CN113621953A - Phosphating solution and preparation method thereof - Google Patents
Phosphating solution and preparation method thereof Download PDFInfo
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- CN113621953A CN113621953A CN202110772653.1A CN202110772653A CN113621953A CN 113621953 A CN113621953 A CN 113621953A CN 202110772653 A CN202110772653 A CN 202110772653A CN 113621953 A CN113621953 A CN 113621953A
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- phosphating
- phosphating solution
- acid
- hydrofluoric acid
- cobalt nitrate
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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
- C23C22/34—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
Abstract
The invention relates to the technical field of metal surface treatment, in particular to a phosphating solution and a preparation method thereof. The phosphating solution comprises the following components in percentage by weight: 15-35% of phosphoric acid, 30-50% of nitric acid, 10-25% of zinc oxide, 4-8% of manganese carbonate, 1-2.5% of accelerator, 0.5-1.5% of complexing agent, 3-8% of hydrofluoric acid, complexing iron ion stabilizer and a plurality of parts of deionized water. The phosphating solution does not generate phosphating slag, does not need to clean the phosphating slag, solves the technical problem that the phosphating solution does not contain nickel under the environment-friendly requirement, saves the cost for subsequent waste liquid treatment, has good phosphating film forming compactness, good alkali resistance, thinness and strong medicament universality, and is suitable for the phosphating treatment of various types of steel and iron coating.
Description
Technical Field
The invention relates to the technical field of metal surface treatment, in particular to a phosphating solution and a preparation method thereof.
Background
The phosphorizing liquid is a mixed chemical reagent, which is mainly prepared from phosphoric acid, zinc nitrate, nitric acid, zinc dihydrogen phosphate, manganese dihydrogen phosphate and water. The main operation is to form a uniform and compact phosphating film on the surface of steel metal, improve the corrosion resistance of steel, and improve the binding force with paint and the salt spray performance. The existing phosphating solution is contacted with the surface of steel, the surface of the steel is dissolved, hydrogen ions in the phosphating solution near the surface are reduced, when the pH value is increased from 3.0 to 4.6, a film forming reaction is caused, and zinc phosphate and zinc iron phosphate films are generated on the metal surface to form a phosphating film. Part of the dissolved iron ions are consumed as the constituent of the phosphating film, and the other part of the dissolved iron ions react to form iron which is left in the phosphating solution, so that the phosphating reaction is difficult to smoothly proceed. In the market, an oxidant is added to oxidize ferrous ions into ferric ions to generate iron phosphide, and the iron phosphide (phosphorization slag) is harmful solid waste and solid waste.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a phosphating solution, which solves the technical problems that iron residues exist in the use of the existing phosphating solution, and phosphating slag solid waste is generated.
In order to achieve the purpose, the invention adopts the following scheme:
the phosphating solution comprises the following components in percentage by weight: 15-35% of phosphoric acid, 30-50% of nitric acid, 10-25% of zinc oxide, 4-8% of manganese carbonate, 1-2.5% of accelerator, 0.5-1.5% of complexing agent, 3-8% of hydrofluoric acid, complexing iron ion stabilizer and a plurality of parts of deionized water.
Preferably, the composition comprises the following components in percentage by weight: 28% of phosphoric acid, 50% of nitric acid, 15% of zinc oxide, 5% of manganese carbonate, 1% of accelerator, 1% of complexing agent, 5% of complexing iron ion stabilizer and 5% of deionized water.
Further, the complex iron ion stabilizer is sodium potassium tartrate.
Further, the accelerant is cobalt nitrate and hydrofluoric acid.
Furthermore, the weight percentage of the cobalt nitrate is 0.5-1.0%, and the weight percentage of the hydrofluoric acid is 0.5-1.5%.
Further, the complexing agent is citric acid.
Specifically, zinc dihydrogen phosphate and manganese dihydrogen phosphate are prepared by phosphoric acid, nitric acid, zinc oxide and manganese carbonate, wherein the zinc dihydrogen phosphate is a main film forming component, and a zinc phosphate crystal film layer is formed on the metal surface; the manganese dihydrogen phosphate is a secondary component of film formation, a manganese phosphate salt crystallization film layer is formed on the surface of metal, the crystallization is in a hemispherical state, the corrosion resistance and alkali resistance of the film layer are improved, the generation thickness of a phosphating film is reduced, and the weight of the phosphating film is reduced.
Specifically, the cobalt nitrate can promote the speed of a film on a phosphating film, refine the granularity of phosphating crystals and improve the corrosion resistance of the phosphating film. The citric acid can complex ferric ions, and the generation of phosphorization slag is reduced. The hydrofluoric acid can accelerate the film forming speed on the phosphating film, refine phosphating crystals and reduce the content of free aluminum ions in phosphating solution. The complexing iron ion stabilizer can reduce the generation of iron ions in the phosphating solution.
The second purpose of the invention is to provide a preparation method of the phosphating solution.
In order to achieve the purpose, the invention adopts the following scheme:
the preparation method of the phosphating solution comprises the following steps:
1) weighing phosphoric acid, nitric acid, zinc oxide, manganese carbonate and deionized water according to the weight percentage to prepare zinc nitrate, zinc dihydrogen phosphate, zinc nitrate, manganese nitrate and manganese dihydrogen phosphate;
2) adding cobalt nitrate, citric acid, sodium potassium tartrate and hydrofluoric acid into the solution obtained in the step 1) in sequence, and stirring until the cobalt nitrate, the citric acid, the sodium potassium tartrate and the hydrofluoric acid are completely dissolved to obtain the phosphating solution.
Further, when the temperature of the solution in the step 2) is lower than 40 ℃, adding cobalt nitrate, citric acid, potassium sodium tartrate and hydrofluoric acid in sequence, and stirring until the cobalt nitrate, the citric acid, the potassium sodium tartrate and the hydrofluoric acid are completely dissolved to obtain the phosphating solution.
The invention adopts the technical principle that:
the existing phosphating solution is contacted with the surface of steel, the surface of the steel is dissolved, hydrogen ions in the phosphating solution near the surface are reduced, when the pH value is increased from 3.0 to 4.6, a film forming reaction is caused, and zinc phosphate and zinc iron phosphate films are generated on the metal surface to form a phosphating film. Iron ions are stabilized into ferrous ions by adding an iron ion complexing stabilizer, redundant ferrous ions participate in film formation, the film formation film layer is mainly made of ferric phosphate, a film layer with a high P ratio is obtained, the iron ions are consumed, and therefore phosphated slag is not generated.
The invention has the beneficial effects that:
1. the production of phosphate-free slag without cleaning the phosphate slag (the phosphate slag is produced when the traditional phosphating solution is used for treatment, the main component is ferric phosphate which is toxic and harmful solid waste, the treatment needs to be recovered by professional institutions, and the cost is 10000 yuan/ton in 5000 plus materials);
2. the environment-friendly product does not contain nickel, replaces ternary nickel-containing phosphating solution, solves the technical problem that the environment-friendly requirement cannot contain nickel, saves the cost for subsequent waste liquid treatment, and has carcinogenicity due to the fact that nickel is heavy metal;
3. the phosphating film has good compactness, good alkali resistance, thinness and strong medicament universality, and is suitable for the phosphating treatment of various steel and iron coating.
Drawings
FIG. 1 is a drawing of a phosphorized electron microscope of an iron plate in example 3 of the present invention.
FIG. 2 is a diagram showing a phosphating film of a standard iron plate under different conditions in example 4 of the present invention.
FIG. 3 is a coding diagram of the electrophoretic paint of example 5 of the present invention.
Fig. 4 is a corrosion detection diagram of embodiment 8 of the present invention.
Detailed Description
The technical solution of the present invention is further explained with reference to the drawings and the embodiments.
Phosphating parameters and process conditions:
the process comprises the following steps: degreasing → washing → surface tone → phosphating → washing
Implementation parameters of phosphorization:
total acidity: 18-25
Free acidity of 0.5-1.5
Accelerator (b): 0.1-0.2
Temperature: 25-40 deg.C
Example 1 phosphating solution
A phosphating solution was prepared according to the formulation components of Table 1.
TABLE 1 phosphating solution formulation
EXAMPLE 2 preparation of phosphating solution
Weighing the raw materials of the formulas 1 to 5 in the embodiment 1, adding deionized water, phosphoric acid and nitric acid into a stirring cylinder, uniformly stirring, then adding zinc oxide, and stirring until the zinc oxide is completely dissolved; adding manganese carbonate and stirring until the manganese carbonate is completely dissolved; when the temperature of the solution in the stirring cylinder is lower than 40 ℃, adding cobalt nitrate, citric acid, potassium sodium tartrate and hydrofluoric acid into the stirring cylinder in sequence, and stirring until the cobalt nitrate, the citric acid, the potassium sodium tartrate and the hydrofluoric acid are completely dissolved.
Example 3 treatment of bare iron sheet
The phosphating solutions prepared in formulations 1 to 4 of example 2 were used to treat bare iron plates, and after treatment, as shown in fig. 1, phosphating crystals were uniform and dense, spherical and mainly manganese salt crystals.
Example 4
The standard iron plate is treated by the phosphating solution prepared by the formulas 1-5 in the embodiment 2, as shown in figure 2 (the formulas 1-5 are from left to right), the phosphating film of the iron plate in the formulas 1-4 is uniform and compact, the appearance is light gray, and the standard reaches the national standard (GB/T6807-; the iron plate of formula 5 is obviously red brown with the color of the phosphating film gray, and the phosphating films in the upper half and the middle are not mottled uniformly.
Example 5
The phosphating solution prepared by the formula 1 in the example 2 is used for treating an iron plate to form a thin film by phosphating, the film weight is 1.2-1.6 g/square meter, the impact resistance is improved, and as shown in figure 3, particularly for products with the requirements of code printing and character carving, the paint falling of the code printing and character carving cut part can be ensured (GBT 9792-2003).
The experimental steps are as follows:
1. film-removing test solution preparation
Ethylene diamine tetraacetic acid dihydrate tetrasodium salt (EDTA tetrasodium salt) 90g/L
Triethanolamine 4g/L
2. Putting the test piece into a baking oven at 100 ℃ for baking for 10 minutes;
3. after cooling, weighing by using a precision electronic scale until the weight is accurate to 0.0001g, and recording m 1;
4. dipping the test piece for 5 minutes at the temperature of 75 +/-5 ℃ of the film stripping liquid, quickly taking out the test piece, washing the test piece by using tap water, quickly dipping the test piece for 5 seconds by using deionized water at the temperature of 90-100 ℃, and quickly taking out the test piece for drying by using a hair drier;
5. putting the test piece into a baking oven at 100 ℃ and baking for 10 minutes;
6. after cooling, the weight is again measured and m2 recorded
7. Computing
Description of the symbols: m is the film weight per square meter, M1 is the test piece weight before film stripping, M2 is the test piece weight after film stripping, and S is the test piece area.
Example 6 salt spray Performance testing
The manual salt spray environment simulation test is that a salt spray test box which is test equipment with a certain volume space is utilized, and the salt spray environment is caused to examine the salt spray corrosion resistance performance quality of a product in the volume space by a manual method. Compared with the natural environment, the salt concentration of the chloride in the salt spray environment can be several times or dozens of times of that in the salt spray environment of the common natural environment, so that the corrosion speed is greatly improved, and the time for obtaining the result is greatly shortened when the salt spray test is carried out on the product. If a product sample is tested in a natural exposure environment, the corrosion may take 1 year, and if the product sample is tested in an artificial simulated salt fog environment, similar results can be obtained within dozens of hours or even shorter.
The iron plates treated by the phosphating solutions of the formulas 1 to 4 in the examples can meet the requirement of the neutral salt spray performance test for 1000 hours by matching with the electrophoretic paint, and the iron plates treated by the phosphating solution of the formula 5 can meet the requirement of the neutral salt spray performance test for 600 hours by matching with the electrophoretic paint.
The salt spray machine measurement parameters are as follows:
TABLE 2
Example 7 adhesion test
After the iron plates were treated with the phosphating solutions of formulations 1 to 5 of example 2, adhesion was measured, formulations 1 to 4, with a level of adhesion of 0 for the formulation 5 and a level of adhesion of 1 for the formulation 5.
The adhesive force detection method comprises the following steps:
method for detecting adhesive force of coating film by adopting grid cutting method
When the grid marking method is adopted, a 11-gauge sewing machine needle is adopted as a marking needle, 6 strips of marks are marked on each grid of 1mm in the vertical and horizontal directions of the surface of a paint film, the whole depth of the paint film is cut through, and then the paint film is not dropped off completely by lightly touching with fingers.
According to the ISO standard, 6 stages are divided:
level 0: the paint film is complete, and no square lattice falls off;
level 1: the falling of a paint film at the cutting intersection is not more than 5 percent;
and 2, stage: the falling of a paint film is more than 5 percent and not more than 15 percent;
and 3, level: the large pieces of the paint film fall off, and are not more than 35 percent;
4, level: the large pieces of the paint film fall off, and are not more than 65%;
and 5, stage: the paint film is largely peeled off, which is more than 65 percent.
Example 8 Corrosion detection
The phosphating solution of the formulas 1 to 4 of the embodiment 2 is subjected to corrosion detection, the detection result is shown in figure 4, the treated phosphating solution of the formulas 1 to 4 resists 3 percent of saline water, and the phosphating solution has no corrosion within 2 hours (GB/T6807-2001).
The detection method comprises the following steps:
immediately immersing a phosphorized sample (cooled to room temperature) into a 3% sodium chloride (NaCl) aqueous solution, keeping the temperature at 15-25 ℃ for a specified time, taking out the sample, cleaning, blow-drying, and visually checking whether the phosphorized surface is rusted or not.
Numbering: 1 (formulation 1), 2 (formulation 2), 3 (formulation 3), 4 (formulation 4), 5 (formulation 1+ 2).
Finally, the above embodiments are only for illustrating the technical solutions of the present invention and not for limiting, although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions may be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, and all of them should be covered in the claims of the present invention.
Claims (8)
1. The phosphating solution is characterized by comprising the following components in percentage by weight: 15-35% of phosphoric acid, 30-50% of nitric acid, 10-25% of zinc oxide, 4-8% of manganese carbonate, 1-2.5% of accelerator, 0.5-1.5% of complexing agent, 3-8% of complexing iron ion stabilizer and a plurality of parts of deionized water.
2. The phosphating solution according to claim 1, which is characterized by comprising the following components in percentage by weight: 28% of phosphoric acid, 50% of nitric acid, 15% of zinc oxide, 5% of manganese carbonate, 1% of accelerator, 1% of complexing agent, 5% of complexing iron ion stabilizer and 5% of deionized water.
3. The phosphating solution according to claim 2, wherein the complex iron ion stabilizer is sodium potassium tartrate.
4. The phosphating solution according to claim 2, wherein the accelerators are cobalt nitrate and hydrofluoric acid.
5. The phosphating solution according to claim 4, wherein the cobalt nitrate is 0.5-1.0 wt% and the hydrofluoric acid is 0.5-1.5 wt%.
6. The phosphating solution according to claim 2, wherein the complexing agent is citric acid.
7. A process for preparing a phosphating solution according to any one of claims 1 to 6, characterized by comprising the following steps:
1) weighing phosphoric acid, nitric acid, zinc oxide, manganese carbonate and deionized water according to the weight percentage to prepare zinc nitrate, zinc dihydrogen phosphate, zinc nitrate, manganese nitrate and manganese dihydrogen phosphate;
2) adding cobalt nitrate, citric acid, sodium potassium tartrate and hydrofluoric acid into the solution obtained in the step 1) in sequence, and stirring until the cobalt nitrate, the citric acid, the sodium potassium tartrate and the hydrofluoric acid are completely dissolved to obtain the phosphating solution.
8. The method for preparing the phosphating solution according to claim 4, wherein when the temperature of the solution in the step 2) is lower than 40 ℃, cobalt nitrate, citric acid, sodium potassium tartrate and hydrofluoric acid are sequentially added and stirred until the cobalt nitrate, the citric acid, the sodium potassium tartrate and the hydrofluoric acid are completely dissolved to obtain the phosphating solution.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115261837A (en) * | 2022-06-30 | 2022-11-01 | 东风商用车有限公司 | Pre-painting treatment process for steel-aluminum mixed base material |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1414484A (en) * | 1972-05-03 | 1975-11-19 | Pyrene Chemical Services Ltd | Treatment of zinc surfaces |
| CN102953055A (en) * | 2012-11-07 | 2013-03-06 | 长沙沃尔金属表面技术有限公司 | Black phosphating liquid and use method thereof |
| CN105543826A (en) * | 2015-12-29 | 2016-05-04 | 钢铁研究总院 | Normal-temperature phosphating solution forming phosphating film highly resistant to corrosion, preparing method and phosphating technology |
| CN107699879A (en) * | 2017-11-24 | 2018-02-16 | 重庆信人科技发展有限公司 | A kind of without phosphorus silane oxidation agent |
| CN108048826A (en) * | 2017-12-29 | 2018-05-18 | 辽宁科技大学 | A kind of wire drawing derusting phosphating liquor and preparation method thereof |
| CN112011791A (en) * | 2020-08-28 | 2020-12-01 | 立邦涂料（重庆）化工有限公司 | Formation agent based on phosphoric acid without surface conditioning process and sodium sulfite promoter and preparation method thereof |
-
2021
- 2021-07-08 CN CN202110772653.1A patent/CN113621953A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1414484A (en) * | 1972-05-03 | 1975-11-19 | Pyrene Chemical Services Ltd | Treatment of zinc surfaces |
| CN102953055A (en) * | 2012-11-07 | 2013-03-06 | 长沙沃尔金属表面技术有限公司 | Black phosphating liquid and use method thereof |
| CN105543826A (en) * | 2015-12-29 | 2016-05-04 | 钢铁研究总院 | Normal-temperature phosphating solution forming phosphating film highly resistant to corrosion, preparing method and phosphating technology |
| CN107699879A (en) * | 2017-11-24 | 2018-02-16 | 重庆信人科技发展有限公司 | A kind of without phosphorus silane oxidation agent |
| CN108048826A (en) * | 2017-12-29 | 2018-05-18 | 辽宁科技大学 | A kind of wire drawing derusting phosphating liquor and preparation method thereof |
| CN112011791A (en) * | 2020-08-28 | 2020-12-01 | 立邦涂料（重庆）化工有限公司 | Formation agent based on phosphoric acid without surface conditioning process and sodium sulfite promoter and preparation method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115261837A (en) * | 2022-06-30 | 2022-11-01 | 东风商用车有限公司 | Pre-painting treatment process for steel-aluminum mixed base material |
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