CN111962107A - Copper-nickel-tin electroplating method for chip component - Google Patents
Copper-nickel-tin electroplating method for chip component Download PDFInfo
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- CN111962107A CN111962107A CN202010790090.4A CN202010790090A CN111962107A CN 111962107 A CN111962107 A CN 111962107A CN 202010790090 A CN202010790090 A CN 202010790090A CN 111962107 A CN111962107 A CN 111962107A
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- 238000009713 electroplating Methods 0.000 title claims abstract description 38
- 238000000034 method Methods 0.000 title claims abstract description 28
- VRUVRQYVUDCDMT-UHFFFAOYSA-N [Sn].[Ni].[Cu] Chemical compound [Sn].[Ni].[Cu] VRUVRQYVUDCDMT-UHFFFAOYSA-N 0.000 title claims abstract description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 40
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 39
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 19
- 239000010949 copper Substances 0.000 claims abstract description 13
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052802 copper Inorganic materials 0.000 claims abstract description 12
- 238000007747 plating Methods 0.000 claims description 34
- PEVJCYPAFCUXEZ-UHFFFAOYSA-J dicopper;phosphonato phosphate Chemical compound [Cu+2].[Cu+2].[O-]P([O-])(=O)OP([O-])([O-])=O PEVJCYPAFCUXEZ-UHFFFAOYSA-J 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 10
- 230000007935 neutral effect Effects 0.000 claims description 10
- RYCLIXPGLDDLTM-UHFFFAOYSA-J tetrapotassium;phosphonato phosphate Chemical compound [K+].[K+].[K+].[K+].[O-]P([O-])(=O)OP([O-])([O-])=O RYCLIXPGLDDLTM-UHFFFAOYSA-J 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 9
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 9
- RCIVOBGSMSSVTR-UHFFFAOYSA-L stannous sulfate Chemical compound [SnH2+2].[O-]S([O-])(=O)=O RCIVOBGSMSSVTR-UHFFFAOYSA-L 0.000 claims description 9
- 229910000375 tin(II) sulfate Inorganic materials 0.000 claims description 9
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 6
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 6
- 239000004327 boric acid Substances 0.000 claims description 6
- 238000006073 displacement reaction Methods 0.000 claims description 6
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 6
- 239000000654 additive Substances 0.000 claims description 4
- 230000000996 additive effect Effects 0.000 claims description 3
- 239000008139 complexing agent Substances 0.000 claims description 3
- 239000013589 supplement Substances 0.000 claims description 3
- 230000008569 process Effects 0.000 abstract description 12
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 238000012423 maintenance Methods 0.000 abstract description 2
- 239000010410 layer Substances 0.000 description 12
- 239000000047 product Substances 0.000 description 10
- 229910006653 SnII Inorganic materials 0.000 description 4
- 239000003814 drug Substances 0.000 description 4
- 230000001681 protective effect Effects 0.000 description 4
- 238000005476 soldering Methods 0.000 description 4
- 238000003466 welding Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000001488 sodium phosphate Substances 0.000 description 3
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 3
- 229910000406 trisodium phosphate Inorganic materials 0.000 description 3
- 235000019801 trisodium phosphate Nutrition 0.000 description 3
- 229910001021 Ferroalloy Inorganic materials 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000004512 die casting Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 239000011241 protective layer Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- FTLYMKDSHNWQKD-UHFFFAOYSA-N (2,4,5-trichlorophenyl)boronic acid Chemical compound OB(O)C1=CC(Cl)=C(Cl)C=C1Cl FTLYMKDSHNWQKD-UHFFFAOYSA-N 0.000 description 1
- 229910000640 Fe alloy Inorganic materials 0.000 description 1
- 241000204031 Mycoplasma Species 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910000856 hastalloy Inorganic materials 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 229940085605 saccharin sodium Drugs 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910001432 tin ion Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/12—Electroplating: Baths therefor from solutions of nickel or cobalt
-
- 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
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- 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
A chip component copper-nickel-tin electroplating method comprises the following steps of first pretreatment, second copper electroplating, third nickel electroplating, fourth tin electroplating and fifth aftertreatment; JY-P001 is used in the pretreatment, wherein JY-P00130-60 ml/L is adopted, the pH value is 3.0-5.0, and the temperature is maintained at 40-50 ℃; the copper-nickel-tin electroplating process for the chip component is characterized in that the electroplating process is optimized, a production line is optimized, a production method is optimized, and a good maintenance mode is adopted, so that the productivity of the production line and the quality of products are improved, and the aim of saving energy is fulfilled.
Description
Technical Field
The invention relates to a chip component electroplating method, in particular to a chip component copper-nickel-tin electroplating method.
Background
At present, modern technology is improved at any time, electronic products are developed rapidly, and people increasingly rely on the electronic products in life; with the increasing demand of people on electronic products, most of chip components as important components of the electronic products need to be electroplated; along with the increasing deepening of users on the quality requirement, the traditional electroplating processing defects of the chip components are more and more obvious, and the electroplating method in the prior art has the technical problems that the thickness uniformity of a plating layer is poor, the film thickness cannot be guaranteed, the high-temperature impact cannot be borne, the surface of the plating layer is easy to oxidize, and no tin coating or poor soldering tin is easy to occur.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides the copper-nickel-tin electroplating method for the chip component, which can improve the uniform thickness and pressure of a plating layer when the component is electroplated and can ensure that the plating layer is not easily oxidized.
The invention is realized by adopting the following technical scheme: a chip component copper nickel tin electroplating method comprises the following steps;
the first step of pretreatment, the second step of copper electroplating, the third step of nickel electroplating, the fourth step of tin electroplating and the fifth step of post-treatment;
adding JY-P001 into the pretreatment tank during pretreatment, wherein JY-P00130-60 ml/L is adopted, the pH value is 3.0-5.0, and the temperature is maintained at 40-50 ℃;
during the second step of copper electroplating, adding copper pyrophosphate, potassium pyrophosphate and JY-Cu001 into a copper plating tank, wherein the components of the copper pyrophosphate, the potassium pyrophosphate and the JY-Cu001 are as follows:
40-70g/L of copper pyrophosphate, 360g/L, JY-Cu0010.2-0.4ml/L of potassium pyrophosphate and the pH value of the solution is 8.2-8.8, and the temperature in the electroplating pool is maintained at 50-70 ℃;
when nickel is electroplated in the third step, nickel sulfate, nickel chloride, boric acid, JY-Ni003 and JY-Ni004 are added into a nickel-plating tank, wherein the nickel sulfate, the nickel chloride, the boric acid, the JY-Ni003 and the JY-Ni004 comprise the following components:
360g/L of nickel sulfate 300-;
and when the tin plating is carried out in the fourth step, adding stannous sulfate, JY-Sn005, JY-Sn006 and JY-Sn007 into the tin plating tank, wherein the stannous sulfate, JY-Sn005, JY-Sn006 and JY-Sn007 comprise the following components:
25-30g/L, JY-Sn 00580-140 g/L, JY-Sn 006150-250 g/L, JY-Sn00715-45ml/L of stannous sulfate, maintaining the pH value at 4.0-4.5 and the temperature at 20-30 ℃;
when the post-treatment is carried out in the fifth step, JY-BH001 is added into a post-treatment groove, wherein the JY-BH001 contains the components
JY-BH001 concentration is 20-40ml/L, and the maintained temperature is 35-40 ℃.
JY-P001 is a coarsening agent, JY-Cu001 pyrocopper additive, JY-Ni003 nickel displacement agent, JY-Ni004 nickel supplement, JY-Sn005 neutral tin complexing agent, JY-Sn006 neutral tin conductive liquid, JY-Sn007 neutral tin displacement agent and JY-BH001 tin high-temperature resistant protective liquid.
Compared with the prior art, the copper-nickel-tin electroplating process for the chip component has the advantages that the production line is optimized, the production method is optimized, and a good maintenance mode is achieved through the optimized electroplating process, so that the productivity of the production line and the quality of a product are improved, the purpose of energy conservation is achieved, most chip components can be compatible, and the batch production capacity is improved by at least more than 1 time, so that the production line can be greatly compressed, and the production cost is greatly reduced.
Drawings
FIG. 1 is a schematic diagram of JY-SnII neutral tin.
FIG. 2 is a schematic diagram of acid tin plating.
FIG. 3 is a schematic view of tinning of a mycoplasma system.
FIG. 4 is a schematic view of the RENCHUAN system tin plating.
FIG. 5 is a diagram illustrating the result after JY-B001 welding.
FIG. 6 is a graphical representation of trisodium phosphate welding results.
Detailed Description
The present invention is further described below with reference to specific embodiments, and it should be noted that, without conflict, any combination between the embodiments or technical features described below may form a new embodiment.
A chip component copper-nickel-tin electroplating method comprises the following steps of first pretreatment, second copper electroplating, third nickel electroplating, fourth tin electroplating and fifth aftertreatment;
pretreatment: taking die-cast inductor 2520 as an example: the substrate is special and is formed by die-casting ferroalloy with poor impedance and no magnetism, the internal structure of the product is formed by winding an inductor and then die-casting and packaging the inductor by the ferroalloy, and the external structure is insulated and protected by a special packaging layer; the lead wire is stripped by the inductance terminal through laser, so that a layer of oxide film is formed on the surface of the iron alloy with the original impedance difference through laser high-temperature engraving; the formed oxide film can increase the difficulty of electroplating, the outer protective layer is afraid of acid, the substrate has oxide film, and the electric conductivity is poor.
The following is the comparative case of traditional activation without pretreatment and coarsening using JY-P001:
the PH value working range of JY-P001 is 3.0-4.0, the corrosion to the non-metal layer is very weak, but the PH value working range has very effective removing effect on the metal oxide film; and has activating effect on the metal surface. The efficiency of plating at the back can be greatly improved, the possibility of bulging of the terminal is reduced, and the binding force of the terminal is improved;
adding JY-P001 into the pretreatment tank during pretreatment, wherein JY-P00130-60 ml/L is adopted, the pH value is 3.0-5.0, and the temperature is maintained at 40-50 ℃;
JY-P001: removing the oxide film on the metal surface, improving the activity of the metal surface and improving the binding force of a plating layer;
during the second step of copper electroplating, adding copper pyrophosphate, potassium pyrophosphate and JY-Cu001 into a copper plating tank, wherein the components of the copper pyrophosphate, the potassium pyrophosphate and the JY-Cu001 are as follows:
40-70g/L of copper pyrophosphate, 360g/L, JY-Cu0010.2-0.4ml/L of potassium pyrophosphate
Maintaining the temperature in the electroplating pool at 50-70 deg.C and pH at 8.2-8.8;
JY-Cu 001: the permeability of the liquid medicine is increased, so that the current density distribution is more uniform, and the uniformity of the plating layer is better;
in the copper plating process, the uniformity of a plating layer is greatly improved when 0.2-0.4ml/L of JY-Cu001 is added when the temperature of copper pyrophosphate is adjusted to be 15g/L and 300g/L of potassium pyrophosphate is 60 ℃;
the deep plating capability of the single-sided terminal is particularly important, the product is in a sheet type and is very easy to be stacked together, and when the products are stacked, the terminal surface becomes a dead angle, which is very unfavorable for electroplating. Through the adjustment of the components, the addition of JY-Cu001 and the vibration assistance of the frame, the standard deviation of the copper film thickness can be controlled to be below 1.0, and the following is the data comparison measured by a Feichel film thickness meter:
the data show that the film thickness uniformity after improvement is greatly improved;
when nickel is electroplated in the third step, nickel sulfate, nickel chloride, boric acid, JY-Ni003 and JY-Ni004 are added into a nickel groove, wherein the nickel sulfate, the nickel chloride, the boric acid, the JY-Ni003 and the JY-Ni004 comprise the following components:
360g/L of nickel sulfate 300-;
JY-Ni 003: the difference between the high current area and the low current area is leveled up depending on the high current area, so that the burning probability of the high area is reduced; the current application range is improved, and the uniformity of a plating layer is improved;
JY-Ni 004: the penetration capacity of the liquid medicine is improved, the depth capacity of the liquid medicine is increased, the current density distribution is more uniform, and the film thickness uniformity is better;
JY-NI003 and JY-NI004 additives are used in the nickel plating link, compared with the traditional saccharin sodium and sodium dodecyl sulfate, the deep plating capacity is stronger, and the current use range is wider. Taking a product of 0603400 chip resistors and 100K as an example, the thickness of a nickel film requires 5 microns; the traditional nickel plating process needs 125 amperes of 140 minutes, but after JY-Ni003 and JY-Ni004 are used, the current can be used for 135 amperes, and the operation time can be reduced to 120 minutes. Electronic plating is greatly different from hardware plating, although the nickel surface appearance is still very attractive under the current density of 15ASD through the Hastelloy for 3A times and 3 minutes, compared with the traditional process, JY-Ni003 and JY-Ni004 used by the method are similarly poor in tin-feeding phenomenon under the current of 135A times, and JY-Ni003 and JY-Ni004 used by the method are still very full in tin-soldering.
And when the tin plating is carried out in the fourth step, adding stannous sulfate, JY-Sn005, JY-Sn006 and JY-Sn007 into the tin plating tank, wherein the stannous sulfate, JY-Sn005, JY-Sn006 and JY-Sn007 comprise the following components:
25-30g/L, JY-Sn 00580-140 g/L, JY-Sn 006150-250 g/L, JY-Sn00715-45ml/L of stannous sulfate, maintaining the pH value at 4.0-4.5 and the temperature at 20-30 ℃; tin ions are complexed, so that the conductivity of the liquid medicine is improved, and the current density is improved;
tin is one of the difficulties of the tin plating process, and tin is used as an important protective layer of a nickel layer, so that the tin soldering result after steam aging can be ensured only by ensuring certain thickness and needing the fineness of crystal lattices (after the product is put on boiling water and is aged for 8 hours by steam, the tin soldering experiment is carried out);
FIGS. 1, 2, 3 and 4 are lattice comparisons of JY-SnII tin plating process and other tin plating processes in the market.
As can be seen from the picture, the lattice diameter of JY-SnII tin is about 5 microns, and the similar tin plating lattice level in the market can be basically achieved;
the JY-SnII tinning process has the greatest advantage over other similar processes that the number of sticky sheets is small, and even double sheets can be avoided under the conditions of reasonable plating accompanying objects, rotating speed and drum design.
When the post-treatment is carried out in the fifth step, JY-BH001 is added into a post-treatment groove, wherein the JY-BH001 contains the components
JY-BH001 concentration is 20-40ml/L, and the maintained temperature is 35-40 ℃; forming a nano protective film by means of JY-BH 001;
the post-treatment protection is carried out by JY-B001, so that the tin surface is more green, a nano protective film can be formed on the tin surface under the low-temperature condition (the traditional trisodium phosphate is at 50-70 ℃, and the JY-B001 working temperature is 35-40 ℃), and the solderability and the oxidation resistance of the tin surface can be ensured during SMD welding;
FIGS. 5, 6 are comparisons of the weld after SMD welding with X-ray imaging using JY-B001 protection and trisodium phosphate neutralization:
JY-P001 is a coarsening agent, JY-Cu001 pyrocopper additive, JY-Ni003 nickel displacement agent, JY-Ni004 nickel supplement, JY-Sn005 neutral tin complexing agent, JY-Sn006 neutral tin conductive liquid, JY-Sn007 neutral tin displacement agent and JY-BH001 tin high-temperature resistant protective liquid
The above embodiments are only preferred embodiments of the present invention, and the protection scope of the present invention is not limited thereby, and any insubstantial changes and substitutions made by those skilled in the art based on the present invention are within the protection scope of the present invention.
Claims (3)
1. A chip component copper-nickel-tin electroplating method is characterized by comprising the following steps: comprises the following steps
The first step of pretreatment, the second step of copper electroplating, the third step of nickel electroplating, the fourth step of tin electroplating and the fifth step of post-treatment;
during pretreatment, JY-P001 is added into a pretreatment tank, wherein JY-P00130-60 ml/L is adopted, the pH value is 3.0-5.0, and the temperature is maintained at 40-50 ℃;
during the second step of copper electroplating, adding copper pyrophosphate, potassium pyrophosphate and JY-Cu001 into a copper plating tank, wherein the components of the copper pyrophosphate, the potassium pyrophosphate and the JY-Cu001 are as follows:
40-70g/L of copper pyrophosphate, 360g/L, JY-Cu0010.2-0.4ml/L of potassium pyrophosphate;
the temperature in the electroplating pool is maintained at 50-70 ℃, and the pH value in the electroplating pool is 8.2-8.8.
2. The copper-nickel-tin electroplating method for the chip component as claimed in claim 1, wherein the method comprises the following steps: when nickel is electroplated in the third step, nickel sulfate, nickel chloride, boric acid, JY-Ni003 and JY-Ni004 are added into a nickel-plating tank, wherein the nickel sulfate, the nickel chloride, the boric acid, the JY-Ni003 and the JY-Ni004 comprise the following components:
360g/L of nickel sulfate 300-;
and when the tin plating is carried out in the fourth step, adding stannous sulfate, JY-Sn005, JY-Sn006 and JY-Sn007 into the tin plating tank, wherein the stannous sulfate, JY-Sn005, JY-Sn006 and JY-Sn007 comprise the following components:
25-30g/L, JY-Sn 00580-140 g/L, JY-Sn 006150-250 g/L, JY-Sn00715-45ml/L of stannous sulfate, maintaining the pH value at 4.0-4.5 and the temperature at 20-30 ℃;
when the post-treatment is carried out in the fifth step, JY-BH001 is added into a post-treatment tank, wherein the JY-BH001 comprises the components
JY-BH001 concentration is 20-40ml/L, and the maintained temperature is 35-40 ℃.
3. The copper-nickel-tin electroplating method for the chip component as claimed in claim 2, wherein the method comprises the following steps: JY-P001 is a coarsening agent, JY-Cu001 pyrocopper additive, JY-Ni003 nickel displacement agent, JY-Ni004 nickel supplement, JY-Sn005 neutral tin complexing agent, JY-Sn006 neutral tin conductive liquid, JY-Sn007 neutral tin displacement agent and JY-BH001 tin high-temperature resistant protection liquid.
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Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
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CN108368627A (en) * | 2015-12-15 | 2018-08-03 | 三菱综合材料株式会社 | The manufacturing method of tin plating copper tip material |
CN110158121A (en) * | 2019-05-19 | 2019-08-23 | 南通弘扬金属制品有限公司 | Anti- tin must CP wire production technology |
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Publication number | Priority date | Publication date | Assignee | Title |
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CN108368627A (en) * | 2015-12-15 | 2018-08-03 | 三菱综合材料株式会社 | The manufacturing method of tin plating copper tip material |
CN110158121A (en) * | 2019-05-19 | 2019-08-23 | 南通弘扬金属制品有限公司 | Anti- tin must CP wire production technology |
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Application publication date: 20201120 |