CN114214718A - Electrolytic deplating liquid composition of copper plating hanger and method for cyclically regenerating deplating liquid - Google Patents
Electrolytic deplating liquid composition of copper plating hanger and method for cyclically regenerating deplating liquid Download PDFInfo
- Publication number
- CN114214718A CN114214718A CN202111630020.3A CN202111630020A CN114214718A CN 114214718 A CN114214718 A CN 114214718A CN 202111630020 A CN202111630020 A CN 202111630020A CN 114214718 A CN114214718 A CN 114214718A
- Authority
- CN
- China
- Prior art keywords
- stripping solution
- copper plating
- copper
- deplating
- hanger
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 81
- 239000010949 copper Substances 0.000 title claims abstract description 81
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 80
- 238000007747 plating Methods 0.000 title claims abstract description 67
- 239000000203 mixture Substances 0.000 title claims abstract description 63
- 238000000034 method Methods 0.000 title claims abstract description 27
- 230000001172 regenerating effect Effects 0.000 title claims abstract description 15
- 239000007788 liquid Substances 0.000 title description 5
- 238000005260 corrosion Methods 0.000 claims abstract description 32
- 230000007797 corrosion Effects 0.000 claims abstract description 32
- 239000003112 inhibitor Substances 0.000 claims abstract description 31
- 229910001431 copper ion Inorganic materials 0.000 claims abstract description 28
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims abstract description 28
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims abstract description 28
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000012716 precipitator Substances 0.000 claims abstract description 15
- 229910002651 NO3 Inorganic materials 0.000 claims abstract description 14
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims abstract description 14
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 14
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims abstract description 14
- 239000004312 hexamethylene tetramine Substances 0.000 claims abstract description 14
- 239000007787 solid Substances 0.000 claims abstract description 14
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 7
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 24
- 238000000576 coating method Methods 0.000 claims description 15
- 239000011248 coating agent Substances 0.000 claims description 14
- 150000001412 amines Chemical class 0.000 claims description 12
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical group [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 12
- 239000003760 tallow Substances 0.000 claims description 12
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 8
- 239000008139 complexing agent Substances 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- 230000008929 regeneration Effects 0.000 claims description 7
- 238000011069 regeneration method Methods 0.000 claims description 7
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical group [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 claims description 6
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 claims description 6
- 235000010344 sodium nitrate Nutrition 0.000 claims description 6
- 239000004317 sodium nitrate Substances 0.000 claims description 6
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 4
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 4
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 4
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 4
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000005642 Oleic acid Substances 0.000 claims description 4
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 4
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 4
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 3
- 239000001509 sodium citrate Substances 0.000 claims description 3
- 238000011084 recovery Methods 0.000 abstract description 5
- 238000004064 recycling Methods 0.000 abstract description 2
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 238000009472 formulation Methods 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 3
- 238000009713 electroplating Methods 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- YPJKMVATUPSWOH-UHFFFAOYSA-N nitrooxidanyl Chemical compound [O][N+]([O-])=O YPJKMVATUPSWOH-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- -1 hydrogen ions Chemical class 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910001453 nickel ion Inorganic materials 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25F—PROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
- C25F5/00—Electrolytic stripping of metallic layers or coatings
Abstract
The invention belongs to the technical field of plating layer deplating methods, and particularly relates to an electrolytic deplating solution composition of a copper plating hanger and a method for recycling deplating solution, wherein the electrolytic deplating solution composition of the copper plating hanger comprises nitrate, a coordination agent, an accelerator, a solid corrosion inhibitor and an organic corrosion inhibitor, the solid corrosion inhibitor is a mixture of thiourea and hexamethylenetetramine, and the weight ratio of the thiourea to the hexamethylenetetramine is 1: (0.2-4), the pH of the electrolytic stripping solution composition of the copper plating hanger is adjusted to 6.5-7.5 by adopting a pH regulator, the composition can rapidly remove the copper plating layer, and when the stripping solution fails due to the increase of the copper content, a precipitator is added to remove copper ions in the stripping solution so as to regenerate the stripping solution, thereby effectively solving the problem that the stripping solution is difficult to recover. The method for circularly regenerating the electrolytic stripping solution of the copper plating hanger overcomes the problems of difficult treatment and difficult recovery after the stripping solution is invalid.
Description
Technical Field
The invention belongs to the technical field of plating layer deplating methods, and particularly relates to an electrolytic deplating solution composition of a copper plating hanger and a method for circularly regenerating the deplating solution.
Background
In the electroplating process, along with the progress of the electroplating (chemical plating) process flow, the hanger serving as the support body of the plated part is also plated with various corresponding metal coatings. Because the hanger needs to be used repeatedly, when one batch of plated parts is plated and the next batch of plated parts is electroplated, the plating layer on the hanger needs to be thoroughly removed before the hanger can be used continuously. The hanger generally adopts a stainless steel base material, and the deplating process of the coating of the hanger must meet the following requirements: firstly, the coating can be removed quickly and completely, and secondly, the hanger is not corroded.
After the deplating solution is used for a certain time, the deplating effect is gradually lost along with the increase of metal ions of the solution, and the solution becomes waste liquid. The main problems faced by the recovery of the copper stripping solution at present are: the acidity is high, the content of copper and nickel ions is high, the components are complex and difficult to treat, and the recovery cost is high.
Disclosure of Invention
In order to solve the problems, the invention provides an electrolytic stripping solution composition of a copper plating rack and a method for circularly regenerating the stripping solution. The method for circularly regenerating the electrolytic stripping solution of the copper plating hanger overcomes the problems of difficult treatment and difficult recovery after the stripping solution is invalid, and the technical content of the invention is as follows:
the first purpose of the invention is to disclose an electrolytic stripping solution composition of a copper plating hanger, which is characterized in that: according to the weight portion, the corrosion inhibitor comprises 120-180 parts of nitrate, 60-120 parts of coordination agent, 0.5-10 parts of accelerator, 2.5-12 parts of solid corrosion inhibitor and 0.5-3 parts of organic corrosion inhibitor, wherein the solid corrosion inhibitor is a mixture of thiourea and hexamethylenetetramine, and the weight ratio of the thiourea to the hexamethylenetetramine is 1: (0.2-4), and adjusting the pH of the electrolytic stripping solution composition of the copper plating hanger to 6.5-7.5 by using a pH regulator.
In some embodiments of the present invention, the nitrate in the above-mentioned electrolytic stripping solution composition formula system of the copper plating hanger is sodium nitrate.
In some embodiments of the present invention, the complexing agent in the formula system of the electrolytic stripping solution composition for the copper plating hanger is at least one of EDTA, ethanolamine, triethylamine, oleic acid and sodium citrate.
In some embodiments of the present invention, the accelerator in the formulation system of the electrolytic stripping solution composition for the copper plating hanger is thiocyanide.
In some embodiments of the present invention, the organic corrosion inhibitor in the formula system of the electrolytic stripping solution composition for the copper plating hanger is a mixture of tallow amine and triethylene diamine, and the weight ratio of the tallow amine to the triethylene diamine is 1: (1-3).
The second purpose of the invention is to provide a method for circularly regenerating the electrolytic stripping solution of a copper plating hanger, which has the technical points that: the method comprises the following steps:
step one, placing a hanger containing a copper coating in an electrolytic stripping solution at the temperature of 30-50 ℃ and the temperature of 30-50A/dm2Carrying out deplating treatment under the current density to remove the copper coating on the surface of the hanger;
and step two, when the concentration of copper ions in the deplating solution reaches 60-80g/L, adding a precipitator to precipitate the copper ions, and filtering and removing the copper ions to realize the regeneration of the deplating solution.
In some embodiments of the present invention, the amount of the precipitant added in the second step of the above-mentioned recycling method for the copper plating rack is 70-90% of the molar concentration of the copper ions in the deplating solution.
Compared with the prior art, the invention has the beneficial effects that:
the electrolytic stripping solution composition of the copper plating rack and the method for circularly regenerating the stripping solution can quickly strip the copper plating layer, and when the stripping solution loses efficacy due to the increase of the copper content, a precipitator is added to remove copper ions in the stripping solution so as to regenerate the stripping solution, thereby effectively solving the problem that the stripping solution is difficult to recover.
The method for circularly regenerating the electrolytic stripping solution of the copper plating hanger overcomes the problems of difficult treatment and difficult recovery after the stripping solution is invalid.
Detailed Description
The electrolytic stripping solution composition of the copper plating hanger comprises:
120-180 parts by weight of nitrate: the invention adopts nitrate as the main salt of the stripping solution. Nitrate radical is an oxidant of metals such as copper, nickel and chromium, and has an action on the metals, namely nitrate radical ions discharge at an anode to dissolve and strip the metals of the plating layer, thereby achieving the purpose of removing the plating layer. In addition, the stainless steel matrix is prevented from being dissolved, the conductivity of the solution is improved, and the allowable content range is wider;
60-120 parts by weight of a complexing agent: the coordination agent has the function of coordinating with the plating layer ions, does not generate the accumulation of plating layer metal ions, purifies the solution and stabilizes the deplating rate;
0.5-10 parts by weight of accelerator: the accelerator has the function of adjusting the deplating speed, and different amounts of accelerators can be added to adjust the deplating speed according to production requirements;
2.5-12 parts of solid corrosion inhibitor and 0.5-3 parts of organic corrosion inhibitor: the corrosion inhibitor has the functions of inhibiting the dissolution of the stainless steel matrix to the maximum extent, promoting the complete removal of the metal coating by a chemical or electrochemical method to have the effects of inhibiting corrosion or passivating, keeping the original smoothness and improving the surface activity, and has the main mechanism of preventing hydrogen ions from approaching the surface of the matrix to form an effective barrier.
The solid corrosion inhibitor is a mixture of thiourea and hexamethylenetetramine, and the weight ratio of the thiourea to the hexamethylenetetramine is 1: (0.2-4), and adjusting the pH of the electrolytic stripping solution composition of the copper plating hanger to 6.5-7.5 by using a pH regulator.
In some embodiments of the present invention, the nitrate in the above-mentioned electrolytic stripping solution composition formula system of the copper plating hanger is sodium nitrate.
In some embodiments of the present invention, the complexing agent in the formula system of the electrolytic stripping solution composition for the copper plating hanger is at least one of EDTA, ethanolamine, triethylamine, oleic acid and sodium citrate.
In some embodiments of the present invention, the accelerator in the formulation system of the electrolytic stripping solution composition for the copper plating hanger is thiocyanide.
In some embodiments of the present invention, the organic corrosion inhibitor in the formula system of the electrolytic stripping solution composition for the copper plating hanger is a mixture of tallow amine and triethylene diamine, and the weight ratio of the tallow amine to the triethylene diamine is 1: (1-3).
According to the formula, the method for circularly regenerating the electrolytic stripping solution of the copper plating hanger comprises the following steps:
step one, placing a hanger containing a copper coating in an electrolytic stripping solution at the temperature of 30-50 ℃ and the temperature of 30-50A/dm2Carrying out deplating treatment under the current density to remove the copper coating on the surface of the hanger;
and step two, when the concentration of copper ions in the deplating solution reaches 60-80g/L, adding a precipitator to precipitate the copper ions, filtering and removing the copper ions to realize regeneration of the deplating solution, wherein the addition amount of the precipitator is 70-90% of the molar concentration of the copper ions in the deplating solution, the precipitate can be separated by filtration or filter pressing, and the metal copper can be recovered by three processes of burning, dissolving and electrolyzing after separation.
Embodiments of the present invention will be described in detail below with reference to examples, but it will be understood by those skilled in the art that the following examples are only illustrative of the present invention and should not be construed as limiting the scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer.
Example 1
The electrolytic stripping solution composition of the copper plating hanger comprises 140g/L of nitrate, 90g/L of coordination agent, 5g/L of accelerator, 2.5g/L of solid corrosion inhibitor and 1.5g/L of organic corrosion inhibitor, wherein the solid corrosion inhibitor is a mixture of thiourea and hexamethylenetetramine, and the weight ratio of the thiourea to the hexamethylenetetramine is 1: 0.2, adjusting the pH of the electrolytic stripping solution composition of the copper plating hanger to 6.5-7.5 by adopting a pH regulator.
In some embodiments of the present invention, the nitrate in the above-mentioned electrolytic stripping solution composition formula system of the copper plating hanger is sodium nitrate.
In an embodiment of the present invention, the complexing agent in the formula system of the electrolytic stripping solution composition for the copper plating hanger is EDTA.
In some embodiments of the present invention, the accelerator in the formulation system of the electrolytic stripping solution composition for the copper plating hanger is thiocyanide.
In some embodiments of the present invention, the organic corrosion inhibitor in the formula system of the electrolytic stripping solution composition for the copper plating hanger is a mixture of tallow amine and triethylene diamine, and the weight ratio of the tallow amine to the triethylene diamine is 1: 2.
according to the formula, the method for circularly regenerating the electrolytic stripping solution of the copper plating hanger comprises the following steps:
step one, placing a hanger containing a copper coating in an electrolytic stripping solution at the temperature of 30 ℃ and the temperature of 30A/dm2Carrying out deplating treatment under the current density to remove the copper coating on the surface of the hanger;
and step two, when the concentration of the copper ions in the deplating solution reaches 70g/L, adding a precipitator to precipitate the copper ions, filtering and removing the copper ions to realize the regeneration of the deplating solution, wherein the addition amount of the precipitator is 80 percent of the molar concentration of the copper ions in the deplating solution.
Example 2
The electrolytic stripping solution composition of the copper plating hanger comprises 120g/L of nitrate, 60g/L of coordination agent, 0.5g/L of accelerator, 7g/L of solid corrosion inhibitor and 0.5-3g/L of organic corrosion inhibitor, wherein the solid corrosion inhibitor is a mixture of thiourea and hexamethylenetetramine, and the weight ratio of the thiourea to the hexamethylenetetramine is 1: 2.1, adjusting the pH of the electrolytic stripping solution composition of the copper plating hanger to 6.5-7.5 by adopting a pH regulator.
In some embodiments of the present invention, the nitrate in the above-mentioned electrolytic stripping solution composition formula system of the copper plating hanger is sodium nitrate.
In an embodiment of the present invention, the complexing agent in the formula system of the electrolytic stripping solution composition for the copper plating hanger is ethanolamine.
In some embodiments of the present invention, the accelerator in the formulation system of the electrolytic stripping solution composition for the copper plating hanger is thiocyanide.
In some embodiments of the present invention, the organic corrosion inhibitor in the formula system of the electrolytic stripping solution composition for the copper plating hanger is a mixture of tallow amine and triethylene diamine, and the weight ratio of the tallow amine to the triethylene diamine is 1: 1.
according to the formula, the method for circularly regenerating the electrolytic stripping solution of the copper plating hanger comprises the following steps:
step one, placing a hanger containing a copper coating in an electrolytic stripping solution at the temperature of 30 ℃ and the temperature of 40A/dm2Carrying out deplating treatment under the current density to remove the copper coating on the surface of the hanger;
and step two, when the concentration of the copper ions in the deplating solution reaches 60g/L, adding a precipitator to precipitate the copper ions, filtering and removing the copper ions to realize the regeneration of the deplating solution, wherein the addition amount of the precipitator is 70% of the molar concentration of the copper ions in the deplating solution.
Example 3
The electrolytic stripping solution composition of the copper plating hanger comprises 180g/L of nitrate, 120g/L of coordination agent, 10g/L of accelerator, 12g/L of solid corrosion inhibitor and 3g/L of organic corrosion inhibitor, wherein the solid corrosion inhibitor is a mixture of thiourea and hexamethylenetetramine, and the weight ratio of the thiourea to the hexamethylenetetramine is 1: and 4, adjusting the pH value of the electrolytic stripping solution composition of the copper plating hanger to 6.5-7.5 by adopting a pH regulator.
In some embodiments of the present invention, the nitrate in the above-mentioned electrolytic stripping solution composition formula system of the copper plating hanger is sodium nitrate.
In some embodiments of the present invention, the complexing agent in the electrolytic stripping solution composition formula system of the copper plating rack is oleic acid.
In some embodiments of the present invention, the accelerator in the formulation system of the electrolytic stripping solution composition for the copper plating hanger is thiocyanide.
In some embodiments of the present invention, the organic corrosion inhibitor in the formula system of the electrolytic stripping solution composition for the copper plating hanger is a mixture of tallow amine and triethylene diamine, and the weight ratio of the tallow amine to the triethylene diamine is 1: 3.
according to the formula, the method for circularly regenerating the electrolytic stripping solution of the copper plating hanger comprises the following steps:
step one, placing a hanger containing a copper coating in an electrolytic stripping solution at the temperature of 30 ℃ and the temperature of 50A/dm2Deplating treatment is carried out under current density to remove the hanging toolA copper plating layer on the surface;
and step two, when the concentration of the copper ions in the deplating solution reaches 80g/L, adding a precipitator to precipitate the copper ions, filtering and removing the copper ions to realize the regeneration of the deplating solution, wherein the addition amount of the precipitator is 90 percent of the molar concentration of the copper ions in the deplating solution.
Test examples
The electrolytic deplating solutions of the copper plating hangers prepared in examples 1 to 3 were subjected to performance tests, and the specific results are shown in tables 1 to 2. Taking example 1 as an example, the copper content and the deplating speed of the deplating solution are tested, and the test results are shown in Table 3. The deplating solutions of examples 1 to 3 were tested for their regeneration capacity and the results are shown in Table 4.
TABLE 1
TABLE 2
TABLE 3
TABLE 4
As can be seen from the above test data, the current density using the stripping solution of the invention is 30-50A/dm2When in use, the deplating speed is 540-. When the concentration of copper ions reaches 60g/L, the deplating speed is onThe copper content is slowly reduced, and after the copper is removed by adding a precipitator, the deplating capacity of the deplating solution can be recovered by more than 90 percent.
In conclusion, the hanger substrate is effectively protected by adding the specific accelerator and the specific corrosion inhibitor under the condition of ensuring quick deplating. And after the deplating solution loses efficacy, a precipitator can be added to remove copper, so that the deplating solution can recover performance, and the copper salt obtained by precipitation can be recovered by a specific process to obtain metal copper, so that the method has wide application prospect in the electroplating industry.
While particular embodiments of the present invention have been illustrated and described, it would be obvious that various other changes and modifications can be made without departing from the spirit and scope of the invention. It is therefore intended to cover in the appended claims all such changes and modifications that are within the scope of this invention.
Claims (7)
1. The electrolytic stripping solution composition of the copper plating hanger is characterized in that: according to the weight portion, the corrosion inhibitor comprises 120-180 parts of nitrate, 60-120 parts of coordination agent, 0.5-10 parts of accelerator, 2.5-12 parts of solid corrosion inhibitor and 0.5-3 parts of organic corrosion inhibitor, wherein the solid corrosion inhibitor is a mixture of thiourea and hexamethylenetetramine, and the weight ratio of the thiourea to the hexamethylenetetramine is 1: (0.2-4), and adjusting the pH of the electrolytic stripping solution composition of the copper plating hanger to 6.5-7.5 by using a pH regulator.
2. The copper plating hanger electrolytic stripping solution composition according to claim 1, characterized in that: the nitrate is sodium nitrate.
3. The copper plating hanger electrolytic stripping solution composition according to claim 1, characterized in that: the complexing agent is at least one of EDTA, ethanolamine, triethylamine, oleic acid and sodium citrate.
4. The copper plating hanger electrolytic stripping solution composition according to claim 1, characterized in that: the accelerator is thiocyanide.
5. The copper plating hanger electrolytic stripping solution composition according to claim 1, characterized in that: the organic corrosion inhibitor is a mixture of tallow amine and triethylene diamine, and the weight ratio of the tallow amine to the triethylene diamine is 1: (1-3).
6. The method for circularly regenerating the electrolytic stripping solution of the copper plating hanger is characterized by comprising the following steps: the method comprises the following steps:
step one, placing a hanger containing a copper coating in an electrolytic stripping solution at the temperature of 30-50 ℃ and the temperature of 30-50A/dm2Carrying out deplating treatment under the current density to remove the copper coating on the surface of the hanger;
and step two, when the concentration of copper ions in the deplating solution reaches 60-80g/L, adding a precipitator to precipitate the copper ions, and filtering and removing the copper ions to realize the regeneration of the deplating solution.
7. The method for cyclically regenerating the electrolytic stripping solution of the copper plating hanger according to claim 6, characterized in that: and in the second step, the addition amount of the precipitator is 70-90% of the molar concentration of the copper ions in the deplating solution.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111630020.3A CN114214718A (en) | 2021-12-28 | 2021-12-28 | Electrolytic deplating liquid composition of copper plating hanger and method for cyclically regenerating deplating liquid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111630020.3A CN114214718A (en) | 2021-12-28 | 2021-12-28 | Electrolytic deplating liquid composition of copper plating hanger and method for cyclically regenerating deplating liquid |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114214718A true CN114214718A (en) | 2022-03-22 |
Family
ID=80706498
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111630020.3A Pending CN114214718A (en) | 2021-12-28 | 2021-12-28 | Electrolytic deplating liquid composition of copper plating hanger and method for cyclically regenerating deplating liquid |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114214718A (en) |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1900384A (en) * | 2006-07-05 | 2007-01-24 | 北京航空航天大学 | Process for removing part surface oxidized skin using supersonic wave and electrolytic combination |
| CN102877114A (en) * | 2012-09-24 | 2013-01-16 | 东莞市导谷电子材料科技有限公司 | Stripping agent for stainless steel electroplating rack |
| CN103572293A (en) * | 2013-09-10 | 2014-02-12 | 上海应用技术学院 | Environment-friendly de-plating liquid of copper plating layer and de-plating process of reproducible de-plating liquid |
| CN105401210A (en) * | 2015-11-30 | 2016-03-16 | 惠州市博美化工制品有限公司 | Environment-friendly stainless steel substrate plating stripping agent |
| CN109234792A (en) * | 2017-08-30 | 2019-01-18 | 博罗县美兴达科技有限公司 | A kind of electroplated coating electrolytic deplating process agent |
| CN110629278A (en) * | 2019-09-20 | 2019-12-31 | 深圳市祺鑫天正环保科技有限公司 | Electrolytic stripping liquid and method for simultaneously stripping copper layer and tin layer on hanger |
| CN111850670A (en) * | 2020-08-04 | 2020-10-30 | 郑州知淘信息科技有限责任公司 | Electrolytic stripping solution for steel electroplating hanger and stripping method |
| CN113388456A (en) * | 2021-06-08 | 2021-09-14 | 安徽省复和利泰节能环保科技有限公司 | Medium-high pressure boiler anti-corrosion and scale-inhibiting cleaning agent and preparation method thereof |
| CN113564684A (en) * | 2021-07-07 | 2021-10-29 | 江门市瑞期精细化学工程有限公司 | Electrolytic stripping agent and application thereof |
-
2021
- 2021-12-28 CN CN202111630020.3A patent/CN114214718A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1900384A (en) * | 2006-07-05 | 2007-01-24 | 北京航空航天大学 | Process for removing part surface oxidized skin using supersonic wave and electrolytic combination |
| CN102877114A (en) * | 2012-09-24 | 2013-01-16 | 东莞市导谷电子材料科技有限公司 | Stripping agent for stainless steel electroplating rack |
| CN103572293A (en) * | 2013-09-10 | 2014-02-12 | 上海应用技术学院 | Environment-friendly de-plating liquid of copper plating layer and de-plating process of reproducible de-plating liquid |
| CN105401210A (en) * | 2015-11-30 | 2016-03-16 | 惠州市博美化工制品有限公司 | Environment-friendly stainless steel substrate plating stripping agent |
| CN109234792A (en) * | 2017-08-30 | 2019-01-18 | 博罗县美兴达科技有限公司 | A kind of electroplated coating electrolytic deplating process agent |
| CN110629278A (en) * | 2019-09-20 | 2019-12-31 | 深圳市祺鑫天正环保科技有限公司 | Electrolytic stripping liquid and method for simultaneously stripping copper layer and tin layer on hanger |
| CN111850670A (en) * | 2020-08-04 | 2020-10-30 | 郑州知淘信息科技有限责任公司 | Electrolytic stripping solution for steel electroplating hanger and stripping method |
| CN113388456A (en) * | 2021-06-08 | 2021-09-14 | 安徽省复和利泰节能环保科技有限公司 | Medium-high pressure boiler anti-corrosion and scale-inhibiting cleaning agent and preparation method thereof |
| CN113564684A (en) * | 2021-07-07 | 2021-10-29 | 江门市瑞期精细化学工程有限公司 | Electrolytic stripping agent and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107419271B (en) | A kind of agent of environment protection chemical strip and strip method for nickel coating | |
| CN108950562B (en) | Two-stage tin stripping method for PCB | |
| CN101457360A (en) | Organic acid type roughening liquid | |
| CN111850670A (en) | Electrolytic stripping solution for steel electroplating hanger and stripping method | |
| EP2471977B1 (en) | Method for removing impurities from plating solution | |
| CN111321436A (en) | Cyanide-free copper plating solution assistant and copper plating solution | |
| CN112410791A (en) | High-speed environment-friendly chemical stripping solution for nickel coating and preparation method thereof | |
| CN114232030B (en) | PCB methanesulfonic acid tin stripping waste liquid recycling method | |
| CN102534701A (en) | Method for removing impurities from plating solution | |
| CN112899738B (en) | Steel matrix direct cyanide-free copper plating electroplating solution under strong acid condition and preparation method thereof | |
| US6833479B2 (en) | Antimisting agents | |
| US4913787A (en) | Gold plating bath and method | |
| CN114214718A (en) | Electrolytic deplating liquid composition of copper plating hanger and method for cyclically regenerating deplating liquid | |
| CN105177694A (en) | Electrogilding solution organic impurity removing method | |
| CN105019010A (en) | Technology for recycling precious metal palladium from electronic element and electrochemical stripping solution applied to technology | |
| NL8004399A (en) | ELECTROLYTIC STRIP SHEET AND STRIP METHOD. | |
| CN108707901B (en) | Recyclable tin stripping solution and preparation method and use method thereof | |
| CN111020587B (en) | Deplating liquid for removing nickel layer on copper surface and deplating process thereof | |
| CN106087032A (en) | A kind of environment-friendly type is de-hangs powder | |
| EP3686319A1 (en) | Indium electroplating compositions and methods for electroplating indium on nickel | |
| CN114763613B (en) | Stripping solution for stripping metal cadmium plating layer and stripping method thereof | |
| CN112210778A (en) | Tin stripping liquid | |
| KR101994247B1 (en) | Method of removing impurities from plating liquid | |
| CN110872706B (en) | Long-life high-corrosion-resistance chemical nickel solution and preparation and application thereof | |
| CN110306233B (en) | Ammonia nitrogen-free electrolytic stripping agent and use method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20220322 |