CN105088210A - Novel chromium-free acidic galvanizing color passivating solution and preparation method thereof - Google Patents
Novel chromium-free acidic galvanizing color passivating solution and preparation method thereof Download PDFInfo
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- CN105088210A CN105088210A CN201410191969.1A CN201410191969A CN105088210A CN 105088210 A CN105088210 A CN 105088210A CN 201410191969 A CN201410191969 A CN 201410191969A CN 105088210 A CN105088210 A CN 105088210A
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Abstract
The invention discloses a novel chromium-free acidic galvanizing color passivating solution and a preparation method thereof. In the field of metal surface electroplating anticorrosion field, the chromium pollution is severe, and the acidic galvanized film easily falls off; and the provided passivating solution can solve the problems mentioned above. Furthermore, the passivating solution does not contain any chromium in any valent. The passivating solution comprises titanate (2-10 g/L), sulfate (1-30.0 g/L), hydrogen peroxide (5 to 15 mL/L), a complexing agent (2-10 g/L), and the balance being water. The pH value of the passivating solution is 1.0 to 1.5. Nontoxic titanate is used to replace chromium salt and is taken as the main raw material of passivating solution, the shortages of conventional technology such as high toxicity, environment pollution, and the like are overcome, moreover, other components in the passivating solution are pollution-free to the environment, the passivating solution completely meets the environment protection standards such as National Electroplating Wastewater Discharge Standards, EU (Europe Union) RoHS Command, and the like. At the same time, the phenomenon that a film easily falls off in acidic galvanizing is avoided; the titanate is passivated to form a film, which is similar to a chromium salt passivated film having a network structure, thus the corrosion resistant performance is greatly improved, moreover, the processing steps are simplified, and the passivating solution is convenient for industrial application.
Description
Technical field
The present invention relates to metallic surface electroplating anticorrosion technique, particularly a kind of passivating solution and preparation method can with high anti-corrosion colored protective membrane, belongs to technical field of metal material surface treatment.
Background technology
Electro-galvanizing is one of important means of steel anti-corrosive, and zinc-plated iron-steel is important in multiple industries such as automobile, electric power, traffic, buildings.But zinc coating easily corrodes in wet condition, affect outward appearance and the work-ing life of product.Current most popular anti-corrosion method is chromium passivating, and its advantage is that chromic salts passive film has high anti-corrosion and smooth densification, plays a protective role in the environment of corrosion to matrix metal.But sexavalent chrome is acid strong, serious harm HUMAN HEALTH and environment and be strictly limited use, and in acid zinc plating, there is the phenomenon easily falling film.The chromium-free deactivation of current domestic report mainly contains titanium salt passivation, tungstate passivation, molybdate passivation film, organism passivation, phytic acid passivation, pick liquid, the false transformant passivating solution of phosphoric acid salt etc., although reach the requirement of environmental protection, but there is imperfection part, as: production cost improves, working conditions and work-ing life etc. factor impact, and these chromium-free passivating films exist, and corrosion resisting property is poor, the limitation of the scope of use, passivation time are longer, easily falls the shortcomings such as film in acid zinc plating.The Chrome-free color passivation solution of current domestic report is all failed to solve and fall film phenomenon in acid zinc plating, and passivation time has all exceeded 40 minutes, and the time going out white embroidery through neutral salt spray test is no more than 48 hours.
Chinese patent CN103215583A Chrome-free color passivating agent discloses the method using molybdate passivation film, although this kind of color passivation solution can reach chromatic passivation outward appearance, but composition is too complicated and also have organism in passivating solution, big for environment pollution, wayward aborning.
Summary of the invention
The object of the invention is the deficiency overcoming existing passivating technique, provide a kind of containing toxic substance, handled product performance are excellent, production cost is low electro-galvanizing titanium salt cleaning inactivating process.
Technical scheme of the present invention is: after the electro-galvanizing washing on the steel-iron components surface through electroplating processes, carry out optical processing, then washing is taken out, put into titanium salt passivating solution again, carry out titanium salt Passivation Treatment, finally the part of coating through transpassivation is taken out, then carry out drying or seasoning with loft drier.
Being operating as in titanium salt Passivation Treatment process: the part being coated with zinc after bright dipping is put into the passivating solution be made up of titanium salt, hydrogen peroxide, vitriol, complexing agent, the pH value controlling passivating solution is 1.5-2.0, stop 15-20 second under room temperature, then take out, adopt and dry or seasoning.
The invention provides a kind of Chrome-free acid zinc plating color passivation solution and preparation method, the composition of this passivating solution is: titanium salt: 2-10g/L, and its Main Function is as main film-former, vitriol 1-30.0g/L, as secondary film formers, hydrogen peroxide 5-15ml/L, its Main Function is as oxygenant, complexing agent 2-10g/L, complexation of metal ions, make solution maintain longer stability, all the other are water, and passivating solution pH value is 1.0-1.5.。
The early stage electro-galvanizing process of the present invention to iron and steel parts adopts existing technique, goes out optical processing and also can adopt existing technological process.The operation going out photoreduction process can be: add in the light-emitting solution be made up of nitric acid and water by being coated with zinc component, takes out after stopping 3-5 second under room temperature; In light-emitting solution, each constituent and content thereof are nitric acid 2-5ml/L, and all the other are water.
The preparation method of this passivating solution is:
A, take the titanium salt of 2-10g/L according to volume total amount balance or platform balance, pour in the water of 1/2 volume total amount, be stirred well to dissolving, obtain the titanium salt aqueous solution;
B, take or measure hydrogen peroxide 5-15ml/L according to volume total amount, add while stirring in the titanium salt solution of step A preparation, obtain the mixing solutions of titanium salt, hydrogen peroxide;
C, to take 1-30g/L vitriol according to volume total amount and add in the titanium salt of step B preparation, hydrogen peroxide mixed solution while stirring;
D, to take 2-10.0g/L complexing agent according to volume total amount and add in the titanium salt of step C preparation, hydrogen peroxide, vitriol mixing solutions while stirring;
E, in D step gained titanium salt, hydrogen peroxide, vitriol, complexing agent mixing solutions, add water and be settled to volume required, with pH meter or pH test paper for instrument, by 1:10 salpeter solution or 1:10 sodium hydroxide solution adjust ph to 1.0-1.5, and stir.
The material that provides of raw material titanium salt used in above-mentioned preparation technology, vitriol, hydrogen peroxide, complexing agent is commercially available chemical pure product, and water is purified water or tap water.
The present invention compared with prior art advantage is that (1) corrosion resisting property is excellent, and reach 80 hours through the neutral salt spray corrosion test white rust time, the resistance to red rust time reaches 200 hours; (2) environment friendly and pollution-free, not containing any valence state chromium and toxic substance in passivating solution; (3) after zinc-plated process, color is gorgeous, and film surface presents multicolored look, and light evenly; (4) thoroughly solve the phenomenon that acid zinc plating falls film, facilitate industrial application.
In sum, the present invention adopts titanium salt to carry out passivation, all having a clear superiority in raising electro-galvanizing chromium-free passivating film corrosion resistance and simple operation flow process etc., and thoroughly can solve the phenomenon falling film in acid zinc plating, is a kind of electro-galvanizing Surface treatment passivation solution having application prospect.
Accompanying drawing explanation
Accompanying drawing is a kind of novel non-chrome acid zinc plating color passivation solution of the present invention and preparation method and preparation technology's schema.
Specific embodiments
Below in conjunction with embodiment, substance of the present invention is described further.
Embodiment 1: preparation 1L novel non-chrome acid zinc plating color passivation solution; This passivation technology is used for carrying out follow-up Passivation Treatment to the zinc-plated steel plate in local.
(1) according to following formula batching: titanous chloride 2g, hydrogen peroxide 5ml, sodium sulfate 1g, citric acid 2g, all the other are water.
(2) novel non-chrome acid zinc plating color passivation solution is prepared through following method, for subsequent use:
A) weigh in the balance and get 2.0g titanous chloride, pour into and 500ml water is housed, cumulative volume, more than in the glass beaker of 1.0L, stirs with glass stick;
B) measure the hydrogen peroxide of 5ml with transfer pipet, add with glass stick in the titanium trichloride aqueous solution of a step preparation while stirring, until mix;
C) weigh in the balance get 1g sodium sulfate add while stirring b step preparation titanous chloride, in hydrogen peroxide mixed solution, until mix dissolving;
D) weigh in the balance get 2g citric acid add while stirring the titanous chloride of step c preparation, hydrogen peroxide, in sodium sulfate mixing solutions, until mix dissolving;
E) in Step d gained titanous chloride, hydrogen peroxide, sodium sulfate, citric acid mixing solutions, add water and be settled to 1.0L, with pH meter or pH test paper for instrument, by 1:10 salpeter solution or 1:10 sodium hydroxide solution adjust ph to 1.0-1.5, and stir
(3) this steel plate carried out eliminating rust before electroplating, oil removing, after the pre-treatment such as activation, put into electroplate liquid to electroplate, the plating solution composition of zincincation and operational condition are: the pH value of zinc chloride 60g/L, Repone K 200g/L, boric acid 30g/L, appropriate additive, plating solution remains on about 5.8, and current density is 1.2A/dm
2, temperature is room temperature, and electroplating time is 25 minutes, obtains electrogalvanizing steel plate, for subsequent use.
(4) prepare light-emitting solution: by analytically pure concentrated nitric acid according to 1% concentration mix with tap water, for subsequent use
(5) the electrogalvanizing steel plate tap water obtained through step 3 is cleaned clean after immerse in the light-emitting solution that step 4 prepares, stop 5 seconds under room temperature, clean up with tap water after taking-up, then immerse in passivating solution that step 2 prepares, soak after 15 seconds, take out and dry or seasoning.
Use the steel plate appearance after the process of this passivation technology to be even, multicolored outward appearance, go out the white rust time more than 72 hours through neutral salt spray test.
Embodiment 2: preparation 10L novel non-chrome acid zinc plating color passivation solution; This passivation technology be used for certain Machine Steel casing carry out overall zinc-plated after Passivation Treatment.
(1) according to following formula batching: titanous chloride 60g, hydrogen peroxide 100ml, sodium sulfate 150g, citric acid 60g, all the other are water.
(2) environment-friendly type zinc electroplating with black chromate conversion coating liquid is prepared through following method, for subsequent use:
A) weigh in the balance and get 60g titanous chloride, pour into and 5L water is housed, cumulative volume, more than in the plastic tank of 10L, stirs with wooden stick;
B) measure the hydrogen peroxide of 100ml with measuring cup or graduated cylinder, add with wooden stick in the titanium trichloride aqueous solution of a step preparation while stirring, until mix;
C) weigh in the balance get 150g sodium sulfate add while stirring b step preparation titanous chloride, in hydrogen peroxide mixed solution, until mix dissolving;
D) weigh in the balance get 60g citric acid add while stirring the titanous chloride of step c preparation, hydrogen peroxide, in sodium sulfate mixing solutions, until mix dissolving;
E) in Step d gained titanous chloride, hydrogen peroxide, sodium sulfate, citric acid mixing solutions, add water and be settled to 10L, with pH meter or pH test paper for instrument, by 1:10 salpeter solution or 1:10 sodium hydroxide solution adjust ph to 1.0-1.5, and stir
(3) this steel plate carried out eliminating rust before electroplating, oil removing, after the pre-treatment such as activation, put into electroplate liquid to electroplate, the plating solution composition of zincincation and operational condition are: the pH value of zinc chloride 60g/L, Repone K 200g/L, boric acid 30g/L, appropriate additive, plating solution remains on about 5.8, and current density is 1.2A/dm
2, temperature is room temperature, and electroplating time is 30 minutes, obtains electrogalvanizing steel plate, for subsequent use.
(4) prepare light-emitting solution: by analytically pure concentrated nitric acid according to 1% concentration mix with tap water, for subsequent use
(5) the electrogalvanizing steel plate tap water obtained through step 3 is cleaned clean after immerse in the light-emitting solution that step 4 prepares, stop 5 seconds under room temperature, clean up with tap water after taking-up, then immerse in passivating solution that step 2 prepares, soak after 15 seconds, take out and dry or seasoning.
Use the steel plate appearance after the process of this passivation technology to be even, multicolored outward appearance, go out the white rust time more than 80 hours through neutral salt spray test.
Embodiment 3: preparation 100L novel non-chrome acid zinc plating color passivation solution, this passivation technology is for the Passivation Treatment after certain steel pipe integral electro-galvanizing on air compressor machine.
(1) according to following formula batching: titanous chloride 1000g, hydrogen peroxide 1500ml, sodium sulfate 3000g, citric acid 1000g, all the other are water.
(2) novel non-chrome acid zinc plating color passivation solution is prepared through following method, for subsequent use:
A) weigh in the balance and get 1000g titanous chloride, pour into and 50L water is housed, cumulative volume, more than in the plastic tank of 100L, stirs with wooden stick;
B) measure the hydrogen peroxide of 1500ml with measuring cup, add with wooden stick in the titanium trichloride aqueous solution of a step preparation while stirring, until mix;
C) weigh in the balance get 3000g sodium sulfate add while stirring b step preparation titanous chloride, in hydrogen peroxide mixed solution, until mix dissolving;
D) weigh in the balance get 1000g citric acid add while stirring the titanous chloride of step c preparation, hydrogen peroxide, in sodium sulfate mixing solutions, until mix dissolving;
E) in Step d gained titanous chloride, hydrogen peroxide, sodium sulfate, citric acid mixing solutions, add water and be settled to 100L, with pH meter or pH test paper for instrument, by 1:10 salpeter solution or 1:10 sodium hydroxide solution adjust ph to 1.0-1.5, and stir
(3) this steel plate carried out eliminating rust before electroplating, oil removing, after the pre-treatment such as activation, put into electroplate liquid to electroplate, the plating solution composition of zincincation and operational condition are: the pH value of zinc chloride 60g/L, Repone K 200g/L, boric acid 30g/L, appropriate additive, plating solution remains on about 5.8, and current density is 1.2A/dm
2, temperature is room temperature, and electroplating time is 35 minutes, obtains electrogalvanizing steel plate, for subsequent use.
(4) prepare light-emitting solution: by analytically pure concentrated nitric acid according to 1% concentration mix with tap water, for subsequent use
(5) the electrogalvanizing steel plate tap water obtained through step 3 is cleaned clean after immerse in the light-emitting solution that step 4 prepares, stop 5 seconds under room temperature, clean up with tap water after taking-up, then immerse in passivating solution that step 2 prepares, soak after 15 seconds, take out and dry or seasoning.
Use the steel plate appearance after the process of this passivation technology to be even, multicolored outward appearance, go out the white rust time more than 85 hours through neutral salt spray test.
Claims (4)
1. novel non-chrome acid zinc plating color passivation solution and a preparation method, is characterized in that this passivating solution is made up of following component:
Titanium salt: 2-10g/L vitriol 1-30.0g/L hydrogen peroxide 5-15ml/L complexing agent 2-10g/L
All the other are water.
2. a kind of novel non-chrome acid zinc plating color passivation solution as claimed in claim 1 and preparation method, is characterized in that this passivating solution is prepared by following method:
A, take the silicate of 2-10g/L according to volume total amount, pour in the water of 1/2 volume total amount, be stirred well to dissolving, obtain the titanium salt aqueous solution;
B, measure the hydrogen peroxide of 5-15ml/L according to volume total amount, add while stirring in the titanium salt aqueous solution of step A preparation, obtain the mixing solutions of titanium salt, hydrogen peroxide;
C, take 1-30g/L vitriol according to volume total amount, add while stirring in the mixing solutions of the titanium salt of step B preparation, hydrogen peroxide, obtain the mixing solutions of titanium salt, hydrogen peroxide, vitriol;
D, take the complexing agent of 2-10g/L according to volume total amount, add while stirring in the mixing solutions of the titanium salt of step C preparation, hydrogen peroxide, vitriol, obtain titanium salt, hydrogen peroxide, the mixing solutions of vitriol, the mixing solutions of complexing agent;
E, to D step gained titanium salt, hydrogen peroxide, vitriol, add water in the mixing solutions of complexing agent and be settled to volume required, and to stir.
3. a kind of novel non-chrome acid zinc plating color passivation solution as described in claim 1 and 2 and preparation method, it is characterized in that described titanium salt is one or several in titanous chloride, titanyl sulfate, titanium sulfate, vitriol is one or both in potassium sulfate, sodium sulfate, complexing agent is propanedioic acid, succinic acid, citric acid, one or several in tartrate, Seignette salt.
4. a kind of novel non-chrome acid zinc plating color passivation solution as described in claim 1,2 and 3 and preparation method, it is characterized in that described titanium salt, hydrogen peroxide, vitriol, complexing agent are commercially available chemical pure product, water is purified water or tap water.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107090576A (en) * | 2017-05-22 | 2017-08-25 | 厦门建霖健康家居股份有限公司 | A kind of kirsite chromium-free passivation liquid |
| CN108754475A (en) * | 2018-05-28 | 2018-11-06 | 昆明理工大学 | A kind of environment-friendly type blue and white passivation solution and preparation method thereof |
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| CN101235498A (en) * | 2008-02-28 | 2008-08-06 | 武汉钢铁(集团)公司 | Chromium-free inactivating liquid used for galvanized steel sheet surface |
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- 2014-05-08 CN CN201410191969.1A patent/CN105088210A/en active Pending
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| CN101235498A (en) * | 2008-02-28 | 2008-08-06 | 武汉钢铁(集团)公司 | Chromium-free inactivating liquid used for galvanized steel sheet surface |
| CN103060789A (en) * | 2013-02-04 | 2013-04-24 | 云南滇科涂镀层材料有限公司 | Whole chromium-free high-corrosion-resistant zinc-coated iridescent passivation solution and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107090576A (en) * | 2017-05-22 | 2017-08-25 | 厦门建霖健康家居股份有限公司 | A kind of kirsite chromium-free passivation liquid |
| CN108754475A (en) * | 2018-05-28 | 2018-11-06 | 昆明理工大学 | A kind of environment-friendly type blue and white passivation solution and preparation method thereof |
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