CN104164663A - Normal-temperature quick phosphating solution for cold molding of metal and preparation method thereof - Google Patents

Abstract

A normal-temperature rapid phosphating solution for metal cold plastic forming and its preparation method. The mass ratio of each component is: 10-13 parts of phosphoric acid, 3-5 parts of nitric acid, 6-10 parts of zinc oxide, and 1-3 parts of accelerator , 0.5~2 parts of nickel nitrate, 0.1~0.4 parts of sodium citrate, 0.2~0.6 parts of Maziv salt, 0.2~0.9 parts of stabilizer, 5~15 parts of alcohol and 40~70 parts of water. At room temperature, stir and mix the materials in a certain order to obtain a clear and transparent phosphating concentrate, which can be used for phosphating after diluting with water at a mass ratio of 1:5~15. The phosphating solution of the present invention is used at normal temperature, has fast phosphating speed, and strong corrosion resistance; raw materials are cheap and non-toxic, can be prepared with tap water, and basically no phosphating slag is produced; the formed phosphating film is dense and uniform, free from hanging ash and Yellowing phenomenon; the phosphating solution is not easy to freeze in winter, which is convenient for low-temperature construction, and the drying speed of the phosphating film is faster.

Description

Normal temperature rapid phosphating solution for metal cold plastic forming and preparation method thereof

technical field

The invention belongs to the technical field of fine chemicals, and in particular relates to a surface phosphating treatment solution suitable for metal cold plastic forming and a preparation method thereof.

Background technique

Metal workpieces, especially steel workpieces, should undergo corresponding phosphating and saponification surface pretreatment before cold plastic processing, which is not only beneficial to the rust removal, degreasing, passivation and lubrication of the workpiece surface, but also helps the workpiece in the cold working process. Anti-wear and anti-friction, improve processing efficiency and improve workpiece forming quality. Therefore, phosphating treatment on the surface of steel workpieces has become an essential pretreatment process in the field of cold plastic processing. The phosphating systems currently used in China can be simply classified into zinc-based, zinc-calcium-based, zinc-manganese-based, and manganese-based systems according to the main functional ingredients. According to the temperature conditions of phosphating treatment, they can be divided into room temperature phosphating , Low-temperature phosphating and medium-high temperature phosphating processes. The main function of phosphating is to form a layer of porous phosphating film on the surface of steel workpieces, which is conducive to subsequent efficient coating and anti-rust and anti-corrosion. However, for workpieces that require cold plastic processing, not only phosphating treatment is required on the workpiece, but also saponification treatment is required to meet the special lubrication requirements of cold plastic molding processing. However, most of the current phosphating solutions are designed according to a single phosphating process, which are mostly "broad-spectrum" and not targeted enough, especially for the combined surface treatment of "phosphating-saponification" that requires saponification follow-up after phosphating The design of the process and phosphating solution still lacks more refined scientific rationality, which often leads to the phenomenon of dust hanging and yellowing on the surface of the workpiece after joint treatment, which affects the quality stability of the cold plastic processed workpiece. For this reason, it is of great significance to design and prepare a phosphating solution system suitable for cold plastic processing.

Contents of the invention

The object of the present invention is to provide a kind of rapid phosphating treatment solution at room temperature which is suitable for cold plastic processing and forming, and is highly targeted. The phosphating treatment solution is non-toxic and harmless, the preparation process is simple, the phosphating efficiency is high, and the produced The phosphating layer is dense, uniform, and has strong corrosion resistance, which avoids the phenomenon of dust hanging and yellowing on the surface of the workpiece after conventional combined treatment, and improves the quality stability of the workpiece.

In order to achieve the above object, the technical solution adopted by the present invention is: the rapid phosphating solution at room temperature for metal cold plastic forming, which is composed of the phosphating concentrated solution as the basic component and the dilution water added during use, in the phosphating concentrated solution The weight ratio of each component is: 10-13 parts of phosphoric acid, 3-5 parts of nitric acid, 6-10 parts of zinc oxide, 1-3 parts of accelerator, 0.5-2 parts of nickel nitrate, 0.1-0.4 parts of sodium citrate 0.2-0.6 parts of Maziv salt, 0.2-0.9 parts of stabilizer, 5-15 parts of alcohol, 40-70 parts of water; the amount of dilution water added is 5-15 times the mass of the phosphating concentrate.

The preparation method of normal temperature fast phosphating solution for metal cold plastic molding, the specific preparation steps are:

(1) Take water and alcohol according to the ratio of parts by weight, and divide it into two halves, mix half of the water and alcohol into an acid-resistant container, add phosphoric acid and nitric acid to it under stirring conditions, and fully After mixing, mixed acid solution A is obtained for subsequent use;

(2) Put the remaining half of the water and the other half of the alcohol in step (1) into a container, and add zinc oxide, accelerator, nickel nitrate, sodium citrate and Maziv salt into it under stirring conditions, After fully mixing, suspension B is obtained and set aside;

(3) Add the suspension B prepared in step (2) into the mixed acid solution A prepared in step (1) under stirring conditions, continue to stir until completely dissolved, then add a stabilizer to the mixed solution, fully After mixing, a clear and transparent phosphating concentrate is obtained for storage and standby;

(4) The phosphating concentrated solution prepared in step (3) needs to be diluted during application, and the amount of diluted water added is 5 to 15 times the mass of the phosphating concentrated solution. After stirring evenly, the working phosphating solution can be obtained .

The mass purity of the phosphoric acid is 80%; the mass purity of nitric acid is 60%; the mass purity of alcohol is 95%.

The accelerator is sodium fluoride or sodium nitrite; the stabilizer is at least one of hydroxyethylene diphosphoric acid, urotropine or sodium hexametaphosphate.

Described water is industrial tap water, deionized water or distilled water.

The total acidity of the phosphating solution is 30-55 points, the free acidity is 5-8 points, and the ratio of the total acidity to the free acidity is 6-11.

Beneficial effects of the present invention:

(1) Common industrial raw materials are used in the component formula, the cost is low, and the raw materials are non-toxic. Tap water can be used as a solvent for preparation and use, and the obtained phosphating solution basically has no phosphating residues and environmental pollution Small.

(2) The preparation process of the phosphating solution of the present invention is simple and can be used at room temperature. The phosphating speed is fast, and the resulting phosphating layer is dense and uniform, and has strong corrosion resistance, which can effectively prevent the surface of the workpiece from easily appearing after phosphating. Hanging dust, yellowing and other phenomena occur, which improves the quality stability of the workpiece.

(3) In the case of light corrosion and less oil stain on the surface of the workpiece, the phosphating solution of the present invention can be directly phosphating without rust and oil removal in advance, thereby simplifying the phosphating process and reducing pollution.

(4) The phosphating solution of the present invention is highly targeted, and is especially suitable for cold plastic molding of workpieces, and the phosphating solution is not easy to freeze in winter, and has strong adaptability to low-temperature construction environments. At the same time, the phosphorus on the surface of the workpiece after phosphating The drying speed of the chemical film is faster, and the phosphating efficiency is improved.

Detailed ways

The present invention will be described in further detail below in conjunction with the examples, but it should not be used as a limitation to the protection scope of the present invention.

Normal temperature rapid phosphating solution for metal cold plastic forming, its basic component is phosphating concentrate, which is diluted with water when used, in parts by mass, the ratio of each component in the phosphating concentrate is: phosphoric acid 10 ~13 parts, 3~5 parts of nitric acid, 6~10 parts of zinc oxide, 1~3 parts of accelerator, 0.5~2 parts of nickel nitrate, 0.1~0.4 parts of sodium citrate, 0.2~0.6 parts of Maziv salt, stabilizer 0.2~0.9 parts, 5~15 parts of alcohol, 40~70 parts of water.

According to the following method, the normal temperature rapid phosphating concentrate for metal cold plastic molding is prepared:

1. Add half of the total amount of water and total alcohol into the acid-resistant container, slowly add phosphoric acid and nitric acid in turn through continuous stirring, and stir evenly to obtain a mixed acid solution A;

2. Add zinc oxide, accelerator, nickel nitrate, sodium citrate and Maziv salt in turn to the other half of the mixed solvent of alcohol and water under stirring conditions, and after fully stirring, suspension B is obtained;

3. Slowly add suspension B to liquid A, stir vigorously while adding until completely dissolved, then add stabilizer to the mixed solution, and get a clear and transparent phosphating concentrate under stirring.

Said phosphoric acid is calculated as industrial phosphoric acid with H ₃ PO ₄ content of 80%, and other concentrations of phosphoric acid can be converted into 80% content before corresponding compounding.

The said nitric acid is calculated with the industrial nitric acid whose _HNO3 content is 60%, and the nitric acid of other concentrations can be converted into 60% content before corresponding batching.

The said alcohol is calculated based on industrial alcohol with a C ₂ H ₅ OH content of 95%, and alcohols with other concentrations can be converted into 95% content for corresponding batching.

The accelerator is sodium fluoride or sodium nitrite.

The stabilizer is at least one of hydroxyethylene diphosphoric acid, urotropine or sodium hexametaphosphate.

Described solvent water can be industrial tap water, deionized water, distilled water.

During phosphating operation, dilute the above-mentioned phosphating concentrated solution with water according to the ratio of 1:5~15 (mass ratio), and after stirring evenly, a light green and transparent phosphating working solution can be obtained, so that the total acidity in it is 30~55 points, The free acidity is 5~8 points, and the ratio of total acidity to free acidity is 6~11. Phosphating can be done by immersion or brushing, but dynamic dipping is best. The dipping temperature is 5~35°C, and the dipping time is 2~10 minutes. After phosphating treatment, the surface color of the phosphating layer is light gray, the crystal film is dense and uniform, and there is no hanging ash and yellowing phenomenon; the copper sulfate spot test of the phosphating film is ≥10 minutes, and the 3% sodium chloride test is ≥ 2 hours, neutral salt spray test ≥ 40 hours.

Among them, the detection methods of total acidity, free acidity, copper sulfate drop test and 3% sodium chloride test are all carried out in accordance with relevant national standards (such as GB6807-91, GB6817-96).

Example 1:

At room temperature, add 20kg of tap water and 2.5kg of alcohol into an acid-resistant container, and through continuous stirring, first slowly add 10kg of phosphoric acid, stir well, then slowly add 3kg of nitric acid, stir well, and obtain mixed acid solution A; add 20kg of Tap water and 2.5kg alcohol were added successively under stirring 6kg zinc oxide, 1kg sodium fluoride, 0.5kg nickel nitrate, 0.1kg sodium citrate, 0.2kg Maziv salt, and fully stirred to obtain suspension B; Slowly add to liquid A, stir vigorously while adding until completely dissolved, then add 0.2kg of hydroxyethylene diphosphoric acid, and stir to obtain a clear and transparent phosphating concentrate.

Dilute the obtained phosphating concentrate with water according to the mass ratio of 1:5, stir evenly, and then it can be used for phosphating. Under the condition of 5°C, the workpiece is dipped for 2 minutes, and the obtained phosphating film is dense and uniform, free of dust and yellow, and is light gray. According to the measurement, the copper sulfate drop test result of the phosphating film is 12 minutes, the test result of 3% sodium chloride is 131 minutes, and the neutral salt spray test result is 43 hours.

Example 2:

At room temperature, add 35kg of tap water and 7.5kg of alcohol into an acid-resistant container, and through continuous stirring, first slowly add 13kg of phosphoric acid, stir well, then slowly add 5kg of nitric acid, stir well, and obtain mixed acid solution A; add 35kg of Tap water and 7.5kg alcohol were added successively under stirring 10kg zinc oxide, 3kg sodium nitrite, 2kg nickel nitrate, 0.4kg sodium citrate, 0.6kg Maziv salt, and fully stirred to obtain suspension B; Add it into liquid A, stir vigorously while adding, until it is completely dissolved, then add 0.9kg of urotropine, and stir to obtain a clear and transparent phosphating concentrate.

Dilute the obtained phosphating concentrate with water according to the mass ratio of 1:15, stir evenly, and then it can be used for phosphating. Under the condition of 35°C, the workpiece is dipped for 10 minutes, and the obtained phosphating film is dense and uniform, free of dust and yellow, and is light gray. According to the measurement, the copper sulfate drop test result of the phosphating film is 16 minutes, the test result of 3% sodium chloride is 158 minutes, and the neutral salt spray test result is 47 hours.

Example 3:

At room temperature, add 28kg of tap water and 5kg of alcohol into an acid-resistant container, and through constant stirring, first slowly add 12kg of phosphoric acid, stir evenly, then slowly add 4kg of nitric acid, and stir evenly to obtain a mixed acid solution A; Add 28kg of tap water into another container and 5kg of alcohol, respectively add 8kg of zinc oxide, 2kg of sodium fluoride, 1.5kg of nickel nitrate, 0.3kg of sodium citrate, and 0.4kg of Maziv salt under stirring, and stir well to obtain suspension B; Add it into liquid A, stir vigorously while adding, until it is completely dissolved, then add 0.5kg of sodium hexametaphosphate, and stir to obtain a clear and transparent phosphating concentrate.

Dilute the obtained phosphating concentrate with water according to the mass ratio of 1:10, stir evenly, and then it can be used for phosphating. Under the condition of 20 ℃, the workpiece is dipped for 6 minutes, and the phosphating film obtained is dense and uniform, free of dust and yellow, and is light gray. According to the measurement, the copper sulfate spot test result of the phosphating film is 14 minutes, the test result of 3% sodium chloride is 149 minutes, and the neutral salt spray test result is 46 hours.

Example 4:

At room temperature, add 30kg of distilled water and 7kg of alcohol into an acid-resistant container, and through continuous stirring, first slowly add 11kg of phosphoric acid, stir well, then slowly add 4kg of nitric acid, stir well, and obtain mixed acid solution A; add 30kg of tap water into another container and 7kg alcohol, respectively add 6kg zinc oxide, 2kg sodium nitrite, 1.5kg nickel nitrate, 0.3kg sodium citrate, 0.5kg Maziv salt under stirring, and fully stir to obtain suspension B; Add it into liquid A, stir vigorously while adding it until it is completely dissolved, then add 0.2kg of hydroxyethylene diphosphoric acid and 0.5kg of urotropine, and get a clear and transparent phosphating concentrate under stirring.

Dilute the obtained phosphating concentrate with water according to the mass ratio of 1:13, stir evenly, and then it can be used for phosphating. Under the condition of 30°C, the workpiece is dipped for 8 minutes, and the obtained phosphating film is dense and uniform, free of dust and yellow, and is light gray. According to the measurement, the copper sulfate drop test result of the phosphating film is 18 minutes, the test result of 3% sodium chloride is 168 minutes, and the neutral salt spray test result is 44 hours.

Example 5:

At room temperature, add 32kg of tap water and 6kg of alcohol into an acid-resistant container, and through continuous stirring, first slowly add 10kg of phosphoric acid, stir evenly, then slowly add 5kg of nitric acid, and stir evenly to obtain a mixed acid solution A; Add 32kg of tap water into another container and 6kg of alcohol, add 7kg of zinc oxide, 2kg of sodium fluoride, 1kg of nickel nitrate, 0.2kg of sodium citrate, and 0.6kg of Maziv’s salt in turn under stirring, and stir well to obtain suspension B; slowly add suspension B to Add to liquid A, stir vigorously while adding until completely dissolved, then add 0.1kg hydroxyethylene diphosphoric acid, 0.3kg urotropine and 0.2kg sodium hexametaphosphate, and get clear and transparent phosphating concentrate under stirring liquid. the

Dilute the obtained phosphating concentrate with water according to the mass ratio of 1:15, stir evenly, and then it can be used for phosphating. Under the condition of 25 ℃, the workpiece is dipped for 6 minutes, and the obtained phosphating film is dense and uniform, free of dust and yellow, and is light gray. According to the measurement, the copper sulfate drop test of the phosphating film is 15 minutes, the test result of 3% sodium chloride is 152 minutes, and the neutral salt spray test is 47 hours.

Claims (6)

1. metal cold is molded with ordinary-temp fast bonderizing liquor, it is characterized in that, additional diluting water forms by the phosphatization concentrated solution as basic ingredient and while using, and in described phosphatization concentrated solution, the parts by weight proportioning of each component is: 40 ~ 70 parts, 5 ~ 15 parts of 0 ~ 13 part of phosphatase 11s, 3 ~ 5 parts, nitric acid, 6 ~ 10 parts, zinc oxide, 1 ~ 3 part of promotor, 0.5 ~ 2 part of nickelous nitrate, 0.1 ~ 0.4 part of Trisodium Citrate, 0.2 ~ 0.6 part of Mazhev salt, 0.2 ~ 0.9 part of stablizer, alcohol and water; The add-on of diluting water is 5 ~ 15 times of phosphatization concentrated solution quality.

2. the molded preparation method with ordinary-temp fast bonderizing liquor of metal cold according to claim 1, is characterized in that, concrete preparation process is:

(1), fetch water respectively and alcohol in described parts by weight ratio, and by its dimidiation, wherein half water and alcohol mix and put into acid-resistant container, under agitation condition, add wherein phosphoric acid and nitric acid, after fully mixing, obtain mixed acid solution A, for subsequent use;

(2), get remaining second half water of step (1) and second half alcohol and put into a container, under agitation condition, add wherein zinc oxide, promotor, nickelous nitrate, Trisodium Citrate and Mazhev salt, after fully mixing, obtain suspension B, for subsequent use;

(3), the suspension B that under agitation condition, step (2) made adds in the mixed acid solution A that step (1) makes, continue to be stirred to completely and dissolve, then, in mixing solutions, add stablizer, after fully mixing, obtain the phosphatization concentrated solution of clear, storage, for subsequent use;

(4), the phosphatization concentrated solution that makes of step (3) needs dilution in the time of application, the diluting water amount adding is 5 ~ 15 times of phosphatization concentrated solution quality, after stirring, can acquisition work Phosphating Solution.

3. metal cold according to claim 1 and 2 is molded with ordinary-temp fast bonderizing liquor, it is characterized in that: the quality purity of described phosphoric acid is 80%; The quality purity of nitric acid is 60%; The quality purity of alcohol is 95%.

4. metal cold according to claim 1 and 2 is molded with ordinary-temp fast bonderizing liquor, it is characterized in that: described promotor is Sodium Fluoride or Sodium Nitrite; Described stablizer is at least one in hydroxy ethylidene-diphosphate, urotropine or Sodium hexametaphosphate 99.

5. metal cold according to claim 1 and 2 is molded with ordinary-temp fast bonderizing liquor, it is characterized in that: described water is industrial tap water, deionized water or distilled water.

6. metal cold according to claim 1 and 2 is molded is characterized in that: the total acidity of described Phosphating Solution is 30 ~ 55 points with ordinary-temp fast bonderizing liquor, and free acidity is 5 ~ 8 points, and total acidity is 6 ~ 11 with the ratio of free acidity.