CN112323106A - Rapid silver plating process - Google Patents
Rapid silver plating process Download PDFInfo
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- CN112323106A CN112323106A CN202011137257.3A CN202011137257A CN112323106A CN 112323106 A CN112323106 A CN 112323106A CN 202011137257 A CN202011137257 A CN 202011137257A CN 112323106 A CN112323106 A CN 112323106A
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- silver
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- water
- silver plating
- plating
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- 229910052709 silver Inorganic materials 0.000 title claims abstract description 213
- 239000004332 silver Substances 0.000 title claims abstract description 213
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 200
- 238000007747 plating Methods 0.000 title claims abstract description 153
- 238000000034 method Methods 0.000 title claims abstract description 52
- 238000005406 washing Methods 0.000 claims abstract description 90
- 239000003814 drug Substances 0.000 claims abstract description 84
- 239000007788 liquid Substances 0.000 claims abstract description 51
- 238000007654 immersion Methods 0.000 claims abstract description 31
- 239000000758 substrate Substances 0.000 claims abstract description 31
- 238000001035 drying Methods 0.000 claims abstract description 18
- -1 silver ions Chemical class 0.000 claims abstract description 13
- 239000008139 complexing agent Substances 0.000 claims abstract description 11
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000004140 cleaning Methods 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 80
- 239000003795 chemical substances by application Substances 0.000 claims description 32
- 238000006073 displacement reaction Methods 0.000 claims description 16
- 238000005238 degreasing Methods 0.000 claims description 15
- HKSGQTYSSZOJOA-UHFFFAOYSA-N potassium argentocyanide Chemical group [K+].[Ag+].N#[C-].N#[C-] HKSGQTYSSZOJOA-UHFFFAOYSA-N 0.000 claims description 14
- NNFCIKHAZHQZJG-UHFFFAOYSA-N potassium cyanide Chemical group [K+].N#[C-] NNFCIKHAZHQZJG-UHFFFAOYSA-N 0.000 claims description 13
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 7
- RIRXDDRGHVUXNJ-UHFFFAOYSA-N [Cu].[P] Chemical group [Cu].[P] RIRXDDRGHVUXNJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 238000005282 brightening Methods 0.000 claims description 5
- 230000005484 gravity Effects 0.000 claims description 5
- 239000003223 protective agent Substances 0.000 claims description 5
- 239000000243 solution Substances 0.000 claims 1
- 238000000576 coating method Methods 0.000 abstract description 23
- 239000011248 coating agent Substances 0.000 abstract description 22
- 239000000463 material Substances 0.000 abstract description 19
- 238000009713 electroplating Methods 0.000 abstract description 11
- 238000002791 soaking Methods 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 29
- 238000012360 testing method Methods 0.000 description 17
- 238000001514 detection method Methods 0.000 description 12
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 6
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 238000005260 corrosion Methods 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- 238000009825 accumulation Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000004299 exfoliation Methods 0.000 description 3
- 238000005498 polishing Methods 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- 229910021607 Silver chloride Inorganic materials 0.000 description 2
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 2
- 239000000908 ammonium hydroxide Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 2
- 230000003746 surface roughness Effects 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910001361 White metal Inorganic materials 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- NWFNSTOSIVLCJA-UHFFFAOYSA-L copper;diacetate;hydrate Chemical compound O.[Cu+2].CC([O-])=O.CC([O-])=O NWFNSTOSIVLCJA-UHFFFAOYSA-L 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 239000010969 white metal Substances 0.000 description 1
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
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D21/00—Processes for servicing or operating cells for electrolytic coating
- C25D21/12—Process control or regulation
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/18—Electroplating using modulated, pulsed or reversing current
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D7/00—Electroplating characterised by the article coated
Abstract
The application relates to the field of electroplating, and particularly discloses a rapid silver plating process. The process comprises the following steps: surface cleaning, pre-silver plating, silver immersion plating, washing I, silver protection, washing II and drying; in immersion silver plating: adding silver salt according to 20-40g/L of silver ions, 135g/L of complexing agent 101-; the pulse plating current density is 1-2ASD, the frequency is 800-1200HZ, and the duty ratio is 25-35%. This application is through soaking the cooperation of silver-plating liquid medicine, pulse plating, improves the degree of consistency of silver-plating layer, need not to corrode and thins the substrate, also can make silver-plating layer satisfy minimum thickness value and maximum thickness value requirement, the whole thickness of electronic components does not exceed standard. Moreover, the density of the silver coating can be improved, and the roughness of the silver coating is greatly reduced. Moreover, the method omits the step of corroding and thinning the base material, and improves the overall efficiency of the silver plating process.
Description
Technical Field
The application relates to the field of electroplating, in particular to a rapid silver plating process.
Background
Silver is a silvery white metal with an atomic weight of 107.8682 and a density of 10.49g/cm3The electrochemical equivalent is 4.025g/A, and the standard electrode potential is 0.81V. As one of the common types of plating layers, silver plating has excellent conductivity, solderability, polishability, and chemical stability, and is widely used in various electronic components of electronic products.
The thickness of the silver plating is one of the parameters of great interest in the silver plating process. On the one hand, in order to ensure the conductivity, solderability, polishability of the silver plating and the protection of the substrate used for electronic components, a minimum thickness value is usually set for the silver plating according to actual requirements. On the other hand, with the development of electronic technology, electronic products tend to be miniaturized, and the requirements on the assembly matching degree of electronic components are higher and higher, so that the requirements on the size of the electronic components are also higher and higher. For example, for a chip-shaped electronic component, on the premise that the thickness of the substrate used for the electronic component is determined, the thickness of the silver plating layer of the chip-shaped electronic component is required not to exceed a set maximum value, otherwise, the electronic component cannot be assembled into a reserved space of an electronic product. Therefore, according to actual requirements, it is usually necessary to set a maximum thickness value for the silver plating layer of the electronic component.
At present, in the process of plating silver on a substrate of an electronic component, the uniformity of the thickness of a silver plating layer is poor, and the difference value between the minimum thickness value and the maximum thickness value of the silver plating layer is large. In order to meet the requirement of the minimum thickness value of the silver coating, the silver plating time cannot be shortened, and the maximum thickness value of the silver coating often exceeds the standard, so that the overall thickness of an electronic component exceeds the standard, and the electronic component cannot be assembled in a reserved space of an electronic product.
Therefore, the means disclosed in the related art is to firstly corrode the substrate surface of the electronic component by using a corrosive agent to reduce the thickness of the substrate, and then to carry out silver plating, that is, to ensure that the silver plating layer meets the requirements of the minimum thickness value and the maximum thickness value by thinning the corrosion of the substrate, and the whole thickness of the electronic component does not exceed the standard. However, the corrosion causes the substrate to have a hollow and uneven surface, which not only easily causes the quality of the substrate not to reach the standard, but also reduces the interface bonding force between the substrate and the silver plating layer, and further influences the accumulation growth of silver ions in the silver plating process, reduces the compactness of the silver plating layer, increases the roughness of the silver plating layer, and thus seriously influences the conductivity, weldability, polishing property, chemical stability and other properties of the silver plating layer.
Disclosure of Invention
In order to abandon the scheme that the silver coating meets the requirements of the minimum thickness value and the maximum thickness value and the whole thickness of an electronic component does not exceed the standard by corroding and thinning a base material, the application provides a rapid silver plating process, which adopts the following technical scheme:
a rapid silver plating process, which comprises the following steps of:
surface cleaning, pre-silver plating, silver immersion plating, water washing I and drying,
wherein the content of the first and second substances,
the immersion silver plating step comprises: the adopted liquid medicine is prepared from a medicament and water, wherein the medicament comprises silver salt, a complexing agent, a displacement agent and a brightening agent; according to the dosage of the medicament added into each liter of water, silver salt is added according to the adding amount of 20-40g/L silver ions, 135g/L complexing agent 101, 15-25ml/L displacement agent and 5-15ml/L brightener; pulse plating is adopted, the current density is 1-2ASD, the frequency is 800-.
The immersion silver plating is an important step for determining the silver plating quality in the silver plating process, and the test result shows that the phenomenon of poor thickness uniformity of a silver plating layer can be greatly improved by adopting the immersion silver plating step in the technical scheme, the base material does not need to be thinned by corrosion, the silver plating layer can meet the requirements of the minimum thickness value and the maximum thickness value, and the integral thickness of the electronic component does not exceed the standard. Moreover, the test result of the application also shows that the silver immersion plating step in the technical scheme can improve the density of the silver plating layer and greatly reduce the roughness of the silver plating layer, so that the characteristics of the silver plating layer such as conductivity, weldability, polishing property, chemical stability and the like are enhanced. The main reason why the above-mentioned effects can be achieved by the present application is to adjust the chemical components and the plating parameters in a matching manner.
In the liquid medicine for immersion silver plating, the displacement agent belongs to a surfactant, and can improve the surface tension of a product during electroplating, so that silver ions can realize rapid and uniform dispersion electroplating on the surface of the product, and the uniformity of the thickness of a silver plating layer is improved. The brightener can remove oil stains, oxidized and unoxidized impurities on the surface of the product by improving the surface activity of the product, not only can improve the glossiness of the surface of the product, but also is beneficial to improving the bonding compactness of plating particles, thereby improving the density of a silver plating. According to the method, the concentration of silver ions is improved to 20-40g/L, the walking agent and the brightener with proper proportion are added, pulse electroplating is adopted, pulse electroplating parameters are debugged according to the composition of liquid medicine, the proper pulse electroplating parameters matched with the liquid medicine are obtained, and finally, the silver plating layer with high thickness uniformity and high density is obtained.
Moreover, compared with the traditional scheme in the related technology, the method omits the step of corroding and thinning the base material, thereby improving the overall operation efficiency of the silver plating process.
Preferably, in the silver pre-plating step: the adopted liquid medicine is prepared from a medicament and water, wherein the medicament comprises a silver salt and a complexing agent; according to the dosage of the medicament added into each liter of water, silver salt is added according to the adding amount of 1.0-2.5g/L of silver ions, and the complexing agent is 100-; the adopted current density is 0.25-0.75ASD, and the time is 0.4-0.5 min.
By adopting the technical scheme, the composition and concentration of each liquid medicine are controlled, the adjustment of treatment process parameters is matched, a layer of thin silver bottom is quickly formed before immersion plating of silver, and the binding force of copper materials and silver is increased.
Preferably, a silver protection step and a water washing II step are further included between the water washing I step and the drying step, wherein in the silver protection step: the liquid medicine is silver protective agent, the addition amount is 20-60ml/L, and the temperature is 45-55 ℃;
by adopting the technical scheme, a layer of protective film is formed on the surface of the silver plating layer, so that the oxidation resistance of the silver plating layer is improved.
Preferably, in the immersion silver plating step and the pre-silver plating step, the temperature of the liquid medicine is 15-30 ℃.
Preferably, the surface cleaning step includes electrolytic degreasing, washing a, acid washing, and washing b, wherein in the electrolytic degreasing: the adopted liquid medicine is prepared by adding oil removing powder into water, the specific gravity of the liquid medicine is 7-16Be, and the temperature of the liquid medicine is 50-65 ℃; the adopted current density is 7.5-12.5ASD, and the time of electrolytic degreasing is 0.8-1 min;
in the water washing step a: the pH value of the washing water is changed when the pH value is more than 8 in the washing process;
in acid washing: the adopted liquid medicine is a sulfuric acid aqueous solution with the mass concentration of 6-8% and the pH value of less than 1, the time is 0.4-0.5min, and the temperature is normal temperature;
and b, washing with water: the pH of the wash water is changed when it is less than 6 during the washing process.
By adopting the technical scheme, the composition and concentration of each liquid medicine are controlled, and the oil stain and the oxidation film on the surface of the base material are removed by matching with the adjustment of treatment process parameters, and meanwhile, the base material is not damaged.
Preferably, in the step of washing I and washing II: the washing water is replaced when the conductivity of the washing water is more than 20 us/cm.
Along with the extension of the washing time, the conductivity of the washing water is continuously increased, and when the conductivity exceeds a preset limit, the washing water is replaced in time, so that the washing cleanliness can be guaranteed.
Preferably, in the drying step: drying at 100 +/-20 ℃.
Preferably, the silver salt is potassium silver cyanide, and the complexing agent is potassium cyanide.
Preferably, the displacement agent is a silver brightener A agent, and the brightener is a silver brightener B agent.
Preferably, the substrate in question is phosphor copper.
In summary, the present application has the following beneficial effects:
1. according to the method, the silver plating layer is formed by the silver immersion plating liquid medicine and is adjusted in matching with the proportion and the pulse electroplating parameters, the thickness uniformity of the silver plating layer is improved, the thinned substrate is not required to be corroded, the requirement of the minimum thickness value and the maximum thickness value of the silver plating layer can be met, and the integral thickness of an electronic component does not exceed the standard.
2. The technical scheme of this application can improve the density of silver-plated layer, alleviates silver-plated layer inflation phenomenon to can strengthen characteristics such as conductivity, solderability, polishing nature and chemical stability of silver-plated layer.
3. Compared with the traditional scheme in the related technology, the method omits the step of corroding and thinning the base material, thereby improving the overall operation efficiency of the silver plating process.
Detailed Description
The present application is described in further detail below.
Introduction of raw materials
The base material adopted in the following embodiment is made of phosphor copper, is sheet-shaped, and has the thickness of 0.125-0.129 mm; the adopted oil removing powder is alloy electric release oil powder purchased from Huapu; silver brightener A and silver brightener B are both purchased from Qitai; the silver protectant used was purchased from Zhengte, model number 307.
Example 1
A rapid silver plating process adopts a substrate which is phosphor copper, the substrate is flaky, the thickness of the substrate is 0.129mm, and the substrate is treated by the following steps: electrolytic degreasing, washing a, acid washing, washing b, pre-silver plating, immersion silver plating, washing I, silver protection, washing II and drying to obtain a product, wherein:
in electrolytic degreasing: the adopted liquid medicine is prepared by adding oil removing powder into water, the specific gravity of the liquid medicine is 7Be, and the temperature of the liquid medicine is 50 ℃; adopting direct current, wherein the current density is 7.5ASD, and the time for electrolytic degreasing is 0.8 min;
in the water washing step a: the pH value of the washing water is changed when the pH value is more than 8 in the washing process;
in acid washing: the adopted liquid medicine is a sulfuric acid aqueous solution with the mass concentration of 6% and the pH value of less than 1, the time is 0.4min, and the temperature is normal temperature;
and b, washing with water: the pH value of the washing water is changed when the pH value is less than 6 in the washing process;
in the silver pre-plating step: the adopted liquid medicine is prepared from a medicament and water, wherein the medicament comprises silver potassium cyanide and potassium cyanide; according to the dosage of the medicament added into each liter of water, the silver potassium cyanide is added according to the addition amount of 1.0g/L silver ions, and the potassium cyanide is 140 g/L; the temperature of the liquid medicine is 15 ℃; adopting direct current with current density of 0.25ASD for 0.4 min;
in the step of immersion silver plating: the adopted liquid medicine is prepared from a medicament and water, wherein the medicament comprises silver potassium cyanide, a displacement agent and a brightening agent; according to the dosage of the medicament added into each liter of water, the silver potassium cyanide is added according to the addition amount of 40g/L silver ions, 101g/L potassium cyanide, 25ml/L displacement agent and 5ml/L brightener; the temperature of the liquid medicine is 15 ℃; pulse plating is adopted, the current density is 1ASD, the frequency is 800HZ, the duty ratio is 25 percent, and the time is 2.5 min; wherein the displacement agent is a silver brightener A agent, and the brightener is a silver brightener B agent;
and (3) water washing I: when the conductivity of the washing water is more than 20us/cm, the washing water is replaced;
in the silver protection step: the liquid medicine is a silver protective agent, the addition amount is 20ml/L, and the temperature is 45 ℃;
and (2) washing II: when the conductivity of the washing water is more than 20us/cm, the washing water is replaced;
in the drying step: drying at 80 deg.C.
Example 2
A rapid silver plating process adopts a substrate which is phosphor copper, the substrate is sheet-shaped, the thickness of the substrate is 0.128mm, and the substrate is treated by the following steps: electrolytic degreasing, washing a, acid washing, washing b, pre-silver plating, immersion silver plating, washing I, silver protection, washing II and drying to obtain a product, wherein:
in electrolytic degreasing: the adopted liquid medicine is prepared by adding oil removing powder into water, the specific gravity of the liquid medicine is 10Be, and the temperature of the liquid medicine is 55 ℃; adopting direct current, wherein the current density is 10ASD, and the time for electrolytic degreasing is 0.9 min;
in the water washing step a: the pH value of the washing water is changed when the pH value is more than 8 in the washing process;
in acid washing: the adopted liquid medicine is a sulfuric acid aqueous solution with the mass concentration of 7% and the pH value of less than 1, the time is 0.45min, and the temperature is normal temperature;
and b, washing with water: the pH value of the washing water is changed when the pH value is less than 6 in the washing process;
in the silver pre-plating step: the adopted liquid medicine is prepared from a medicament and water, wherein the medicament comprises silver potassium cyanide and potassium cyanide; according to the dosage of the medicament added into each liter of water, the silver potassium cyanide is added according to the addition amount of 2.0g/L silver ions, and the potassium cyanide is 120 g/L; the temperature of the liquid medicine is 25 ℃; adopting direct current with current density of 0.50ASD for 0.45 min;
in the step of immersion silver plating: the adopted liquid medicine is prepared from a medicament and water, wherein the medicament comprises silver potassium cyanide, a displacement agent and a brightening agent; according to the dosage of the medicament added into each liter of water, the silver potassium cyanide is added according to the adding amount of 30g/L silver ion, 120g/L potassium cyanide, 20ml/L displacement agent and 10ml/L brightener; the temperature of the liquid medicine is 25 ℃; pulse electroplating is adopted, the current density is 1.5ASD, the frequency is 1000HZ, the duty ratio is 30 percent, and the time is 3 min; wherein the displacement agent is a silver brightener A agent, and the brightener is a silver brightener B agent;
and (3) water washing I: when the conductivity of the washing water is more than 20us/cm, the washing water is replaced;
in the silver protection step: the liquid medicine is a silver protective agent, the addition amount is 40ml/L, and the temperature is 50 ℃;
and (2) washing II: when the conductivity of the washing water is more than 20us/cm, the washing water is replaced;
in the drying step: drying at 100 deg.C.
Example 3
A rapid silver plating process adopts a substrate which is phosphor copper, the substrate is flaky, the thickness of the substrate is 0.129mm, and the substrate is treated by the following steps: electrolytic degreasing, washing a, acid washing, washing b, pre-silver plating, immersion silver plating, washing I, silver protection, washing II and drying to obtain a product, wherein:
in electrolytic degreasing: the adopted liquid medicine is prepared by adding oil removing powder into water, the specific gravity of the liquid medicine is 16Be, and the temperature of the liquid medicine is 65 ℃; adopting direct current, wherein the current density is 12.5ASD, and the time for electrolytic degreasing is 1 min;
in the water washing step a: the pH value of the washing water is changed when the pH value is more than 8 in the washing process;
in acid washing: the adopted liquid medicine is a sulfuric acid aqueous solution with the mass concentration of 8% and the pH value of less than 1, the time is 0.5min, and the temperature is normal temperature;
and b, washing with water: the pH value of the washing water is changed when the pH value is less than 6 in the washing process;
in the silver pre-plating step: the adopted liquid medicine is prepared from a medicament and water, wherein the medicament comprises silver potassium cyanide and potassium cyanide; according to the dosage of the medicament added into each liter of water, the silver potassium cyanide is added according to the addition amount of 2.5g/L silver ions, and the potassium cyanide is 100 g/L; the temperature of the liquid medicine is 30 ℃; adopting direct current with current density of 0.75ASD for 0.5 min;
in the step of immersion silver plating: the adopted liquid medicine is prepared from a medicament and water, wherein the medicament comprises silver potassium cyanide, a displacement agent and a brightening agent; according to the dosage of the medicament added into each liter of water, the silver potassium cyanide is added according to the addition amount of 20g/L silver ion, 135g/L potassium cyanide, 15ml/L displacement agent and 15ml/L brightener; the temperature of the liquid medicine is 30 ℃; pulse plating is adopted, the current density is 2ASD, the frequency is 1200HZ, the duty ratio is 35 percent, and the time is 3.3 min; wherein the displacement agent is a silver brightener A agent, and the brightener is a silver brightener B agent;
and (3) water washing I: when the conductivity of the washing water is more than 20us/cm, the washing water is replaced;
in the silver protection step: the adopted liquid medicine is a silver protective agent, the addition amount is 60ml/L, and the temperature is 55 ℃;
and (2) washing II: when the conductivity of the washing water is more than 20us/cm, the washing water is replaced;
in the drying step: drying at 120 deg.C.
Comparative example 1
A rapid silver plating process, which is different from the embodiment 2 in that: the thickness of the base material is 0.128 mm; in the step of immersion plating silver, 10ml/L of silver brightener A and 20ml/L of silver brightener B are added.
Comparative example 2
A rapid silver plating process, which is different from the embodiment 2 in that the thickness of the substrate is 0.128 mm; in the step of immersion plating silver, 30ml/L of silver brightener A and 3ml/L of silver brightener B are added.
Comparative example 3
A rapid silver plating process, which is different from the embodiment 2 in that the thickness of the base material is 0.129 mm; in the step of immersion plating silver, 10ml/L of silver brightener A and 3ml/L of silver brightener B are added.
Comparative example 4
A rapid silver plating process, which is different from the embodiment 2 in that the thickness of the base material is 0.127 mm; in the step of immersion plating silver, 30ml/L of silver brightener A and 20ml/L of silver brightener B are added.
Comparative example 5
A rapid silver plating process, which is different from the embodiment 2 in that the thickness of the base material is 0.127 mm; in the silver immersion step, the current density was 0.5 ASD.
Comparative example 6
A rapid silver plating process, which is different from the embodiment 2 in that the thickness of the substrate is 0.128 mm; in the silver immersion step, the current density was 2.0 ASD.
Comparative example 7
A rapid silver plating process, which is different from the embodiment 2 in that the thickness of the substrate is 0.128 mm; in the immersion silver plating step, the frequency is 750 Hz.
Comparative example 8
A rapid silver plating process, which is different from the embodiment 2 in that the thickness of the base material is 0.127 mm; in the immersion silver plating step, the frequency is 1250 Hz.
Comparative example 9
A rapid silver plating process, which is different from the embodiment 2 in that the thickness of the base material is 0.129 mm; in the immersion silver plating step, the duty ratio is 20%.
Comparative example 10
A rapid silver plating process, which is different from the embodiment 2 in that the thickness of the substrate is 0.128 mm; in the immersion silver plating step, the duty ratio is 40%.
Comparative example 11
A silver plating process, which is different from example 2 in that: the thickness of the base material is 0.129 mm; in the step of immersion silver plating:
adopting the liquid medicine disclosed in the prior art, wherein the liquid medicine is prepared from a medicament and water, and the medicament comprises silver chloride, potassium cyanide, potassium carbonate, carbon disulfide and ammonium hydroxide; according to the dosage of the added medicament in each liter of water, silver chloride is added according to the addition amount of 18g/L silver ions, 45g/L potassium cyanide, 18g/L potassium carbonate, 0.04g/L carbon disulfide and 0.8ml/L ammonium hydroxide aqueous solution with the volume concentration of 30 percent;
pulse plating was used with a current density of 0.4ASD, a frequency of 800HZ and a duty cycle of 16%.
Silver coating thickness uniformity detection
The products obtained in examples 1 to 3 and comparative examples 1 to 11 were examined for uniformity of thickness of silver plating. The detection method comprises the following steps: selecting 10 detection points on the surface of the product, detecting the thickness of the silver coating by using an x-ray coating thickness gauge, wherein the maximum value minus the minimum value of the 10 detection results is the silver coating thickness difference of the product, and the smaller the silver coating thickness difference is, the better the thickness uniformity of the silver coating is. The results are shown in Table 1.
TABLE 1 silver coating thickness uniformity test results
As can be seen from table 1, the difference in the thickness of the silver plating layer of the products obtained in examples 1 to 3 is significantly reduced compared to that of comparative example 11, which shows that the silver plating process provided by the present application can greatly improve the phenomenon of poor uniformity of the thickness of the silver plating layer. The silver plating process is applied to the production of parts of electronic components, the thinning base material does not need to be corroded, the silver plating layer can meet the requirements of the minimum thickness value and the maximum thickness value, the whole thickness of the electronic components does not exceed the standard, and the step of corroding the thinning base material can be omitted, so that the whole operation efficiency of the silver plating process of the parts of the electronic components can be greatly improved.
The main reason why the silver plating process of the present application can achieve the above-mentioned effects is due to the adjustment of the chemical composition and the plating parameters, as can be further seen in connection with example 2 and comparative examples 1 to 10.
Detection of density of silver plating layer
The thickness measurement of the electroplating product can also use a micrometer, and the micrometer is used for measuring the sum of the thicknesses of the base material and the two silver coatings. The inventor of the application adopts a method which is rapid and direct in practice aiming at the density detection of the silver plating layer, and the principle of the method is as follows: the thickening of the silver plating layer lies in the accumulation production of silver, and when the accumulation growth of silver is irregularly arranged, the poor uniformity of the silver plating layer can not only occur, but also the poor density and the high surface roughness of the silver plating layer can be caused. That is, when the density of the silver plating layer is poor, the surface roughness and uniformity of the silver plating layer are also poor, some silver plating layers are thick, and some silver plating layers are thin. At the moment, when a micrometer and an X-ray film thickness meter are used for detecting the same product together, the film thickness meter detects a point, and if a thin part is just detected, the data is low; when the micrometer is attached to the surface of the silver plating layer, the thickness of the measured value is more deviated to the thickest position due to the support of the thickest position of the silver plating layer, and the data of the micrometer is larger than that of a film thickness meter.
In the detection, a micrometer and an X-ray film thickness meter are adopted to measure the same double-sided silver-plated product. And measuring the total thickness of the product by using a micrometer, and measuring the total thickness of the silver plating layer by using the micrometer with the total thickness minus the thickness of the substrate red as the product. And measuring the thickness of the silver plating on two sides of the product by adopting an X-ray film thickness meter, wherein the sum of the two sides is used for measuring the total thickness of the silver plating by the X-ray film thickness meter. The difference between the total thickness of the silver coating measured by the micrometer and the total thickness of the silver coating measured by the X-ray film thickness meter is smaller, the compactness is better, and the compactness of the product is quickly reflected. Wherein, 1 micro inch is 0.0000254 mm.
The results of this test are shown in table 2.
TABLE 2 silver coating density detection results
As can be seen from table 2, compared to comparative example 11, the difference between the total thickness of the silver plating layer measured by the micrometer and the total thickness of the silver plating layer measured by the X-ray film thickness meter is smaller for the products corresponding to examples 1 to 3, which reflects that the silver plating layer obtained by the silver plating process of the present application has higher compactness. The main reason for this should also be attributed to the adjustment of the formulation of the bath and the plating parameters, as can be seen in example 2 and comparative examples 1 to 10.
Other detection of silver plating
In addition to the above-described uniformity and density tests for each of the products obtained in examples 1 to 3 and comparative examples 1 to 11, the following tests were carried out for each of the products.
And (3) appearance detection: observing the silver plating layer under a microscope, and checking whether the surface of the silver plating layer has uniform color and has no phenomena of dirt, oxidation, flow marks, deformation, color difference, bubbling, peeling, plating leakage and the like. According to the order of superiority and inferiority, A, B, C grades are divided.
And (3) detecting the binding force: and bending the product electroplating area by 90 degrees back and forth twice by using pliers, sticking the coating by using 600#3M type gummed paper, and observing whether the silver coating falls off or not after the gummed paper is torn.
And (3) salt spray testing: and (3) putting the product into a salt spray machine with the temperature of 35 ℃ and the mass concentration of salt water of 5% for 24 hours, then taking out the product, cleaning the product with clear water, and observing whether the silver coating area has the bad phenomena of verdigris, oxidation and the like by naked eyes. According to the order of superiority and inferiority, A, B, C grades are divided.
And (3) tin pick-up test: the tin dipping test is a test method for testing the solderability of the silver coating of the product, and during operation, the product is placed into a tin furnace and dipped with tin for 3-5 seconds at 245 +/-5 ℃, and the tin coating degree is more than 95 percent to meet the requirement.
And (3) high-temperature testing: and (3) placing the product into a high-temperature furnace, baking the product in a high-temperature baking oven at the temperature of 260 +/-5 ℃ for 3 minutes, and observing whether the silver coating area is yellowed or not by naked eyes. According to the order of superiority and inferiority, A, B, C grades are divided.
The results of the above tests are shown in Table 3.
TABLE 3 silver coating other test results
| Product(s) | Appearance detection | Binding force detection | Salt spray test | Degree of tin deposition | High temperature testing |
| Example 1 | Class A | Is not fallen off | Class A | 98％ | Class A |
| Example 2 | Class A | Is not fallen off | Class A | 97％ | Class A |
| Example 3 | Class A | Is not fallen off | Class A | 98％ | Class A |
| Comparative example 1 | Class C | Is not fallen off | Class A | 96％ | Class A |
| Comparative example 2 | Class B | Severe exfoliation | Class C | 80％ | Class B |
| Comparative example 3 | Class C | Severe exfoliation | Class C | 84％ | Class C |
| Comparative example 4 | Class B | Is not fallen off | Class B | 85％ | Class B |
| Comparative example 5 | Class B | Slight detachment | Class B | 85％ | Class C |
| Comparative example 6 | Class C | Is not fallen off | Class A | 87％ | Class B |
| Comparative example 7 | Class C | Severe exfoliation | Class B | 79％ | Class B |
| Comparative example 8 | Class B | Slight detachment | Class B | 82％ | Class A |
| Comparative example 9 | Class B | Slight detachment | Class B | 83％ | Class A |
| Comparative example 10 | Class B | Slight detachment | Class B | 84％ | Class B |
| Comparative example 11 | Class A | Is not fallen off | Class A | 95％ | Class A |
As can be seen from Table 3, the products obtained in examples 1 to 3 of the present application are excellent in appearance, silver plating adhesion, corrosion resistance, solderability, and high temperature resistance, and meet the requirements. It can also be seen from a combination of example 2 and comparative examples 1 to 10 that the products of the present application perform well in the above-mentioned properties, primarily because of the rational combination of the bath components and plating parameters. Wherein, salt spray test and high temperature test also indirectly reflect that the silver plating layer of this application has few inside space, and the density is good.
The present embodiment is only for explaining the present application, and it is not limited to the present application, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present application.
Claims (10)
1. The rapid silver plating process is characterized in that a substrate is subjected to the treatment comprising the following steps: surface cleaning, pre-silvering, immersion silvering, water washing I and drying, wherein,
the immersion silver plating step comprises: the adopted liquid medicine is prepared from a medicament and water, wherein the medicament comprises silver salt, a complexing agent, a displacement agent and a brightening agent; according to the dosage of the medicament added into each liter of water, silver salt is added according to the adding amount of 20-40g/L silver ions, 135g/L complexing agent 101, 15-25ml/L displacement agent and 5-15ml/L brightener; pulse plating is adopted, the current density is 1-2ASD, the frequency is 800-.
2. The rapid silver plating process according to claim 1, wherein in the pre-silver plating step: the adopted liquid medicine is prepared from a medicament and water, wherein the medicament comprises a silver salt and a complexing agent; according to the dosage of the medicament added into each liter of water, silver salt is added according to the adding amount of 1.0-2.5g/L of silver ions, and the complexing agent is 100-; the adopted current density is 0.25-0.75ASD, and the time is 0.4-0.5 min.
3. The rapid silver plating process according to claim 1, further comprising a silver protection step and a water washing II step between the water washing I step and the drying step, wherein the silver protection step comprises the following steps: the liquid medicine is silver protective agent, the addition amount is 20-60ml/L, and the temperature is 45-55 ℃.
4. The rapid silver plating process according to claim 1, wherein the temperature of the chemical solution in the immersion silver plating step and the pre-silver plating step is 15-30 ℃.
5. The rapid silver plating process according to claim 1, characterized in that: the surface cleaning step comprises electrolytic degreasing, water washing a, acid washing and water washing b, wherein,
in electrolytic degreasing: the adopted liquid medicine is prepared by adding oil removing powder into water, the specific gravity of the liquid medicine is 7-16Be, and the temperature of the liquid medicine is 50-65 ℃; the adopted current density is 7.5-12.5ASD, and the time of electrolytic degreasing is 0.8-1 min;
in the water washing step a: the pH value of the washing water is changed when the pH value is more than 8 in the washing process;
in acid washing: the adopted liquid medicine is a sulfuric acid aqueous solution with the mass concentration of 6-8% and the pH value of less than 1, the time is 0.4-0.5min, and the temperature is normal temperature;
and b, washing with water: the pH of the wash water is changed when it is less than 6 during the washing process.
6. The rapid silver plating process according to claim 1, wherein in the water wash I and water wash II steps: the washing water is replaced when the conductivity of the washing water is more than 20 us/cm.
7. The rapid silver plating process according to claim 1, wherein in the drying step: drying at 100 +/-20 ℃.
8. The process according to any one of claims 1 to 7, wherein the silver salt is potassium silver cyanide and the complexing agent is potassium cyanide.
9. The rapid silver plating process according to any one of claims 1 to 7, wherein the displacement agent is silver brightener A agent and the brightener is silver brightener B agent.
10. The rapid silver plating process according to any one of claims 1 to 7, wherein the substrate is phosphor copper.
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