CN109536940A - A kind of zinc-plated passivator and Zincing passivation method - Google Patents
A kind of zinc-plated passivator and Zincing passivation method Download PDFInfo
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- CN109536940A CN109536940A CN201811556364.2A CN201811556364A CN109536940A CN 109536940 A CN109536940 A CN 109536940A CN 201811556364 A CN201811556364 A CN 201811556364A CN 109536940 A CN109536940 A CN 109536940A
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/48—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 not containing phosphates, hexavalent chromium compounds, fluorides or complex fluorides, molybdates, tungstates, vanadates or oxalates
- C23C22/53—Treatment of zinc or alloys based thereon
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/46—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing oxalates
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- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Treatment Of Metals (AREA)
Abstract
The present invention provides a kind of zinc-plated passivator and Zincing passivation method.Zinc-plated passivator provided by the invention, comprising: 50-150 parts of chromic salt, 10-50 parts of oxidant, 5-30 parts of film forming accelerating, 5-30 parts of complexing agent, 5-30 parts of metal salt and 0.1-10 parts of dyestuff.Dyestuff includes one or more of aniline blue, methyl blue and methylenum careuleum.There is preferable appearance after the zinc-plated passivator passivation workpiece obtained with passivator and Zincing passivation method provided by the invention.
Description
Technical field
The invention belongs to electroplating chemical technical fields, and in particular to a kind of zinc-plated passivator and Zincing passivation method.
Background technique
Electrogalvanizing is the effective way for improving steel-iron components resistance to corrosion, is widely used in building, and traffic is mechanical,
Electronics, in many fields such as aviation.But in a humid environment, zinc coat easily corrodes, and coating surface is made to form dark gray
Or corrosion product, that is, white rust of white loose；Time has been grown red rust will occurs after the meeting, to lose anti-corrosion effect.In order to improve plating
The corrosion resistance of layer must immerse passivating solution in iron and steel parts electrogalvanizing, part and be passivated processing, be formed on the surface of zinc coat
Fine and close passivating film extends the service life of iron and steel parts to further increase the corrosion resistance of components.
Routine zincincation is all by electrochemical deoiling, electrolytic degreasing, acid activation, electrogalvanizing, goes out light, passivation, baking at present
Dry and etc. to obtain 2~20 microns thick of zinc-plated protective layer, by blue blunt or white passivation, corrosion resistance is usually preferable.Traditional
Zinc-plated indigo plant is blunt to mostly use Cr VI to be passivated greatly, but since Cr VI is a kind of carcinogen, there is severe toxicity, meeting in use
Great damage is caused to human health.Trivalent chrome blue is changed to by original sexavalence chromium passivating for meet the requirement of environmental protection Zincing passivation
It is blunt.However present trivalent chrome blue it is blunt technology it is immature, the blue that zinc-plated trivalent chrome blue in the market is blunt to be obtained is general and side
Angle is easy jaundice or is not pure blue with purple, is not able to satisfy pursuit of most of clients to appearance high request.
Summary of the invention
In view of the deficiencies of the prior art, the present invention provides a kind of color effects better zinc-plated passivator and Zincing passivation
Method.
The present invention provides a kind of zinc-plated passivator, by weight, comprising: 50-150 parts of chromic salt, oxidant 10-
50 parts, 5-30 parts of film forming accelerating, 5-30 parts of complexing agent, 5-30 parts of metal salt and 0.1-10 parts of dyestuff.
Preferably, described chromic salt 80-100 parts, 30-40 parts of oxidant, 10-20 parts of film forming accelerating, complexing agent 10-
20 parts, 10-20 parts of metal salt and 0.1-5 parts of dyestuff.
It preferably, further include 0.1-5 parts of wetting agent.Preferably, the wetting agent includes polyoxyethylene aliphatic alcohol ether, polyoxy
Vinyl alkyl phenolic ether, one or more of polyoxyethylene aliphatic alcohol ether and polyoxyethylene polyoxypropylene block copolymer.
Preferably, the dyestuff includes one or more of aniline blue, methyl blue and methylenum careuleum.
Preferably, the chromic salt is chromic nitrate and/or chromium sulfate.
Preferably, the oxidant include one of nitrate, halate, persulfate, hydrogen peroxide and quadrivalent cerium or
It is several.
Preferably, the film forming accelerating include: one or more of nitrate anion, sulfate radical, fluorine ion, organic acid from
Son.
Preferably, the complexing agent includes ammonium acid fluoride, sodium fluoride, ammonium fluoride, oxalic acid, citric acid, tartaric acid and the third two
One or more of acid.
Preferably, the metal salt includes one or more of nickel sulfate, cobaltous sulfate and cerous nitrate.
The present invention also provides a kind of zinc-plated passivator, by weight, by 50-150 parts of chromic salt, oxidant 10-
0.1-10 parts of 50 parts, 5-30 parts of film forming accelerating, 5-30 parts of complexing agent, 5-30 parts of metal salt and dyestuff, 0.1-5 parts of wetting agent
It is water composition with surplus.
The present invention also provides a kind of Zincing passivation methods, which comprises the steps of:
(1) by 50-150 parts of chromic salt, 10-50 parts of oxidant, 5-30 parts of film forming accelerating, 5-30 parts of complexing agent, gold
Belong to salt 5-30 parts and dyestuff 0.1-10 parts, 0.1-5 parts of wetting agent to stir in water, adjusting pH is that 1-5 obtains passivator, spare；
(2) it is then washed, goes out light with the nitric acid of 0.2-0.5%, be passivated with the passivator of step (1), it is described
Passivation temperature is 18-35 DEG C.Passivation time is 25-40 seconds.
Zinc-plated passivator Zincing passivation method provided by the invention, plating piece surface can have preferable color after passivation
Effect.
Specific embodiment
Technical solution of the present invention is described in further detail combined with specific embodiments below, so that the technology of this field
Personnel can better understand the present invention and can be practiced, but illustrated embodiment is not as a limitation of the invention.
The embodiment of the present invention provides a kind of zinc-plated passivator, by weight, comprising: 50-150 parts of chromic salt, oxygen
10-50 parts of agent, 5-30 parts of film forming accelerating, 5-30 parts of complexing agent, 5-30 parts of metal salt and 0.1-10 parts of dyestuff.
In a preferred embodiment, chromic salt 80-100 parts, 30-40 parts of oxidant, 10-20 parts of film forming accelerating, complexing
10-20 parts of agent, 10-20 parts of metal salt and 0.1-5 parts of dyestuff.
It in a preferred embodiment, further include 0.1-5 parts of wetting agent.In a preferred embodiment, wetting agent includes polyoxyethylene
Fatty alcohol ether, polyoxyethylated alkyl phenol, one in polyoxyethylene aliphatic alcohol ether and polyoxyethylene polyoxypropylene block copolymer
Kind is several.
In a preferred embodiment, dyestuff includes one or more of aniline blue, methyl blue and methylenum careuleum.
In a preferred embodiment, chromic salt is chromic nitrate and/or chromium sulfate.
In a preferred embodiment, the effect of oxidant is to make metal ionization.Including nitrate, halate, persulfate,
One or more of hydrogen peroxide and quadrivalent cerium.
In a preferred embodiment, film forming accelerating includes: one of nitrate anion, sulfate radical, fluorine ion, organic acid or several
Kind ion.
In a preferred embodiment, complexing agent include ammonium acid fluoride, sodium fluoride, ammonium fluoride, oxalic acid, citric acid, tartaric acid and
One or more of malonic acid.
In a preferred embodiment, metal salt is mainly used for participating in film forming, and adjustment is passivated film outward appearance and improves corrosion resistance, metal
Salt includes one or more of nickel sulfate, cobaltous sulfate and cerous nitrate.
The present invention also embodiment provides a kind of zinc-plated passivator, by weight, by 50-150 parts of chromic salt, oxidation
10-50 parts of agent, 5-30 parts of film forming accelerating, 5-30 parts of complexing agent, 5-30 parts of metal salt and 0.1-10 parts of dyestuff, wetting agent
0.1-5 parts are water composition with surplus.
In a preferred embodiment, by 80-100 parts of chromic salt, 30-40 parts of oxidant, 10-20 parts of film forming accelerating, network
0.1-5 parts of 10-20 parts of mixture, 10-20 parts of metal salt and dyestuff, 0.1-5 parts of wetting agent and surplus are that water forms
In a preferred embodiment, dyestuff includes one or more of aniline blue, methyl blue and methylenum careuleum.
In a preferred embodiment, dyestuff is 1-5 parts.
The embodiment of the present invention also provides a kind of Zincing passivation method, includes the following steps:
(1) by 50-150 parts of chromic salt, 10-50 parts of oxidant, 5-30 parts of film forming accelerating, 5-30 parts of complexing agent, gold
Belong to salt 5-30 parts and dyestuff 0.1-10 parts, 0.1-5 parts of wetting agent to stir in water, adjusting pH is that 1-5 obtains passivator, spare；
(2) it is then washed, goes out light with the nitric acid of 0.2-0.5%, be passivated with the passivator of step (1), be passivated
Temperature is 18-35 DEG C.Passivation time is 25-40 seconds, is completed after then drying.
In a preferred embodiment, it is 2.2-2.8 that pH value is adjusted in step (1).
In order to have further understanding and understanding to technical solution of the present invention, several preferred embodiments pair are now enumerated
It is described in further details.Specific formula is as shown in table 1.
Table 1
The formula of embodiment 1-3 and comparative example 1-2 in table 1 are stirred, adjusting pH value with pH adjusting agent is 2.2-2.8, point
Passivator is not obtained, it is spare.
The application method for the passivator that above-described embodiment 1-3 and comparative example 1-2 are obtained is as follows:
The zinc-plated laggard property three-level washing of workpiece, then the nitric acid of 0.2-0.5% goes out light, then washes again, then uses respectively
Above-mentioned passivator temperature be 18-35 DEG C be passivated, passivation time be 25-40 seconds, washed again through three-level after passivation, then into
It is completed after row is dry.
Effect example
By embodiment 1, embodiment 2, embodiment 3 and comparative example 1, comparative example 2 be passivated after workpiece carry out appearance test, in
Property salt spray test and hundred lattice test.Specific data are as shown in table 2.
Neutral salt spray test (NSS:Neutral Salt Spray test) is at specific chamber (electroplating device)
It is interior, it will be sprayed containing (5 scholar 0.5) % sodium chloride, the salt water that pH value is 6.5~7.2 by spraying device, salt fog allowed to settle
Onto part to be tested, its surface corrosion state is observed by certain time.The temperature requirement of chamber is wet in (35 ± 2) DEG C
Degree is greater than 95%, and amount of fog is 1~2mL/ (hcm2), and nozzle exit pressure is 78.5~137.3kPa (0.8~1.4kgf/cm2).
Hundred lattice test (D3359): drawing 10*10 on test sample surface with sharp blade (knife edge angle is 15-30 °)
The small grid of 1mm*1mm, each scribing line answer deep and paint bottom, are cleaned down the fragment of test zone with hairbrush；With viscous
Attached power 350-400g/cm2Adhesive tape (3M61 adhesive tape or other equivalent) tested small grid of firmly stopping, and exerted oneself with erasing rubber
Adhesive tape is wiped, to increase the contact area and dynamics of adhesive tape Yu tested region；Adhesive tape one end is held, it is fast in vertical direction
Speed shuts down gummed paper, and same position carries out 2 same tests.Then it is observed.
Table 2
It is preferable that the passivator that can be seen that the present embodiment 1-3 from the data of table 2 is passivated rear appearance color, and mist
Change test and hundred lattice test results are preferable.
In comparative example 1, it is added without dyestuff, the workpiece after passivation has a small amount of jaundice, and appearance is poor.In comparative example 2, change
The formula rate of embodiment 1, the workpiece appearance after obtaining passivator passivation is poor, and salt spray test effect is poor.
To sum up, illustrating that the formula of the present embodiment 1-3 is reasonable, the workpiece appearance after obtained passivator passivation is preferable,
And also it is able to achieve preferable salt spray test result and hundred lattice test results.
The above description is only a preferred embodiment of the present invention, is not intended to limit the scope of the invention, all utilizations
Equivalent structure or equivalent flow shift made by present specification is applied directly or indirectly in other relevant technologies
Field is included within the scope of the present invention.
Claims (10)
1. a kind of zinc-plated passivator, which is characterized in that by weight, comprising: 50-150 parts of chromic salt, oxidant 10-
50 parts, 5-30 parts of film forming accelerating, 5-30 parts of complexing agent, 5-30 parts of metal salt and 0.1-10 parts of dyestuff.
2. zinc-plated passivator as described in claim 1, which is characterized in that described chromic salt 80-100 parts, oxidant 30-
40 parts, 10-20 parts of film forming accelerating, 10-20 parts of complexing agent, 10-20 parts of metal salt and 0.1-5 parts of dyestuff.
3. zinc-plated passivator as described in claim 1, which is characterized in that further include 0.1-5 parts of wetting agent.Preferably, institute
Stating wetting agent includes polyoxyethylene aliphatic alcohol ether, polyoxyethylated alkyl phenol, alkyl phenol polyoxyethylene ether and polyoxyethylene polyoxy
One or more of propylene-based block copolymer.
4. zinc-plated passivator as described in claim 1, which is characterized in that the dyestuff includes aniline blue, methyl blue and Asia
One or more of first indigo plant.
Zinc-plated use passivator 5. as described in claim 1, which is characterized in that the chromic salt be chromic nitrate, chromium sulfate and
One of chromium chloride is a variety of.
6. zinc-plated passivator as described in claim 1, which is characterized in that the oxidant includes nitrate, halate, mistake
One or more of sulfate, hydrogen peroxide and quadrivalent cerium, the film forming accelerating include: nitrate anion, sulfate radical, fluorine ion,
One or more of organic acid ion.
Zinc-plated use passivator 7. as described in claim 1, which is characterized in that the complexing agent include ammonium acid fluoride, sodium fluoride,
One or more of ammonium fluoride, oxalic acid, citric acid, tartaric acid, sulfuric acid and malonic acid.
8. zinc-plated passivator as described in claim 1, which is characterized in that the metal salt includes nickel sulfate, cobaltous sulfate, fluorine
Change one or more of sodium and cerous nitrate.
9. a kind of zinc-plated passivator, which is characterized in that by weight, by 50-150 parts of chromic salt, oxidant 10-50
Part, 5-30 parts of film forming accelerating, 5-30 parts of complexing agent, 5-30 parts of metal salt and 0.1-10 parts of dyestuff, 0.1-5 parts of wetting agent and
Surplus is water composition.
10. a kind of Zincing passivation method, which comprises the steps of:
(1) by 50-150 parts of chromic salt, 10-50 parts of oxidant, 5-30 parts of film forming accelerating, 5-30 parts of complexing agent, metal salt
5-30 parts and dyestuff 0.1-10 parts, 0.1-5 parts of wetting agent are stirred in water, and adjusting pH is that 1-5 obtains passivator, spare；
(2) it is then washed, goes out light with the nitric acid of 0.2-0.5%, be passivated with the passivator of step (1), the passivation
Temperature is 18-35 DEG C.Passivation time is 25-40 seconds.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110172689A (en) * | 2019-05-09 | 2019-08-27 | 东北大学 | A kind of room temperature zinc layers trivalent chromium colorful inactivating treatment liquid and preparation and application |
| CN111364034A (en) * | 2020-02-18 | 2020-07-03 | 广州传福化学技术有限公司 | Nitrogen-free galvanized trivalent chromium color passivator and preparation method thereof |
| CN111394688A (en) * | 2020-04-29 | 2020-07-10 | 郑州中原利达新材料有限公司 | Trivalent chromium passivation solution for powder zinc impregnation process |
| CN112126919A (en) * | 2020-08-24 | 2020-12-25 | 安徽未来表面技术有限公司 | Passivation method of aluminum hexavalent chromium passivator |
| CN113445038A (en) * | 2021-06-29 | 2021-09-28 | 永新县晨阳磁电科技有限公司 | Chromium-free passivation solution and passivation method for neodymium iron boron zinc coating |
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| CN1981402A (en) * | 2004-05-03 | 2007-06-13 | 霍尼韦尔国际公司 | Methods and composition for cleaning and passivating fuel cell systems |
| CN103572273A (en) * | 2012-08-06 | 2014-02-12 | 常熟华冶薄板有限公司 | Color passivated galvanized steel plate and manufacturing method thereof |
| CN107236948A (en) * | 2017-06-07 | 2017-10-10 | 广州传福化学技术有限公司 | It is a kind of to suppress the passivator that zinc coating trivalent chromium is oxidized to Cr VI |
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2018
- 2018-12-19 CN CN201811556364.2A patent/CN109536940A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1981402A (en) * | 2004-05-03 | 2007-06-13 | 霍尼韦尔国际公司 | Methods and composition for cleaning and passivating fuel cell systems |
| CN103572273A (en) * | 2012-08-06 | 2014-02-12 | 常熟华冶薄板有限公司 | Color passivated galvanized steel plate and manufacturing method thereof |
| CN107236948A (en) * | 2017-06-07 | 2017-10-10 | 广州传福化学技术有限公司 | It is a kind of to suppress the passivator that zinc coating trivalent chromium is oxidized to Cr VI |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110172689A (en) * | 2019-05-09 | 2019-08-27 | 东北大学 | A kind of room temperature zinc layers trivalent chromium colorful inactivating treatment liquid and preparation and application |
| CN111364034A (en) * | 2020-02-18 | 2020-07-03 | 广州传福化学技术有限公司 | Nitrogen-free galvanized trivalent chromium color passivator and preparation method thereof |
| CN111394688A (en) * | 2020-04-29 | 2020-07-10 | 郑州中原利达新材料有限公司 | Trivalent chromium passivation solution for powder zinc impregnation process |
| CN112126919A (en) * | 2020-08-24 | 2020-12-25 | 安徽未来表面技术有限公司 | Passivation method of aluminum hexavalent chromium passivator |
| CN113445038A (en) * | 2021-06-29 | 2021-09-28 | 永新县晨阳磁电科技有限公司 | Chromium-free passivation solution and passivation method for neodymium iron boron zinc coating |
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