CN113755911A - Cyanide-free silver-plated anti-tarnish agent and application thereof - Google Patents
Cyanide-free silver-plated anti-tarnish agent and application thereof Download PDFInfo
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- CN113755911A CN113755911A CN202111157736.6A CN202111157736A CN113755911A CN 113755911 A CN113755911 A CN 113755911A CN 202111157736 A CN202111157736 A CN 202111157736A CN 113755911 A CN113755911 A CN 113755911A
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- 238000007747 plating Methods 0.000 claims abstract description 112
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 102
- 229910052709 silver Inorganic materials 0.000 claims abstract description 102
- 239000004332 silver Substances 0.000 claims abstract description 102
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 58
- 238000002845 discoloration Methods 0.000 claims abstract description 32
- -1 sulfuric acid compound Chemical class 0.000 claims abstract description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims abstract description 15
- 239000002904 solvent Substances 0.000 claims abstract description 15
- 229940124530 sulfonamide Drugs 0.000 claims abstract description 15
- GPTONYMQFTZPKC-UHFFFAOYSA-N sulfamethoxydiazine Chemical compound N1=CC(OC)=CN=C1NS(=O)(=O)C1=CC=C(N)C=C1 GPTONYMQFTZPKC-UHFFFAOYSA-N 0.000 claims abstract description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000004359 castor oil Substances 0.000 claims abstract description 8
- 235000019438 castor oil Nutrition 0.000 claims abstract description 8
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 claims abstract description 8
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims abstract description 6
- XYXNTHIYBIDHGM-UHFFFAOYSA-N ammonium thiosulfate Chemical compound [NH4+].[NH4+].[O-]S([O-])(=O)=S XYXNTHIYBIDHGM-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052938 sodium sulfate Inorganic materials 0.000 claims abstract description 6
- 235000011152 sodium sulphate Nutrition 0.000 claims abstract description 6
- 229960002229 sulfametoxydiazine Drugs 0.000 claims abstract description 5
- 229960000551 sulfacetamide sodium Drugs 0.000 claims abstract description 4
- IHCDKJZZFOUARO-UHFFFAOYSA-M sulfacetamide sodium Chemical compound O.[Na+].CC(=O)[N-]S(=O)(=O)C1=CC=C(N)C=C1 IHCDKJZZFOUARO-UHFFFAOYSA-M 0.000 claims abstract description 4
- QWCJHSGMANYXCW-UHFFFAOYSA-N sulfaphenazole Chemical compound C1=CC(N)=CC=C1S(=O)(=O)NC1=CC=NN1C1=CC=CC=C1 QWCJHSGMANYXCW-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229960004818 sulfaphenazole Drugs 0.000 claims abstract description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 24
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 24
- BRWIZMBXBAOCCF-UHFFFAOYSA-N hydrazinecarbothioamide Chemical compound NNC(N)=S BRWIZMBXBAOCCF-UHFFFAOYSA-N 0.000 claims description 12
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 12
- 239000001508 potassium citrate Substances 0.000 claims description 12
- 229960002635 potassium citrate Drugs 0.000 claims description 12
- QEEAPRPFLLJWCF-UHFFFAOYSA-K potassium citrate (anhydrous) Chemical compound [K+].[K+].[K+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O QEEAPRPFLLJWCF-UHFFFAOYSA-K 0.000 claims description 12
- 235000011082 potassium citrates Nutrition 0.000 claims description 12
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 12
- 230000007797 corrosion Effects 0.000 abstract description 3
- 238000005260 corrosion Methods 0.000 abstract description 3
- 238000003860 storage Methods 0.000 abstract description 3
- 239000011248 coating agent Substances 0.000 description 30
- 238000000576 coating method Methods 0.000 description 30
- 238000009713 electroplating Methods 0.000 description 29
- 239000010410 layer Substances 0.000 description 29
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 10
- 238000002425 crystallisation Methods 0.000 description 10
- 230000008025 crystallization Effects 0.000 description 10
- 238000001514 detection method Methods 0.000 description 10
- 238000000034 method Methods 0.000 description 9
- 239000011247 coating layer Substances 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 239000003223 protective agent Substances 0.000 description 7
- 238000002474 experimental method Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000004876 x-ray fluorescence Methods 0.000 description 5
- 238000005494 tarnishing Methods 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- NHPBNQZEXDUUIO-UHFFFAOYSA-N [Ag+].[Ag+].[O-][N+]([O-])=O.[O-][N+]([O-])=O Chemical compound [Ag+].[Ag+].[O-][N+]([O-])=O.[O-][N+]([O-])=O NHPBNQZEXDUUIO-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- FYDGRHCYVIUOSL-UHFFFAOYSA-L S(=O)([O-])[O-].[Ag+2] Chemical compound S(=O)([O-])[O-].[Ag+2] FYDGRHCYVIUOSL-UHFFFAOYSA-L 0.000 description 1
- 206010052428 Wound Diseases 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- GTBQRHOYAUGRPV-UHFFFAOYSA-N methanesulfonic acid;silver Chemical compound [Ag].CS(O)(=O)=O GTBQRHOYAUGRPV-UHFFFAOYSA-N 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000001579 optical reflectometry Methods 0.000 description 1
- QBTNYCSQBPHLKP-UHFFFAOYSA-L potassium;silver;diiodide Chemical compound [K+].[Ag+].[I-].[I-] QBTNYCSQBPHLKP-UHFFFAOYSA-L 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- VXHVELPLHCCGQL-UHFFFAOYSA-N pyridine-3-carboxylic acid;silver Chemical compound [Ag].OC(=O)C1=CC=CN=C1 VXHVELPLHCCGQL-UHFFFAOYSA-N 0.000 description 1
- ZNFFXFIEWVNCJO-UHFFFAOYSA-N pyrrolidine-2,5-dione;silver Chemical compound [Ag].O=C1CCC(=O)N1 ZNFFXFIEWVNCJO-UHFFFAOYSA-N 0.000 description 1
- NGBNXJUWQPLNGM-UHFFFAOYSA-N silver;azane Chemical compound N.[Ag+] NGBNXJUWQPLNGM-UHFFFAOYSA-N 0.000 description 1
- OYNOOANKSLJSCV-UHFFFAOYSA-N silver;thiourea Chemical compound [Ag].NC(N)=S OYNOOANKSLJSCV-UHFFFAOYSA-N 0.000 description 1
- DHCDFWKWKRSZHF-UHFFFAOYSA-N sulfurothioic S-acid Chemical compound OS(O)(=O)=S DHCDFWKWKRSZHF-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/46—Electroplating: Baths therefor from solutions of silver
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electroplating And Plating Baths Therefor (AREA)
Abstract
The invention relates to a cyanide-free silver plating anti-tarnish agent, which comprises the following components in percentage by mass: 0.1-2g/L of sulfuric acid compound, 10-25g/L of sulfonamide compound and water as solvent. Wherein the sulfuric acid compound is one or more of castor oil sodium sulfate, sodium dodecyl sulfate or ammonium thiosulfate. Wherein the sulfonamide compound is one or more of 2-p-aminobenzenesulfonamido-5-methoxyl pyrimidine, sulfamethoxydiazine, sulfacetamide sodium or sulfaphenazole. The silver plating anti-discoloration agent improves the anti-discoloration performance of silver-plated parts, is particularly remarkable in improving the corrosion resistance of the silver-plated parts, reduces the storage cost of the silver-plated parts, and can be widely applied to the technical field of silver plating.
Description
Technical Field
The invention belongs to the technical field of electroplating, and relates to a cyanide-free silver-plated anti-tarnish agent and application thereof.
Background
Electroplating is a process of plating a thin layer of other metals or alloys on the surface of some metals by using the principle of electrolysis, and is a process of attaching a layer of metal film on the surface of a metal or other material workpiece by using the action of electrolysis so as to play a role in preventing metal oxidation and also play a role in improving wear resistance, conductivity, light reflection, corrosion resistance and the like. Silver is a noble metal with silvery white color, malleability, plasticity and light reflecting ability, and is one of the most widely used noble metals due to its excellent performance and relatively low cost. Silver has the best electrical conductivity among all metals, and has good thermal conductivity, ductility, light reflectivity, corrosion resistance and welding performance, and the silver coating has excellent electrical conductivity, decoration, weldability and lower contact resistance, and is widely applied and in great demand in the industrial fields of aviation, electronics, communication and the like. The traditional silver plating adopts a cyanide system containing high toxicity, the total content of cyanide in plating solution of the system reaches 100-200 g/L, the content of cyanide in washing water after plating is extremely high, 0.05 g of cyanide can kill people, wounds are poisoned by contacting the cyanide immediately, the cyanide is greatly safe in use and transportation, and the cyanide has great harm to human and environment historically; the research of the cyanide-free silver plating process originates from the fifties of the last century, the process is widely applied in industrial production at present, the stability, the dispersion capacity, the deep plating capacity and the like of the plating solution completely reach the cyanide process level, the appearance of the plating layer is equivalent to the cyanide level, but the anti-discoloration performance of the plating layer is poorer than that of the cyanide process, the phenomenon that the plating layer is placed in the atmospheric environment and the cyanide-free silver plating layer is not discolored for about 200 days is mainly reflected, the cyanide-free silver plating layer can only be discolored for about 60 days at present, the important significance is achieved for improving the anti-discoloration performance of the existing cyanide-free silver plating layer through research, the silver plating layer is ensured not discolored in about 200 days in the atmospheric environment, and the popularization and application of the cyanide-free silver plating process are greatly promoted through the success of the research result.
Disclosure of Invention
In view of the above, the present invention provides an anti-tarnishing agent for cyanide-free silver plating and a cyanide-free silver plating solution containing the anti-tarnishing agent.
In order to achieve the purpose, the invention provides the following technical scheme:
1. the anti-tarnish agent for cyanide-free silver plating comprises the following components: the sulfuric acid compound is one or more of castor oil sodium sulfate, sodium dodecyl sulfate and ammonium thiosulfate; the sulfonamide compound is one or more of 2-p-aminobenzene sulfonamide-5-methoxyl pyrimidine, sulfamethoxydiazine, sulfacetamide sodium and sulfaphenazole.
Further, the silver-plated anti-tarnish agent comprises the following components in percentage by mass: 0.1-2g/L of sulfuric acid compound, 10-25g/L of sulfonamide compound and water as solvent.
Further, the silver-plated anti-tarnish agent comprises the following components in percentage by mass: 0.5-1.5g/L of sulfuric acid compound, 15-20g/L of sulfonamide compound and water as solvent.
Further, the silver-plated anti-tarnish agent comprises the following components in percentage by mass: sodium dodecyl sulfate 1g/L, 2-sulfanilamide-5-methoxypyrimidine 20g/L, and water as solvent.
2. The application of the anti-discoloring agent in cyanide-free silver plating comprises the following components: the sulfuric acid compound is one or more of castor oil sodium sulfate, sodium dodecyl sulfate and ammonium thiosulfate; the sulfonamide compound is one or more of 2-p-aminobenzene sulfonamide-5-methoxyl pyrimidine, sulfamethoxydiazine, sulfacetamide sodium and sulfaphenazole.
Further, the silver-plated anti-tarnish agent comprises the following components in percentage by mass: 0.1-2g/L of sulfuric acid compound, 10-25g/L of sulfonamide compound and water as solvent.
Further, the silver-plated anti-tarnish agent comprises the following components in percentage by mass: 0.5-1.5g/L of sulfuric acid compound, 15-20g/L of sulfonamide compound and water as solvent.
Further, the silver-plated anti-tarnish agent comprises the following components in percentage by mass: sodium dodecyl sulfate 1g/L, 2-sulfanilamide-5-methoxypyrimidine 20g/L, and water as solvent.
3. The cyanide-free silver plating solution comprises the following components in percentage by mass:
sulfate compound 3-60mg/L
Sulfonamide compound 300-750mg/L
Silver nitrate 25-35g/L
Potassium carbonate 30-60g/L
45-80g/L potassium citrate
0.1-0.8g/L of thiosemicarbazide.
Further, the cyanide-free silver plating solution comprises the following components in percentage by mass: 30mg/L of sodium dodecyl sulfate, 600mg/L of 2-p-aminobenzenesulfonamido-5-methoxypyrimidine, 35g/L of silver nitrate, 40g/L of potassium carbonate, 60g/L of potassium citrate and 0.5g/L of thiosemicarbazide.
The invention has the beneficial effects that: the anti-tarnishing agent for cyanide-free silver plating can improve the anti-tarnishing performance of plated workpieces, greatly prolongs the storage and use time of the silver-plated workpieces in atmospheric environment, and reduces the cost compared with the use of the silver-plated workpieces. According to the invention, a large number of experiments show that sulfuric acid compounds such as castor oil sodium sulfate, sodium dodecyl sulfate, ammonium thiosulfate and the like can promote a silver layer to form larger crystal grains in the electroplating process, and the anti-discoloration performance of the silver layer is improved; the further combination of sulfonamide compounds can improve the connectivity among the larger grains and reduce the porosity. The two components complement each other under a proper concentration to avoid the discoloration of the bottom layer metal due to oxidation, and the discoloration resistance of the whole plating layer is integrally enhanced. The anti-discoloration agent is simple and non-toxic, has low actual dosage and concentration and low cost, and is suitable for mass industrial production. The invention solves the problem that the cyanide-free silver plating layer is easy to discolor, reduces the storage cost of cyanide-free silver plating products, thereby promoting the development of cyanide-free electroplating and being widely applied to the field of cyanide-free silver plating processes.
Drawings
In order to make the object, technical scheme and beneficial effect of the invention more clear, the invention provides the following drawings for explanation:
FIG. 1 is a graph showing the test patterns of the respective samples in example 1;
FIG. 2 is a graph showing the results of testing each sample in example 2;
FIG. 3 is a graph showing the results of testing each sample in example 3;
FIG. 4 is a graph showing the results of testing each sample in example 4;
FIG. 5 is a graph showing the results of testing each sample in example 5.
Detailed Description
The preferred embodiments of the present invention will be described in detail below. The experimental procedures, in which specific conditions are not specified in the examples, are generally carried out under conventional conditions or under conditions recommended by the manufacturers.
Example 1
The cyanide-free silver plating anti-discoloration agent comprises the following components in percentage by mass:
sodium dodecyl sulfate 0.5g/L
2-p-aminobenzenesulfonamido-5-methoxypyrimidine 15g/L
The solvent is deionized water.
The preparation method of the cyanide-free silver plating anti-tarnish agent comprises the following steps:
1) preparing a sodium dodecyl sulfate solution: dissolving 0.5g of sodium dodecyl sulfate in 200ml of warm deionized water at 50 ℃, and stirring to completely dissolve until the solution is clear for later use;
2) preparing a solution of 2-p-aminobenzenesulfonamido-5-methoxypyrimidine: dissolving 15g of 2-p-aminobenzenesulfonamido-5-methoxypyrimidine in 500ml of deionized water, slowly adding 50% of analytically pure potassium hydroxide solution until the pH value is 10-13, promoting dissolution, and stirring to completely dissolve until the solution is clear for later use.
3) Preparing a cyanide-free silver plating anti-discoloration agent: and (2) slowly adding the sodium dodecyl sulfate prepared in the step (1) into the 2-p-aminobenzenesulfonamide-5-methoxypyrimidine solution prepared in the step (2), then using deionized water to fix the volume to 1L, and continuously stirring to uniformly mix the materials.
Performance detection
The cyanide-free silver plating prepared in example 1 was appliedAdding 30ml of anti-color-changing agent into 1L of cyanide-free silver plating solution, and placing the workpiece at 0.5A/dm2And after electroplating for 2 hours at 40 ℃, taking out the electroplated workpiece, measuring the thickness of the silver coating by using an X-ray fluorescence instrument, and observing the color change time in an atmospheric environment.
The cyanide-free silver plating solution used in this embodiment is: 30g/L of silver nitrate, 50g/L of potassium carbonate, 70g/L of potassium citrate and 0.6g/L of thiosemicarbazide.
The cyanide-free silver plating solution system applicable to the cyanide-free silver plating anti-discoloration agent is wide, such as thiosulfate silver plating, sulfite silver plating, methanesulfonic acid silver plating, succinimide silver plating, nicotinic acid silver plating, imidodisulfonic acid ammonium silver plating (N-S silver plating), thiourea silver plating, potassium iodide silver plating and silver nitrate silver plating. The embodiment of the invention mainly uses a silver nitrate silver plating system. The cyanide-free silver plating solution comprises: 25-35g/L of silver nitrate, 30-60g/L of potassium carbonate, 45-80g/L of potassium citrate and 0.1-0.8g/L of thiosemicarbazide. Preferably: 28-32g/L of silver nitrate, 40-45g/L of potassium carbonate, 60-70g/L of potassium citrate and 0.3-0.5g/L of thiosemicarbazide.
And electroplating the same workpiece by using cyanide-free silver plating solution without the anti-color-changing agent under the same condition. The thickness of the silver plating layer was measured using an X-ray fluorometer, and the silver plating layer was left in the atmospheric environment to observe the discoloration time.
The result of the detection
The thickness of the silver coating of the electroplating workpiece added with the cyanide-free silver plating anti-discoloration agent is 25 mu m, the crystallization of the coating is fine and bright, the coating does not discolor after being placed in an atmospheric environment for 200 days (see A in the attached figure 1), and the coating slightly yellows after being placed in an atmospheric environment for 250 days (see B in the attached figure 1).
The thickness of the silver coating of the electroplating workpiece without the cyanide-free silver plating anti-discoloration agent is 24 mu m, the crystallization of the coating is fine and bright, and the coating turns yellow after being placed in the atmospheric environment for 65 days (see C in the attached figure 1).
Example 2
The silver plating anti-discoloration agent of the embodiment has the following concentration ratio of components:
sodium dodecyl sulfate 1g/L
2-p-aminobenzenesulfonamido-5-methoxypyrimidine 20g/L
The solvent is deionized water.
The preparation method of the cyanide-free silver plating anti-tarnish agent is the same as that of the example 1, except that the amount of each component is calculated according to the mixture ratio.
Performance detection
30ml of the cyanide-free silver plating anti-discoloration agent prepared in example 2 was added to 1L of cyanide-free silver plating solution, and the work piece was set at 0.5A/dm2And after electroplating for 2 hours at 40 ℃, taking out the plated workpiece, treating the workpiece by using a protective agent, drying the workpiece, measuring the thickness of the silver plating layer by using an X-ray fluorescence instrument, and placing the workpiece in an atmospheric environment to wait for a natural color change experiment. The cyanide-free silver plating solution used in this embodiment is: 35g/L of silver nitrate, 40g/L of potassium carbonate, 60g/L of potassium citrate and 0.5g/L of thiosemicarbazide.
And electroplating the same workpiece by using cyanide-free silver plating solution without the anti-color-changing agent under the same condition. After electroplating, the coating is treated by a protective agent and then dried, and then the coating is placed in an atmospheric environment to observe the discoloration time.
The result of the detection
The thickness of the silver coating of the electroplating workpiece added with the cyanide-free silver plating anti-discoloration agent prepared in the example 2 is 26 mu m, the crystallization of the coating is fine and bright, the coating does not discolor after being placed in an atmospheric environment for 204 days (see A in the attached figure 2), and the coating slightly yellows after being placed for 252 days (see B in the attached figure 2).
The thickness of the silver coating of the electroplating workpiece without the cyanide-free silver plating anti-discoloration agent is 22 mu m, the crystallization of the coating is fine and bright, and the coating is yellow after being placed in the atmospheric environment for 52 days (see C in the attached figure 2).
Example 3
The silver plating anti-discoloration agent of the embodiment has the following concentration ratio of components:
castor oil sodium sulfate 0.5g/L
Sulfamidoyl sodium 5g/L
Sulfabenazole 5g/L
The solvent is deionized water.
The preparation method of the cyanide-free silver plating anti-tarnish agent is the same as that of the example 1, except that the amount of each component is calculated according to the mixture ratio.
Performance detection
30ml of the cyanide-free silver plating anti-tarnish agent prepared in example 3 was added to 1L of cyanide-free silver plating solution, and the work piece was placed therein at 0.5A/dm2And after electroplating for 2 hours at 40 ℃, taking out the plated workpiece, treating the workpiece by using a protective agent, drying the workpiece, measuring the thickness of the silver plating layer by using an X-ray fluorescence instrument, and placing the workpiece in an atmospheric environment to wait for a natural color change experiment. The cyanide-free silver plating solution used in this embodiment is: 30g/L of silver nitrate, 60g/L of potassium carbonate, 80g/L of potassium citrate and 0.8g/L of thiosemicarbazide.
And electroplating the same workpiece by using cyanide-free silver plating solution without the anti-color-changing agent under the same condition. After electroplating, the coating is treated by a protective agent and then dried, and then the coating is placed in an atmospheric environment to observe the discoloration time.
The result of the detection
The thickness of the silver plating layer of the electroplating workpiece added with the cyanide-free silver plating anti-discoloration agent prepared in the example 3 is 28 microns, the plating layer is fine and bright in crystallization, the plating layer is not discolored after being placed in an atmospheric environment for 206 days (see A in the attached figure 3), and the plating layer is slightly yellowed after being placed for 256 days (see B in the attached figure 3).
The thickness of the silver coating of the electroplating workpiece without the cyanide-free silver plating anti-discoloration agent is 23 mu m, the crystallization of the coating is fine and bright, and the coating turns yellow after being placed in the atmospheric environment for 56 days (see C in the attached figure 3).
Example 4
The silver plating anti-discoloration agent of the embodiment has the following concentration ratio of components:
sodium castor oil sulfate 1g/L
Ammonium thiosulfate 1g/L
Sulfamethoxydiazine 25g/L
The solvent is deionized water.
The preparation method of the cyanide-free silver plating anti-tarnish agent is the same as that of the example 1, except that the amount of each component is calculated according to the mixture ratio.
Performance detection
30ml of the cyanide-free silver plating anti-tarnish agent prepared in example 4 was added to 1L of cyanide-free silver plating solution, and the work piece was placed therein at 0.5A/dm2Electroplating for 2 hours at 40 ℃, taking out the plated workpiece, and treating the workpiece with a protective agentDrying, measuring the thickness of the silver plating layer by using an X-ray fluorescence instrument, and placing in an atmospheric environment to wait for a natural color change experiment. The cyanide-free silver plating solution used in this embodiment is: 28g/L of silver nitrate, 40g/L of potassium carbonate, 55g/L of potassium citrate and 0.6g/L of thiosemicarbazide.
And electroplating the same workpiece by using cyanide-free silver plating solution without the anti-color-changing agent under the same condition. After electroplating, the coating is treated by a protective agent and then dried, and then the coating is placed in an atmospheric environment to observe the discoloration time.
The result of the detection
The thickness of the silver coating layer of the electroplating workpiece added with the cyanide-free silver plating anti-discoloration agent prepared in the example 4 is 24 mu m, the crystallization of the coating layer is fine and bright, the coating layer is not discolored after being placed in an atmospheric environment for 202 days (see A in the attached figure 4), and the coating layer is slightly yellowed after being placed for 253 days (see B in the attached figure 4).
The thickness of the silver plating layer of the electroplating workpiece without the cyanide-free silver plating anti-discoloration agent is 21 mu m, the crystallization of the plating layer is fine and bright, and the plating layer turns yellow after being placed in the atmospheric environment for 62 days (see C in the attached figure 4).
Example 5
The silver plating anti-discoloration agent of the embodiment has the following concentration ratio of components:
sodium castor oil sulfate 1g/L
Sulfatopyrazole 15g/L
The solvent is deionized water.
The preparation method of the cyanide-free silver plating anti-tarnish agent is the same as that of the example 1, except that the amount of each component is calculated according to the mixture ratio.
Performance detection
30ml of the cyanide-free silver plating anti-tarnish agent prepared in example 5 was added to 1L of cyanide-free silver plating solution, and the work piece was placed therein at 0.5A/dm2And after electroplating for 2 hours at 40 ℃, taking out the plated workpiece, treating the workpiece by using a protective agent, drying the workpiece, measuring the thickness of the silver plating layer by using an X-ray fluorescence instrument, and placing the workpiece in an atmospheric environment to wait for a natural color change experiment. The cyanide-free silver plating solution used in this embodiment is: 30g/L of silver nitrate, 50g/L of potassium carbonate, 60g/L of potassium citrate and 0.6g/L of thiosemicarbazide.
And electroplating the same workpiece by using cyanide-free silver plating solution without the anti-color-changing agent under the same condition. After electroplating, the coating is treated by a protective agent and then dried, and then the coating is placed in an atmospheric environment to observe the discoloration time.
The result of the detection
The thickness of the silver coating layer of the electroplating workpiece added with the cyanide-free silver plating anti-discoloration agent prepared in the example 5 is 27 micrometers, the crystallization of the coating layer is fine and bright, the coating layer is not discolored after being placed in an atmospheric environment for 204 days (see A in the attached figure 5), and the coating layer is slightly yellowed after being placed for 253 days (see B in the attached figure 5).
The thickness of the silver coating of the electroplating workpiece without the cyanide-free silver plating anti-discoloration agent is 24 mu m, the crystallization of the coating is fine and bright, and the coating is placed in the atmosphere for 59 days to turn yellow (see C in the attached figure 5).
The above examples further show that the cyanide-free silver plating anti-tarnish agent of the present invention has a significant effect on improving the anti-tarnish performance of the silver plating layer, a series of problems caused by the color change of the plating layer are avoided, one difficulty in cyanide-free electroplating is solved, and the requirements in the current production application can be basically satisfied.
Finally, it is noted that the above-mentioned preferred embodiments illustrate rather than limit the invention, and that, although the invention has been described in detail with reference to the above-mentioned preferred embodiments, it will be understood by those skilled in the art that various changes in form and detail may be made therein without departing from the scope of the invention as defined by the appended claims.
Claims (8)
1. The anti-tarnish agent for cyanide-free silver plating is characterized in that the anti-tarnish agent for cyanide-free silver plating comprises the following components: the sulfuric acid compound is one or more of castor oil sodium sulfate, sodium dodecyl sulfate and ammonium thiosulfate; the sulfonamide compound is one or more of 2-p-aminobenzene sulfonamide-5-methoxyl pyrimidine, sulfamethoxydiazine, sulfacetamide sodium and sulfaphenazole.
2. The anti-tarnish agent for cyanide-free silver plating according to claim 1, wherein the anti-tarnish agent for silver plating comprises the following components by mass: 0.1-2g/L of sulfuric acid compound, 10-25g/L of sulfonamide compound and water as solvent.
3. The anti-tarnish agent for cyanide-free silver plating according to claim 1, wherein the anti-tarnish agent for silver plating comprises the following components by mass: 0.5-1.5g/L of sulfuric acid compound, 15-20g/L of sulfonamide compound and water as solvent.
4. The anti-tarnish agent for cyanide-free silver plating according to claim 1, wherein the anti-tarnish agent for silver plating comprises the following components by mass: sodium dodecyl sulfate 1g/L, 2-sulfanilamide-5-methoxypyrimidine 20g/L, and water as solvent.
5. Use of the anti-discoloration agent according to any one of claims 1 to 4 in cyanide-free silver plating.
6. The cyanide-free silver plating solution is characterized by comprising the following components in percentage by mass:
sulfate compound 3-60mg/L
Sulfonamide compound 300-750mg/L
Silver nitrate 25-35g/L
Potassium carbonate 30-60g/L
45-80g/L potassium citrate
0.1-0.8g/L of thiosemicarbazide.
7. The cyanide-free silver plating solution according to claim 6, comprising the following components in concentration by mass:
sulfate compound 30mg/L
Sulfonamide compound 600mg/L
Silver nitrate 25-35g/L
Potassium carbonate 30-60g/L
45-80g/L potassium citrate
0.1-0.8g/L of thiosemicarbazide.
8. The cyanide-free silver plating solution according to claim 6, comprising the following components in concentration by mass: 30mg/L of sodium dodecyl sulfate, 600mg/L of 2-p-aminobenzenesulfonamido-5-methoxypyrimidine, 35g/L of silver nitrate, 40g/L of potassium carbonate, 60g/L of potassium citrate and 0.5g/L of thiosemicarbazide.
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| KR101115592B1 (en) * | 2011-05-19 | 2012-03-05 | 주식회사 에이엔씨코리아 | Non-cyanide silver plating solution and method for forming plating using it |
| CN105154930A (en) * | 2015-08-21 | 2015-12-16 | 无锡桥阳机械制造有限公司 | Cyanide-free silver plating electroplating liquid and electroplating method thereof |
| CN109321953A (en) * | 2018-12-07 | 2019-02-12 | 重庆立道新材料科技有限公司 | A kind of curing agent and its application silver-plated for non-cyanide alkali |
| CN111575750A (en) * | 2020-07-13 | 2020-08-25 | 南昌航空大学 | Cyanide-free electroplating nano-silver additive |
| CN111663157A (en) * | 2020-07-13 | 2020-09-15 | 广州三孚新材料科技股份有限公司 | Cyanide-free silver plating electroplating solution and preparation method thereof |
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2021
- 2021-09-28 CN CN202111157736.6A patent/CN113755911A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| KR101115592B1 (en) * | 2011-05-19 | 2012-03-05 | 주식회사 에이엔씨코리아 | Non-cyanide silver plating solution and method for forming plating using it |
| CN105154930A (en) * | 2015-08-21 | 2015-12-16 | 无锡桥阳机械制造有限公司 | Cyanide-free silver plating electroplating liquid and electroplating method thereof |
| CN109321953A (en) * | 2018-12-07 | 2019-02-12 | 重庆立道新材料科技有限公司 | A kind of curing agent and its application silver-plated for non-cyanide alkali |
| CN111575750A (en) * | 2020-07-13 | 2020-08-25 | 南昌航空大学 | Cyanide-free electroplating nano-silver additive |
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