CN112962089A - Environment-friendly and efficient nickel-free manganese phosphating agent and preparation method and application thereof - Google Patents
Environment-friendly and efficient nickel-free manganese phosphating agent and preparation method and application thereof Download PDFInfo
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- CN112962089A CN112962089A CN202110124772.6A CN202110124772A CN112962089A CN 112962089 A CN112962089 A CN 112962089A CN 202110124772 A CN202110124772 A CN 202110124772A CN 112962089 A CN112962089 A CN 112962089A
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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
- C23C22/08—Orthophosphates
- C23C22/18—Orthophosphates containing manganese cations
Abstract
The invention discloses an environment-friendly high-efficiency nickel-free manganese phosphating agent as well as a preparation method and application thereof. The water is used as solvent, and is prepared from phosphoric acid, nitric acid, hydrogen peroxide, manganese carbonate, built-in accelerator and the balance of water. The phosphating agent is a high-efficiency, energy-saving and environment-friendly nickel-free manganese phosphating agent completely different from the traditional manganese phosphating agent. Can quickly form a compact phosphating film on the surface of a workpiece, and improves the production efficiency. The phosphating film obtained by the phosphating agent treatment of the invention can be seen to be granular in crystallization by Scanning Electron Microscope (SEM) detection and analysis, and the crystallization surface of the phosphating film has no dew point. The property greatly improves the friction resistance, corrosion resistance, self-lubricating property and the like of the phosphating film. The phosphating agent is stable, and the components in the agent are reasonably matched, so that the phosphating agent is an efficient, energy-saving and environment-friendly nickel-free manganese series phosphating agent.
Description
Technical Field
The invention relates to an environment-friendly, efficient and antirust nickel-free manganese phosphating agent suitable for processing cold-rolled steel, cast steel, steel parts, screws, standard parts and powder metallurgy parts.
Background
The manganese series phosphating film has certain corrosion resistance due to high hardness, and is widely applied to the aspects of lubrication, corrosion resistance, wear resistance and the like in the metal surface treatment. The manganese phosphating solution is a necessary agent for phosphating metal workpieces, and a phosphating film which is fine in crystallization, more uniform and more compact can be formed on the surface of the workpiece after the workpiece is treated by the manganese phosphating process, so that the tolerance of the phosphating film is improved, and the processibility of the phosphating film is improved. However, the phosphating films processed by manganese phosphating generally belong to thick film phosphating, so that the manganese phosphating workpieces can not meet the requirements of some precise instruments during later assembly. Although the heavy metal ions such as nickel and cobalt do not generate a replacement reaction with the surface of the workpiece, the heavy metals can form a large number of phosphorization crystal nuclei on the surface of the workpiece, and the crystal nuclei can increase the activation points of phosphorization and accelerate the phosphorization reaction rate, so that the heavy metals are applied to manganese series phosphorization agents in a large amount. However, the classification of these heavy metals such as nickel in national standard is also a first pollutant, and has great harm to human body and environment. With the continuous tightening of environmental protection policies, the problem of nickel emission is also the problem that needs to be solved by various manufacturers.
Disclosure of Invention
The method aims to solve the requirements of size precision of workpieces and the environmental protection problem which is more and more emphasized. The invention provides a nickel-free manganese phosphating medicament which not only can meet the size requirement of subsequent precision workpieces, but also achieves the effects of energy conservation and emission reduction due to the fact that a built-in accelerant is used for replacing the action of heavy metals such as nickel in the phosphating medicament.
The technical scheme adopted by the invention is as follows: an environment-friendly high-efficiency nickel-free manganese phosphating agent takes water as a solvent and comprises the following components in percentage by mass:
in the invention, the phosphoric acid is not limited to phosphoric acid with certain concentration, and the pure substance accounts for 15-40% of the whole formula. The nitric acid is not limited to nitric acid with certain concentration, and the pure substance accounts for 8% -20% of the whole formula. The manganese carbonate is not limited to any concentration, and the pure substance accounts for 8% -30% of the whole formula.
Preferably, the environment-friendly high-efficiency nickel-free manganese phosphating agent comprises the following components in percentage by mass:
preferably, the above-mentioned environmentally-friendly and efficient nickel-free manganese-based phosphating agent is an agent with built-in accelerator selected from NO3 -、ClO3 -、H2O2、NO2 -One or more than two of perborate, fluoroborate, quaternary tetrol phosphate, tartaric acid, citric acid and organic acid containing hydroxyl or carboxyl are mixed and compounded.
Preferably, the above-mentioned environmentally-friendly and efficient nickel-free manganese phosphating agent comprises, by mass, 1.8-2.5:1 phosphoric acid and nitric acid.
Preferably, the environment-friendly high-efficiency nickel-free manganese phosphating agent comprises the following components in percentage by mass:
an environment-friendly and efficient preparation method of a nickel-free manganese phosphating agent comprises the following steps:
(1) putting the phosphoric acid metered by the formula into a reaction kettle, and starting stirring;
(2) adding nitric acid with a formula metering into a reaction kettle;
(3) adding water with a formula metering amount into a reaction kettle;
(4) finally, adding hydrogen peroxide, manganese carbonate and built-in accelerator which are measured according to the formula into the reaction kettle in sequence;
(5) stirring for 60-80 min.
The invention provides an application of an environment-friendly and efficient nickel-free manganese phosphating agent in forming a manganese phosphating film on the surface of a metal workpiece.
Preferably, the method is as follows, the environment-friendly and high-efficiency nickel-free manganese phosphating agent is prepared into working solution with the concentration of 70-80 g/L.
Preferably, the method is as follows:
1) hot water washing: spraying the metal workpiece with hot water at 42-48 ℃ for 90-100 s;
2) pre-degreasing: spraying and pretreating the metal workpiece subjected to hot water washing for 60-70 s by using a degreasing agent at 42-48 ℃;
3) degreasing treatment: the metal workpiece after pre-degreasing is sequentially treated before entering the groove, after entering the groove and after exiting the groove: spraying a degreasing agent at 42-48 ℃ for 10-15 s before entering the tank, soaking the tank in the degreasing agent at 42-48 ℃ for 40-50 s after entering the tank, and spraying the tank with the degreasing agent at 42-48 ℃ for 10-15 s after leaving the tank;
4) washing with water: the metal workpiece after degreasing treatment is sequentially treated before entering the groove, after entering the groove and after being discharged at room temperature: spraying water for 5-10 s before entering the tank, soaking in water for 20-30 s after entering the tank, and spraying water for 5-10 s after leaving the tank;
5) and (3) performing table tone processing: soaking the washed metal workpiece in a surface conditioning agent at room temperature for surface conditioning for 30-120 s;
6) and (3) phosphating treatment: dipping the metal workpiece subjected to surface conditioning treatment in working solution with the concentration of 70-80g/L, and carrying out phosphating treatment for 350s at 95 ℃;
7) pure water washing for the first time: spraying the metal workpiece subjected to phosphating treatment for 30-40 s by using pure water at room temperature;
8) and (3) pure water washing for the second time: placing the metal workpiece subjected to the first pure water washing at room temperature, and sequentially carrying out: spraying 5-10 s of water before entering the tank, soaking in water for 10-20 s after entering the tank, and spraying 5-10 s of water after leaving the tank.
Preferably, the metal workpiece is cold rolled steel, cast steel, steel parts, screws, standard parts and parts of powder metallurgy material.
The invention has the beneficial effects that: the environment-friendly and efficient nickel-free manganese phosphating agent is an efficient, energy-saving and environment-friendly nickel-free manganese phosphating agent completely different from the traditional manganese phosphating agent. Can quickly form a compact phosphating film on the surface of a workpiece, and improves the production efficiency. The phosphating film obtained by the treatment of the environment-friendly and efficient nickel-free manganese phosphating agent can be seen to be granular in crystallization and have no dew point on the surface of the phosphating film crystal when being detected and analyzed by a Scanning Electron Microscope (SEM). The property greatly improves the friction resistance, corrosion resistance and self-lubricating property of the phosphating film. The environment-friendly and efficient nickel-free manganese phosphating agent is stable and has reasonable component matching.
Drawings
FIG. 1 is a photograph showing the crystallization of a film on a metal workpiece after manganese-based phosphating.
FIG. 2 is a surface etch pit depth image of a metal workpiece after manganese phosphating.
FIG. 3 is a photograph showing 48H salt spray results of oil-coating after manganese phosphating of a metal workpiece.
Detailed Description
The following examples are provided for a better understanding of the present invention, and are not to be construed as limiting the scope of the present invention, which is not intended to be limited to the best mode, but rather is to be construed as being within the scope of the present invention.
The specific experimental procedures or conditions not specified in the examples were performed according to the procedures or conditions of the conventional experimental procedures described in the literature in the field. The reagents or apparatus used are not indicated by the manufacturer and are commercially available.
Examples 1 to 3A composition of an environmentally friendly and highly effective phosphating agent without nickel manganese series
The nickel-free manganese phosphating agent is prepared by taking water as a solvent according to the mass percent in the following table 1.
TABLE 1
| Name of raw materials | Example 1 | Example 2 | Example 3 |
| Phosphoric acid | 30％ | 30％ | 30％ |
| |
15％ | 15％ | 15％ |
| Hydrogen peroxide solution | 0.5％ | 0.5％ | 0.5％ |
| |
16％ | 16％ | 16％ |
| Built-in accelerator | 0.5％ | 0.6％ | 0.7％ |
| Water (W) | Balance of | Balance of | Balance of |
In example 1, the composition of the built-in accelerator was: the sodium fluoborate is prepared from 0.3 part of sodium fluoborate and 0.5 part of sodium nitrite according to the mass part ratio.
In example 2, the composition of the built-in accelerator was: according to the mass portion ratio, the material consists of 0.2 portion of sodium nitrite and 0.3 portion of tartaric acid.
In example 3, the composition of the built-in accelerator was: the sodium borate.
Preparation method of (di) nickel-free manganese series phosphating agent
(1) Putting the phosphoric acid metered by the formula into a reaction kettle, and starting stirring;
(2) adding nitric acid with a formula metering into a reaction kettle;
(3) adding water with a formula metering amount into a reaction kettle;
(4) finally, adding hydrogen peroxide, manganese carbonate and built-in accelerator which are measured according to the formula into the reaction kettle in sequence;
(5) stirring for 60-80 min.
Example 4 application of an environmentally friendly and efficient phosphating agent without nickel and manganese
The method comprises the following steps:
1) hot water washing: spraying the metal workpiece with hot water at 42-48 ℃ for 90-100 s;
2) pre-degreasing: spraying and pretreating the metal workpiece subjected to hot water washing for 60-70 s by using a degreasing agent at 42-48 ℃;
3) degreasing treatment: and (3) carrying out degreasing treatment on the pre-degreased metal workpiece by spraying before entering the tank, dipping after entering the tank and spraying after leaving the tank. Namely: spraying a degreasing agent at 42-48 ℃ for 10-15 s before entering the tank, soaking the tank in the degreasing agent at 42-48 ℃ for 40-50 s after entering the tank, and spraying the tank with the degreasing agent at 42-48 ℃ for 10-15 s after leaving the tank;
4) washing with water: the degreased metal workpiece is subjected to water washing treatment of spraying before entering the tank, dipping after entering the tank and spraying after leaving the tank in sequence at room temperature, namely, the metal workpiece is sprayed with water for 5 to 10 seconds before entering the tank, dipped in the water for 20 to 30 seconds after entering the tank, and sprayed with water for 5 to 10 seconds after leaving the tank;
5) and (3) performing table tone processing: soaking the washed metal workpiece in a surface conditioning agent at room temperature (25 +/-3 ℃) for surface conditioning for 30-120 s;
6) and (3) phosphating treatment:
the working solutions with the concentration of 75g/L prepared by adding water into the environment-friendly and efficient nickel-free manganese phosphating agents prepared in the embodiments 1, 2 and 3 are used as the working solutions of the invention.
The working solution with the concentration of 95g/L is prepared by adding water into the commercial traditional nickel-manganese-containing phosphating agent and is used as a comparative example.
Respectively soaking the metal workpiece subjected to surface conditioning treatment in the working solution with the concentration of 75g/L and the working solution with the comparative example with the concentration of 95g/L, and respectively carrying out phosphating treatment for 350s at 95 ℃;
7) pure water washing for the first time: spraying pure water at room temperature (25 +/-3 ℃) for 30-40 seconds after phosphating treatment on the metal workpiece;
8) and (3) pure water washing for the second time: and (3) placing the workpiece subjected to the first pure water washing at room temperature, and sequentially carrying out water washing treatment of spraying before entering the tank, soaking in the tank and spraying after leaving the tank, namely spraying 5-10 s with water before entering the tank, soaking 10-20 s in water after entering the tank, and spraying 5-10 s with water after leaving the tank to obtain the metal workpiece subjected to phosphating treatment.
(II) sample preparation detection
The method comprises the following steps: dividing the metal workpieces after phosphating into two groups, cutting the first group, and analyzing the sample by using a Scanning Electron Microscope (SEM) to obtain the phosphating corrosion depth, the phosphating film crystallization state and the phosphating corrosion pit distribution. And the second group uses a portable film measuring instrument to detect the thickness and the weight of the processed phosphating film. And after the detection in the steps is finished, performing an oiling salt spray experiment on the sample by using an NR-307A oil sample, wherein the experiment period is 48H. The results are shown in Table 2 to Table 5, and in FIG. 1 to FIG. 3.
TABLE 2 film weight on metal workpiece after manganese phosphating
| Number/item | Post-phosphating weight | Weight after demoulding | Film weight |
| Example 1 | 70.313g | 70.277g | 17.391g/㎡ |
| Example 2 | 70.237g | 70.198g | 18.840g/㎡ |
| Example 3 | 70.263g | 70.225g | 18.357g/㎡ |
| Comparative example | 13.043g/㎡ | 13.043g/㎡ | 13.043g/㎡ |
TABLE 3 film thickness on Metal workpiece after manganese-based phosphating
| Number/class | Film thickness mu m after manganese series phosphorization processing | Substrate μm | Film thickness μm |
| Example 1 | 10.1 | 6.24 | 3.86 |
| Example 2 | 11.19 | 6.24 | 4.95 |
| Example 3 | 11.12 | 6.24 | 4.88 |
| Comparative example | 17.18 | 6.24 | 10.94 |
TABLE 4 film crystal size and photograph and surface etch depth on manganese phosphating metal workpieces
| Numbering | Crystal photo | Crystal size | Depth of corrosion after phosphating of substrate |
| Example 1 | A in FIG. 1 | 1-3μm | A in FIG. 2 |
| Example 2 | B in FIG. 1 | 1-3μm | B in FIG. 2 |
| Example 3 | C in FIG. 1 | 1-3μm | C in FIG. 2 |
| Comparative example | D in FIG. 1 | 8-10μm | D in FIG. 2 |
TABLE 5 manganese phosphating of metallic workpieces after oiling 48H salt spray results
1. From the combination of the film weight and the film thickness of the manganese phosphating workpieces in the tables 2 and 3, the film weight of the phosphating film processed by matching the nickel-free manganese phosphating agent in the embodiment 1 can reach 17.391 g/square meter when the film thickness is 3.86 microns. When the phosphating film prepared by using the nickel-free manganese phosphating agent in the embodiment 2 of the invention is used in a matching way, the film weight can reach 18.840 g/square meter when the film thickness is 4.95 mu m. When the phosphating film prepared by using the nickel-free manganese phosphating agent in the embodiment 3 of the invention is used in a matching way, the film weight can reach 18.357 g/square meter when the film thickness is 4.88 mu m. When the thickness of the processed phosphating film is 10.94 mu m, the upper film thickness can only reach 13.043 g/square meter by matching with the traditional manganese phosphating agent. Therefore, the phosphating film processed by the nickel-free manganese phosphating agent has a much higher compactness than the phosphating film processed by the traditional manganese phosphating agent.
2. As can be seen from the analysis in Table 4, the size requirement of the workpiece can be ensured to the maximum extent by using the nickel-free manganese phosphating agent of the invention under the same phosphating process condition. The influence degree on the size of the workpiece is very small and only has the influence size of 1-3 mu m, while the film thickness of the processed workpiece has a larger influence on the workpiece through the traditional manganese series phosphating agent, and the influence size can reach 8-10 mu m, so that the assembly of the workpiece is greatly influenced.
As can be seen from the analysis of the crystal photo in FIG. 1, the crystal size of the phosphate film processed by using the nickel-free manganese-based phosphating agent of the invention is 4-5 times smaller than that of the conventional manganese-based phosphating agent under the same phosphating process condition.
As can be seen from the analysis of the corrosion depth in FIG. 2, the corrosion degree of the phosphating film formed by phosphating the nickel-free manganese phosphating agent disclosed by the invention is 1-2 μm lower than that of the conventional manganese phosphating surface conditioner on the surface of a workpiece. Therefore, the structural integrity of the workpiece can be greatly guaranteed, and the service life of the workpiece is not negatively affected by phosphorization.
3. As can be seen from the analysis of the oil-coated salt spray after 48H in Table 5 and FIG. 3, the workpieces phosphated by the phosphating agent of the invention without nickel-manganese series have no corrosion after 48H salt spray, are not corroded by the salt spray, and have no corrosion phenomenon on the surfaces of the workpieces. In the comparative example, slight pitting corrosion can be found at the edge of the workpiece which is phosphated by matching with the traditional manganese phosphating. This is because the traditional manganese series phosphorization, the higher porosity of the phosphorized film can not better hinder the corrosion of the salt solution under the salt fog environment. The nickel-free manganese series phosphating agent can achieve 48H corrosion-free phosphating films matched with the nickel-free manganese series phosphating agent after being coated with oil salt mist.
Claims (10)
1. The environment-friendly high-efficiency nickel-free manganese phosphating agent is characterized by taking water as a solvent and comprising the following components in percentage by mass:
2. the environment-friendly high-efficiency nickel-free manganese phosphating agent according to claim 1, which is characterized by comprising the following components in percentage by mass:
3. the agent for the environmentally friendly and highly effective phosphating without nickel-manganese series according to claim 1 or 2, wherein the built-in accelerator is selected from NO3 -、ClO3 -、H2O2、NO2 -One or more than two of perborate, fluoroborate, quaternary tetrol phosphate, tartaric acid, citric acid and organic acid containing hydroxyl or carboxyl are mixed and compounded.
4. The environmentally friendly and efficient nickel-free manganese-based phosphating agent according to claim 3, wherein the mass ratio of phosphoric acid to nitric acid is 1.8-2.5: 1.
5. The environment-friendly high-efficiency nickel-free manganese phosphating agent according to claim 4, which is characterized by comprising the following components in percentage by mass:
6. the method for preparing the nickel-manganese-based phosphating agent with environmental protection and high efficiency as claimed in claim 1 is characterized by comprising the following steps:
(1) putting the phosphoric acid metered by the formula into a reaction kettle, and starting stirring;
(2) adding nitric acid with a formula metering into a reaction kettle;
(3) adding water with a formula metering amount into a reaction kettle;
(4) finally, adding hydrogen peroxide, manganese carbonate and built-in accelerator which are measured according to the formula into the reaction kettle in sequence;
(5) stirring for 60-80 min.
7. The use of the environmentally friendly and efficient nickel-free manganese-based phosphating agent as claimed in any one of claims 1 to 5 for forming a manganese-based phosphating film on the surface of a metal workpiece.
8. The use of claim 7, wherein the method comprises formulating the environmentally friendly and highly effective nickel-free manganese-based phosphating agent of any one of claims 1 to 5 into a working solution with a concentration of 70 to 80 g/L.
9. Use according to claim 8, characterized in that the method is as follows:
1) hot water washing: spraying the metal workpiece with hot water at 42-48 ℃ for 90-100 s;
2) pre-degreasing: spraying and pretreating the metal workpiece subjected to hot water washing for 60-70 s by using a degreasing agent at 42-48 ℃;
3) degreasing treatment: the metal workpiece after pre-degreasing is sequentially treated before entering the groove, after entering the groove and after exiting the groove: spraying a degreasing agent at 42-48 ℃ for 10-15 s before entering the tank, soaking the tank in the degreasing agent at 42-48 ℃ for 40-50 s after entering the tank, and spraying the tank with the degreasing agent at 42-48 ℃ for 10-15 s after leaving the tank;
4) washing with water: the metal workpiece after degreasing treatment is sequentially treated before entering the groove, after entering the groove and after being discharged at room temperature: spraying water for 5-10 s before entering the tank, soaking in water for 20-30 s after entering the tank, and spraying water for 5-10 s after leaving the tank;
5) and (3) performing table tone processing: soaking the washed metal workpiece in a surface conditioning agent at room temperature for surface conditioning for 30-120 s;
6) and (3) phosphating treatment: dipping the metal workpiece subjected to surface conditioning treatment in working solution with the concentration of 70-80g/L, and carrying out phosphating treatment for 350s at 95 ℃;
7) pure water washing for the first time: spraying the metal workpiece subjected to phosphating treatment for 30-40 s by using pure water at room temperature;
8) and (3) pure water washing for the second time: placing the metal workpiece subjected to the first pure water washing at room temperature, and sequentially carrying out: spraying 5-10 s of water before entering the tank, soaking in water for 10-20 s after entering the tank, and spraying 5-10 s of water after leaving the tank.
10. Use according to claim 6, wherein the metal pieces are cold rolled steel, cast steel, steel parts, screws, standard parts and parts of powder metallurgy material.
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