CN101876071B - Environmentally-friendly black chrome-silver-free zinc-plating passivation solution and preparation method thereof - Google Patents
Environmentally-friendly black chrome-silver-free zinc-plating passivation solution and preparation method thereof Download PDFInfo
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- CN101876071B CN101876071B CN2009102182395A CN200910218239A CN101876071B CN 101876071 B CN101876071 B CN 101876071B CN 2009102182395 A CN2009102182395 A CN 2009102182395A CN 200910218239 A CN200910218239 A CN 200910218239A CN 101876071 B CN101876071 B CN 101876071B
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- 238000002161 passivation Methods 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims description 9
- 238000007747 plating Methods 0.000 title abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 26
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 18
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims abstract description 15
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical group [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims abstract description 14
- 150000002815 nickel Chemical class 0.000 claims abstract description 11
- 229910000365 copper sulfate Inorganic materials 0.000 claims abstract description 10
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims abstract description 10
- 239000011790 ferrous sulphate Substances 0.000 claims abstract description 10
- 235000003891 ferrous sulphate Nutrition 0.000 claims abstract description 10
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims abstract description 10
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims abstract description 10
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims abstract description 9
- 229960000583 acetic acid Drugs 0.000 claims abstract description 9
- 239000012362 glacial acetic acid Substances 0.000 claims abstract description 9
- 239000001632 sodium acetate Substances 0.000 claims abstract description 9
- 235000017281 sodium acetate Nutrition 0.000 claims abstract description 9
- 239000004115 Sodium Silicate Substances 0.000 claims abstract description 7
- 229910052911 sodium silicate Inorganic materials 0.000 claims abstract description 7
- 239000000243 solution Substances 0.000 claims description 49
- 239000000203 mixture Substances 0.000 claims description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 12
- 238000009713 electroplating Methods 0.000 claims description 12
- 229910052725 zinc Inorganic materials 0.000 claims description 12
- 239000011701 zinc Substances 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 11
- 239000011259 mixed solution Substances 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 235000019353 potassium silicate Nutrition 0.000 claims description 8
- 229960004249 sodium acetate Drugs 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 238000007744 chromate conversion coating Methods 0.000 claims description 6
- 239000000463 material Substances 0.000 abstract description 14
- 230000008569 process Effects 0.000 abstract description 12
- 230000007797 corrosion Effects 0.000 abstract description 8
- 238000005260 corrosion Methods 0.000 abstract description 8
- 150000003839 salts Chemical class 0.000 abstract description 8
- 238000011282 treatment Methods 0.000 abstract description 7
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 abstract description 6
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 abstract description 6
- 238000012360 testing method Methods 0.000 abstract description 5
- 230000007935 neutral effect Effects 0.000 abstract description 4
- 239000007921 spray Substances 0.000 abstract description 4
- 230000008901 benefit Effects 0.000 abstract description 3
- 239000003795 chemical substances by application Substances 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- 150000001844 chromium Chemical class 0.000 abstract 2
- 150000001879 copper Chemical class 0.000 abstract 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 abstract 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 abstract 1
- 229910000831 Steel Inorganic materials 0.000 description 19
- 239000010959 steel Substances 0.000 description 19
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 16
- 239000008399 tap water Substances 0.000 description 14
- 235000020679 tap water Nutrition 0.000 description 14
- 229910052804 chromium Inorganic materials 0.000 description 10
- 239000011651 chromium Substances 0.000 description 10
- 238000005516 engineering process Methods 0.000 description 9
- 238000005246 galvanizing Methods 0.000 description 9
- 239000000047 product Substances 0.000 description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 241001163841 Albugo ipomoeae-panduratae Species 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 239000013256 coordination polymer Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000007598 dipping method Methods 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- ICGLOTCMOYCOTB-UHFFFAOYSA-N [Cl].[Zn] Chemical compound [Cl].[Zn] ICGLOTCMOYCOTB-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229960001781 ferrous sulfate Drugs 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 238000011010 flushing procedure Methods 0.000 description 2
- 238000002203 pretreatment Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 241001062009 Indigofera Species 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
- 229910001209 Low-carbon steel Inorganic materials 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
- 230000002421 anti-septic effect Effects 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
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- 238000011161 development Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 230000000415 inactivating effect Effects 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- HEQBUZNAOJCRSL-UHFFFAOYSA-N iron(ii) chromite Chemical compound [O-2].[O-2].[O-2].[Cr+3].[Fe+3] HEQBUZNAOJCRSL-UHFFFAOYSA-N 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 229940068041 phytic acid Drugs 0.000 description 1
- 235000002949 phytic acid Nutrition 0.000 description 1
- 239000000467 phytic acid Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
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Landscapes
- Electroplating Methods And Accessories (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
- Chemical Treatment Of Metals (AREA)
Abstract
The invention provides black passivation solution for zinc-plating post treatment. 1 liter of black passivation solution consists of 10 to 20g of sodium silicate, 20 to 30g of copper sulfate, 0.5 to 1.5g of nickel sulfate, 0.5 to 1.5g of ferrous sulfate, 1 to 3g of sodium acetate, 20 to 40mL of glacial acetic acid, 3 to 7mL of sulfuric acid (98 percent) and the balance of water. A zinc-plating material processed by the passivation solution has a uniform, bright and black appearance and high corrosion resistance, is free of rust for over 200h through a neutral salt spray test and can achieve the same effect as that achieved by the conventional black chrome-silver-contained passivation process in appearance and performance. The passivation solution has the advantages of thoroughly solving the problem of environment pollution caused by a chromium salt used by the conventional black zinc-plating passivation process, eliminating the use of a silver salt at the same time and greatly reducing the cost thereof by substituting silicate for the chromium salt as a main film-forming material and a copper salt, a nickel salt and a ferric salt for the silver salt as a blackening agent, along with stability and reliability and high film-forming efficiency.
Description
Technical field
The present invention relates to the surface treatment technology of material field, environment-friendly type zinc electroplating with black chromate conversion coating liquid of specifically a kind of chrome-silver-free of the aftertreatment fluid of using as electro-galvanizing iron and steel component and preparation method thereof.
Background technology
Material corrosion and material antiseptic engineering are directly connected to the expanding economy and the people's life security, and surface engineering technology is to solve component of machine and material corrosion and most economical effective means of protection and method.
Electro-galvanizing is the effective way that improves the steel material surface resistance to corrosion, is widely used at present in many fields such as building, traffic, machinery, electronics, aviation.Especially in hygrothermal environment, zinc coating is prone to corrode, and makes coating surface form corrosion product---the white rust of lead or white loose but in a humid environment; Time has been grown and red rust can occur, thereby loses preservative effect.In order to improve the solidity to corrosion of coating, must after steel material surface is zinc-plated, carry out Passivation Treatment to coating again, so that form fine and close passive film, thereby further improve the solidity to corrosion of material on the zinc coating surface, prolong the work-ing life of material.
It is that the solution of staple carries out Passivation Treatment that the aftertreatment technology of at present nearly all zinc-plating material such as galvanized sheet etc. all adopts with sexavalent chrome or trivalent chromium; Because sexavalent chrome toxicity is high and carcinogenic easily; National governments' strictness limit it and use and discharge, and especially in the RoHS of European Union instruction, clearly ban use of any part and product of handling through the sexavalent chrome passivating technique; Although trivalent chromium passivation process is much littler than chromic contaminative; But the zinc-plating material through the trivalent chromium passivation still can be oxidized to sexavalent chrome after after a while; That is to say the chromic toxicity problem of inreal solution in fact, use trivalent chromium passivation process so a lot of countries and regions also begin restriction.In addition, be to contain chromium passivating technology because China extensively adopts on the zinc electroplating with black chromate conversion coating operation, caused a large amount of needs products zinc-plated and black passivation of industries such as electronics, machinery, five metals to export, had a strong impact on the foreign trade of China.
Therefore, the chromium-free passivation liquid of exploitation compliance with environmental protection requirements must become development trend from now on.The domestic and international at present research for Unchromium Passivation of Galvanized Zinc Layer liquid mainly contains molybdate system, titanium salt system, rare-earth system, silicate systems, phytic acid system and organic-compound system etc.; But these chromium-free deactivation systems all can only form the passive film of (indigo plant) white or coloured appearance on the zinc coating surface; For on producing, using a lot of black passivation galvanized parts, still rely on sexavalent chrome or trivalent chromium passivation process so far fully.
Also have, in a lot of galvanized workpiece black inactivation process,, also need in passivating solution, to add silver salt usually as blackening agent for surface, but brought higher production cost thus except doing with chromic salts the main filmogen, very big to zinc-plated economic benefit of enterprises influence.Therefore in the exploitation non-chromium inactivating technique, also need consider how to reduce or even cancel use to silver salt.
Summary of the invention
The present invention is just for overcoming the deficiency that the prior art passivating solution exists; A kind of environment-friendly type zinc electroplating with black chromate conversion coating liquid of chrome-silver-free is provided; Its excellent property, cost is low, efficient is high, can satisfy the silicate passivating solution of electro-galvanizing iron and steel component black passivation requirement, and its preparation method.
Technical scheme of the present invention is: on the basis of existing chromic salts passivation technology; Replace chromic salts as main film forming substance with silicate; Replace silver salt as blackening agent for surface with materials such as copper sulfate, single nickel salt, ferrous sulfate; Simultaneously other various auxiliary film forming matters are selected and optimized, invention is a kind of black passivation solution that is used for zinc-plated aftertreatment of complete chrome-silver-free, is made up of following component:
Said water glass, copper sulfate, single nickel salt, ferrous sulfate, sodium-acetate, Glacial acetic acid min. 99.5, sulfuric acid are commercial CP product.
Said silicate black passivation solution is prepared through following method:
A, water glass is dissolved in the less water, obtains consoluet sodium silicate aqueous solution;
B, sulfuric acid is added in the sodium silicate aqueous solution of A step, mix;
C, copper sulfate is added in the mixing solutions of B step, mix;
D, single nickel salt is added in the mixing solutions of C step, mix;
E, ferrous sulfate is added in the mixed solution of D step, mix;
F, sodium-acetate is added in the mixed solution of E step, mix;
G, Glacial acetic acid min. 99.5 is added in the mixed solution of F step, mix;
H, in the mixing solutions of G step, add water and be settled to volume requiredly, use rare H by ordinary method
2SO
4Or dilute NaOH solution adjustment pH value to 2.0～2.5, promptly get the silicate black passivation solution.
Use said silicate black passivation solution to the method that the electrogalvanizing part carries out Passivation Treatment to be: the iron and steel parts water that will pass through electrogalvanizing cleans up; After carrying out the bright dipping processing according to a conventional method; Taking-up part washing is immersed part in the said silicate black passivation solution again, soak 1～2 minute under the room temperature after; After taking out also water cleaning, dry getting final product.
Said electro-galvanizing operation adopts existing maturation process and gets.
Said bright dipping is treated to: the part after zinc-plated is put into by HNO
3And H
2In the light-emitting solution that O forms, after soaking 3～5 seconds under the room temperature, taking-up gets final product, and wherein the concrete proportioning of light-emitting solution is: mass concentration is 65% HNO
35～15mL/L, all the other are H
2O.
The purging method of said part after zinc-plated, bright dipping and passivation is: the tap water flushing, and perhaps in the groove of cleaning water is housed or rinsing in the pond, until the plating piece surface cleaning totally is advisable.
The drying means of said zinc-plated part after passivation is: dry naturally, perhaps use drier, perhaps dry with baking box.
Employed water is tap water in each technological process involved in the present invention, or zero(ppm) water.
The present invention compared with prior art has advantage and effect: adopt such scheme; Promptly with water glass as staple; And be equipped with auxiliary film forming matters such as copper sulfate, single nickel salt, ferrous sulfate, sodium-acetate, Glacial acetic acid min. 99.5, sulfuric acid and be mixed with clean silicate black passivation solution, be used for the postorder Passivation Treatment of electro-galvanizing product, can make the outward appearance of galvanizing production demonstrate not only black but also bright good visual effect; Significantly improved the solidity to corrosion of zinc-plated or material simultaneously; Through salt-fog test, the rust time reached more than 200 hours, all can reach the existing effect that contains chrome black look passivation technology in outward appearance and aspect of performance.In addition; Owing to do not contain sexavalent chrome and trivalent chromium in the passivating solution of the present invention; Fundamentally solved the existing chromium passivating technology problem of environment pollution caused that contains; Meeting environmental protection standards such as China's national sewage comprehensive emission standard (GB 8978-1996) and the RoHS of European Union instruction fully, is a kind of chromium-free passivation liquid truly, can promote the cleaner production of electro-galvanizing product passivation procedure to a great extent; Simultaneously; Relatively inexpensive mantoquita, nickel salt, molysite have replaced traditional silver salt blackout passivation technology, and the passivating solution preparation cost is reduced greatly, and this passivating solution is reliable and stable; Film forming efficiency is high; Instead is existing fully contains the argentiferous black passivation solution of chromium, also accepted by manufacturing enterprise easily aspect cost and the passivation efficiency, and be a kind of environment-friendly type passivation liquid that has application prospect.
Embodiment
Below in conjunction with embodiment the present invention is described further.
Embodiment 1:
1) get the raw materials ready by following prescription: water glass 10g/L, copper sulfate 20g/L, single nickel salt 0.5g/L, ferrous sulfate 0.5g/L, sodium-acetate 1g/L, Glacial acetic acid min. 99.5 20mL/L, sulfuric acid (98%) 3mL/L, all the other are water, raw materials used commercial CP product, the H of being
2O is a tap water;
2) be mixed with the silicate black passivation solution through following method, subsequent use:
A, the 10g water glass is dissolved in the less water, obtains consoluet sodium silicate aqueous solution;
In B, the sodium silicate aqueous solution, mix 3mL sulfuric acid (98%) adding A step;
In C, the mixing solutions, mix 20g copper sulfate adding B step;
In D, the mixing solutions, mix 0.5g single nickel salt adding C step;
In E, the mixed solution, mix 0.5g ferrous sulfate adding D step;
In F, the mixed solution, mix 1g sodium-acetate adding E step;
In G, the mixed solution, mix 20mL Glacial acetic acid min. 99.5 adding F step;
H, in the mixing solutions of G step, add water and be settled to 1 liter, use rare H by ordinary method
2SO
4Or about dilute NaOH solution adjustment pH value to 2.0, promptly get the silicate black passivation solution;
3) electrogalvanizing steel plate obtains through following method: before the mild steel plate of 80mm * 40mm * 1.5mm is being electroplated by routine eliminate rust, after the pre-treatments such as oil removing, activation; Put into conventional electroplate liquid and carry out electroplating processes, the plating bath of zinc-plated treatment process is formed and operational condition is: ZnCl
2: the pH value of 50g/L, KCl:200g/L, No. 1 additive 12mL/L of chlorine zinc, No. 2 additive 6mL/L of chlorine zinc, plating bath is 6.0, and current density is 1.0A/dm
2, temperature is a room temperature, electroplating time is 25 minutes, gets electrogalvanizing steel plate, and is subsequent use;
4) preparation light-emitting solution: with chemical pure HNO
3(mass percent concentration 65%) is mixed with light-emitting solution by 10mL/L and tap water, and (every premium on currency adds the HNO of 10mL
3), subsequent use;
5) will be through 3) electrogalvanizing steel plate clean up the back with tap water and immerse 4) light-emitting solution in, stopped 5 seconds under the room temperature, take out the back and clean up with tap water; Immerse 2 again) passivating solution in; Soak under the room temperature after 1 minute, take out, after tap water cleans up, use drier.
Steel plate galvanized after this passivating solution is handled appears evenly, bright, appearance of black, through neutral salt spray test, goes out the white rust time and can reach 200 hours.
Embodiment 2:
1) get the raw materials ready by following prescription: water glass 15g/L, copper sulfate 25g/L, single nickel salt 1.0g/L, ferrous sulfate 1.0g/L, sodium-acetate 2g/L, Glacial acetic acid min. 99.5 30mL/L, sulfuric acid (98%) 5mL/L, all the other are water, raw materials used commercial CP product, the H of being
2O is a zero(ppm) water.
2) to be mixed with the pH value be about 2.2 silicate black passivation solution for warp and embodiment 1 identical method, subsequent use:
3) electrogalvanizing steel plate obtains through following method: before the Q235 steel plate of 100mm * 60mm * 2mm is being electroplated by routine eliminate rust, after the pre-treatments such as oil removing, activation; Put into conventional electroplate liquid and carry out electroplating processes; The plating bath of zinc-plated treatment process is formed and operational condition is: the pH value of ZnO:10g/L, NaOH:120g/L, Z50 alkaline zinc plating additive 8mL/L, plating bath is 12, and current density is 2.0A/dm
2, temperature is a room temperature, electroplating time is 15 minutes, gets electrogalvanizing steel plate, and is subsequent use;
4) preparation light-emitting solution: with chemical pure HNO
3(mass percent concentration 65%) is mixed with light-emitting solution by 15mL/L and tap water, and (every premium on currency adds the HNO of 15mL
3), subsequent use;
5) with 3) steel plate galvanized immerse 4) light-emitting solution in, stopped 3 seconds under the room temperature, take out the back and clean up, put into 2 again with tap water) passivating solution, soaked 2 minutes under the room temperature, take out this steel plate then, dry down at 80 ℃ with air dry oven.
Steel plate galvanized after this passivating solution is handled appears evenly, bright, appearance of black, through neutral salt spray test, goes out the white rust time and can reach 280 hours.
Embodiment 3:
1) get the raw materials ready by following prescription: water glass 20g/L, copper sulfate 30g/L, single nickel salt 1.5gg/L, ferrous sulfate 1.5g/L, sodium-acetate 3g/L, Glacial acetic acid min. 99.5 40mL/L, sulfuric acid (98%) 7mL/L, all the other are water, raw materials used commercial CP product, the H of being
2O is a tap water.
2) to be mixed with the pH value be about 2.5 silicate color passivation solution for warp and embodiment 1 identical method, subsequent use;
3) certain machine steel shell is carried out the processing of alkaline zinc-electroplating: certain machine steel shell is implemented to electroplate after routine rust cleaning, oil removing, weak etch, preimpregnation etc. are handled, and the plating bath of zincincation is formed and operational condition is: ZnO 10g/L, NaOH120g/L, Z50 alkaline zinc plating additive 8mL/L, current density 2.5A/dm
2, temperature is room temperature, electroplating time is 30 minutes, the electro-galvanizing shell, subsequent use;
4) preparation light-emitting solution: with chemical pure HNO
3(mass percent concentration 65%) is mixed with light-emitting solution by 5mL/L and tap water, and (every premium on currency adds the HNO of 5mL
3), subsequent use;
5) with 3) electro-galvanizing steel shell clean with tap water after, put into 4) light-emitting solution, soaked 5 seconds under the room temperature, take out the back with the tap water flushing, put into 2 again) passivating solution, soaked 90 seconds under the room temperature, take out after tap water cleans up, dry naturally.
Zinc-plated steel shell after using this passivating solution to handle appears evenly, light, appearance of black, through neutral salt spray test, goes out the white rust time and can reach 240 hours.
Claims (1)
1. the zinc electroplating with black chromate conversion coating liquid of a chrome-silver-free is characterized in that being made up of following component:
All the other are water;
The preparation method of the zinc electroplating with black chromate conversion coating liquid of described chrome-silver-free prepares according to the following steps:
A, water glass is dissolved in the less water, obtains consoluet sodium silicate aqueous solution;
B, the sulfuric acid of concentration 98% is added in the sodium silicate aqueous solution of A step, mix;
C, copper sulfate is added in the mixing solutions of B step, mix;
D, single nickel salt is added in the mixing solutions of C step, mix;
E, ferrous sulfate is added in the mixed solution of D step, mix;
F, sodium-acetate is added in the mixed solution of E step, mix;
G, Glacial acetic acid min. 99.5 is added in the mixed solution of F step, mix;
H, in the mixing solutions of G step, add water and be settled to volume requiredly, use rare H by ordinary method
2SO
4Or dilute NaOH solution adjustment pH value to 2.0～2.5, promptly get the silicate black passivation solution.
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| CN2009102182395A CN101876071B (en) | 2009-11-24 | 2009-11-24 | Environmentally-friendly black chrome-silver-free zinc-plating passivation solution and preparation method thereof |
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| CN102392240B (en) * | 2011-11-18 | 2013-08-28 | 东莞市东辉贸易有限公司 | Zinc alloy blackening liquid |
| CN103014689A (en) * | 2012-12-29 | 2013-04-03 | 云南滇科涂镀层材料有限公司 | Environment-friendly galvanization, black Zn-Fe alloy passivation solution and preparation method |
| CN103540921B (en) * | 2013-10-29 | 2016-08-17 | 昆明理工大学 | A kind of electrogalvanizing environmental protection passivating solution |
| CN103849864B (en) * | 2014-02-24 | 2016-12-07 | 昆明理工大学 | A kind of galvanized chromium-free color passivation solution, preparation and using method |
| CN105063698B (en) * | 2015-08-27 | 2017-10-03 | 广东欧珀移动通信有限公司 | The surface treatments and surface treatment method of stainless steel substrate |
| CN105331917B (en) * | 2015-11-02 | 2017-12-22 | 常熟风范电力设备股份有限公司 | A kind of method of steel structure surface plating zinc-nickel double-layer passivating film |
| CN105568274A (en) * | 2015-12-31 | 2016-05-11 | 安徽红桥金属制造有限公司 | Environment-friendly galvanizing passivator and preparation method thereof |
| CN106319500A (en) * | 2016-08-25 | 2017-01-11 | 上海航天设备制造总厂 | Treatment solution and treatment method for zinc coating black conversion film |
| CN106835108A (en) * | 2016-12-30 | 2017-06-13 | 张庆 | A kind of environmentally friendly inorganic organic passivation film of modified graphene oxide |
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| WO2019006614A1 (en) * | 2017-07-03 | 2019-01-10 | 深圳市宏昌发科技有限公司 | Passivator, metal workpiece and surface passivation process therefor |
| CN109056019A (en) * | 2018-07-27 | 2018-12-21 | 昆明理工大学 | A kind of electrogalvanizing black passivation solution and preparation method thereof |
| CN114855152A (en) * | 2022-04-20 | 2022-08-05 | 许昌学院 | Environment-friendly iron-based phosphorus-free film treatment composition and treatment agent for metal surface, and preparation method and application of treatment agent |
-
2009
- 2009-11-24 CN CN2009102182395A patent/CN101876071B/en not_active Expired - Fee Related
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