CN114807944A - Environment-friendly deplating agent and preparation method and use method thereof - Google Patents
Environment-friendly deplating agent and preparation method and use method thereof Download PDFInfo
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- CN114807944A CN114807944A CN202110122304.5A CN202110122304A CN114807944A CN 114807944 A CN114807944 A CN 114807944A CN 202110122304 A CN202110122304 A CN 202110122304A CN 114807944 A CN114807944 A CN 114807944A
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- 238000000034 method Methods 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 140
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 124
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 102
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims abstract description 102
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 65
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 62
- 239000000080 wetting agent Substances 0.000 claims abstract description 48
- 229940044631 ferric chloride hexahydrate Drugs 0.000 claims abstract description 44
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 claims abstract description 44
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims abstract description 43
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims abstract description 43
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 43
- 239000002904 solvent Substances 0.000 claims abstract description 28
- 238000003756 stirring Methods 0.000 claims description 54
- 238000001816 cooling Methods 0.000 claims description 8
- 238000005303 weighing Methods 0.000 claims description 8
- 239000008399 tap water Substances 0.000 claims description 7
- 235000020679 tap water Nutrition 0.000 claims description 7
- 229920000604 Polyethylene Glycol 200 Polymers 0.000 claims description 6
- 239000008118 PEG 6000 Substances 0.000 claims description 3
- 229920002582 Polyethylene Glycol 600 Polymers 0.000 claims description 3
- 229920002584 Polyethylene Glycol 6000 Polymers 0.000 claims description 3
- 239000012964 benzotriazole Substances 0.000 claims description 2
- 125000003354 benzotriazolyl group Chemical group N1N=NC2=C1C=CC=C2* 0.000 claims description 2
- YHMYGUUIMTVXNW-UHFFFAOYSA-N 1,3-dihydrobenzimidazole-2-thione Chemical compound C1=CC=C2NC(S)=NC2=C1 YHMYGUUIMTVXNW-UHFFFAOYSA-N 0.000 claims 1
- CMGDVUCDZOBDNL-UHFFFAOYSA-N 4-methyl-2h-benzotriazole Chemical compound CC1=CC=CC2=NNN=C12 CMGDVUCDZOBDNL-UHFFFAOYSA-N 0.000 claims 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 abstract description 38
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 29
- 229910052802 copper Inorganic materials 0.000 abstract description 29
- 239000010949 copper Substances 0.000 abstract description 29
- 239000004033 plastic Substances 0.000 abstract description 20
- 229910052763 palladium Inorganic materials 0.000 abstract description 19
- 239000011248 coating agent Substances 0.000 abstract description 16
- 238000000576 coating method Methods 0.000 abstract description 16
- 239000000126 substance Substances 0.000 abstract description 14
- 230000007797 corrosion Effects 0.000 abstract description 11
- 238000005260 corrosion Methods 0.000 abstract description 11
- 230000000694 effects Effects 0.000 abstract description 10
- 239000000463 material Substances 0.000 abstract description 9
- 229910000881 Cu alloy Inorganic materials 0.000 abstract description 7
- 229910052751 metal Inorganic materials 0.000 abstract description 7
- 239000002184 metal Substances 0.000 abstract description 7
- 239000000758 substrate Substances 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 238000007747 plating Methods 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- FHXXWAWFWPVOAX-UHFFFAOYSA-N benzimidazole-2-thione Chemical compound C1=CC=CC2=NC(=S)N=C21 FHXXWAWFWPVOAX-UHFFFAOYSA-N 0.000 description 7
- 230000008569 process Effects 0.000 description 6
- 238000004140 cleaning Methods 0.000 description 4
- 238000005530 etching Methods 0.000 description 4
- XEMZLVDIUVCKGL-UHFFFAOYSA-N hydrogen peroxide;sulfuric acid Chemical compound OO.OS(O)(=O)=O XEMZLVDIUVCKGL-UHFFFAOYSA-N 0.000 description 3
- 238000002791 soaking Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 231100000086 high toxicity Toxicity 0.000 description 2
- LJRGBERXYNQPJI-UHFFFAOYSA-M sodium;3-nitrobenzenesulfonate Chemical compound [Na+].[O-][N+](=O)C1=CC=CC(S([O-])(=O)=O)=C1 LJRGBERXYNQPJI-UHFFFAOYSA-M 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- 239000004734 Polyphenylene sulfide Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 238000010329 laser etching Methods 0.000 description 1
- 238000010330 laser marking Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- -1 methylbenzotriazole 2-sulfenyl benzimidazole Chemical compound 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007788 roughening Methods 0.000 description 1
- 238000005488 sandblasting Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
-
- 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
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/10—Etching compositions
- C23F1/14—Aqueous compositions
- C23F1/16—Acidic compositions
- C23F1/28—Acidic compositions for etching iron group metals
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
Abstract
The invention discloses an environment-friendly deplating agent, a preparation method and a use method thereof, wherein each liter of the environment-friendly deplating agent contains: 20-100 g of sodium persulfate, 100-300 mL of concentrated sulfuric acid, 2-10 g of ferric chloride hexahydrate, 0.005-0.1 g of wetting agent, 1-10 g of imidazole slow release agent and 1-10 g of citric acid, wherein the solvent is water. The environment-friendly deplating agent disclosed by the invention is safe and environment-friendly, has a low use temperature (30-40 ℃), and has the characteristics of clean nickel removal, no corrosion to a substrate and high nickel removal speed; sodium persulfate and ferric chloride hexahydrate are used as main substances for dissolving a nickel layer, and an imidazole slow release agent and citric acid are added, so that copper or copper alloy of a metal base material cannot be corroded while the nickel stripping effect is ensured, and the copper corrosion speed is less than 0.33 mu m/min; in addition, in the production process of products such as the prior printed circuit board, the plastic antenna oscillator and the like, a palladium layer is arranged between the base material and the nickel coating, and the environment-friendly deplating agent disclosed by the invention can be used for removing the palladium layer between the base material and the nickel coating after the nickel coating is removed.
Description
Technical Field
The invention relates to the technical field of deplating agents, in particular to an environment-friendly deplating agent and a preparation method and a use method thereof.
Background
Deplating is a process of removing a coating on the surface of a workpiece, and is an inevitable process in the field of electroplating. The existing deplating method generally comprises two methods: the first is chemical deplating, which is to soak the deplated part in deplating solution and the principle is to remove the plating layer by using a chemical dissolving method; the other method is electrolytic deplating, the deplated parts are placed in a deplating solution for electrolysis, the electrolytic method has weak corrosion to the base material, can recycle certain metals and is beneficial to environmental protection, but needs to provide a power supply and a deplating tank, sometimes needs special hangers, has high one-time investment cost, is only suitable for conductive circuits, cannot use electrolytic deplating for isolated metal circuits, and is not favorable for workshops which are not produced in large scale.
The chemical method for removing the nickel coating at present comprises the following three liquid medicine systems: the cyanide-system chemical deplating solution contains a cyanide-containing compound with high toxicity, which can cause serious pollution to the environment and harm human health; the chemical deplating agent of the sodium m-nitrobenzenesulfonate system has high use temperature, the use temperature is usually 60-70 ℃, the nickel deplating time is long, and in addition, the sodium m-nitrobenzenesulfonate has high toxicity and is not easy to use in large quantity; thirdly, the chemical deplating agent of the sulfuric acid-hydrogen peroxide system has the disadvantages of complicated nickel removing steps, long nickel removing time and high copper etching speed.
Disclosure of Invention
The invention aims to overcome the defects, provides an environment-friendly deplating agent which is safe and environment-friendly, has low use temperature (30-40 ℃), and has the characteristics of clean nickel removal, no corrosion to a substrate and high nickel removal speed; sodium persulfate and ferric chloride hexahydrate are adopted as main substances for dissolving a nickel layer, and an imidazole slow-release agent and citric acid are added, so that a nickel stripping effect is ensured, the nickel stripping speed reaches 0.3 mu m/3 min-0.5 mu m/3min, and meanwhile, copper or copper alloy of a metal base material is also ensured not to be corroded by a stripping solution, the copper corrosion speed is less than 0.33 mu m/min, namely the thickness of corroded copper per minute is less than 0.33 mu m; in addition, the invention also provides a preparation method and a use method of the environment-friendly deplating agent.
In order to achieve the above object, the first aspect of the present invention provides an environment-friendly deplating agent, wherein each liter of the environment-friendly deplating agent comprises: 20-100 g of sodium persulfate, 100-300 mL of concentrated sulfuric acid, 2-10 g of ferric chloride hexahydrate, 0.005-0.1 g of wetting agent, 1-10 g of imidazole slow release agent and 1-10 g of citric acid, wherein the solvent is water.
In the environment-friendly deplating agent, sodium persulfate and ferric chloride hexahydrate are used as main substances for dissolving a nickel layer, and an imidazole slow-release agent is added, so that the nickel deplating effect is ensured, copper or copper alloy on a metal base material is also ensured not to be corroded by deplating solution, the copper corrosion speed is less than 0.33 mu m/min, namely the copper corrosion thickness per minute is less than 0.33 mu m, and citric acid in the environment-friendly deplating agent also has a slow-release effect, so that the copper surface is kept in a bright state; the environment-friendly deplating agent disclosed by the invention is low in use temperature, and can be used for rapidly removing the nickel coating on the surface of metal copper or copper alloy at the temperature of 30-40 ℃; the wetting agent has better wetting effect on small holes and rough surfaces; in addition, the ferric chloride hexahydrate in the environment-friendly deplating agent can also remove a palladium layer between the metal copper or copper alloy and the nickel plating layer.
Preferably, each liter of the environment-friendly deplating agent contains: 30-80 g of sodium persulfate, 150-250 mL of concentrated sulfuric acid, 2-5 g of ferric chloride hexahydrate, 0.01-0.05 g of wetting agent, 2-8 g of imidazole slow release agent and 2-8 g of citric acid, and the solvent is water.
Preferably, each liter of the environment-friendly deplating agent contains: 50g of sodium persulfate, 200mL of concentrated sulfuric acid, 5g of ferric chloride hexahydrate, 0.01g of wetting agent, 5g of imidazole slow-release agent and 5g of citric acid, wherein the solvent is water.
Preferably, the mass fraction of the concentrated sulfuric acid is 98%.
Preferably, the wetting agent is any one of PEG200, PEG600 and PEG 6000.
Preferably, the imidazole slow release agent is benzotriazole, 2-sulfenyl benzimidazole or methylbenzotriazole 2-sulfenyl benzimidazole.
Preferably, the solvent is pure water or tap water.
The environment-friendly deplating agent provided by the invention can adopt pure water as a solvent and also can adopt tap water as a solvent, so that the production cost of the deplating agent is greatly reduced.
The second aspect of the invention provides a preparation method of the environment-friendly deplating agent, which comprises the following steps:
s1, weighing sodium persulfate, concentrated sulfuric acid, ferric chloride hexahydrate, a wetting agent, an imidazole slow-release agent, citric acid and water according to the formula amount;
s2, taking half volume of water, adding concentrated sulfuric acid into the water, stirring and cooling the water to room temperature, adding sodium persulfate, stirring and dissolving the sodium persulfate, adding ferric chloride hexahydrate, stirring and dissolving the ferric chloride hexahydrate, adding a wetting agent, stirring and dissolving the wetting agent, continuously adding a slow-release agent, stirring and dissolving the slow-release agent, adding citric acid, stirring the slow-release agent uniformly, and fixing the volume by using the balance of water to obtain the environment-friendly deplating agent.
The third aspect of the invention provides a use method of the environment-friendly deplating agent, which comprises the following steps: immersing a nickel-plated workpiece into a deplating agent, and performing nickel deplating under the stirring condition; wherein the temperature of the deplating agent is 30-40 ℃.
Preferably, the temperature of the deplating agent is 35 ℃.
Compared with the prior art, the invention has the beneficial effects that:
1. the environment-friendly deplating agent disclosed by the invention is safe and environment-friendly, has a low use temperature (30-40 ℃), and has the characteristics of clean nickel removal, no corrosion to a substrate and high nickel removal speed; sodium persulfate and ferric chloride hexahydrate are used as main substances for dissolving a nickel layer, and an imidazole slow-release agent and citric acid are added, so that a nickel stripping effect is ensured, the nickel stripping speed reaches 0.3 mu m/3 min-0.5 mu m/3min, and simultaneously, copper or copper alloy on a base material is also ensured not to be corroded by a stripping solution, the copper corrosion speed is less than 0.33 mu m/min, namely the thickness of corroded copper per minute is less than 0.33 mu m.
2. In the production process of products such as a printed circuit board, a plastic antenna oscillator and the like, a palladium layer is arranged between a base material and a nickel coating, and after the nickel coating is removed, the palladium layer between the base material and the nickel coating can be removed by the environment-friendly deplating agent (ferric chloride hexahydrate has the function of removing the palladium layer).
3. The preparation method of the environment-friendly deplating agent has the advantages of simple process, convenient operation, wide raw material source and low cost.
Detailed Description
The present invention will be further described with reference to specific embodiments in order to make the technical means, inventive features, objectives and effects of the invention easy to understand.
Example 1
The embodiment discloses an environment-friendly deplating agent, and each liter of the environment-friendly deplating agent contains: 20g of sodium persulfate, 100mL of concentrated sulfuric acid, 2g of ferric chloride hexahydrate, 0.005g of wetting agent, 1g of imidazole slow-release agent and 1g of citric acid, wherein the solvent is water.
The mass fraction of the concentrated sulfuric acid in this example is 98%.
The wetting agent in this example is PEG 200.
The imidazole slow release agent in the embodiment is 2-sulfenyl benzimidazole.
The solvent in this example was pure water.
The preparation method of the environment-friendly deplating agent in the embodiment comprises the following steps:
s1, weighing sodium persulfate, concentrated sulfuric acid, ferric chloride hexahydrate, a wetting agent, an imidazole slow-release agent, citric acid and water according to the formula amount;
s2, taking half volume of water, adding concentrated sulfuric acid into the water, stirring and cooling the water to room temperature, adding sodium persulfate, stirring and dissolving the sodium persulfate, adding ferric chloride hexahydrate, stirring and dissolving the sodium persulfate, adding wetting agent, stirring and dissolving the wetting agent, continuously adding slow-release agent, stirring and dissolving the slow-release agent, adding citric acid, stirring the mixture uniformly, and finally adding the balance of water to a constant volume to obtain the environment-friendly deplating agent.
Example 2
The embodiment discloses an environment-friendly deplating agent, and each liter of the environment-friendly deplating agent contains: 100g of sodium persulfate, 300mL of concentrated sulfuric acid, 10g of ferric chloride hexahydrate, 0.1g of wetting agent, 10g of imidazole slow-release agent and 10g of citric acid, wherein the solvent is water.
The mass fraction of the concentrated sulfuric acid in this example is 98%.
The wetting agent in this example is any of PEG 600.
The imidazole slow release agent in the embodiment is 2-sulfenyl benzimidazole.
The solvent in this example was pure water.
The preparation method of the environment-friendly deplating agent in the embodiment comprises the following steps:
s1, weighing sodium persulfate, concentrated sulfuric acid, ferric chloride hexahydrate, a wetting agent, an imidazole slow-release agent, citric acid and water according to the formula amount;
s2, taking half volume of water, adding concentrated sulfuric acid into the water, stirring and cooling the water to room temperature, adding sodium persulfate, stirring and dissolving the sodium persulfate, adding ferric chloride hexahydrate, stirring and dissolving the ferric chloride hexahydrate, adding a wetting agent, stirring and dissolving the wetting agent, continuously adding a slow-release agent, stirring and dissolving the slow-release agent, adding citric acid, stirring the slow-release agent uniformly, and fixing the volume by using the balance of water to obtain the environment-friendly deplating agent.
Example 3
The embodiment discloses an environment-friendly deplating agent, and each liter of the environment-friendly deplating agent contains: 30g of sodium persulfate, 150mL of concentrated sulfuric acid, 2g of ferric chloride hexahydrate, 0.01g of wetting agent, 2g of imidazole slow-release agent and 2g of citric acid, wherein the solvent is water.
The mass fraction of the concentrated sulfuric acid in this example is 98%.
The wetting agent in this example is PEG 6000.
The imidazole slow release agent in the embodiment is 2-sulfenyl benzimidazole.
The solvent in this example was pure water.
The preparation method of the environment-friendly deplating agent in the embodiment comprises the following steps:
s1, weighing sodium persulfate, concentrated sulfuric acid, ferric chloride hexahydrate, a wetting agent, an imidazole slow-release agent, citric acid and water according to the formula amount;
s2, taking half volume of water, adding concentrated sulfuric acid into the water, stirring and cooling the water to room temperature, adding sodium persulfate, stirring and dissolving the sodium persulfate, adding ferric chloride hexahydrate, stirring and dissolving the ferric chloride hexahydrate, adding a wetting agent, stirring and dissolving the wetting agent, continuously adding a slow-release agent, stirring and dissolving the slow-release agent, adding citric acid, stirring the slow-release agent uniformly, and fixing the volume by using the balance of water to obtain the environment-friendly deplating agent.
Example 4
The embodiment discloses an environment-friendly stripping agent, wherein each liter of the environment-friendly stripping agent contains: 80g of sodium persulfate, 250mL of concentrated sulfuric acid, 5g of ferric chloride hexahydrate, 0.05g of wetting agent, 8g of imidazole slow-release agent and 8g of citric acid, wherein the solvent is water.
The mass fraction of the concentrated sulfuric acid in this example is 98%.
The wetting agent in this example is PEG 200.
The imidazole slow release agent in the embodiment is 2-sulfenyl benzimidazole.
The solvent in this example was pure water.
The preparation method of the environment-friendly deplating agent in the embodiment comprises the following steps:
s1, weighing sodium persulfate, concentrated sulfuric acid, ferric chloride hexahydrate, a wetting agent, an imidazole slow-release agent, citric acid and water according to the formula amount;
s2, taking half volume of water, adding concentrated sulfuric acid into the water, stirring and cooling the water to room temperature, adding sodium persulfate, stirring and dissolving the sodium persulfate, adding ferric chloride hexahydrate, stirring and dissolving the ferric chloride hexahydrate, adding a wetting agent, stirring and dissolving the wetting agent, continuously adding a slow-release agent, stirring and dissolving the slow-release agent, adding citric acid, stirring the slow-release agent uniformly, and fixing the volume by using the balance of water to obtain the environment-friendly deplating agent.
Example 5
The embodiment discloses an environment-friendly deplating agent, and each liter of the environment-friendly deplating agent contains: 50g of sodium persulfate, 200mL of concentrated sulfuric acid, 5g of ferric chloride hexahydrate, 0.01g of wetting agent, 5g of imidazole slow-release agent and 5g of citric acid, wherein the solvent is water.
The mass fraction of the concentrated sulfuric acid in this example is 98%.
The wetting agent in this example is PEG 200.
The imidazole slow release agent in the embodiment is 2-sulfenyl benzimidazole.
The solvent in this example was pure water.
The preparation method of the environment-friendly deplating agent in the embodiment comprises the following steps:
s1, weighing sodium persulfate, concentrated sulfuric acid, ferric chloride hexahydrate, a wetting agent, an imidazole slow-release agent, citric acid and water according to the formula amount;
s2, taking half volume of water, adding concentrated sulfuric acid into the water, stirring and cooling the water to room temperature, adding sodium persulfate, stirring and dissolving the sodium persulfate, adding ferric chloride hexahydrate, stirring and dissolving the ferric chloride hexahydrate, adding a wetting agent, stirring and dissolving the wetting agent, continuously adding a slow-release agent, stirring and dissolving the slow-release agent, adding citric acid, stirring the slow-release agent uniformly, and fixing the volume by using the balance of water to obtain the environment-friendly deplating agent.
Example 6
The embodiment discloses an environment-friendly deplating agent, and each liter of the environment-friendly deplating agent contains: 50g of sodium persulfate, 200mL of concentrated sulfuric acid, 5g of ferric chloride hexahydrate, 0.01g of wetting agent, 5g of imidazole slow-release agent and 5g of citric acid, wherein the solvent is water.
The mass fraction of the concentrated sulfuric acid in this example is 98%.
The wetting agent in this example is PEG 200.
The imidazole slow release agent in the embodiment is 2-sulfenyl benzimidazole.
The solvent in this example was tap water.
The preparation method of the environment-friendly deplating agent in the embodiment comprises the following steps:
s1, weighing sodium persulfate, concentrated sulfuric acid, ferric chloride hexahydrate, a wetting agent, an imidazole slow-release agent, citric acid and water according to the formula amount;
s2, taking half volume of water, adding concentrated sulfuric acid into the water, stirring and cooling the water to room temperature, adding sodium persulfate, stirring and dissolving the sodium persulfate, adding ferric chloride hexahydrate, stirring and dissolving the ferric chloride hexahydrate, adding a wetting agent, stirring and dissolving the wetting agent, continuously adding a slow-release agent, stirring and dissolving the slow-release agent, adding citric acid, stirring the slow-release agent uniformly, and fixing the volume by using the balance of water to obtain the environment-friendly deplating agent.
Comparative example
The comparative example discloses a sulfuric acid-hydrogen peroxide system deplating agent, and each liter of the sulfuric acid-hydrogen peroxide system deplating agent contains: 98% and 100mL of sulfuric acid (the mass fraction of the sulfuric acid is 98%), 30% and 100mL of hydrogen peroxide (the mass fraction of the hydrogen peroxide is 30%), and the solvent is pure water. The solvent in the comparative example can only be pure water, because if the solvent is tap water, under an acidic condition, the chloride ions of the tap water can inhibit the oxidation of the hydrogen peroxide and influence the nickel removing effect of the hydrogen peroxide.
Test examples
The stripping agents in examples 1-6 and comparative example are used to strip the nickel layer and palladium layer in the preparation process of the plastic antenna element, and then the stripping solution in examples 1-6 and comparative example is used to test the effect of stripping the nickel coating.
The preparation process of the plastic antenna oscillator comprises the following steps:
(1) and forming: polyphenylene sulfide is subjected to injection molding to obtain a plastic antenna oscillator body with a preset structure;
(2) and cleaning: cleaning the plastic antenna oscillator body in an oil-removing wetting agent, removing dust and oil stains on the surface of the plastic antenna oscillator body, and increasing the wettability of the surface of the plastic antenna oscillator body (the cleaning time is 3min, the cleaning temperature is 50 ℃, and the mass fraction of the oil-yielding wetting agent is 5%);
(3) and roughening the sand blasting surface: the roughness of the surface of the plastic antenna oscillator body is increased;
(4) pre-dipping: soaking the plastic antenna oscillator in hydrochloric acid with the mass fraction of 20% for 1min at room temperature, and removing alkaline substances on the surface of the plastic antenna oscillator body;
(5) and palladium activation: soaking the pre-soaked plastic antenna oscillator body in palladium water with the palladium content of 50ppm for 3min at 30 ℃;
(6) and peptizing: soaking the plastic antenna oscillator body activated by palladium in sulfuric acid with the mass fraction of 1% for 2min at room temperature;
(7) and nickel plating: carrying out chemical nickel plating treatment on the dispergated plastic antenna oscillator body to form a nickel plating layer on the surface of the oscillator body; the chemical nickel plating time is 3min, and the thickness is 0.3-0.5 μm;
(8) forming a separation line on the nickel coating through laser etching, and marking out a region of a preset circuit pattern layer;
(9) and copper plating: plating a copper layer (the thickness of the copper layer is 8 mu m) on the area of the preset circuit pattern layer;
(10) and nickel removing: removing the nickel layer except the preset circuit pattern layer region.
The deplating operation in the step (10) was performed by using the deplating agents in examples 1 to 6 and comparative example, respectively, on 7 plastic antenna element bodies each having been plated with copper.
When the deplating solution in the embodiments 1 to 6 is adopted for nickel deplating treatment, the plastic antenna oscillator product which is plated with copper is placed in a nickel deplating agent, and nickel deplating is carried out under the stirring condition; wherein the temperature of the deplating agent is 35 ℃.
When the deplating treatment in the comparative example 1 is also carried out, the plastic antenna oscillator product which finishes copper plating is placed in a deplating agent, and the nickel is removed under the stirring condition; wherein the temperature of the deplating agent is normal temperature.
In the test process, stirring is continued after the nickel layer is removed, and palladium removal is carried out. The nickel layer on the plastic antenna oscillator body is grey, the palladium layer is black, the substrate layer is white, and the nickel layer or the palladium layer can be rapidly and accurately observed through naked eyes or a microscope to determine whether the nickel layer or the palladium layer is removed completely.
The only difference between example 5 and example 6 is that the solvent in example 5 is pure water and the solvent in example 6 is tap water.
Recording the time required by complete removal of the nickel coating in the nickel removing process as the nickel removing time;
and (3) measuring the thickness of the copper layer by an X-ray coating analyzer before the operation of the step (10), after the deplating operation is finished, measuring the thickness of the copper layer by the X-ray coating analyzer, and calculating the copper etching speed, wherein the copper etching speed is equal to the copper etching thickness/nickel removing time.
Specific process parameters and nickel and palladium removing results when the stripping agent of examples 1 to 6 and the stripping agent of comparative example were used for the stripping operation in step (10) in this test example are shown in table 1.
Wherein, the evaluation standard of the cleanliness of nickel stripping is as follows: and observing whether the nickel coating on the surface of the plastic antenna oscillator body is completely removed, whether the nickel coating is residual or not, continuously stirring to remove palladium after nickel removal is finished, and observing whether the palladium layer on the plastic antenna oscillator body is removed or not.
TABLE 1
As can be seen from Table 1, the environment-friendly deplating agent disclosed by the invention is safe and environment-friendly, has a low use temperature (30-40 ℃), and has the characteristics of clean nickel removal, no corrosion to a substrate and high nickel removal speed; sodium persulfate and ferric chloride hexahydrate are used as main substances for dissolving a nickel layer, and an imidazole slow release agent and citric acid are added, so that the nickel stripping effect is ensured, the nickel stripping speed reaches 0.3 mu m/3 min-0.5 mu m/3min, and simultaneously, copper or copper alloy is prevented from being corroded by a stripping solution, the copper corrosion speed is less than 0.33 mu m/min, namely the thickness of corroded copper per minute is less than 0.33 mu m. In addition, ferric chloride hexahydrate in the environment-friendly deplating agent has the function of removing the palladium layer.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (10)
1. The environment-friendly deplating agent is characterized in that each liter of the environment-friendly deplating agent contains: 20-100 g of sodium persulfate, 100-300 mL of concentrated sulfuric acid, 2-10 g of ferric chloride hexahydrate, 0.005-0.1 g of wetting agent, 1-10 g of imidazole slow release agent and 1-10 g of citric acid, wherein the solvent is water.
2. The environment-friendly deplating agent according to claim 1, wherein each liter of the environment-friendly deplating agent comprises: 30-80 g of sodium persulfate, 150-250 mL of concentrated sulfuric acid, 2-5 g of ferric chloride hexahydrate, 0.01-0.05 g of wetting agent, 2-8 g of imidazole slow release agent and 2-8 g of citric acid, wherein the solvent is water.
3. The environment-friendly deplating agent according to claim 1, wherein each liter of the environment-friendly deplating agent comprises: 50g of sodium persulfate, 200mL of concentrated sulfuric acid, 5g of ferric chloride hexahydrate, 0.01g of wetting agent, 5g of imidazole slow-release agent and 5g of citric acid, wherein the solvent is water.
4. The environment-friendly deplating agent according to claim 1, wherein the mass fraction of the concentrated sulfuric acid is 98%.
5. The environment-friendly deplating agent according to claim 1, wherein the wetting agent is any one of PEG200, PEG600 and PEG 6000.
6. The environment-friendly deplating agent as claimed in claim 1, wherein the imidazole slow-release agent is benzotriazole, 2-sulfanylbenzimidazole or methylbenzotriazole.
7. The environment-friendly deplating agent according to claim 1, wherein the solvent is pure water or tap water.
8. The preparation method of the environment-friendly deplating agent as claimed in any one of claims 1 to 7, which is characterized by comprising the following steps:
s1, weighing sodium persulfate, concentrated sulfuric acid, ferric chloride hexahydrate, a wetting agent, an imidazole slow-release agent, citric acid and water according to the formula amount;
s2, taking half volume of water, adding concentrated sulfuric acid into the water, stirring and cooling the water to room temperature, adding sodium persulfate, stirring and dissolving the sodium persulfate, adding ferric chloride hexahydrate, stirring and dissolving the ferric chloride hexahydrate, adding a wetting agent, stirring and dissolving the wetting agent, continuously adding a slow-release agent, stirring and dissolving the slow-release agent, adding citric acid, stirring the slow-release agent uniformly, and fixing the volume by using the balance of water to obtain the environment-friendly deplating agent.
9. The use method of the environment-friendly deplating agent as claimed in any one of claims 1 to 7, is characterized by comprising the following steps: immersing a nickel-plated workpiece into a deplating agent, and performing nickel deplating under the stirring condition; wherein the temperature of the deplating agent is 30-40 ℃.
10. The use method of the environment-friendly deplating agent according to claim 9, wherein the temperature of the deplating agent is 35 ℃.
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