CN105586583B - A kind of galvanized steel plain sheet trivalent chromium passivator concentrate and preparation method - Google Patents
A kind of galvanized steel plain sheet trivalent chromium passivator concentrate and preparation method Download PDFInfo
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- CN105586583B CN105586583B CN201610143385.6A CN201610143385A CN105586583B CN 105586583 B CN105586583 B CN 105586583B CN 201610143385 A CN201610143385 A CN 201610143385A CN 105586583 B CN105586583 B CN 105586583B
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- galvanized steel
- trivalent chromium
- plain sheet
- concentrate
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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
- C23C22/07—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing phosphates
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/07—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing phosphates
- C23C22/08—Orthophosphates
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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
- C23C2222/00—Aspects relating to chemical surface treatment of metallic material by reaction of the surface with a reactive medium
- C23C2222/10—Use of solutions containing trivalent chromium but free of hexavalent chromium
Abstract
The invention discloses a kind of galvanized steel plain sheet trivalent chromium passivator concentrate.Its bulk composition and dosage include：5 10 parts of chromic nitrate, 10 20 parts of biphosphate chromium, 15 parts of inorganic acid, 5 10 parts of sealer acidic silicasol, 0.5 2 parts of sodium hypophosphite, 0.5 2 parts of cobalt nitrate, 0.1 2 parts of complexing agent organic acid, 50 65 parts of deionized water.Trivalent chromium passivator provided by the invention can continuously be passivated film forming in automobile using hot-galvanized steel plate surface, and the passivation reaction time is fast, film salt-fog resistant time length, and workpiece is handled suitable for automobile hot-dip galvanizing sheet steel dipping, roller coat.Especially suitable for serialization passivation technology.
Description
Technical field
The present invention relates to a kind of trivalent chromium passivator, specially galvanized steel plain sheet trivalent chromium passivator concentrate, belong to metal
Field of surface treatment.
Technical background
Steel-iron components will generally be passivated processing after electrogalvanizing or galvanizing, white to prevent from producing in the short time
Rust.With the emergence of Domestic Automotive Industry, full-sized car industry is continuously increased to steel plate demand, while to board quality, ring
Guaranteed request also constantly increases.This just needs to ensure that certain yield meets the environmental requirement of various countries again when handling sheet material.
Traditional Cr VI color passivating agent causes serious pollution to environment, and vehicle steel plate surface Passivation Treatment more and more uses
Trivalent chromium passivator.And existing trivalent chromium passivation process has that product quality is unstable, and the passivating solution life-span is low, passivating process is not
It is easy to control, the defects of corrosion resistance of passivating film is poor.It is stable to produce a product quality, can serialization to galvanized steel sheet surface
Being passivated the passivating solution of processing turns into the task of top priority, has wide market prospects.
The content of the invention
It is an object of the invention to：There is provided a kind of economic and practical, good corrosion resistance, can serialization to galvanized steel sheet surface
It is passivated the environment-friendlytrivalent trivalent chromium passivating agent of processing.
To achieve these goals, the present invention adopts the following technical scheme that：
A kind of galvanized steel plain sheet trivalent chromium passivator concentrate, its bulk composition and dosage include：Chromic nitrate 5-10 parts, phosphoric acid
Dihydro chromium 10-20 parts, inorganic acid 1-5 parts, sealer acidic silicasol 5-10 parts, sodium hypophosphite 0.5-2 parts, cobalt nitrate 0.5-2
Part, complexing agent organic acid 0.1-2 parts, deionized water 50-65 parts.
Bulk composition and dosage are preferably 8 parts of chromic nitrate, 15 parts of biphosphate chromium, phosphatase 24 part, sealer acidic silicasol
8 parts, 1 part of sodium hypophosphite, 1 part of cobalt nitrate, 1 part of maleic acid, 62 parts of deionized water.
Inorganic acid is the one or more in nitric acid, sulfuric acid, phosphoric acid, preferably phosphoric acid.Complexing agent organic acid be malic acid,
One or more in citric acid, maleic acid, gluconic acid, preferably maleic acid.
The present invention uses the commercially available 35% biphosphate chromium aqueous solution and chromic nitrate, for main film forming agent, and adds membrane structure
Modifying agent cobalt nitrate, there is activation to the passivating solution for forming passivating film, improve passivating film corrosion resistance.Can be in galvanized steel sheet surface
Fine and close diaphragm is formed, film forming speed is fast, and film forming is uniform, and membrane structure is stable.
The Ludox that the present invention uses is commercially available acidic silicasol, granularity 10-30nm, dioxide-containing silica 29-31%,
PH value 2.0-4.0.Acidic silicasol is filled in the skeleton of passivating film in passivating process, can be in metal surface and metal
Ion crosslinks, and forms the diaphragm of new silicon network structure, overcomes the shortcomings that trivalent chromium passivation is without self-healing ability, collaboration
Main film forming agent further improves the corrosion resistance of galvanized steel plain sheet.The introducing of acidic silicasol, moreover it is possible to the adhesive force of passivating film is improved,
Improve follow-up coating performance.
For the inorganic acid that the present invention uses for the industrial phosphoric acid of nitric acid, sulfuric acid, phosphoric acid, preferably 85% content, phosphoric acid can
Stable sour environment is provided, prolonged guarantee system trivalent chromium stabilizes.And there is certain phosphatization in passivating process
Effect, further increase the stability and corrosion resistance of film forming.And the follow-up application for improving product is cooperateed with acidic silicasol
Performance.
Present invention introduces sodium hypophosphite, can significantly improve the corrosion-proof wear performance of passivating film, make film layer dense uniform, film layer
It is more firm.Organic acid is introduced as complexing agent, preferably maleic acid.The speed and passivating solution stability of film forming are controlled, makes work
Liquid keeps good passivation effect for a long time.
The preparation method of described trivalent chromium passivator concentrate, its step are as follows：
1) a certain amount of deionized water is taken, adds inorganic acid, organic acid is sufficiently stirred to obtain acidic aqueous solution.
2) to adding acidic silicasol, sodium hypophosphite in step 1), cobalt nitrate, being sufficiently stirred dissolving, solution is obtained.
3) into step 2), addition biphosphate chromium, chromic nitrate fully mix, and it is dense to obtain homogeneous blackish green trivalent chromium passivator
Contracting liquid finished product.
The present invention is a kind of galvanized steel plain sheet trivalent chromium passivator concentrate, is had compared with existing commercially available trivalent chromium following aobvious
Write advantage：
1. passivator film forming corrosion resistance time length of the present invention, film forming are uniform and stable.
2. it can be used in serialization Passivation Treatment, and system can keep stable.
3. membrane structure is stable, follow-up application ability is improved.
Embodiment
Embodiment 1
A kind of galvanized steel plain sheet trivalent chromium passivator concentrate, is made up of the raw material of following parts by weight, 8 parts of chromic nitrate, phosphoric acid
15 parts of dihydro chromium, phosphatase 24 part, 8 parts of sealer acidic silicasol, 1 part of sodium hypophosphite, 1 part of cobalt nitrate, 1 part of maleic acid, deionization
62 parts of water.
Embodiment 2
A kind of galvanized steel plain sheet trivalent chromium passivator concentrate, is made up of the raw material of following parts by weight, 7 parts of chromic nitrate, phosphoric acid
20 parts of dihydro chromium, 1 part of nitric acid, 3 parts of phosphoric acid, 5 parts of sealer acidic silicasol, 0.5 part of sodium hypophosphite, 2 parts of cobalt nitrate, malic acid
2 parts, 61.5 parts of deionized water.
Embodiment 3
A kind of galvanized steel plain sheet trivalent chromium passivator concentrate, is made up of the raw material of following parts by weight, 10 parts of chromic nitrate, phosphoric acid
13 parts of dihydro chromium, 4 parts of sulfuric acid, 6 parts of sealer acidic silicasol, 0.5 part of sodium hypophosphite, 1 part of cobalt nitrate, 1 part of maleic acid, lemon
1 part of acid, 63.5 parts of deionized water.
Embodiment 4
A kind of galvanized steel plain sheet trivalent chromium passivator concentrate, is made up of the raw material of following parts by weight, 5 parts of chromic nitrate, phosphoric acid
20 parts of dihydro chromium, 2 parts of sulfuric acid, 3 parts of phosphoric acid, 9 parts of sealer acidic silicasol, 2 parts of sodium hypophosphite, 0.5 part of cobalt nitrate, glucose
2 parts of acid, 56.5 parts of deionized water.
Embodiment 5
A kind of galvanized steel plain sheet trivalent chromium passivator concentrate, is made up of the raw material of following parts by weight, 6 parts of chromic nitrate, phosphoric acid
19 parts of dihydro chromium, 2 parts of nitric acid, 10 parts of sealer acidic silicasol, 1.5 parts of sodium hypophosphite, 1.5 parts of cobalt nitrate, malic acid 0.5
Part, 0.5 part of maleic acid, 59 parts of of deionized water
The preparation method of above-described embodiment：
1) a certain amount of deionized water is taken, adds inorganic acid, organic acid is sufficiently stirred to obtain acidic aqueous solution.
2) to adding acidic silicasol, sodium hypophosphite in step 1), cobalt nitrate, being sufficiently stirred dissolving, solution is obtained.
3) into step 2), addition biphosphate chromium, chromic nitrate fully mix, and it is dense to obtain homogeneous blackish green trivalent chromium passivator
Contracting liquid finished product.
The application method of above-described embodiment：
The concentration that trivalent chromium deactivating liquid of the present invention is configured to 5-10% with deionized water uses.It will need to do Passivation Treatment
Steel plate carries out serialization roller coat spray or is dipped into the groove equipped with passivating solution, is heated to 20-40 DEG C, processing time 30-90
Second, subsequent handling is directly carried out after passivation terminates.
In order to verify the using effect of the present invention, existing Example 1 carries out compliance test result, as a result as follows：
Passivating film color is homogeneous blue and white, and leather film thickness is consistent, neutral salt spray test >=120h.Follow-up spraying jail
Gu.
Finally illustrate, the above embodiments are merely illustrative of the technical solutions of the present invention and it is unrestricted, although with reference to compared with
The present invention is described in detail good embodiment, it will be understood by those within the art that, can be to the skill of the present invention
Art scheme is modified or equivalent substitution, and without departing from the objective and scope of technical solution of the present invention, it all should cover at this
Among the right of invention.
Claims (1)
1. a kind of galvanized steel plain sheet trivalent chromium passivator concentrate, it is characterised in that described galvanized steel plain sheet trivalent chromium passivator is dense
The bulk composition and dosage of contracting liquid are as follows：8 parts of chromic nitrate, 15 parts of biphosphate chromium, phosphatase 24 part, sealer acidity silicon
8 parts of colloidal sol, 1 part of sodium hypophosphite, 1 part of cobalt nitrate, 1 part of maleic acid, 62 parts of deionized water, its galvanized steel plain sheet trivalent
The preparation method of chromium passivating agent concentrate, it in turn includes the following steps：
（1）A certain amount of deionized water is taken, adds phosphoric acid, maleic acid is sufficiently stirred to obtain acidic aqueous solution；
（2）To step（1）Middle addition acidic silicasol, sodium hypophosphite, cobalt nitrate, dissolving is sufficiently stirred, obtains solution；
（3）To step（2）Middle addition biphosphate chromium, chromic nitrate fully mix, and obtain homogeneous blackish green trivalent chromium passivator concentration
Liquid finished product.
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| CN201610143385.6A CN105586583B (en) | 2016-03-11 | 2016-03-11 | A kind of galvanized steel plain sheet trivalent chromium passivator concentrate and preparation method |
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| CN105586583B true CN105586583B (en) | 2018-01-09 |
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| CN107815676B (en) * | 2017-11-24 | 2020-05-12 | 沈阳帕卡濑精有限总公司 | Multifunctional trivalent chromium passivator capable of continuously and rapidly treating surface of strip steel and preparation method and application thereof |
| CN111074254A (en) * | 2018-10-19 | 2020-04-28 | 沧州华润化工有限公司 | Preparation method of trivalent chromium passivator for surface passivation of metal plate |
| CN109853012A (en) * | 2019-03-06 | 2019-06-07 | 成都飞机工业（集团）有限责任公司 | A kind of passivating method of cyanide zinc plating wastewater |
| CN113445036A (en) * | 2021-07-20 | 2021-09-28 | 科文特亚环保电镀技术（江苏）有限公司 | Zinc-nickel alloy blue passivator and preparation process thereof |
| JP7169409B1 (en) | 2021-08-10 | 2022-11-10 | 日本ペイント・サーフケミカルズ株式会社 | Hexavalent chromium-free aqueous surface treatment liquid, surface treated metal and surface treatment method |
Citations (1)
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| CN104073075A (en) * | 2013-09-05 | 2014-10-01 | 攀钢集团攀枝花钢铁研究院有限公司 | Trivalent chromium coating, preparation method thereof and hot-dip metallic material |
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| US5393354A (en) * | 1993-10-07 | 1995-02-28 | Mcgean-Rohco, Inc. | Iridescent chromium coatings and method |
| CN100564599C (en) * | 2007-10-11 | 2009-12-02 | 上海交通大学 | High corrosion resistant trivalent chromium blue-white deactivator and preparation method thereof |
| CN101812681B (en) * | 2010-05-27 | 2012-02-01 | 贵阳华科电镀有限公司 | Passivation formula of zincification trivalent chromium |
| CN102400126A (en) * | 2011-11-17 | 2012-04-04 | 广州三孚新材料科技有限公司 | Two-in-one trivalent chromium blue white passivation solution for passivation and sealing and use process thereof |
| CN103215580B (en) * | 2013-03-25 | 2016-01-27 | 沈阳帕卡濑精有限总公司 | There is for surface of steel plate fast filming the trivalent chromium passivator of high anti-corrosion |
| CN103741129B (en) * | 2014-01-22 | 2015-09-30 | 哈尔滨三泳工大科技有限公司 | The high anti-corrosion blue-white deactivator of zinc coating trivalent chromium |
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| CN104073075A (en) * | 2013-09-05 | 2014-10-01 | 攀钢集团攀枝花钢铁研究院有限公司 | Trivalent chromium coating, preparation method thereof and hot-dip metallic material |
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Effective date of registration: 20220707 Address after: 443200 Qixingtai Shipbuilding Industrial Park, Zhijiang City, Yichang City, Hubei Province Patentee after: Yichang Xinhui Shipbuilding Co.,Ltd. Address before: 443002 No. 8, University Road, Yichang, Hubei Patentee before: CHINA THREE GORGES University |