CN113881934A - Zinc-based phosphating solution with less slag and ash - Google Patents

Zinc-based phosphating solution with less slag and ash Download PDF

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Publication number
CN113881934A
CN113881934A CN202111298668.5A CN202111298668A CN113881934A CN 113881934 A CN113881934 A CN 113881934A CN 202111298668 A CN202111298668 A CN 202111298668A CN 113881934 A CN113881934 A CN 113881934A
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percent
zinc
less
phosphating solution
slag
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CN113881934B (en
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许峻豪
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Hunan Jinhua Science & Technology Group Co ltd
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Hunan Jinhua Science & Technology Group Co ltd
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    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C22/00Chemical 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
    • C23C22/05Chemical 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
    • C23C22/06Chemical 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
    • C23C22/07Chemical 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
    • C23C22/08Orthophosphates
    • C23C22/12Orthophosphates containing zinc cations
    • C23C22/17Orthophosphates containing zinc cations containing also organic acids

Abstract

A zinc phosphating solution with less slag and less ash relates to the technical field of phosphating solutions, and comprises the following components in percentage by mass: 16-17% of phosphoric acid, 4-5% of zinc oxide, 26.5-27.5% of zinc nitrate, 1.5-5% of N-hydroxyethyl ethylenediamine triacetic acid, 0.5-2% of 1, 10-phenanthroline, 0.5-2.5% of hydrogen peroxide and 44-50% of deionized water. The invention can reduce the phosphorus ash and slag generated on the surface of the steel pipe in the phosphorization process, improve the phosphorization effect and improve the quality of a phosphorization film.

Description

Zinc-based phosphating solution with less slag and ash
Technical Field
The invention relates to the technical field of phosphating solutions, in particular to a zinc phosphating solution with less slag and less ash.
Background
The zinc phosphating solution is one of important materials for corrosion prevention of metal materials, and aims to provide corrosion prevention protection for base metals, prime before paint spraying, improve the adhesive force and corrosion prevention capability of a coating layer, play a role in friction reduction and lubrication in metal processing and the like.
The zinc phosphating solution is usually used in the cold drawing operation of the common steel pipe, but phosphorous slag and phosphorous ash can be generated in the using process. In the later stage of using the phosphating solution, the situation is particularly serious, a large amount of phosphorus slag or phosphorus ash can cover the steel pipe, on one hand, the thickness of a phosphating film on the surface of the steel pipe is uneven, because the wall thickness of the pulled pipe is uneven due to uneven pulling force in the drawing process of the steel pipe, and then due to the coverage of a large amount of phosphorus slag and phosphorus ash, patches or stripes can be more easily formed on the surface of the pipe, the appearance and the quality of the steel pipe are influenced, and the mould is damaged by uneven friction resistance; on the other hand, a large amount of phosphorus slag and phosphorus ash not only increase the work load of workers for removing slag and ash, but also lead to the reduction of the service life of the phosphating solution due to the gradual deterioration of the stability of the phosphating solution, so the consumption is correspondingly increased, and the cost of environmental protection and treatment is increased.
Disclosure of Invention
The invention aims to provide a zinc phosphating solution with less slag and less ash, which reduces the generation of phosphorite and phosphorite slag on the surface of a steel pipe in the phosphating process, improves the phosphating effect and improves the quality of a phosphating film.
In order to solve the technical problems, the invention adopts the following technical scheme: a zinc phosphating solution with less slag and less ash comprises the following components in percentage by mass: 16-17% of phosphoric acid, 4-5% of zinc oxide, 26.5-27.5% of zinc nitrate, 1.5-5% of N-hydroxyethyl ethylenediamine triacetic acid, 0.5-2% of 1, 10-phenanthroline, 0.5-2.5% of hydrogen peroxide and 44-50% of deionized water.
Preferably, the zinc phosphating solution with less slag and less ash comprises the following components in percentage by mass: 16.4 percent of phosphoric acid, 4.3 percent of zinc oxide, 26.8 percent of zinc nitrate, 3.6 percent of N-ethoxyl ethylene diamine triacetic acid, 1.3 percent of 1, 10-diazophenanthrene, 2 percent of hydrogen peroxide and 45.6 percent of deionized water.
Wherein the phosphoric acid is 85% phosphoric acid; the zinc oxide is 98% pure zinc oxide; the zinc nitrate is 98% pure zinc nitrate; the hydrogen peroxide is hydrogen peroxide with the concentration of 30 percent.
The invention has the beneficial effects that: the zinc phosphating solution provided by the invention is used in the cold drawing operation process of the steel pipe, so that the generation of phosphorus slag and phosphorus ash can be reduced to a great extent, the phosphating effect can be improved, and the quality of a phosphating film formed on the surface of the steel pipe is improved.
Detailed Description
The present invention will be further described with reference to the following examples for facilitating understanding of those skilled in the art, and the description of the embodiments is not intended to limit the present invention.
Example 1
A zinc phosphating solution with less slag and less ash comprises the following components in percentage by mass: 16.4% of phosphoric acid, 4.3% of zinc oxide, 26.8% of zinc nitrate, 1.5% of N-hydroxyethyl ethylenediamine triacetic acid, 1.3% of 1, 10-diazophenanthrene, 2% of hydrogen peroxide and 47.7% of deionized water.
Example 2
A zinc phosphating solution with less slag and less ash comprises the following components in percentage by mass: 16.4 percent of phosphoric acid, 4.3 percent of zinc oxide, 26.8 percent of zinc nitrate, 3.6 percent of N-ethoxyl ethylene diamine triacetic acid, 1.3 percent of 1, 10-diazophenanthrene, 2 percent of hydrogen peroxide and 45.6 percent of deionized water.
Example 3
A zinc phosphating solution with less slag and less ash comprises the following components in percentage by mass: 16.4% of phosphoric acid, 4.3% of zinc oxide, 26.8% of zinc nitrate, 4.6% of N-hydroxyethyl ethylenediamine triacetic acid, 1.3% of 1, 10-diazophenanthrene, 2% of hydrogen peroxide and 44.6% of deionized water.
Comparative example 1
A zinc phosphating solution with less slag and less ash comprises the following components in percentage by mass: 16.4% of phosphoric acid, 4.3% of zinc oxide, 26.8% of zinc nitrate, 1, 10-phenanthroline, 2% of hydrogen peroxide and 49.2% of deionized water.
The component data comparative ratios of the above examples and comparative examples are shown in table 1 below.
TABLE 1 comparison of component data for examples 1-3 and comparative example 1
Figure DEST_PATH_IMAGE002
Performance testing
The zinc phosphating solutions of the examples and the comparative examples were subjected to performance tests, specifically, the zinc phosphating solution with a total acidity of 20 points was placed in a 500ml beaker, then a common carbon steel water pipe was taken and placed in the beaker, phosphating was performed at a phosphating temperature of 70 ℃ for 20 minutes, then the carbon steel water pipe after phosphating was taken out and tested, and the obtained data are shown in table 2 below.
TABLE 2 Performance of carbon steel water pipe after phosphating of examples 1-3 and comparative example 1
Figure DEST_PATH_IMAGE004
As shown in the test results in Table 2, the addition of N-hydroxyethylethylene diamine triacetic acid (HEDTA) can significantly inhibit the production of phosphorous slag, and the inhibition effect is better when the amount is 4.6%, but in practical production application, the person skilled in the art can choose to use N-hydroxyethylethylene diamine triacetic acid (HEDTA) in the amount of 3.6% in the formulation according to the consideration of production cost.
Example 4
A zinc phosphating solution with less slag and less ash comprises the following components in percentage by mass: 16.4 percent of phosphoric acid, 4.3 percent of zinc oxide, 26.8 percent of zinc nitrate, 3.6 percent of N-ethoxyl ethylene diamine triacetic acid, 0.5 percent of 1, 10-diazophenanthrene, 2 percent of hydrogen peroxide and 46.4 percent of deionized water.
Example 5
A zinc phosphating solution with less slag and less ash comprises the following components in percentage by mass: 16.4 percent of phosphoric acid, 4.3 percent of zinc oxide, 26.8 percent of zinc nitrate, 3.6 percent of N-ethoxyl ethylene diamine triacetic acid, 1.3 percent of 1, 10-diazophenanthrene, 2 percent of hydrogen peroxide and 45.6 percent of deionized water.
Example 6
A zinc phosphating solution with less slag and less ash comprises the following components in percentage by mass: 16.4 percent of phosphoric acid, 4.3 percent of zinc oxide, 26.8 percent of zinc nitrate, 3.6 percent of N-ethoxyl ethylene diamine triacetic acid, 1.8 percent of 1, 10-diazophenanthrene, 2 percent of hydrogen peroxide and 45.1 percent of deionized water.
Comparative example 2
A zinc phosphating solution with less slag and less ash comprises the following components in percentage by mass: 16.4% of phosphoric acid, 4.3% of zinc oxide, 26.8% of zinc nitrate, 3.6% of N-hydroxyethyl ethylenediamine triacetic acid, 2% of hydrogen peroxide and 46.9% of deionized water.
The component data comparison ratios of the above examples and comparative examples are shown in table 3 below.
TABLE 3 comparison of component data for examples 4-6 and comparative example 2
Figure DEST_PATH_IMAGE006
Performance testing
The zinc phosphating solutions of the examples and the comparative examples were subjected to performance tests, specifically, the zinc phosphating solution with a total acidity of 20 points was placed in a 500ml beaker, then a common carbon steel water pipe was taken and placed in the beaker, phosphating was performed at a phosphating temperature of 70 ℃ for 20 minutes, and then the carbon steel water pipe after phosphating was taken out and tested, and the obtained data are shown in table 4 below.
TABLE 4 Performance of phosphatized carbon steel water pipes of examples 4-6 and comparative example 2
Figure DEST_PATH_IMAGE008
From the test results in table 4, it can be seen that the addition of 1, 10-phenanthroline (phen) has a great influence on ferrous iron in the solution and also on the quality of the phosphating film, and it can be seen that the addition of 1, 10-phenanthroline (phen) can reduce the content of ferrous iron in the phosphating solution, so as to improve the quality of the phosphating film, and the effect is better when the amount is 1.8%, but because the effect when the amount is 1.3% is not much different from that, in practical production application, a person skilled in the art can select 1.3% 1, 10-phenanthroline (phen) to be used in the formulation according to the consideration of production cost.
Example 7
A zinc phosphating solution with less slag and less ash comprises the following components in percentage by mass: 16.4 percent of phosphoric acid, 4.3 percent of zinc oxide, 26.8 percent of zinc nitrate, 3.6 percent of N-ethoxyl ethylene diamine triacetic acid, 1.3 percent of 1, 10-diazophenanthrene, 0.5 percent of hydrogen peroxide and 47.7 percent of deionized water.
Example 8
A zinc phosphating solution with less slag and less ash comprises the following components in percentage by mass: 16.4 percent of phosphoric acid, 4.3 percent of zinc oxide, 26.8 percent of zinc nitrate, 3.6 percent of N-ethoxyl ethylene diamine triacetic acid, 1.3 percent of 1, 10-diazophenanthrene, 2 percent of hydrogen peroxide and 45.6 percent of deionized water.
Example 9
A zinc phosphating solution with less slag and less ash comprises the following components in percentage by mass: 16.4 percent of phosphoric acid, 4.3 percent of zinc oxide, 26.8 percent of zinc nitrate, 3.6 percent of N-ethoxyl ethylene diamine triacetic acid, 1.3 percent of 1, 10-diazophenanthrene, 2.5 percent of hydrogen peroxide and 44.6 percent of deionized water.
Comparative example 3
A zinc phosphating solution with less slag and less ash comprises the following components in percentage by mass: 16.4 percent of phosphoric acid, 4.3 percent of zinc oxide, 26.8 percent of zinc nitrate, 3.6 percent of N-ethoxyl ethylene diamine triacetic acid, 1.3 percent of 1, 10-diazocine and 49.2 percent of deionized water.
The component data of each of the above examples and comparative examples are shown in table 5 below.
TABLE 5 comparison of component data for examples 7-9 and comparative example 3
Figure DEST_PATH_IMAGE010
Performance testing
The zinc phosphating solutions of the examples and the comparative examples were subjected to performance tests, specifically, the zinc phosphating solution with a total acidity of 20 points was placed in a 500ml beaker, then a common carbon steel water pipe was taken and placed in the beaker, phosphating was performed at a phosphating temperature of 70 ℃ for 20 minutes, and then the carbon steel water pipe after phosphating was taken out and tested, and the obtained data are shown in table 6 below.
TABLE 6 properties of carbon steel water pipes of examples 7 to 9 and comparative example 3 after phosphating
Figure DEST_PATH_IMAGE012
The test results in table 6 show that the addition of sufficient hydrogen peroxide is also helpful for reducing the generation of phosphorous slag, and actually, the hydrogen peroxide mainly oxidizes ferrous iron in the solution into ferric iron, so that the phosphorous slag is separated out conveniently, and the phosphorous ash on the surface of the steel pipe is reduced to improve the quality of the phosphorous coating. But the dosage of the hydrogen peroxide is not too much, otherwise, the generation of a phosphating film is influenced, so that the effect is better when the dosage of the hydrogen peroxide is 2 percent.
The zinc-based phosphating solution with less slag and ash provided by the embodiment is applied to actual steel pipe cold-drawing production operation, the achieved phosphating effect is better, the adhesion of a phosphating film is stronger, the phosphorus slag generated in the phosphating process is less, the phosphorus ash on the surface of the steel pipe is less, and on the other hand, the slag and ash cleaning workload of workers is reduced to a great extent. And because the ferrous content in the phosphating solution is reduced, the phosphorus slag is easier to separate out, so the stability of the phosphating solution is improved to a certain extent, the waste caused by poor stability of the phosphating solution like the common zinc phosphating solution is avoided, the consumption of the production process is increased, the production cost is reduced, and the cost of environmental protection treatment can be reduced. In conclusion, the zinc phosphating solution with less slag and less ash provided by the invention can well solve the problems of the conventional common zinc phosphating solution and has better use value and prospect.
The above embodiments are preferred implementations of the present invention, and the present invention can be implemented in other ways without departing from the spirit of the present invention.
Some descriptions of the present invention have been simplified to facilitate understanding of the improvement of the present invention over the prior art by those of ordinary skill in the art, and some other elements have been omitted from this document for clarity, and those omitted elements should be recognized by those of ordinary skill in the art to constitute the content of the present invention.

Claims (6)

1. The zinc phosphating solution with less slag and less ash is characterized by comprising the following components in percentage by mass: 16-17% of phosphoric acid, 4-5% of zinc oxide, 26.5-27.5% of zinc nitrate, 1.5-5% of N-hydroxyethyl ethylenediamine triacetic acid, 0.5-2% of 1, 10-phenanthroline, 0.5-2.5% of hydrogen peroxide and 44-50% of deionized water.
2. The zinc-based phosphating solution with less slag and less ash according to claim 1, which is characterized by comprising the following components in percentage by mass: 16.4 percent of phosphoric acid, 4.3 percent of zinc oxide, 26.8 percent of zinc nitrate, 3.6 percent of N-ethoxyl ethylene diamine triacetic acid, 1.3 percent of 1, 10-diazophenanthrene, 2 percent of hydrogen peroxide and 45.6 percent of deionized water.
3. The zinc-based phosphating solution with less slag and less ash according to claim 1, which is characterized in that: the phosphoric acid is 85% phosphoric acid.
4. The zinc-based phosphating solution with less slag and less ash according to claim 1, which is characterized in that: the zinc oxide is 98% pure zinc oxide.
5. The zinc-based phosphating solution with less slag and less ash according to claim 1, which is characterized in that: the zinc nitrate is 98% pure zinc nitrate.
6. The zinc-based phosphating solution with less slag and less ash according to claim 1, which is characterized in that: the hydrogen peroxide is hydrogen peroxide with the concentration of 30 percent.
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Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB8919200D0 (en) * 1988-08-24 1989-10-04 Ardrox Pyrene Ltd Phosphating process
SU1520145A1 (en) * 1988-02-01 1989-11-07 Буйский Химический Завод Composition for phosphatizing a metal surface
CN1057681A (en) * 1991-06-29 1992-01-08 中科院近代物理研究所新技术实验工厂 Phosphating solution at room temperature and compound method thereof
CN102677034A (en) * 2012-05-25 2012-09-19 衡阳市金化科技有限公司 Medium-temperature low-sediment zinc phosphorizing solution
CN103726039A (en) * 2013-11-30 2014-04-16 常熟市东鑫钢管有限公司 Steel pipe alramenting technology
CN106906461A (en) * 2016-04-18 2017-06-30 佛山瑞箭体育器材有限公司 A kind of Phosphating Solution and preparation method thereof
CN107523818A (en) * 2017-09-19 2017-12-29 江山海维科技有限公司 A kind of preparation method of low-temperature metal phosphorizing liquid
CN107743421A (en) * 2015-06-11 2018-02-27 宝洁公司 Apparatus and method for composition to be applied to surface
CN108505025A (en) * 2018-07-03 2018-09-07 湖南金化科技集团有限公司 A kind of manganese phosphating liquor and its application

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
SU1520145A1 (en) * 1988-02-01 1989-11-07 Буйский Химический Завод Composition for phosphatizing a metal surface
GB8919200D0 (en) * 1988-08-24 1989-10-04 Ardrox Pyrene Ltd Phosphating process
US5152849A (en) * 1988-08-24 1992-10-06 Metallgesellschaft Aktiengesellschaft Phosphating process
CN1057681A (en) * 1991-06-29 1992-01-08 中科院近代物理研究所新技术实验工厂 Phosphating solution at room temperature and compound method thereof
CN102677034A (en) * 2012-05-25 2012-09-19 衡阳市金化科技有限公司 Medium-temperature low-sediment zinc phosphorizing solution
CN103726039A (en) * 2013-11-30 2014-04-16 常熟市东鑫钢管有限公司 Steel pipe alramenting technology
CN107743421A (en) * 2015-06-11 2018-02-27 宝洁公司 Apparatus and method for composition to be applied to surface
CN106906461A (en) * 2016-04-18 2017-06-30 佛山瑞箭体育器材有限公司 A kind of Phosphating Solution and preparation method thereof
CN107523818A (en) * 2017-09-19 2017-12-29 江山海维科技有限公司 A kind of preparation method of low-temperature metal phosphorizing liquid
CN108505025A (en) * 2018-07-03 2018-09-07 湖南金化科技集团有限公司 A kind of manganese phosphating liquor and its application

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
许峻豪等: "高温锰系磷化液中络合稳定剂的研究" *
雷作鍼等编译, 机械工业出版社 *

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