CN113584538B - Graphene-nicotinic acid silver plating solution and preparation method thereof - Google Patents

Graphene-nicotinic acid silver plating solution and preparation method thereof Download PDF

Info

Publication number
CN113584538B
CN113584538B CN202110668125.1A CN202110668125A CN113584538B CN 113584538 B CN113584538 B CN 113584538B CN 202110668125 A CN202110668125 A CN 202110668125A CN 113584538 B CN113584538 B CN 113584538B
Authority
CN
China
Prior art keywords
graphene
plating solution
silver plating
silver
solution
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.)
Active
Application number
CN202110668125.1A
Other languages
Chinese (zh)
Other versions
CN113584538A (en
Inventor
周铭
李虓
陈鑫
罗超贵
全金
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nanjing Qinglu New Material Technology Co ltd
Guangxi University of Science and Technology
Original Assignee
Nanjing Qinglu New Material Technology Co ltd
Guangxi University of Science and Technology
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Nanjing Qinglu New Material Technology Co ltd, Guangxi University of Science and Technology filed Critical Nanjing Qinglu New Material Technology Co ltd
Priority to CN202110668125.1A priority Critical patent/CN113584538B/en
Publication of CN113584538A publication Critical patent/CN113584538A/en
Application granted granted Critical
Publication of CN113584538B publication Critical patent/CN113584538B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00Electroplating: Baths therefor
    • C25D3/02Electroplating: Baths therefor from solutions
    • C25D3/46Electroplating: Baths therefor from solutions of silver
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D15/00Electrolytic or electrophoretic production of coatings containing embedded materials, e.g. particles, whiskers, wires

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 graphene-nicotinic acid silver plating solution and a preparation method thereof. The graphene-nicotinic acid silver plating solution is prepared from the following raw materials in parts by weight: 30-50 parts of silver salt, 80-100 parts of complexing agent, 60-70 parts of buffer solution, 60-70 parts of conductive salt, 30-50 parts of additive, 0.3-0.5 part of graphene and 700-1100 parts of water. The graphene-nicotinic acid silver plating solution disclosed by the invention is reasonable in composition and stable in components, can uniformly disperse graphene, and has good popularization and application values.

Description

Graphene-nicotinic acid silver plating solution and preparation method thereof
Technical Field
The invention relates to the technical field of electrochemical composite electrodeposition, in particular to graphene-nicotinic acid silver plating solution and a preparation method thereof.
Background
In the prior art, the silver-based electric contact material is researched and widely applied in the electric contact materials, but high-purity silver metal has the defects of poor adhesion and electric wear resistance, low melting point, low hardness and the like. Silver metal is in a medium containing sulfur or sulfide, and a silver sulfide film is easily formed on the surface of the silver metal. Under the action of direct current, silver metal is easy to volatilize and form electric erosion spikes, so that the silver contact element is easy to form electric arcs and is welded.
Especially under the working conditions of large and medium power contacts, the pure silver-based electric contact material cannot meet the requirements because of severe electric erosion under the strong action of electric arcs.
The graphene with excellent electrical, thermal, mechanical and other properties can be used as a reinforcement to be applied to a metal matrix composite material so as to improve the properties of the metal material and adapt to the application of modern industry. The main method for introducing graphene at present is a composite electrodeposition technology. The electrodeposition method mainly adopts a composite electroplating process, pure silver is used as an anode, a substrate metal is used as a cathode, and a composite plating layer is obtained by transferring and depositing ions and graphene particles in a silver salt solution. Investigation and statistics show that nearly 90% of the current domestic silver electroplating production lines all adopt a cyanide complex system, but the cyanide silver plating solution is extremely toxic. As early as 2005, the national development and improvement commission 40 document has positioned cyanidation electroplating as an obsolete, out-dated production process.
The biggest technical difficulty in introducing graphene after cyaniding electroplating is stopped is that graphene is easy to agglomerate in silver plating solution and is not uniformly dispersed when being compounded on a silver plating layer. Therefore, the cyanide-free silver plating solution with stable components and capable of uniformly dispersing graphene is urgently needed to be found in the field.
Disclosure of Invention
The graphene-nicotinic acid silver plating solution has reasonable composition and stable components, can uniformly disperse graphene, and has good popularization and application values.
The purpose of the invention is realized by the following technical scheme:
the graphene-nicotinic acid silver plating solution is prepared from the following raw materials in parts by weight: 30-50 parts of silver salt, 80-100 parts of complexing agent, 60-70 parts of buffer solution, 60-70 parts of conductive salt, 30-50 parts of additive, 0.3-0.5 part of graphene and 700-1100 parts of water.
The preparation method of the graphene-nicotinic acid silver plating solution comprises the following steps:
s1, dissolving silver salt, a complexing agent, a buffer solution, conductive salt and an additive in water to obtain electroplating solution;
s2, adding ammonia water into the electroplating solution to adjust the pH value to 9.5-10.5 to obtain silver plating solution a;
and S3, taking 30-50% of the silver plating solution a, adding graphene powder particles, uniformly stirring, adding a dispersing agent, performing ultrasonic treatment for 15-30min, adding the rest silver plating solution a, uniformly stirring, and performing ultrasonic treatment again for 15-30min to obtain the silver plating solution.
The silver salt is silver nitrate.
The complexing agent is nicotinic acid.
The buffer solution is ammonium acetate buffer solution, and the concentration of the buffer solution is 60g/L-70g/L.
The conductive salt is potassium carbonate.
The additive is potassium hydroxide.
The graphene-nicotinic acid silver plating solution also comprises a dispersing agent, wherein the dispersing agent is sodium dodecyl sulfate, sodium dodecyl sulfate and polyethylene glycol-400;
wherein the weight ratio of the sodium dodecyl sulfate to the sodium dodecyl sulfate is 1-2, the total weight of the sodium dodecyl sulfate and the sodium dodecyl sulfate is 5-20% of the weight of the added graphene powder, and the addition amount of the polyethylene glycol-400 is 0.5-1% of the weight of the silver plating solution a.
The electroplating using conditions of the silver plating solution a are as follows: the current density of electroplating is 0.2-0.3A/dm 2 The electroplating time is 30-50min, and the temperature is 25-30 ℃.
According to the invention, a primary buffer balance system is formed by using the coordination agent and the buffer solution, and then the dispersing agent with unique composition is matched, so that the uniform and consistent dispersion of the graphene is realized, and the dispersion system has stable property and can fully meet the requirements of an electroplating process. Compared with the prior art, the silver plating layer electroplated by the silver plating solution has better wear resistance and ablation resistance, and has good popularization and application values.
The preparation method of the silver plating solution provided by the invention can make the graphene-nicotinic acid silver plating solution more stable and uniform and better ensure the stability of subsequent electroplating.
The invention also provides the electroplating condition of the silver plating solution in the preferred scheme, and the electroplating condition can better exert the performance of the silver plating solution.
Drawings
FIG. 1 is a contact angle of a plating solution containing graphene under different dispersant systems;
FIG. 2 shows Zeta potential of a plating solution containing graphene plating solution in the same dispersant system;
FIG. 3 shows the morphology of the plating layer prepared by the pure silver plating solution and the silver-graphene plating solution;
FIG. 4 is a Raman spectrum of graphene on the surface of the bump structure in the plating layer shown in FIG. 3 (b);
FIG. 5 is an EDS spectrum of the plated layer after polishing;
fig. 6 is a surface view of the pure silver plating and the silver-graphene plating after 72 hours;
FIG. 7 is a Raman spectrum of graphene on the surface of a coating of a graphene silver plating system of nicotinic acid and succinimide;
FIG. 8 is a topographical view of surface wear scars for each group after dry rubbing;
FIG. 9 is a diagram showing the shape of a contact after 10000 times of on/off operations of each group.
Detailed Description
The invention is further illustrated by the following examples. It should be understood that the examples of the present invention are for illustrative purposes and not intended to limit the present invention. Simple modifications of the invention in accordance with its spirit fall within the scope of the claimed invention.
Example 1
The graphene-nicotinic acid silver plating solution comprises the following components: 30g of silver nitrate, 80g of nicotinic acid, 60g of 60g/L ammonium acetate buffer solution, 60g of potassium carbonate, 30g of potassium hydroxide, 0.3g of graphene and 700g of water;
the environment-friendly coating also comprises a dispersant, wherein the dispersant is sodium dodecyl sulfate, sodium dodecyl sulfate and polyethylene glycol-400;
wherein the weight ratio of the sodium dodecyl sulfate to the sodium dodecyl sulfate is 1, the total weight of the sodium dodecyl sulfate and the sodium dodecyl sulfate is 5 percent of the weight of the added graphene powder, and the adding amount of the polyethylene glycol-400 is 0.5 percent of the weight of the silver plating solution a.
The preparation method of the graphene-nicotinic acid silver plating solution comprises the following steps:
s1, dissolving silver salt, a complexing agent, a buffer solution, conductive salt and an additive in water to obtain electroplating solution;
s2, adding ammonia water into the electroplating solution to adjust the pH value to 9.5 to obtain a silver plating solution a;
and S3, adding graphene powder particles into 30% of the silver plating solution a, uniformly stirring, adding a dispersing agent, performing ultrasonic treatment for 15min, adding the rest silver plating solution a, uniformly stirring, and performing ultrasonic treatment for 15min again to obtain the silver plating solution.
The electroplating using conditions of the silver plating solution a are as follows: the current density of the electroplating is 0.2A/dm 2 The plating time is 30min, and the temperature is 25 ℃.
Example 2
The graphene-nicotinic acid silver plating solution comprises the following components: 50g of silver nitrate, 100g of nicotinic acid, 70g of ammonium acetate buffer solution with the concentration of 70g/L, 70g of potassium carbonate, 50g of potassium hydroxide, 0.5g of graphene and 1100g of water;
the environment-friendly coating also comprises a dispersant, wherein the dispersant is sodium dodecyl sulfate, sodium dodecyl sulfate and polyethylene glycol-400;
wherein the weight ratio of the sodium dodecyl sulfate to the sodium dodecyl sulfate is 1.
The preparation method of the graphene-nicotinic acid silver plating solution comprises the following steps:
s1, dissolving silver salt, a complexing agent, a buffer solution, conductive salt and an additive in water to obtain electroplating solution;
s2, adding ammonia water into the electroplating solution to adjust the pH value to 10.5 to obtain a silver plating solution a;
and S3, adding graphene powder particles into 50% of the silver plating solution a, uniformly stirring, adding a dispersing agent, performing ultrasonic treatment for 30min, adding the rest silver plating solution a, uniformly stirring, and performing ultrasonic treatment for 30min again to obtain the silver plating solution.
The electroplating using conditions of the silver plating solution a are as follows: the current density of the electroplating is 0.3A/dm 2 The electroplating time is 50min, and the temperature is 30 ℃.
Example 3
The graphene-nicotinic acid silver plating solution comprises the following components: 40g of silver nitrate, 90g of nicotinic acid, 65g of ammonium acetate buffer solution with the concentration of 65g/L, 65g of potassium carbonate, 40g of potassium hydroxide, 0.4g of graphene and 900g of water;
the environment-friendly coating also comprises a dispersant, wherein the dispersant is sodium dodecyl sulfate, sodium dodecyl sulfate and polyethylene glycol-400;
wherein the weight ratio of the sodium dodecyl sulfate to the sodium dodecyl sulfonate is 1.5.
The preparation method of the graphene-nicotinic acid silver plating solution comprises the following steps:
s1, dissolving silver salt, a complexing agent, a buffer solution, conductive salt and an additive in water to obtain electroplating solution;
s2, adding ammonia water into the electroplating solution to adjust the pH value to 10 to obtain a silver plating solution a;
and S3, taking 40% of the silver plating solution a, adding graphene powder particles, uniformly stirring, adding a dispersing agent, performing ultrasonic treatment for 15-30min, adding the rest silver plating solution a, uniformly stirring, and performing ultrasonic treatment again for 20min to obtain the silver plating solution.
The electroplating using conditions of the silver plating solution a are as follows: the current density of the electroplating is 0.25A/dm 2 The electroplating time is 40min, and the temperature is 27 ℃.
Example 4
The graphene-nicotinic acid silver plating solution comprises the following components: 45g of silver nitrate, 85g of nicotinic acid, 67g/L of concentration, 63g of ammonium acetate buffer solution, 67g of potassium carbonate, 45g of potassium hydroxide, 0.5g of graphene and 800g of water;
the environment-friendly coating also comprises a dispersant, wherein the dispersant is sodium dodecyl sulfate, sodium dodecyl sulfate and polyethylene glycol-400;
wherein the weight ratio of the sodium dodecyl sulfate to the sodium dodecyl sulfate is 2.
The preparation method of the graphene-nicotinic acid silver plating solution comprises the following steps:
s1, dissolving silver salt, a complexing agent, a buffer solution, conductive salt and an additive in water to obtain electroplating solution;
s2, adding ammonia water into the electroplating solution to adjust the pH value to 9.7 to obtain a silver plating solution a;
and S3, adding graphene powder particles into 35% of the silver plating solution a, uniformly stirring, adding a dispersing agent, performing ultrasonic treatment for 18min, adding the rest silver plating solution a, uniformly stirring, and performing ultrasonic treatment for 16min again to obtain the silver plating solution.
The electroplating using conditions of the silver plating solution a are as follows: the current density of the electroplating is 0.23A/dm 2 The plating time was 37min and the temperature was 26 ℃.
Example 5
The graphene-nicotinic acid silver plating solution comprises the following components: 35g of silver nitrate, 95g of nicotinic acid, 66g of ammonium acetate buffer solution with the concentration of 62g/L, 63g of potassium carbonate, 35g of potassium hydroxide, 0.3g of graphene and 1000g of water;
the environment-friendly coating also comprises a dispersant, wherein the dispersant is sodium dodecyl sulfate, sodium dodecyl sulfate and polyethylene glycol-400;
wherein the weight ratio of the sodium dodecyl sulfate to the sodium dodecyl sulfate is 2.
The preparation method of the graphene-nicotinic acid silver plating solution comprises the following steps:
s1, dissolving silver salt, a complexing agent, a buffer solution, conductive salt and an additive in water to obtain electroplating solution;
s2, adding ammonia water into the electroplating solution to adjust the pH value to 10.2 to obtain a silver plating solution a;
s3, taking 45% of the silver plating solution a, adding graphene powder particles, uniformly stirring, adding a dispersing agent, performing ultrasonic treatment for 25min, adding the rest silver plating solution a, uniformly stirring, and performing ultrasonic treatment for 25min again to obtain the silver plating solution.
The electroplating using conditions of the silver plating solution a are as follows: the current density of the electroplating is 0.28A/dm 2 Electroplating time is 48minThe temperature was 28 ℃.
Experimental example 1 dispersant screening
First, a first screening experiment of the dispersant
1. Experimental samples:
the sample solution is a nicotinic acid cyanide-free silver plating solution as a base solution, and the pH value is controlled by ammonia water. The nicotinic acid cyanide-free silver plating solution is prepared from silver nitrate, nicotinic acid, ammonium acetate, potassium carbonate, potassium hydroxide and ammonia water, and the dosage ratio of the components refers to example 3 except that graphene is not contained.
The base liquid is divided into four groups, each group contains 100 ml of base liquid, and the following components are respectively added:
group A: 50mg of graphene and 5mg of sodium dodecylbenzenesulfonate;
group B: 50mg graphene +5mg sodium dodecyl sulfate;
group C: 50mg graphene +5mg cetyltrimethylammonium bromide;
group D: 50mg of graphene and 5mg of sodium dodecyl sulfate;
2. observation recording
0min: all have no obvious change;
10min: each group is uniformly dispersed solution by visual observation;
20min: each group is uniformly dispersed solution through visual observation;
30min: each group is uniformly dispersed solution through visual observation;
and (4) 40min: the groups A, B and C have the tendency of sedimentation through light transmission observation, but the groups A, B and C are still uniformly dispersed through normal observation, and the group D is not light transmission and is in a uniformly dispersed solution state;
50min: the groups A and C have macroscopic sedimentation tendency, but only have obvious sedimentation,
the condition of group B is slightly better than that of group D, and the group D is still uniform;
and (5) 60min: the group A and the group C have obvious settlement, the group B has no obvious settlement, and the deposition is fluffy
And the group D is still uniform.
3. Conclusion of analysis
After one hour sedimentation observation, the analysis concluded: when only one dispersant is added, the dispersing effect is as follows: group D > group B > group C > group a.
2. Second screening experiment of dispersant
On the basis of a first screening experiment of the dispersing agent, three groups of reagents with better dispersing effect are selected, and the purpose is to verify whether the dispersing effect can be improved by combining two reagents.
1. Experimental samples:
the sample solution is a nicotinic acid cyanide-free silver plating solution as a base solution, and the pH value is controlled by ammonia water. The nicotinic acid cyanide-free silver plating solution is prepared from silver nitrate, nicotinic acid, ammonium acetate, potassium carbonate, potassium hydroxide and ammonia water, and the dosage ratio of the components refers to example 3 except that graphene is not contained.
The base solution was divided into three groups, each group containing 100 ml of base solution, to which the following ingredients were added:
group A-1: 50mg of graphene, 3mg of sodium dodecyl sulfate and 3mg of sodium dodecyl sulfate;
group B-1: 50mg of graphene, 3mg of sodium dodecyl sulfate and 3mg of hexadecyl trimethyl ammonium bromide;
group C-1: 50mg graphene +3mg sodium dodecyl sulfate +3mg cetyltrimethylammonium bromide;
2. observation recording
0min: all have no obvious change;
10min: the group C-1 has macroscopic deposition, is similar to the group B and is fluffy, and the rest groups are uniformly dispersed solution;
20min: c-1 deposition is more obvious, and the rest groups are uniformly dispersed solution;
30min: the B-1 group has a tendency of sedimentation under transparent observation, but is very unobvious;
and (4) 40min: no change is made;
50min: relatively unchanged;
and (5) 60min: b-1 is partially precipitated, and A-1 is still uniformly dispersed and lightproof.
3. Conclusion of analysis
After one hour sedimentation observation, the analysis concluded: when two dispersants are added, the best dispersing effect is compounded sodium dodecyl sulfate and sodium dodecyl sulfate. Therefore, the two dispersants were selected for further examination.
3. Third screening experiment of dispersants
1. Experimental samples:
the sample solution is a nicotinic acid cyanide-free silver plating solution as a base solution, and the pH value is controlled by ammonia water. The nicotinic acid cyanide-free silver plating solution is prepared from silver nitrate, nicotinic acid, ammonium acetate, potassium carbonate, potassium hydroxide and ammonia water, and the dosage ratio of the components refers to example 3 except that graphene is not contained.
The base liquid is divided into three groups, each group contains 100 ml of base liquid, and the following components are respectively added:
a group: 50mg of graphene, 3mg of sodium dodecyl sulfate and 3mg of sodium dodecyl sulfate;
b group: 50mg of graphene;
and c, group: 50mg of graphene +3mg of sodium dodecyl sulfate;
and d, group: 50mg graphene +3mg sodium dodecyl sulphate.
2. Copper plate dispersion angle experiment:
each set of test samples was sampled with a test tube and dropped on a copper plate, and the contact angle thereof is shown in FIG. 1. It can be seen that the contact angles of the plating solutions of the experimental groups a, b, C and d on the copper plate are respectively 19.428 °, 57.381 °, 49.848 ° and 44.564 °, and the contact angle of the experimental group a is far smaller than that of the experimental groups b, C and d, thus proving that the dispersant prepared by compounding sodium dodecyl sulfate and sodium dodecyl sulfate has better graphene dispersing effect.
3. Zeta potential test
The Zeta potential test results of the plating solution for the experimental groups a, b, c and d are shown in figure 2. As can be seen from FIG. 2, the plating solutions of experimental groups a, b, c, d had Zeta potentials of 30.3mV, 1.4mV, 19.2mV, 12.7mV, and D, respectively. The higher the absolute value of Zeta potential, the better the dispersion of the venom, so the combination of sodium dodecyl sulfate and sodium dodecyl sulfate used in the invention has the most good dispersion effect.
Experimental example 2
1. Comparison of coating morphology prepared from pure silver plating solution and silver-graphene plating solution
The silver-graphene plating solution prepared in example 3 of the present invention was used to plate on a copper plate, and the plating morphology is shown in fig. 3, in which (a) shows a pure silver plating layer without graphene, and (b) shows a silver-graphene plating layer, in comparison with a sample obtained by plating a pure silver plating solution on a copper plate. It can be seen from the (a) and (b) figures that both the plating layers are uniformly distributed, wherein the silver-graphene plating solution on the (b) figure is uniformly distributed on the surface of the silver metal without obvious particle shedding and hole structure defects.
2. Coating surface graphene verification
Verification 1: in order to verify whether the surface of the plating layer contains graphene or not, raman and energy spectrum analysis is performed on one convex structure of the plating layer shown in the graph (b) in fig. 3, and as a result, as shown in fig. 4, the content of the element C reaches 8.75wt%, and a raman spectrum also has a distinct characteristic peak of graphene, which can be proved that the introduced second-phase particles of graphene are on the surface of the plating layer.
And (3) verification 2: in order to verify whether the interior of the plating layer contains graphene, the plating layer (b) in fig. 3 is polished by using P2000 sandpaper, and is cleaned by pure water after being polished, and is placed in absolute ethyl alcohol for 5min, and the EDS energy spectrum of the surface is shown in fig. 5, and the content of C is 5.79%, which can be proved to be the part of the introduced graphene second-phase particles in the interior of the plating layer.
Experimental example 3 comparative experiment of plating Properties
The silver-graphene coating of example 3 was compared to a succinimide cyanide-free silver coating containing graphene. Wherein, the silver plating solution used for the succinimide cyanide-free silver plating layer comprises the following components: 500g of silver nitrate; 1000g of succinimide; 1000g of potassium pyrophosphate; 300g of potassium hydroxide.
The specific experimental conditions were as follows:
1. anti-discoloration capability of plating solution
As shown in fig. 6, which shows the visual appearance of (a) the plating layer of example 3 of the present invention and (b) the succinimide plating layer after being left indoors for 72 hours, it can be seen from fig. 6 that the plating layer of example 3 of the present invention has a smoother surface without any visible oxidation, while the succinimide plating layer has been slightly yellowish.
2. Graphene dispersancy
Fig. 7 shows raman spectra of surface graphene of the coating layer after (a) the coating layer of example 3 of the present invention and (b) the succinimide coating layer are prepared as a composite coating layer.
The disappearance of the 2D peak in fig. 7, panel (b), in the Raman spectrum of the composite coating is probably due to the partial agglomeration of the graphene sheets during the co-deposition of the succinimide system, resulting in the multilayer graphene in the composite coating.
In the nicotinic acid silvering system shown in the graph (a) in fig. 7, the characteristic peak of graphene on the surface of the coating is obvious, and no obvious agglomeration phenomenon exists. This shows that the dispersibility of the present invention is more excellent.
3. Comparison of wear resistance of silver plating
As shown in fig. 8, respectively: the method comprises the following steps of (a) a nicotinic acid graphene silver plating system, a succinimide graphene silver plating system and (c) a nicotinic acid silver plating system without adding graphene, wherein the wear scar is formed on a UMT friction wear testing machine, the load is 5N, the diameter of a steel ball is 6-6.5mm, the stroke is 1mm, and the frequency is 5Hz.
The nicotinic acid silver plating system without graphene is prepared from silver nitrate, nicotinic acid, ammonium acetate, potassium carbonate, potassium hydroxide and ammonia water, and the dosage ratio of the components refers to example 3 except that graphene is not added.
As is evident from fig. 8, (a) the composite plating prepared by the silver plating solution of the present invention has a smaller wear area, an average wear scar width of only 190 μm, and an average wear scar depth of only 0.54 μm; the average width of the grinding trace of the composite plating layer prepared by the succinimide silver plating solution of the group (b) is only 210 mu m, and the average depth of the grinding trace is only 0.77 mu m; (c) The average grinding crack width of the composite plating layer prepared by the nicotinic acid silver plating solution without adding graphene reaches 240 mu m, and the average grinding crack depth reaches 1.22 mu m. Therefore, the composite plating layer prepared by the silver plating solution has better wear resistance.
4. Ablation resistance
As shown in fig. 9, respectively: the contact surface condition of the nicotinic acid silver plating system without graphene is 10000A in on-off current intensity, 10N in load and 10000 times in on-off.
As is evident from fig. 9: the ablation effect of the (a) group and the (b) group is better than that of the (c) group; (b) The group has been completely burned through and exposed to the copper-based metal layer, and the surface oxidation is more severe than in group (a). The composite coating prepared by the plating solution of the embodiment 3 of the invention has smaller ablation area, lower oxidation degree and no obvious burn-through mark.
Although the invention has been described in detail hereinabove by way of general description, specific embodiments and experiments, it will be apparent to those skilled in the art that many modifications and improvements can be made thereto based on the invention. Accordingly, it is intended that all such modifications and variations that fall within the spirit of the invention be included within the scope of the following claims.

Claims (2)

1. The graphene-nicotinic acid silver plating solution is characterized by being prepared from the following raw materials in parts by weight: 30-50 parts of silver salt, 80-100 parts of complexing agent, 60-70 parts of buffer solution, 60-70 parts of conductive salt, 30-50 parts of additive, 0.3-0.5 part of graphene and 700-1100 parts of water;
the environment-friendly coating also comprises a dispersant, wherein the dispersant is sodium dodecyl sulfate, sodium dodecyl sulfate and polyethylene glycol-400;
wherein the weight ratio of the sodium dodecyl sulfate to the sodium dodecyl sulfate is 1-2, the total weight of the sodium dodecyl sulfate and the sodium dodecyl sulfate is 5-20% of the weight of the added graphene powder, and the addition amount of the polyethylene glycol-400 is 0.5-1% of the weight of the silver plating solution a;
the preparation method comprises the following steps:
s1, dissolving silver salt, a complexing agent, a buffer solution, conductive salt and an additive in water to obtain electroplating solution;
s2, adding ammonia water into the electroplating solution to adjust the pH value to 9.5-10.5 to obtain a silver plating solution a;
s3, taking 30-50% of the silver plating solution a, adding graphene powder particles, stirring uniformly, adding a dispersing agent, carrying out ultrasonic treatment for 15-30min, adding the rest silver plating solution a, stirring uniformly, and then carrying out ultrasonic treatment again for 15-30min to obtain the silver plating solution a;
the silver salt is silver nitrate;
the complexing agent is nicotinic acid;
the buffer solution is ammonium acetate buffer solution, and the concentration of the buffer solution is 60g/L-70g/L;
the conductive salt is potassium carbonate;
the additive is potassium hydroxide.
2. The graphene-niacin silver plating solution according to claim 1, wherein: the electroplating use conditions of the graphene-nicotinic acid silver plating solution are as follows: the current density of electroplating is 0.2-0.3A/dm 2 The electroplating time is 30-50min, and the temperature is 25-30 ℃.
CN202110668125.1A 2021-06-16 2021-06-16 Graphene-nicotinic acid silver plating solution and preparation method thereof Active CN113584538B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202110668125.1A CN113584538B (en) 2021-06-16 2021-06-16 Graphene-nicotinic acid silver plating solution and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202110668125.1A CN113584538B (en) 2021-06-16 2021-06-16 Graphene-nicotinic acid silver plating solution and preparation method thereof

Publications (2)

Publication Number Publication Date
CN113584538A CN113584538A (en) 2021-11-02
CN113584538B true CN113584538B (en) 2023-03-14

Family

ID=78243997

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202110668125.1A Active CN113584538B (en) 2021-06-16 2021-06-16 Graphene-nicotinic acid silver plating solution and preparation method thereof

Country Status (1)

Country Link
CN (1) CN113584538B (en)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103046091A (en) * 2013-01-09 2013-04-17 西安交通大学 Plating solution and plating method of cyanide-free plating silver
CN107345307A (en) * 2017-06-23 2017-11-14 广东电网有限责任公司电力科学研究院 Composite silver plating liquor and preparation method thereof and electrodeposition technology
CN109368629A (en) * 2018-12-03 2019-02-22 广东电网有限责任公司 A kind of graphene dispersion system and preparation method thereof
CN111101169A (en) * 2018-10-28 2020-05-05 江门市顺高电镀有限公司 Cyanide-free silver electroplating solution

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103046091A (en) * 2013-01-09 2013-04-17 西安交通大学 Plating solution and plating method of cyanide-free plating silver
CN107345307A (en) * 2017-06-23 2017-11-14 广东电网有限责任公司电力科学研究院 Composite silver plating liquor and preparation method thereof and electrodeposition technology
CN111101169A (en) * 2018-10-28 2020-05-05 江门市顺高电镀有限公司 Cyanide-free silver electroplating solution
CN109368629A (en) * 2018-12-03 2019-02-22 广东电网有限责任公司 A kind of graphene dispersion system and preparation method thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
电流密度对烟酸体系电镀银的影响;宋伟星等;《电镀与涂饰》;20180315(第05期);第201-204页 *
表面活性剂复配对石墨烯分散性的影响及其在复合镀银中的应用;郑克勤等;《电镀与涂饰》;20190228;第38卷(第4期);第147-152页 *

Also Published As

Publication number Publication date
CN113584538A (en) 2021-11-02

Similar Documents

Publication Publication Date Title
CN106283134B (en) A kind of rare earth improvement Brush Plating silver plating liquid and its preparation process and application method
CN102277601B (en) Cyanogen-free silver-plating electroplating liquid containing auxiliary complexing agent
CN110344089B (en) Gold sodium sulfite plating solution and electroplating method thereof
CN110219026B (en) Alkaline cyanide-free brush plating solution of multi-coordination system and preparation method thereof
CN115279949A (en) Silver-plated material and method for producing same
CN111334828A (en) Surface treatment method for neodymium iron boron permanent magnet material and product
CN106048672B (en) It is a kind of neutral without cyanogen Brush Plating silver plating liquid and its preparation process and application method
CN102383154A (en) Cyanide-free gold-plating electroplating solution
CN102011154A (en) Gold plating solution for plating gold finger on circuit board
CN113584538B (en) Graphene-nicotinic acid silver plating solution and preparation method thereof
CN103757617A (en) Ni-Cu-La-B quaternary alloy plating solution and method for chemically plating glass fibers by using same
CN102943290A (en) Method for electroplating of nickel-cobalt alloy on electronic packaging casing
CN110284163B (en) Copper plating solution for solar cell and preparation method thereof
CN110528031B (en) Cyanide-free brush plating solution based on EDTA (ethylene diamine tetraacetic acid) multi-element coordination system and preparation method thereof
CN103806054A (en) Pulse plating method of Ag-Ni alloy for electric contact material
CN115440695A (en) High-temperature-resistant ultrathin semiconductor lead frame and preparation method thereof
CN110184631B (en) Cyanide-free gold plating electroplating solution and preparation method and electroplating process thereof
CN110129842A (en) A kind of compound cyanide-free gold electroplating plating solution preparation and gold process is electroplated using its
CN111850629A (en) Cyanide-free alkali copper electroplating solution and electroplating method
CN113737236B (en) High-corrosion-resistance composite coating and preparation method and application thereof
CN116479485B (en) High-reliability lead frame and preparation method thereof
CN112301382B (en) Preparation method of high-ductility low-profile electrolytic copper foil
CN113774446B (en) Nickel coating with high corrosion resistance, preparation method thereof and electroplating liquid
Huang et al. Non-cyanide Electroplating of Gold-Tin Eutectic Alloy for Flip-Chip Packaging of LED
CN107904628B (en) It is a kind of based on ultrasonic wave added malic acid-glycine betaine eutectic solvent electrogalvanizing method

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
GR01 Patent grant
GR01 Patent grant