CN104419921B - A kind of water-soluble silver protecting agent and preparation method thereof, chemical silver plating method and electroplate workpiece - Google Patents
A kind of water-soluble silver protecting agent and preparation method thereof, chemical silver plating method and electroplate workpiece Download PDFInfo
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- CN104419921B CN104419921B CN201310374346.3A CN201310374346A CN104419921B CN 104419921 B CN104419921 B CN 104419921B CN 201310374346 A CN201310374346 A CN 201310374346A CN 104419921 B CN104419921 B CN 104419921B
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- 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
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/42—Coating with noble metals
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- 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
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/1601—Process or apparatus
- C23C18/1633—Process of electroless plating
- C23C18/1689—After-treatment
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- Materials Engineering (AREA)
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- Organic Chemistry (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
- Chemically Coating (AREA)
Abstract
The invention provides a kind of water-soluble silver protecting agent and preparation method thereof; the water-soluble silver protecting agent is containing AEO, N benzyls phenyl acetamide and the aqueous solution for protecting additive, one or more of the protection additive in cyclododecane, 1 octadecylene, 7 octadecylenes, 1 laurylene.The electroplate workpiece obtained present invention also offers a kind of chemical silver plating method and by this method, including first chemical silvering, then carry out silver layer protection processing using the water-soluble silver protecting agent that the present invention is provided.The water-soluble silver protecting agent that the present invention is provided; the diaphragm of one layer of organic molecular structure can be formed on silvering surface; silver layer is avoided to be directly exposed in air or other corrosive environments; silver layer is prevented to be oxidized corrosion; with more preferable resistance to corrosion; ensure its good electric conductivity, the metallic luster for keeping silver coating good.
Description
Technical field
The invention belongs to chemical plating field, more particularly to a kind of water-soluble silver protecting agent and preparation method thereof and one kind chemistry
Silver-coating method and the electroplate workpiece obtained by the chemical silver plating method.
Background technology
Silvering have good electric conductivity, thermal conductivity, solderability, stability and with matrix reliable adhesion, and
And the price of silver compares other noble metals, such as gold, platinum are also much lower, and therefore, argent is in electronics, communication, electrician and decoration
It is widely used etc. industry, particularly in electronic connector, semiconductor, circuit lead frame and printed circuit board (PCB)
Industry, is often required for carrying out silver-plated process.But, the production of above-mentioned electronic component, transport, installation and during use,
With the H in environment2S、SO2、Cl2、NOxWhen being contacted Deng gas, or even when by ultraviolet light, all easily on silvering surface
Corresponding corrosion product is generated, makes its blackening of turning to be yellow, can the big original electrical property of havoc silvering.
Using the method such as chemical passivation, electrolytic passivation, plating Au, Pd, Rh, Pd, Anti- tarnishing processing is carried out to silvering, all may be used
It is corroded the phenomenon of discoloration with improving silvering to some extent.But, all there is Cr in chemical passivation method and electrolytic passivation method6+It is dirty
The problem of dye, Au, Pd, Rh, Pd method are plated, its complex process, cost is also high.At present, also have by using silver in the prior art
Protective agent can for example use BTA and/or benzo tetrazole in silver-plated layer surface formation diaphragm, but it is to silver layer
Protecting effect is undesirable.
The content of the invention
The protecting effect that the present invention solves silver protecting agent in the prior art is poor, causes silver layer surface easily to aoxidize, drop
The technical problem of low coating electric conductivity.
The invention provides a kind of water-soluble silver protecting agent, the water-soluble silver protecting agent is to contain aliphatic alcohol polyethenoxy
Ether, N- benzyls phenyl acetamide and protect additive the aqueous solution, the protection additive be selected from cyclododecane, 1- octadecylenes,
One or more in 7- octadecylenes, 1- laurylenes.
Present invention also offers the preparation method of the water-soluble silver protecting agent, including by AEO, N-
Benzyl phenyl acetamide and protection additive are dissolved in the water, that is, obtain the water-soluble silver protecting agent.
Present invention also offers a kind of chemical silver plating method, this method includes workpiece to be plated being placed into chemical plating liquid
Chemical plating is carried out, silver plate is obtained；Then silver plate is positioned over progress silver layer protection processing in water-soluble silver protecting agent again；Its
It is characterised by, the water-soluble silver protecting agent that the water-soluble silver protecting agent provides for the present invention.
Finally, the invention provides a kind of electroplate workpiece, the electroplate workpiece include workpiece substrates to be plated and
Plating is overlying on the silver coating on the workpiece substrates surface to be plated, and the surface of the silver coating is also covered with silver-colored protective layer；Its feature exists
In the electroplate workpiece chemical silver plating method provided by the present invention is obtained.
The water-soluble silver protecting agent that the present invention is provided, by using AEO, N- benzyl phenyl acetamides
With the compound system of protection additive；, should when protection processing is carried out to chemical silvering layer surface using the water-soluble silver protecting agent
Water-soluble silver protecting agent can carry out parcel absorption on silvering surface, and form covalent bond and coordinate bond with silver atoms, mutually hand over
For forming chain polymer, so that
Can silvering surface formed one layer of organic molecular structure diaphragm, it is to avoid silver layer be directly exposed to air or its
In its corrosive environment, silver layer is prevented to be oxidized corrosion, with more preferable resistance to corrosion, it is ensured that its good electric conductivity.
Embodiment
The invention provides a kind of water-soluble silver protecting agent, the water-soluble silver protecting agent is to contain aliphatic alcohol polyethenoxy
Ether, N- benzyls phenyl acetamide and protect additive the aqueous solution, the protection additive be selected from cyclododecane, 1- octadecylenes,
One or more in 7- octadecylenes, 1- laurylenes.
The water-soluble silver protecting agent that the present invention is provided, by using AEO, N- benzyl phenyl acetamides
With the compound system of protection additive；, should when protection processing is carried out to chemical silvering layer surface using the water-soluble silver protecting agent
Water-soluble silver protecting agent can carry out parcel absorption on silvering surface, and form covalent bond and coordinate bond with silver atoms, mutually hand over
For chain polymer is formed, the diaphragm of one layer of organic molecular structure can be formed on silvering surface, it is to avoid silver layer directly exposes
In air or other corrosive environments, silver layer is prevented to be oxidized corrosion, with more preferable resistance to corrosion, it is ensured that it is good to lead
Electrical property, the metallic luster for keeping silver coating good.
Specifically, in the water-soluble silver protecting agent that the present invention is provided, wherein AEO is non-ionic surface
Activating agent.On the basis of the gross mass of the water-soluble silver protecting agent, the content of AEO is 13-15wt%.
The N- benzyls phenyl acetamide is the protectant one kind of silver-colored complex coordination, and it can be by being conjugated phenyl ring and silvering
The silver atoms formation covalent bond and/or coordinate bond on surface, and chain polymer is alternateed into, so as to be effectively isolated argent
Contact with air, in silver surface one layer of fine and close transparent organic molecular film of formation, plays Anti- tarnishing, increase silver layer corrosion resistance and resists
The effect of oxidation；Organic protective film layer does not influence the electric conductivity and solderability of silver layer simultaneously.With the water-soluble silver protecting agent
Gross mass on the basis of, the contents of N- benzyl phenyl acetamides is 4-9wt%.
In the present invention, it is described protection additive in cyclododecane, 1- octadecylenes, 7- octadecylenes, 1- laurylenes one
Plant or a variety of；These four protection additives are similar because of structure, and with conjugated electrons pair, conjugation is identical, has to argent
Similar suction-operated, can carry out high-quality Absorptive complex wave to silver layer, further lift quality of protection.With the water-soluble silver
On the basis of protectant gross mass, the content of protection additive is 3-7wt%.
In the water-soluble silver protecting agent that the present invention is provided, it can also be protected containing other silver-colored complex coordinations commonly used in the prior art
Agent is protected, for example can be selectively containing one or both of benzo tetrazole, lauryl mercaptan, but be not limited to this.It is preferred that feelings
Under condition, on the basis of the gross mass of the water-soluble silver protecting agent, the content of benzo tetrazole is 4-9wt%.With the water solubility
On the basis of the gross mass of silver protecting agent, the content of lauryl mercaptan is 4-8wt%.
Present invention also offers the preparation method of the water-soluble silver protecting agent, including by AEO, N-
Benzyl phenyl acetamide and protection additive are dissolved in the water, that is, obtain the water-soluble silver protecting agent.
As it was previously stated, benzo tetrazole and/or lauryl mercaptan can also be contained in the water-soluble silver protecting agent, therefore,
When preparing the water-soluble silver protecting agent, correspondingly, in addition to benzo tetrazole and/or lauryl mercaptan are dissolved in the water
Step.
Present invention also offers a kind of chemical silver plating method, this method includes workpiece to be plated being placed into chemical plating liquid
Chemical plating is carried out, silver plate is obtained；Then silver plate is positioned over progress silver layer protection processing in water-soluble silver protecting agent again；Institute
State the water-soluble silver protecting agent that water-soluble silver protecting agent provides for the present invention.At the water-soluble silver protecting agent provided using the present invention
Silver coating after reason has good metallic luster, and with more preferable resistance to corrosion.
Wherein, used in plating process and obtain chemical plating liquid and chemical plating process condition for those skilled in the art
It is known, it is not particularly limited in the present invention, here is omitted.
And to silver plate carry out silver layer protection handle the step of be then：The water solubility that directly silver plate is provided with the present invention
Silver protecting agent is contacted.Specifically, the condition of silver layer protection processing includes：The temperature of water-soluble silver protecting agent is 40-44 DEG C,
Processing time is 2-4min.
As the common knowledge of those skilled in the art, in order that to obtain adhesion more preferable for silver coating, it is preferable that this method is also
The step of pre-treatment is carried out to workpiece to be plated before being included in chemical plating.The pre-treatment includes oil removing, acid etching.In oil removing and acid
Repeatedly washed respectively after erosion.
Finally, the invention provides a kind of electroplate workpiece, the electroplate workpiece include workpiece substrates to be plated and
Plating is overlying on the silver coating on the workpiece substrates surface to be plated, and the surface of the silver coating is also covered with silver-colored protective layer；Its feature exists
In the electroplate workpiece chemical silver plating method provided by the present invention is obtained.
In order that technical problem solved by the invention, technical scheme and beneficial effect are more clearly understood, below in conjunction with
Specific embodiment, the present invention will be described in further detail.It should be appreciated that specific embodiment described herein is only used to
The present invention is explained, is not intended to limit the present invention.Raw material is commercially available employed in embodiment and comparative example, the present invention
It is not particularly limited.
Embodiment 1
（1）Each component is dissolved in the water according to following proportionings, the water-soluble silver protecting agent S1 of the present embodiment is prepared：Fat
Alcohol APEO 13wt%；Benzo tetrazole 4wt%；Lauryl mercaptan 4wt%；Cyclododecane 3wt%；N- benzyl phenylacetyls
Amine 4wt%, surplus is water；
（2）Surface is subjected to ultrasonic oil removing for the workpiece to be plated of copper coating, soaked after washing using 5wt% sulfuric acid solution
Except oxide layer, progress chemical silvering processing in silver plating liquid is put into after washing, silver plating liquid composition is：Pyrovinic acid silver 0.1g/L,
Sodium citrate 0.2g/L, ethylenediamine 0.1 g/L, ceric sulfate 0.1ppm, BTA 0.2ppm, lauryl sodium sulfate
5ppm, peregal 1ppm, it is 9.2 to reconcile pH value with sodium hydroxide solution；Silver plating liquid temperature is 52 DEG C, and the silver-plated time is
10min；Silver plate is obtained after the completion of silver-plated, silver plate is impregnated in step after washing（1）The water-soluble silver protecting agent S1 of preparation
In, 3min is handled at 42 DEG C, then washes and is dried with centrifuge, obtain plating piece S10.
Embodiment 2
Water-soluble silver protecting agent S2 is prepared using step same as Example 1, and carries out chemical silvering, difference exists
In：
Step（1）In, water-soluble silver protecting agent S2 composition is：AEO 14wt%；Benzo tetrazole
7wt%；Lauryl mercaptan 6wt%；Cyclododecane 5wt%；N- benzyl phenyl acetamide 6wt%, surplus is water；
Step（2）In, the condition of silver layer protection processing includes：The temperature of water-soluble silver protecting agent is 44 DEG C, processing time
For 4min.
By above-mentioned steps, the plating piece S20 of the present embodiment is obtained.
Embodiment 3
Water-soluble silver protecting agent S3 is prepared using step same as Example 1, and carries out chemical silvering, difference exists
In：
Step（1）In, water-soluble silver protecting agent S3 composition is：AEO 15wt%；Benzo tetrazole
9wt%；Lauryl mercaptan 8wt%；Cyclododecane 7wt%；N- benzyl phenyl acetamide 9wt%, surplus is water；
Step（2）In, the condition of silver layer protection processing includes：The temperature of water-soluble silver protecting agent is 40 DEG C, processing time
For 2min.
By above-mentioned steps, the plating piece S30 of the present embodiment is obtained.
Embodiment 4
Water-soluble silver protecting agent 4 is prepared using step same as Example 1, and carries out chemical silvering, difference exists
In：
Step（1）In, water-soluble silver protecting agent S4 composition is：AEO 14wt%；Lauryl mercaptan
6wt%；Cyclododecane 5wt%；N- benzyl phenyl acetamide 6wt%, surplus is water；
Step（2）In, the condition of silver layer protection processing includes：The temperature of water-soluble silver protecting agent is 40 DEG C, processing time
For 2min.
By above-mentioned steps, the plating piece S40 of the present embodiment is obtained.
Embodiment 5
Water-soluble silver protecting agent 5 is prepared using step same as Example 1, and carries out chemical silvering, difference exists
In：
Step（1）In, water-soluble silver protecting agent S5 composition is：AEO 14wt%；Benzo tetrazole
7wt%；Cyclododecane 5wt%；N- benzyl phenyl acetamide 6wt%, surplus is water；
Step（2）In, the condition of silver layer protection processing includes：The temperature of water-soluble silver protecting agent is 40 DEG C, processing time
For 2min.
By above-mentioned steps, the plating piece S50 of the present embodiment is obtained.
Embodiment 6
Water-soluble silver protecting agent 6 is prepared using step same as Example 1, and carries out chemical silvering, difference exists
In：
Step（1）In, water-soluble silver protecting agent S6 composition is：AEO 14wt%；Cyclododecane
5wt%；N- benzyl phenyl acetamide 6wt%, surplus is water；
Step（2）In, the condition of silver layer protection processing includes：The temperature of water-soluble silver protecting agent is 40 DEG C, processing time
For 2min.
By above-mentioned steps, the plating piece S60 of the present embodiment is obtained.
Embodiment 7
Water-soluble silver protecting agent S7 is prepared using step same as Example 1, and carries out chemical silvering, difference exists
In：
Step（1）In, water-soluble silver protecting agent S7 composition is：AEO 14wt%；Benzo tetrazole
7wt%；Lauryl mercaptan 6wt%；1- octadecylenes 5wt%；N- benzyl phenyl acetamide 6wt%, surplus is water；
Step（2）In, the condition of silver layer protection processing includes：The temperature of water-soluble silver protecting agent is 44 DEG C, processing time
For 4min.
By above-mentioned steps, the plating piece S70 of the present embodiment is obtained.
Embodiment 8
Water-soluble silver protecting agent S8 is prepared using step same as Example 1, and carries out chemical silvering, difference exists
In：
Step（1）In, water-soluble silver protecting agent S8 composition is：AEO 14wt%；Benzo tetrazole
7wt%；Lauryl mercaptan 6wt%；7- octadecylenes 5wt%；N- benzyl phenyl acetamide 6wt%, surplus is water；
Step（2）In, the condition of silver layer protection processing includes：The temperature of water-soluble silver protecting agent is 44 DEG C, processing time
For 4min.
By above-mentioned steps, the plating piece S80 of the present embodiment is obtained.
Embodiment 9
Water-soluble silver protecting agent S9 is prepared using step same as Example 1, and carries out chemical silvering, difference exists
In：
Step（1）In, water-soluble silver protecting agent S9 composition is：AEO 14wt%；Benzo tetrazole
7wt%；Lauryl mercaptan 6wt%；1- laurylenes 5wt%；N- benzyl phenyl acetamide 6wt%, surplus is water；
Step（2）In, the condition of silver layer protection processing includes：The temperature of water-soluble silver protecting agent is 44 DEG C, processing time
For 4min.
By above-mentioned steps, the plating piece S90 of the present embodiment is obtained.
Comparative example 1
Water-soluble silver protecting agent DS1 is prepared using step same as Example 1, and carries out chemical silvering, difference
It is：
Step（1）In, water-soluble silver protecting agent DS1 composition is：AEO 14wt%；Benzo tetrazole
4wt%；BTA 4wt%；Lauryl mercaptan 6wt%；Surplus is water；
Step（2）In, the condition of silver layer protection processing includes：The temperature of water-soluble silver protecting agent is 44 DEG C, processing time
For 4min.
By above-mentioned steps, the plating piece DS10 of the present embodiment is obtained.
Comparative example 2
Water-soluble silver protecting agent DS2 is prepared using step same as Example 1, and carries out chemical silvering, difference
It is：
Step（1）In, water-soluble silver protecting agent DS2 composition is：AEO 14wt%；Benzo tetrazole
4wt%；BTA 4wt%；Lauryl mercaptan 6wt%；Cyclododecane 5wt%；Surplus is water；
Step（2）In, the condition of silver layer protection processing includes：The temperature of water-soluble silver protecting agent is 44 DEG C, processing time
For 4min.
By above-mentioned steps, the plating piece DS20 of the present embodiment is obtained.
Comparative example 3
Water-soluble silver protecting agent DS3 is prepared using step same as Example 1, and carries out chemical silvering, difference
It is：
Step（1）In, water-soluble silver protecting agent DS3 composition is：AEO 14wt%；Benzo tetrazole
4wt%；BTA 4wt%；Lauryl mercaptan 6wt%；N- benzyl phenyl acetamide 6wt%, surplus is water；
Step（2）In, the condition of silver layer protection processing includes：The temperature of water-soluble silver protecting agent is 44 DEG C, processing time
For 4min.
By above-mentioned steps, the plating piece DS30 of the present embodiment is obtained.
Performance test
Neutral salt spray test condition：In salt-mist corrosion tester, with the salting liquid that sodium chloride content is 5 ± 1%：Temperature
At 35 DEG C, the collection liquid after spraying, pH value is 6.5 ~ 7.2.Allow with the watery hydrochloric acid after dilution or sodium hydroxide adjustment pH value.
35 DEG C of test space temperature；The continuous spray testing time is 72H；Then protected after ordinary atmospheric conditions, stabilization are returned in case
Hold 2H.Outward appearance to each plating piece is detected.Standard：Non-corroding, discoloration, coating come off, and are designated as OK, are otherwise designated as NG.Survey
Test result is as shown in table 1.
Table 1
。
Compare from the test result of upper table 1 as can be seen that the water-soluble silver protecting agent provided using the present invention is to silvering
Carry out after protection processing, plating piece appearance is good, non-corroding, discoloration, coating obscission, hence it is evident that better than the plating in comparative example
Part sample.
Compared from S10-S30 with S40-S60 test result as can be seen that in the water-soluble silver protecting agent that the present invention is provided
When preferably comprising benzo tetrazole, lauryl mercaptan, its protecting effect to silver layer is more preferably.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all essences in the present invention
Any modifications, equivalent substitutions and improvements made within refreshing and principle etc., should be included in the scope of the protection.
Claims (12)
1. a kind of water-soluble silver protecting agent, it is characterised in that the water-soluble silver protecting agent be containing AEO,
The aqueous solution of N- benzyls phenyl acetamide and protection additive, the protection additive is selected from cyclododecane, 1- octadecylenes, 7- ten
One or more in eight alkene, 1- laurylenes；In the water-soluble silver protecting agent, the content of AEO is 13-
The content of 15wt%, N- benzyl phenyl acetamide is 4-9wt%, and the content of protection additive is 3-7wt%.
2. water-soluble silver protecting agent according to claim 1, it is characterised in that also contain in the water-soluble silver protecting agent
Benzo tetrazole.
3. water-soluble silver protecting agent according to claim 2, it is characterised in that in the water-soluble silver protecting agent, benzo
The content of tetrazole is 4-9wt%.
4. water-soluble silver protecting agent according to claim 1, it is characterised in that also contain in the water-soluble silver protecting agent
Lauryl mercaptan.
5. water-soluble silver protecting agent according to claim 4, it is characterised in that in the water-soluble silver protecting agent, 12
The content of mercaptan is 4-8wt%.
6. water-soluble protectant preparation method described in claim 1, it is characterised in that including by aliphatic alcohol polyethenoxy
Ether, N- benzyls phenyl acetamide and protection additive are dissolved in the water, that is, obtain the water-soluble silver protecting agent.
7. preparation method according to claim 6, it is characterised in that also including by benzo tetrazole and/or lauryl mercaptan
The step of being dissolved in the water.
8. a kind of chemical silver plating method, it is characterised in that this method, which includes workpiece to be plated being placed into chemical plating liquid, to be carried out
Chemical plating, obtains silver plate；Then silver plate is positioned over progress silver layer protection processing in water-soluble silver protecting agent again；Its feature
It is, the water-soluble silver protecting agent is the water-soluble silver protecting agent described in claim any one of 1-5.
9. chemical silver plating method according to claim 8, it is characterised in that the condition of silver layer protection processing includes：It is water-soluble
Property silver protecting agent temperature be 40-44 DEG C, processing time is 2-4min.
10. chemical silver plating method according to claim 8, it is characterised in that this method is additionally included in before chemical silvering
The step of pre-treatment is carried out to workpiece to be plated.
11. chemical silver plating method according to claim 10, it is characterised in that the pre-treatment includes oil removing, acid etching.
12. a kind of electroplate workpiece, the electroplate workpiece includes workpiece substrates to be plated and plating is overlying on the workpiece to be plated
The silver coating of substrate surface, the surface of the silver coating is also covered with silver-colored protective layer；Characterized in that, the electroplate workpiece
Obtained as the chemical silver plating method described in claim any one of 8-11.
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| CN107268214A (en) * | 2017-06-20 | 2017-10-20 | 丹阳市斯鲍特体育用品有限公司 | A kind of method that infusion process prepares conductive fencing metallic plastron fabric |
| CN110484901B (en) * | 2018-05-15 | 2022-11-01 | 上海新阳半导体材料股份有限公司 | Chemical silver plating solution, preparation method and application thereof |
| CN109853014B (en) * | 2019-01-29 | 2020-10-27 | 广州鸿葳科技股份有限公司 | Potassium sulfide-resistant silver antioxidant and preparation method thereof |
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| CN101974759A (en) * | 2010-11-23 | 2011-02-16 | 海宁市科泰克金属表面技术有限公司 | Post-treatment protective agent for rare and precious metals |
| CN102162095A (en) * | 2011-03-01 | 2011-08-24 | 济南德锡科技有限公司 | Anti-discoloring protective agent for silver plating and preparation method as well as application method thereof |
| CN102747372A (en) * | 2011-04-22 | 2012-10-24 | 比亚迪股份有限公司 | Copper protective agent and its preparation method and copper protection method |
| CN102747350A (en) * | 2012-07-18 | 2012-10-24 | 深圳市成功科技有限公司 | Gold/silver plating layer surface protective agent |
| CN102816462A (en) * | 2012-08-13 | 2012-12-12 | 中国科学院宁波材料技术与工程研究所 | Preparation method for nano-silver particles coated with organic protection agent on surfaces |
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| CN104419921A (en) | 2015-03-18 |
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