CN112323136A - Deplating solution and deplating method - Google Patents
Deplating solution and deplating method Download PDFInfo
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- CN112323136A CN112323136A CN202011159280.2A CN202011159280A CN112323136A CN 112323136 A CN112323136 A CN 112323136A CN 202011159280 A CN202011159280 A CN 202011159280A CN 112323136 A CN112323136 A CN 112323136A
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25F—PROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
- C25F1/00—Electrolytic cleaning, degreasing, pickling or descaling
- C25F1/02—Pickling; Descaling
- C25F1/04—Pickling; Descaling in solution
Abstract
A deplating solution for removing a surface coating of a workpiece comprises chromium elements, and comprises permanganate and a complexing agent. Mass fraction t of permanganate1The range of t is more than or equal to 30 percent1Less than or equal to 40 percent; the complexing agent component is salt, and the pH value of the deplating solution is more than or equal to 9 and less than or equal to 12. The application also provides a deplating method using the deplating solution.
Description
Technical Field
The application relates to the field of deplating, in particular to a deplating solution and a deplating method.
Background
The coating process has wide application in the industrial field. In the production process of the workpiece, if the surface coating on the workpiece does not meet the product quality requirement, the surface coating needs to be removed and the coating treatment needs to be carried out again so as to be recycled, and the cost is saved.
As the demands of products on the appearance and the mechanical property of workpieces are higher and higher, the components of the surface coating are various. When some deplating liquids deplate surface coatings, workpiece substrates are corroded, and further the surface flatness and the size of the whole workpiece are affected, so that the problem that the film cannot be re-coated is solved.
Disclosure of Invention
In view of the above, it is necessary to provide a deplating solution and a deplating method to solve the problem of corrosion of the deplating solution to the substrate.
A deplating solution for removing a surface coating of a workpiece, wherein the surface coating contains chromium elements, and the deplating solution contains permanganate and a complexing agent; mass fraction t of permanganate1The range of t is more than or equal to 30 percent1Less than or equal to 40 percent; the complexing agent is salt, and the pH value of the deplating solution is more than or equal to 9 and less than or equal to 12.
Further, the permanganate is selected from at least one of sodium permanganate and zinc permanganate.
Further, the permanganate is selected from at least two of sodium permanganate, zinc permanganate, and potassium permanganate.
Further, the complexing agent comprises soluble salt, and the soluble salt is selected from at least one of carbonate, sulfite, hydrosulfate, silicate and metaaluminate.
Further, the complexing agent is selected from at least one of sodium silicate, sodium carbonate and sodium tripolyphosphate.
Further, the mass fraction t of the complexing agent2The range of t is more than or equal to 5 percent2≤20％。
Further, the paint also comprises a solvent, wherein the solvent is water.
A deplating method is used for removing a surface coating of a workpiece, wherein the surface coating contains chromium elements, and comprises the following steps: placing the workpiece in a deplating solution; taking the workpiece as an anode and the counter electrode as a cathode, and applying voltage to perform deplating treatment until the surface coating is removed; cleaning the workpiece with the surface coating removed; drying the cleaned workpiece; wherein, the deplating liquid bagContains permanganate and complexing agent; mass fraction t of permanganate1The range of t is more than or equal to 30 percent1Less than or equal to 40 percent; the complexing agent is salt, and the pH value of the deplating solution is more than or equal to 9 and less than or equal to 12.
Further, the deplating method also comprises the step of adjusting the temperature of the deplating liquid to the temperature T, wherein the temperature T is within the range of 40 ℃ to 90 ℃.
Furthermore, the time of deplating treatment is t, and the range of the time t is more than or equal to 5min and less than or equal to 20 min.
Further, the method also comprises the step of introducing gas into the deplating solution while performing deplating treatment.
Further, the mass fraction t of the complexing agent2The range of t is more than or equal to 5 percent2≤20％。
The deplating solution is suitable for deplating all surface coatings containing metallic element chromium, has wide application range and is not limited to the surface coatings containing one or more specific components; the deplating liquid does not corrode the base material while removing the surface coating, thereby achieving the purpose of removing the surface coating and protecting the base material; the mass fractions of the permanganate and the complexing agent are regulated and controlled, so that the deplating time is short, the production efficiency is improved, and the production cost is reduced; in addition, MnO is generated after the deplating solution deplates the surface coating4 2-Can be recycled after post-treatment.
The following detailed description will further illustrate the present application.
Detailed Description
In order that the above objects, features and advantages of the present application may be more clearly understood, the present application is described in detail below with reference to specific embodiments. In addition, the embodiments and features of the embodiments of the present application may be combined with each other without conflict. In the following description, numerous specific details are set forth to provide a thorough understanding of the present application, and the described embodiments are merely a subset of the embodiments of the present application, rather than all embodiments. All other embodiments obtained by a person of ordinary skill in the art without any inventive work based on the embodiments in the present application are within the scope of protection of the present application.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. The terminology used herein in the description of the present application is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. As used herein, the term "and/or" includes all and any combination of one or more of the associated listed items.
The embodiment of the application provides a deplating solution which is used for removing a surface coating of a workpiece. The surface coating comprises metal element chromium (Cr), and the surface coating can comprise, but is not limited to at least one of various composite materials such as Cr, CrN, CrC, CrSi, CrSiC, CrSiCN, TiCr and TiCrCN; the substrate of the workpiece may include, but is not limited to, stainless steel, plastic, or metal composites, etc., and it is understood that the substrate should be free of the metallic element chromium.
In the related art, a surface plating layer is formed on the surface of a workpiece by a plating process on a workpiece substrate. However, because the requirement of the coating on the appearance quality is high, the defective products in the coating process need to be removed by the deplating process to re-coat the film on the substrate of the workpiece after the deplating is complete. If the substrate of the workpiece is corroded in the deplating process, the quality of the recoating film is influenced, and the recycling of the substrate of the workpiece cannot be realized. In the field of consumer electronics, a shell of an electronic product often requires dozens or even hundreds of processes on the premise of considering both performance and appearance, workpiece coating is generally a relatively later process, and if defective products in the coating process cannot be reprocessed, the cost of the processes before the coating process is lost. Deplating is very important for cost control of the overall electronic housing manufacturing process. In addition, in the actual deplating process, the cost of the deplating process, such as deplating time, needs to be controlled to improve the production efficiency.
The deplating solution comprises permanganate, a complexing agent and a solvent, and the pH value of the deplating solution at normal temperature is more than or equal to 9 and less than or equal to 12. The solvent may be water.
Wherein the permanganate dissolves in the solvent to form permanganate ions (MnO)4 -). The permanganate may be selected from at least one of sodium permanganate, zinc permanganate, and potassium permanganate. Wherein, the solubility of partial permanganate (such as potassium permanganate) is lower than 30% at normal temperature, and the mass fraction of the permanganate can be more than or equal to 30% by mixing with other permanganate (such as sodium permanganate or zinc permanganate) with high solubility; in other embodiments, the solubility of the permanganate may also be increased by raising the temperature.
Wherein the mass fraction of the permanganate in the deplating solution is t1Mass fraction t1The range of t is more than or equal to 25 percent1Less than or equal to 45 percent. In one embodiment of the present application, the mass fraction t of permanganate1The lower limit of the range is selected from one of 25%, 27.5%, 30%, 35.7%, 40%, 42.4%, 45%; mass fraction t of permanganate1The upper limit of the range is selected from one of 26.3%, 32.5%, 34.6%, 36.8%, 40%, 42.5%, 45%. Wherein the mass fraction t of the permanganate1The lower limit and the upper limit of (b) are chosen reasonably, i.e. the lower limit is required to be less than or equal to the upper limit.
Further, the mass fraction t of permanganate in the deplating solution1The range of t is more than or equal to 30 percent1Less than or equal to 40 percent. Mass fraction t of permanganate1Less than 30%, due to MnO in the stripping solution4 -Too low mass fraction of (b) will reduce the reaction rate, thus causing too long reaction time and affecting the production efficiency; mass fraction t of permanganate1When the viscosity of the stripping solution is higher than 40%, the viscosity of the stripping solution is too high, the movement rate of ions in the stripping solution is influenced, and the reaction rate is reduced, so that the production efficiency is influenced due to too long reaction time.
Complexing agent (A)mBn) Is soluble salt, and the complexing agent is strong base weak acid salt. The complexing agent may be at least one selected from the group consisting of carbonate, sulfite, hydrosulfate, silicate, and meta-aluminate. The complexing agent generates a cation (A) when dissolved in the solventn+) And an anion (B)m-). The cation in the complexing agent maySelected from lithium ions (Li)+) Sodium ion (Na)+) And potassium ion (K)+) The anion in the complexing agent may be selected from carbonate ion (CO)3 2-) Sulfite ion (SO)3 2-) Hydrogen sulfate ion (S)2-) Silicic acid radical (SiO)3 2-) And metaaluminate (AlO)2 -) At least one of (1). For example, the complexing agent may be selected from at least one of sodium silicate, sodium carbonate, and sodium tripolyphosphate. The anion has complexing effect in the deplating solution and also has corrosion inhibition effect, so that the base material of the workpiece is prevented from being corroded by the deplating solution. Meanwhile, the anion of the complexing agent can promote the ionization of the solvent to generate hydroxyl ion (OH) in the solvent-) So that the deplating liquid is alkalescent, and the alkalescent environment can increase MnO in the deplating process4 -The oxidation performance of the workpiece is improved, so that the production efficiency is improved, and the base material of the workpiece can be prevented from being corroded by a strong alkaline environment.
MnO in a deplating solution when a workpiece containing a surface coating is placed in the deplating solution for deplating treatment4 -、Bm-、OH-The complex is generated by the reaction with Cr in the surface coating to remove the surface coating, and the action principle is as follows:
Cr+3MnO4 -+4Bm-→3MnO4 2-+Cr(B)4/m -and
Cr+3MnO4 -+4OH-→3MnO4 2-+Cr(OH)4 -，
namely stripping of B in the bathm-With OH-Can simultaneously play a complexing role so as to remove the surface coating; wherein, MnO4 -MnO formation after reaction4 2-，MnO4 2-Is converted into MnO by oxidation after post-treatment (e.g. electrochemical oxidation)4 -Therefore, the method can be recycled, saves energy, reduces emission and reduces production cost.
The mass fraction of the complexing agent in the deplating liquid is t2Mass fraction t2The range of t is more than or equal to 5 percent2≤30% of the total weight of the composition. In one embodiment of the present application, the mass fraction t of complexing agent2The lower limit of the range is selected from one of 5%, 7.5%, 10%, 15.8%, 20%, 22.3%, 28%; mass fraction t of complexing agent2The upper limit of the range is selected from one of 6.4%, 12.5%, 15.6%, 18.8%, 25%, 27.5%, 30%. Wherein the mass fraction t of the complexing agent2The lower limit and the upper limit of (b) are chosen reasonably, i.e. the lower limit is required to be less than or equal to the upper limit. Mass fraction t of complexing agent2The range of t is more than or equal to 5 percent2When the concentration is less than or equal to 30 percent, the pH value of the deplating solution can be within the range of 9 to 12, so that the deplating solution has enough Bm-With OH-React with chromium.
Further, the mass fraction t of the complexing agent in the deplating solution2The range of t is more than or equal to 5 percent2Less than or equal to 20 percent. Mass fraction t of complexing agent2Below 5%, the reaction rate is reduced, resulting in too long reaction time to affect the production efficiency; mass fraction t of complexing agent2When the viscosity is higher than 20%, the viscosity of the deplating solution is too high, the movement rate of ions in the deplating solution is influenced, and the reaction rate is reduced, so that the production efficiency is influenced due to too long reaction time.
The application also provides a deplating method for removing the surface coating of the workpiece, wherein the surface coating comprises a metal element chromium, and the deplating method comprises the following steps:
placing a workpiece containing a surface coating in a deplating solution; taking the workpiece as an anode and the counter electrode as a cathode, and applying voltage to perform deplating treatment until the surface coating is removed; cleaning the workpiece with the surface coating removed; and drying the cleaned workpiece.
The deplating method also comprises the step of adjusting the temperature of the deplating solution to a temperature T, wherein the temperature T is within the range of 40 ℃ to 90 ℃, and the lower limit of the temperature T is selected from one of 40 ℃, 46 ℃, 52 ℃, 63 ℃, 76 ℃, 85 ℃ and 88 ℃; the upper limit of the temperature T range is selected from one of 42 ℃, 48 ℃, 53 ℃, 66 ℃, 78 ℃, 86 ℃ and 90 ℃; the lower limit and the upper limit of the temperature T are reasonably selected, i.e. the lower limit is less than or equal to the upper limit.
In some embodiments, the counter electrode cathode may be carbon. In other embodiments, other materials, such as copper, may be used as the cathode, which is only illustrative and not limiting.
The applied voltage is U, the range of the voltage U is more than or equal to 2V and less than or equal to 15V, and the lower limit of the range of the voltage U is selected from one of 2V, 5V, 7V, 9V, 12V and 15V; the upper limit of the range of the voltage U is selected from one of 2V, 6V, 8V, 10V, 13V, 15V; the lower limit and the upper limit of the voltage U are reasonably selected, that is, the lower limit is required to be less than or equal to the upper limit.
The time of the deplating treatment is t, the deplating time t is based on the time required for completely removing the surface coating, the time t is within the range of 5min to 20min, and the lower limit of the time t is selected from one of 5min, 7min, 9min, 12min, 15min and 19 min; the upper limit of the time t is selected from one of 6min, 8min, 13min, 16min, 18min and 20 min; the lower limit and the upper limit of the time t need to be reasonably selected, namely the lower limit needs to be less than or equal to the upper limit. The time t is within the range of 5min to 20min, so that the surface coating can be completely removed, the production efficiency can be ensured, and the production cost can be reduced.
Furthermore, when the deplating treatment is carried out, gas is introduced into the deplating liquid at the same time, so that the contact area between the deplating liquid and the surface coating of the workpiece is increased, the reaction rate of the deplating liquid and the surface coating is accelerated, and the production efficiency is improved.
The present application will be described below with reference to specific examples. In the following examples, the workpiece substrate was made of stainless steel, and the surface plating layer included 60% titanium (Ti), 15% chromium (Cr), 5% carbon (C), and 20% nitrogen (N).
Example 1
Providing a deplating solution, wherein the deplating solution comprises 25 mass percent of sodium permanganate and 10 mass percent of sodium silicate, and the pH value of the deplating solution at normal temperature is 11.
And (3) placing the workpiece in a deplating solution to perform deplating treatment at 80 ℃, wherein the time required for deplating the surface coating is 30 min.
Example 2
The difference from example 1 is: the mass fraction of the sodium permanganate in the deplating solution is 30 percent. The time required for deplating the surface coating is 18 min.
The rest is the same as embodiment 1, and is not described herein again.
Example 3
The difference from example 1 is: the mass fraction of the sodium permanganate in the deplating solution is 34 percent. The time required for deplating the surface coating is 16 min.
The rest is the same as embodiment 1, and is not described herein again.
Example 4
The difference from example 1 is: the mass fraction of the sodium permanganate in the deplating solution is 38 percent. The time required for deplating the surface coating is 15 min.
The rest is the same as embodiment 1, and is not described herein again.
Example 5
The difference from example 1 is: the mass fraction of the sodium permanganate in the deplating solution is 45 percent. The time required for deplating the surface coating is 25 min.
The rest is the same as embodiment 1, and is not described herein again.
Please refer to table 1, which shows the main parameters and test results of the deplating solutions provided in examples 1-5.
TABLE 1
As can be seen from the data in Table 1, the differences in the mass fraction of sodium permanganate in the stripping solutions provided in examples 1-5 affect the time required to strip the surface coating. Wherein, the sodium permanganate with different mass fractions has no corrosion to the substrate. The concentration of the sodium permanganate is lower than 30%, and the reaction rate can be reduced due to low concentration, so that the deplating time is too long, and the production efficiency is influenced; when the concentration of the sodium permanganate is higher than 40%, the reaction rate is slowed down due to the increase of the solution viscosity, the reaction time is increased, and the production efficiency is influenced. Too large or too small a mass fraction of sodium permanganate merely increases the time required to deplate the surface coating, affecting production efficiency, without corroding the substrate.
Example 6
Providing a deplating solution, wherein the deplating solution comprises 34% of zinc permanganate and 10% of sodium silicate by mass, and the pH value of the deplating solution at normal temperature is 11.
And (3) placing the workpiece in a deplating solution to perform deplating treatment at 80 ℃, wherein the time required for deplating the surface coating is 16 min.
Example 7
The difference from example 6 is: the complexing agent in the deplating solution is sodium carbonate with the mass fraction of 20%, and the time required for deplating the surface coating is 20 min.
The rest is the same as embodiment 6, and the description is omitted here.
Example 8
The difference from example 6 is: the complexing agent in the deplating solution is sodium tripolyphosphate with the mass fraction of 15%, the pH value of the deplating solution is 10 at normal temperature, and the time required for deplating the surface coating is 22 min.
The rest is the same as embodiment 6, and the description is omitted here.
Comparative example 1
The difference from example 6 is: the complexing agent in the deplating solution is sodium hydroxide with the mass fraction of 10%, the pH value of the deplating solution is 13 at normal temperature, and the time required for deplating the surface coating is 12 min. After the reaction, the substrate exhibited moderate corrosion, which was a white line on the substrate surface.
The rest is the same as embodiment 6, and the description is omitted here.
Comparative example 2
The difference from example 6 is: the complexing agent in the stripping solution is sodium hydroxide with the mass fraction of 7%, the pH value of the stripping solution at normal temperature is 11, and the base material is seriously corroded. For convenience, the standard of severe corrosion of a substrate is that a white line appears after the substrate is corroded, and when the length of the white line is greater than 5mm, severe corrosion is defined.
The rest is the same as embodiment 6, and the description is omitted here.
Please refer to table 2, which shows the main parameters and test results of the deplating solutions provided in examples 6-8 and comparative examples 1-2.
TABLE 2
As can be seen from the data in table 2, in examples 6 to 8, the complexing agent in examples 6 to 8 is a weak base and the complexing agent in comparative example 1 is a strong base, as compared with comparative example 1. In comparison with the time required for deplating the surface coating, although comparative example 1 shortened the deplating time, the white lines appeared on the surface of the substrate, i.e., the substrate was moderately corroded, whereas the substrates in examples 6 to 8 were not affected by the weakly alkaline deplating solution; in addition, in comparative example 2, since the content of the complexing agent in the stripping solution was too small, OH in the stripping solution-Too little results in prolonged deplating time. Although the solubility of NaOH is low and the alkalinity is weakened, the strong oxidation of NaOH itself causes severe corrosion of the substrate when the deplating time is increased, resulting in a white line length of more than 5mm appearing on the surface of the substrate, thereby preventing the substrate from being coated again.
Example 9
Providing a deplating solution, wherein the deplating solution comprises 34% of sodium permanganate and 10% of sodium silicate by mass, and the pH value of the deplating solution is 11 at normal temperature.
And (3) placing the workpiece in a deplating solution to perform deplating treatment at 80 ℃, wherein the time required for deplating the surface coating is 16 min.
Example 10
The difference from example 9 is: the mass fraction of the sodium silicate is 10 percent, the pH value of the deplating liquid is 11.5, and the time required for deplating the surface coating is 14 min.
The rest is the same as embodiment 9, and is not described herein again.
Example 11
The difference from example 9 is: the mass fraction of the sodium silicate is 20%, the pH value of the deplating liquid is 12, and the time required for deplating the surface coating is 13 min.
The rest is the same as embodiment 9, and is not described herein again.
Example 12
The difference from example 9 is: the mass fraction of the sodium silicate is 30 percent, the pH value of the deplating liquid is 13, and the time required for deplating the surface coating is 25 min.
The rest is the same as embodiment 9, and is not described herein again.
Please refer to table 3 for the main parameters and test results of the deplating solutions provided in examples 9-12.
TABLE 3
As can be seen from the data in Table 3, the differences in the mass fraction of sodium silicate (complexing agent) in the stripping solutions provided in examples 9-12 affect the time required to strip the surface coating. Wherein, the sodium silicate with different mass fractions has no corrosion to the base material. The concentration of sodium silicate is higher than 20%, the solubility is deteriorated, and simultaneously, the reaction rate is reduced due to the increase of viscosity, the reaction time is long, and the efficiency is influenced. Too large or too small a mass fraction of sodium silicate merely increases the time required to deplate the surface coating, affects production efficiency, and does not corrode the substrate.
The deplating solution is suitable for deplating all surface coatings containing metallic element chromium, has wide application range and is not limited to the surface coatings containing one or more specific components; the deplating liquid does not corrode the base material while removing the surface coating, thereby achieving the purpose of removing the surface coating and protecting the base material; the mass fractions of the permanganate and the complexing agent are regulated and controlled, so that the deplating time is short, the production efficiency is improved, and the production cost is reduced; in addition, MnO is generated after the deplating solution deplates the surface coating4 2-And can be recycled after further post-treatment.
Although the present application has been described in detail with reference to the preferred embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted without departing from the spirit and scope of the present application.
Claims (10)
1. A stripping solution for removing a surface coating of a workpiece, wherein the surface coating comprises chromium elements, the stripping solution comprising:
a permanganate salt; and
a complexing agent;
wherein the mass fraction t of the permanganate1The range of t is more than or equal to 30 percent1The pH value of the deplating liquid is not less than 9 and not more than 12.
2. The deplating solution according to claim 1, wherein,
the permanganate is selected from at least one of sodium permanganate and zinc permanganate.
3. The deplating solution according to claim 1, wherein,
the permanganate is selected from at least two of sodium permanganate, zinc permanganate and potassium permanganate.
4. The deplating solution according to claim 1, wherein,
the complexing agent comprises soluble salt, and the soluble salt is selected from at least one of carbonate, sulfite, hydrosulfate, silicate and metaaluminate.
5. The deplating solution according to claim 4,
the complexing agent is selected from at least one of sodium silicate, sodium carbonate and sodium tripolyphosphate.
6. The deplating solution according to claim 1, wherein,
mass fraction t of complexing agent2The range of t is more than or equal to 5 percent2≤20％。
7. A deplating method for removing a surface coating of a workpiece, wherein the surface coating contains chromium elements, the deplating method comprises the following steps:
placing the workpiece in a deplating solution;
taking the workpiece as an anode and the counter electrode as a cathode, and applying voltage to perform deplating treatment until the surface coating is removed;
cleaning the workpiece with the surface coating removed;
drying the cleaned workpiece;
wherein the content of the first and second substances,
the deplating solution comprises:
a permanganate salt; and
a complexing agent;
the mass fraction t of the permanganate1The range of t is more than or equal to 30 percent1The pH value of the deplating liquid is not less than 9 and not more than 12.
8. The deplating method according to claim 7, further comprising:
and adjusting the temperature of the deplating solution to a temperature T, wherein the temperature T is within the range of 40 ℃ to 90 ℃.
9. The deplating method according to claim 7, wherein,
the time of the deplating treatment is t, and the range of the time t is more than or equal to 5min and less than or equal to 20 min.
10. The deplating method according to claim 7, wherein,
mass fraction t of the complexing agent2The range of t is more than or equal to 5 percent2≤20％。
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113832534A (en) * | 2021-10-12 | 2021-12-24 | 广州阿美新材料有限公司 | Aluminum alloy chromium-containing coating electrolytic stripping agent and stripping method thereof |
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| CN113832534A (en) * | 2021-10-12 | 2021-12-24 | 广州阿美新材料有限公司 | Aluminum alloy chromium-containing coating electrolytic stripping agent and stripping method thereof |
| CN113832534B (en) * | 2021-10-12 | 2024-02-20 | 广州阿美新材料有限公司 | Electrolytic stripping agent for chromium-containing coating of aluminum alloy and stripping method thereof |
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