons carries out modification as physical techniques such as ionic fluid, electron beam and laser beams to passivation film on stainless steel surface, attempts to improve stainless corrosion resisting property.But, in real world applications, major part is still carried out passivation by the method for chemical passivation to stainless steel.
Processed by chemical method, can be formed the passive film of thin layer at stainless steel surface, substantially do not changed outward appearance, the size and shape of base material.Due to the method difference of film forming, film forming mechanism is also inconsistent, but is substantially all to generate the protective membrane of one deck densification at stainless steel surface, makes the isolated gas of stainless steel surface and other external corrosion media.From early stage nitric acid passivation to utilizing the strong oxidizing property material passivation such as potassium bichromate, to the passivating technique that utilizes the configuration of inhibition synergistic effect of latest modern technological, slowly never environmental protection changes to environmental protection.
Summary of the invention
In order to have solved the poor technical problem that reaches not environmental protection of the stainless steel solidity to corrosion when laggard electroplating or electroless plating are combined in plastics, rubber, pottery, the injection moulding of spraying sample existed in the prior art, the invention provides a kind of while not containing nitric acid, hydrofluoric acid, the passivation for stainless steel aqueous solution of potassium bichromate objectionable constituent comprises component: molybdate, sulfamate, organic phosphoric acid, Trisodium Citrate, benzotriazole, ammonia thiosemicarbazide, PH conditioning agent.
The present invention also provides the preparation method of the above-mentioned passivation for stainless steel aqueous solution, comprises step: 1) take molybdate, Trisodium Citrate and sulfamate, three's mixing and water adding stirring and dissolving is obtained to the solution I; 2) take benzotriazole and thiosemicarbazide, both mix and blends are dissolved to obtain to the solution II; 3) by solution I and solution II mix and blend, add organic phosphoric acid, finally with the PH conditioning agent, regulate PH, obtain the passivation for stainless steel aqueous solution.
Passivating solution provided by the invention does not contain nitric acid simultaneously, hydrofluoric acid, and the objectionable constituent such as potassium bichromate, be a kind of novel alkaline passivating solution of environment-friendly type.And the passivation for stainless steel layer after passivating solution provided by the invention is processed is fine and close, preservative property are good, to the stainless steel through after passivating solution provided by the invention is processed with plastic injection-moulded together with after while carrying out electroless plating, stainless steel parts can not react in chemical bronze plating liquid, only have the plastics activated partial to react, make plastic stainless-steel copper facing easy.In addition, this passivating solution can also be for stainless steel and rubber, pottery, and the spraying sample is injection-moulded in the conservation treatment of being electroplated together.Be not limited only to the electroplating technology that stainless steel and plastic injection-moulded combination are carried out.
Embodiment
The invention provides a kind of passivation for stainless steel aqueous solution, comprise component: molybdate, sulfamate, organic phosphoric acid, Trisodium Citrate, benzotriazole, thiosemicarbazide, PH conditioning agent.These components all can be directly by commercially available, and what adopt those skilled in the art to commonly use gets final product, and at this, does not do and repeats.
According to the present invention, described passivating solution PH is 9.5-10.5.
According to the present invention, the content of each component proportion in every liter of passivating solution of described passivating solution is: molybdate 10-20g/L, thionamic acid 1-3g/L, organic phosphoric acid 1-15ml/L, Trisodium Citrate 5-15g/L, benzotriazole 1-10g/L, thiosemicarbazide 0.1-1g/L
.
According to the present invention, the content of each component proportion in every liter of passivating solution of described passivating solution is preferably: molybdate 13-18g/L, thionamic acid 1.5-2g/L, organic phosphoric acid 3-12ml/L, Trisodium Citrate 7-13g/L, benzotriazole 4-8g/L, thiosemicarbazide 0.2-0.8g/L.
According to the present invention, described molybdate is at least one in Sodium orthomolybdate, potassium molybdate, ammonium molybdate.Molybdate can be removed the zone of oxidation of stainless steel surface at a certain temperature, stainless steel surface is played to preliminary microetch role simultaneously, and forms one deck protective membrane to a certain degree.
According to the present invention, described organic phosphoric acid is a kind of in hydroxy ethylene diphosphonic acid, hydroxy butylidene di 2 ethylhexyl phosphonic acid, ethylenediamine tetramethylene phosphoric acid.The present inventor finds by a large amount of experiments; organic phosphoric acid is preferably hydroxy ethylene diphosphonic acid (HEDP) and benzotriazole, thiosemicarbazide three and can be adsorbed in a large number on the surperficial pore after the stainless steel microetch; by the chemical cooperated preliminary film of molybdate reaction formation that acts on, be bound up; then form the protective membrane of one deck densification, this protective membrane has extremely strong strong basicity resisting effect.
In addition, Trisodium Citrate of the present invention is in order to assist to remove stainless zone of oxidation, and free out iron ion or bring other metallic impurity ion in passivating solution in the passivating process of complexing simultaneously, improve the life-span of passivating solution.
According to the present invention, described PH conditioning agent is at least one in sodium hydroxide, potassium hydroxide, ammoniacal liquor.Described PH conditioning agent works to regulate PH.
According to the present invention, described sulfamate is selected from a kind of in thionamic acid sodium, thionamic acid potassium.
According to invention, preferably, the content of each component proportion of described passivating solution in every premium on currency is: molybdate 10g/L, thionamic acid 3g/L, organic phosphoric acid 12ml/L, Trisodium Citrate 10g/L, benzotriazole 4g/L, thiosemicarbazide 0.6g/L.
The present invention also provides the preparation method of passivation for stainless steel liquid of the present invention, and it comprises step: 1) take molybdate, Trisodium Citrate and sulfamate, three's mixing and water adding stirring and dissolving is obtained to the solution I; 2) take benzotriazole and thiosemicarbazide, both mix and blends are dissolved to obtain to the solution II; 3) by solution I and solution II mix and blend, add organic phosphoric acid, finally add the PH conditioning agent to regulate PH, obtain the passivation for stainless steel aqueous solution.
Stainless steel is with the plastic injection-moulded effect that can play raising plastic casing mechanical property together, but, when containing stainless plastic electroplating surface treatment, because a lot of surface treatment agents are strong acid and strong base strong oxidizing properties, therefore need to carry out passivation to stainless steel and can not be corroded or variable color in order to play stainless steel after above-mentioned surface treatment agent is processed.The stainless steel of processing through general passivating solution, can in chemical bronze plating liquid, react, stainless steel after passivating solution Passivation Treatment provided by the invention can not react in chemical bronze plating liquid, just the plastics activated partial has played reaction, thereby has solved the problem of industry about plastic stainless-steel copper facing difficulty.The passivation for stainless steel aqueous solution provided by the invention is a kind of novel environmental protection passivating solution; passivation for stainless steel layer densification after this passivating solution Passivation Treatment; naked eyes can't be seen; not only in surroundings, be conducive to stainless anticorrosion; the plastic electroplating field can also be applied to well; can prevent from containing stainless plastics and electroplate, when electroless plating is processed, stainless steel is corroded.The stainless steel of processing through this passivating solution can be in chemical bronze plating liquid and pyrochemistry nickel-plating liquid Fails To Respond, appearance is without considerable change.
In addition; this passivating solution can also be for stainless steel and rubber; pottery waits and to be injection-moulded in the stainless steel protection that workpiece together electroplated and to process, but but and the non-stainless steel parts spraying on the above-mentioned materials surface, prints potential catalytic chemistry plating or stainless steel protection that directly coating of catalytic chemistry plating particle is carried out for the workpiece of electroless plating is processed.Be not limited only to plating or electroless plating and other process of surface treatment that stainless steel and plastic injection-moulded combination are carried out.
In order to make technical problem solved by the invention, technical scheme and beneficial effect clearer, below in conjunction with embodiment, the present invention is further elaborated.What in embodiment and Comparative Examples, adopt all was commercially available originally.
The concrete operation step of the passivating solution preparation of following examples 1-7 is: concrete operation step is: 1) take molybdate, Trisodium Citrate and sulfamate, three's mixing and water adding stirring and dissolving is obtained to the solution I; 2) take benzotriazole and thiosemicarbazide, both mix and blends are dissolved to obtain to the solution II; 3) by solution I and solution II mix and blend, add organic phosphoric acid, finally with the PH conditioning agent, regulate PH, obtain the passivation for stainless steel aqueous solution.Wherein, the term that 301 stainless steel plates are known to the skilled person; Stainless steel after Passivation Treatment is put into chemical bronze plating liquid and is not reacted after 4 hours and reach the excellent results needed.
Embodiment 1
1, join and get passivating solution: in every premium on currency, the shared weight part of following raw materials is: Sodium orthomolybdate 10g/L, thionamic acid sodium 2g/L, hydroxy ethylene diphosphonic acid 1ml/L, Trisodium Citrate 15g/L, benzotriazole 1g/L, thiosemicarbazide 1g/L; Regulating PH with sodium hydroxide is 9.5, obtains passivating solution;
2, Passivation Treatment: 301 stainless steel plates are Passivation Treatment 60min in above-mentioned passivating solution, and passivation temperature is 65 ℃, and after passivation finishes, water cleans stand-by or dries up preservation.
3, performance test
1. neutral salt spray test: with reference to international GB/T 10125-1997, through the 168h neutral salt spray test, the specimen surface white rust is less than 2%, illustrates that the passive film solidity to corrosion is good.
2. electroless copper experiment: the stainless steel after Passivation Treatment in above-mentioned steps 2 is put into to chemical bronze plating liquid, take out after 4 hours, any reaction does not occur in stainless steel.
Embodiment 2
1, join and get passivating solution: in every premium on currency, the shared weight part of following raw materials is: Sodium orthomolybdate 15g/L, thionamic acid sodium 3g/L, hydroxy ethylene diphosphonic acid 15ml/L, Trisodium Citrate 10g/L, benzotriazole 7g/L, thiosemicarbazide 0.7g/L; Regulating PH with sodium hydroxide is 10.5, obtains passivating solution;
2, Passivation Treatment: 301 stainless steel plates are Passivation Treatment 60min in above-mentioned passivating solution, and passivation temperature is 65 ℃, and after passivation finishes, water cleans stand-by or dries up preservation.
3, performance test
1. neutral salt spray test: with reference to international GB/T 10125-1997, through the 168h neutral salt spray test, the specimen surface white rust is less than 1%, illustrates that the passive film solidity to corrosion is good.
2. electroless copper experiment: the stainless steel after Passivation Treatment in above-mentioned steps 2 is put into to chemical bronze plating liquid, take out after 6 hours, any reaction does not occur in stainless steel.
Embodiment 3
1, join and get passivating solution: in every premium on currency, the shared weight part of following raw materials is: Sodium orthomolybdate 20g/L, thionamic acid sodium 1g/L, hydroxy ethylene diphosphonic acid 10ml/L, Trisodium Citrate 5g/L, benzotriazole 10g/L, thiosemicarbazide 0.1g/L; Regulating PH with sodium hydroxide is 10, obtains passivating solution;
2, Passivation Treatment: 301 stainless steel plates are Passivation Treatment 60min in above-mentioned passivating solution, and passivation temperature is 65 ℃, and after passivation finishes, water cleans stand-by or dries up preservation.
3, performance test
1. neutral salt spray test: with reference to international GB/T 10125-1997, through the 168h neutral salt spray test, the specimen surface white rust is less than 1%, illustrates that the passive film solidity to corrosion is good.
2. electroless copper experiment: the stainless steel after Passivation Treatment in above-mentioned steps 2 is put into to chemical bronze plating liquid, take out after 6 hours, any reaction does not occur in stainless steel.
Embodiment 4
1, join and get passivating solution: in every premium on currency, the shared weight part of following raw materials is: Sodium orthomolybdate 13g/L, thionamic acid sodium 1.5g/L, hydroxy ethylene diphosphonic acid 12ml/L, Trisodium Citrate 13g/L, benzotriazole 4g/L, thiosemicarbazide 0.2g/L; Regulating PH with sodium hydroxide is 10, obtains passivating solution;
2, Passivation Treatment: 301 stainless steel plates are Passivation Treatment 60min in above-mentioned passivating solution, and passivation temperature is 65 ℃, and after passivation finishes, water cleans stand-by or dries up preservation.
3, performance test
1. neutral salt spray test: with reference to international GB/T 10125-1997, through the 168h neutral salt spray test, the specimen surface white rust is less than 1%, illustrates that the passive film solidity to corrosion is good.
2. electroless copper experiment: the stainless steel after Passivation Treatment in above-mentioned steps 2 is put into to chemical bronze plating liquid, take out after 6 hours, any reaction does not occur in stainless steel.
Embodiment 5
1, join and get passivating solution: in every premium on currency, the shared weight part of following raw materials is: potassium molybdate 18g/L, thionamic acid potassium 2g/L, hydroxy butylidene di 2 ethylhexyl phosphonic acid 3ml/L, Trisodium Citrate 7g/L, benzotriazole 8g/L, thiosemicarbazide 0.8g/L; Regulating PH with potassium hydroxide is 10, obtains passivating solution;
2, Passivation Treatment: 301 stainless steel plates are Passivation Treatment 60min in above-mentioned passivating solution, and passivation temperature is 65 ℃, and after passivation finishes, water cleans stand-by or dries up preservation.
3, performance test
1. neutral salt spray test: with reference to international GB/T 10125-1997, through the 168h neutral salt spray test, the specimen surface white rust is less than 2%, illustrates that the passive film solidity to corrosion is good.
2. electroless copper experiment: the stainless steel after Passivation Treatment in above-mentioned steps 2 is put into to chemical bronze plating liquid, take out after 6 hours, the copper corrosion point that is less than 1% is arranged.
Embodiment 6
1, join and get passivating solution: in every premium on currency, the shared weight part of following raw materials is: ammonium molybdate 20g/L, thionamic acid potassium 1g/L, ethylenediamine tetramethylene phosphatase 11 0ml/L, Trisodium Citrate 5g/L, benzotriazole 10g/L, thiosemicarbazide 0.1g/L; Regulating PH with ammoniacal liquor is 10, obtains passivating solution;
2, Passivation Treatment: 301 stainless steel plates are Passivation Treatment 60min in above-mentioned passivating solution, and passivation temperature is 65 ℃, and after passivation finishes, water cleans stand-by or dries up preservation.
3, performance test
1. neutral salt spray test: with reference to international GB/T 10125-1997, through the 168h neutral salt spray test, the specimen surface white rust is less than 2%, illustrates that the passive film solidity to corrosion is good.
2. electroless copper experiment: the stainless steel after Passivation Treatment in above-mentioned steps 2 is put into to chemical bronze plating liquid, take out after 6 hours, any reaction does not occur in stainless steel.
Embodiment 7
1, join and get passivating solution: in every premium on currency, the shared weight part of following raw materials is: ammonium molybdate 20g/L, thionamic acid potassium 1g/L, ethylenediamine tetramethylene phosphatase 11 0ml/L, Trisodium Citrate 5g/L, benzotriazole 10g/L, thiosemicarbazide 0.1g/L; Regulating PH with ammoniacal liquor is 9, obtains passivating solution;
2, Passivation Treatment: 301 stainless steel plates are Passivation Treatment 60min in above-mentioned passivating solution, and passivation temperature is 65 ℃, and after passivation finishes, water cleans stand-by or dries up preservation.
3, performance test
1. neutral salt spray test: with reference to international GB/T 10125-1997, through the 168h neutral salt spray test, the specimen surface white rust is less than 2%, illustrates that the passive film solidity to corrosion is good.
2. electroless copper experiment: the stainless steel after Passivation Treatment in above-mentioned steps 2 is put into to chemical bronze plating liquid, and after 4 hours, minor response has occurred in stainless steel, and after 5 hours, there is 10% copper point on its surface.
Comparative Examples 1
1, join and get passivating solution: in every premium on currency, the shared weight part of following raw materials is: potassium molybdate 40g/L, and potassium fluozirconate 10g/L, 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid 9g/L, citric acid 25g/L, hydrogen peroxide 20g/L, acidic silicasol 25g/L, phosphatase 11 9g/L, obtain passivating solution;
2, Passivation Treatment: 301 stainless steel plates are Passivation Treatment 60min in above-mentioned passivating solution, and passivation temperature is room temperature, and after passivation finishes, water cleans stand-by or dries up preservation.
3, performance test
1. neutral salt spray test: with reference to international GB/T 10125-1997, through the 168h neutral salt spray test, the specimen surface white rust is less than 3%.
2. electroless copper experiment: the stainless steel after Passivation Treatment in above-mentioned steps 2 is put into to chemical bronze plating liquid, i.e. reaction after 1 hour, stainless steel surface whole plated with copper after 2 hours.
Comparative Examples 2
1, join and get passivating solution: in every premium on currency, the shared weight part of following raw materials is: Sodium orthomolybdate 3g/L, sodium wolframate 5g/L, Weibull 3g/L, citric acid 5g/L, hydrogen peroxide 10g/L, water glass 10g/L, as the phosphoric acid 21g/L of pH value conditioning agent, the pH value of resulting passivating solution is 2.4, obtains passivating solution;
2, Passivation Treatment: 301 stainless steels are Passivation Treatment 60min in above-mentioned passivating solution, after passivation finishes, with 75 ℃, toasts 30s.
3, performance test
1. neutral salt spray test: with reference to international GB/T 10125-1997, through the 168h neutral salt spray test, the specimen surface white rust is less than 3%.
2. electroless copper experiment: the stainless steel after Passivation Treatment in above-mentioned steps 2 is put into to chemical bronze plating liquid, react stainless steel surface after 1 hour and start bubbling, stainless steel surface whole plated with copper layer after 2 hours.
By above-described embodiment 1-7 and Comparative Examples 1-2, can be found out, strong through the stainless steel solidity to corrosion of passivating solution Passivation Treatment provided by the invention.The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any modifications of doing within the spirit and principles in the present invention, be equal to and replace and improvement etc., within all should being included in protection scope of the present invention.
Claims (10)
1. a passivation for stainless steel aqueous solution, is characterized in that, comprises component: molybdate, sulfamate, organic phosphoric acid, Trisodium Citrate, benzotriazole, thiosemicarbazide, PH conditioning agent.
2. the passivation for stainless steel aqueous solution according to claim 1, is characterized in that, described passivating solution PH is 9.5-10.5.
3. the passivation for stainless steel aqueous solution according to claim 2, it is characterized in that, the content of its each component proportion in every liter of passivating solution is: molybdate 10-20g/L, sulfamate 1-3g/L, organic phosphoric acid 1-15ml/L, Trisodium Citrate 5-15g/L, benzotriazole 1-10g/L, thiosemicarbazide 0.1-1g/L
.
4. the passivation for stainless steel aqueous solution according to claim 3, it is characterized in that, the content of its each component proportion in every premium on currency is: molybdate 13-18g/L, sulfamate 1.5-2g/L, organic phosphoric acid 3-12ml/L, Trisodium Citrate 7-13g/L, benzotriazole 4-8g/L, thiosemicarbazide 0.2-0.8g/L.
5. the passivation for stainless steel aqueous solution according to claim 1, is characterized in that, described molybdate is at least one in Sodium orthomolybdate, potassium molybdate, ammonium molybdate.
6. the passivation for stainless steel aqueous solution according to claim 1, is characterized in that, described organic phosphoric acid is a kind of in hydroxy ethylene diphosphonic acid, hydroxy butylidene di 2 ethylhexyl phosphonic acid, ethylenediamine tetramethylene phosphoric acid.
7. the passivation for stainless steel aqueous solution according to claim 1, is characterized in that, described PH conditioning agent is a kind of in sodium hydroxide, potassium hydroxide, ammoniacal liquor.
8. the passivation for stainless steel aqueous solution according to claim 1, is characterized in that, described sulfamate is a kind of in thionamic acid sodium, thionamic acid potassium.
9. the passivation for stainless steel aqueous solution according to claim 4, is characterized in that, the content of its each component proportion in every premium on currency is: molybdate 10g/L, sulfamate 3g/L, organic phosphoric acid 12ml/L, Trisodium Citrate 10g/L, benzotriazole 4g/L, thiosemicarbazide 0.6g/L.
10. the preparation method as the described passivation for stainless steel aqueous solution of any one in claim 1-9, it comprises step: 1) take molybdate, Trisodium Citrate and sulfamate, three's mixing and water adding stirring and dissolving is obtained to the solution I; 2) take benzotriazole and thiosemicarbazide, both mix and blends are dissolved to obtain to the solution II; 3) by solution I and solution II mix and blend, add organic phosphoric acid, finally add the PH conditioning agent to regulate PH, obtain the passivation for stainless steel aqueous solution.
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| CN105274541A (en) * | 2014-07-17 | 2016-01-27 | 烟台盛业钢格板有限公司 | Composite for surface treatment of stainless steel grating plate |
| CN106119823A (en) * | 2016-08-29 | 2016-11-16 | 常熟市古里镇白茆新兴网印标牌厂 | Scenic spot signpost |
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| CN106756946A (en) * | 2016-12-16 | 2017-05-31 | 安徽宝恒新材料科技有限公司 | A kind of stainless steel surfaces passivating solution |
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