CN113215631A - Inner hole deposition technology for fine micropores with large depth-diameter ratio - Google Patents
Inner hole deposition technology for fine micropores with large depth-diameter ratio Download PDFInfo
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- CN113215631A CN113215631A CN202110501705.1A CN202110501705A CN113215631A CN 113215631 A CN113215631 A CN 113215631A CN 202110501705 A CN202110501705 A CN 202110501705A CN 113215631 A CN113215631 A CN 113215631A
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- diameter ratio
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- 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
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D15/00—Electrolytic or electrophoretic production of coatings containing embedded materials, e.g. particles, whiskers, wires
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- 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
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- 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
- C25D5/20—Electroplating using ultrasonics, vibrations
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Abstract
The invention discloses a technology for depositing a fine micropore inner hole with a large depth-diameter ratio, which belongs to the field of the deposition of the fine micropore inner hole with the large depth-diameter ratio, utilizes solution stirring and strong cavitation in an ultrasonic field environment to quickly exchange electroplating solution in the hole, increases current density and exhaust speed, thereby improving the deep plating capacity of plating solution, and the thinning capacity of plating layer crystallization is not more than 5: blind hole of 1 or 10: 1, the plating layer in the through hole is completely covered, and the corrosion resistance of the plating layer is greatly improved because the crystallization of the plating layer is more delicate, thereby meeting the requirement of the plating layer in the fine micro hole of a high-end electronic product.
Description
Technical Field
The invention relates to the field of inner hole deposition of fine micropores with large depth-diameter ratio, in particular to a technique for depositing inner holes of fine micropores with large depth-diameter ratio.
Background
The electrochemical deposition method, commonly known as electroplating, is an electrochemical processing method for obtaining a metal film with firm binding force, uniform plating layer and fine surface on the surface of a part by taking a plated conductive part as a cathode and using electrolysis in a plating solution containing a metal plating compound, and is also one of the widely applied surface treatment technologies at present. The method can be divided into the categories of common direct current electroplating, alternating current and direct current superposition electroplating, pulse electroplating and the like according to different voltage and current supply modes of a power supply, wherein the pulse electroplating is divided into single pulse electroplating and double pulse electroplating. And is divided into single metal plating and alloy plating according to the types of the metal elements to be plated. However, when the depth-diameter ratio is greater than 3, the inner wall and the bottom of the hole can not be plated with a plating layer (copper, silver, nickel, gold), and in an electronic product, the surface of the inner hole without the plating layer is gradually oxidized and blackened in the using process, so that poor contact, open circuit and poor or failed signal transmission are caused.
Disclosure of Invention
The invention provides a deposition technology of a fine micropore inner hole with a large depth-diameter ratio to solve the problems.
In order to achieve the purpose, the invention adopts the following technical scheme:
a technology for depositing inner holes of fine micropores with large depth-diameter ratio comprises the following steps:
s1, before electroplating, the prepared composite electroplating solution is subjected to low-current activated carbon adsorption impurity removal and electrolysis impurity removal;
s2, stabilizing the pH value of the composite electroplating solution to 2-5, controlling the concentration of the nano-slurry to 50-150 g/L and the main salt to be nickel sulfamate 380-450 g/L, then electroplating, using the surface treated electrolytic nickel plate as an anode and the surface treated stainless steel plate as a cathode, and electroplating the nanocrystalline coating by adopting a single pulse electrodeposition process, wherein the electrodeposition time is 2-4 h, and the pulse current density is 6.0-8.0A/dm2The duty ratio is 35-65%, the period is 1-2 ms, the electrodeposition temperature is 55-65 ℃, the stirring speed is 200-400 r/min, and the ultrasonic power is constant at 350W.
Preferably, the nanopaste is a high-purity nanopaste particle subjected to impurity removal and wetting treatment.
Preferably, the slow-release acid for adjusting the pH in the composite electroplating solution is boric acid.
Preferably, the composite electroplating liquid also comprises 0.01-0.05g/L of anionic surfactant sodium dodecyl sulfate as a wetting agent
Preferably, the purity of the electrolytic nickel plate for the anode is more than 99.99%, the electrode spacing between the anode and the cathode is 5-10 cm, the specification is 10cm × 0.2 cm, and the area ratio of the anode to the cathode is more than or equal to 6: 1.
preferably, the cathode stainless steel is sequentially polished by metallographic abrasive paper to achieve a mirror surface effect, the cathode stainless steel is placed into 80 ℃ alkaline solution for ultrasonic treatment for 10-12 min to remove dirt and oil, then the base body after oil removal treatment is placed into 80 ℃ deionized water for ultrasonic treatment for 2min to remove the alkaline solution remained on the surface of the stainless steel base body, and finally the base body is placed into dilute sulfuric acid solution for ultrasonic oscillation for 60-80 s to remove rust and activate the surface.
Compared with the prior art, the invention provides a fine micropore inner hole deposition technology with a large depth-diameter ratio, which has the following beneficial effects:
1. the invention has the beneficial effects that: by utilizing solution stirring and strong cavitation in the ultrasonic field environment, the electroplating solution is quickly exchanged in the hole, the current density is increased, and the exhaust speed is increased, so that the deep plating capacity of the electroplating solution is improved, and the depth-diameter ratio of the refining capacity of the coating crystallization is not more than 5: blind hole of 1 or 10: 1, the plating layer in the through hole is completely covered, and the corrosion resistance of the plating layer is greatly improved because the crystallization of the plating layer is more delicate, thereby meeting the requirement of the plating layer in the fine micro hole of a high-end electronic product.
Drawings
FIG. 1 is a diagram of microhardness HV of a coating at different pulse current densities according to an embodiment of the present invention;
FIG. 2 is a diagram of microhardness HV of a coating layer at different duty ratios according to an embodiment of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments.
In the description of the present invention, it is to be understood that the terms "upper", "lower", "front", "rear", "left", "right", "top", "bottom", "inner", "outer", and the like, indicate orientations or positional relationships based on the orientations or positional relationships shown in the drawings, are merely for convenience in describing the present invention and simplifying the description, and do not indicate or imply that the device or element being referred to must have a particular orientation, be constructed and operated in a particular orientation, and thus, should not be construed as limiting the present invention.
Example 1:
a technology for depositing inner holes of fine micropores with large depth-diameter ratio comprises the following steps:
s1, before electroplating, the prepared composite electroplating solution is subjected to low-current activated carbon adsorption impurity removal and electrolysis impurity removal;
s2, stabilizing the pH value of the composite electroplating solution to 4, controlling the concentration of the nano-slurry to 150g/L and the main salt to be nickel sulfamate 450g/L, then electroplating, using the surface treated electrolytic nickel plate as an anode and the surface treated stainless steel plate as a cathode, and electroplating the nanocrystalline plating layer by adopting a single-pulse electrodeposition process, wherein the electrodeposition time is 3h, and the pulse current density is 7.0A/dm2The duty ratio is 55%, the period is 1ms, the electrodeposition temperature is 55 ℃, the stirring speed is 400r/min, and the ultrasonic power is constant at 350W.
Further, preferably, the nanopaste is a nanopaste particle having high purity and subjected to impurity removal and wetting treatment.
Further, preferably, the slow-release acid for adjusting PH in the composite plating solution is boric acid.
Further, preferably, the composite electroplating liquid also comprises 0.05g/L of anionic surfactant sodium dodecyl sulfate as a wetting agent
Further, preferably, the purity of the electrolytic nickel plate for the anode is 99.99% or more, the electrode pitch between the anode and the cathode is 25cm, the specification is 10cm × 0.2 cm, and the area ratio of the anode to the cathode is greater than or equal to 6: 1.
further, preferably, the cathode stainless steel is sequentially polished by metallographic abrasive paper to achieve a mirror surface effect, the cathode stainless steel is placed into 80 ℃ alkaline solution for ultrasonic treatment for 12min to remove dirt and oil, then the base body after oil removal treatment is placed into 80 ℃ deionized water for ultrasonic treatment for 2min to remove the alkaline solution remained on the surface of the stainless steel base body, and finally the base body is placed into dilute sulfuric acid solution for ultrasonic oscillation for 80s to remove the dirt and activate the surface.
Example 2: this example is based on example 1, but differs therefrom in that the pulse current density in S2 was changed to a range of 2-14A/dm2The microhardness HV of the plating layer is shown in FIG. 1;
as shown in fig. 1, as the pulse average current density increased, the microhardness increased first and then decreased, up to 425 HV; when the average current density is low, the lower cathode overpotential limits the formation rate and the growth speed of crystal nuclei; meanwhile, the codeposition process is slow, the quantity of the nano particles coated and embedded by the matrix metal is small, and the reinforcing effect is relatively weak; the two reasons jointly lead to the formation of coarse crystals and loose structures, so that the microhardness is low. When the average current density is increased, the strong electrostatic attraction and the acting force between two phase interfaces promote more nano particles to be attached to the surface of the plated substrate, participate in codeposition and be coated. The nano particles are uniformly dispersed in the coating layer, so that the shielding blocking effect and the fine grain strengthening effect are effectively exerted, the overpotential of the cathode is increased, the fine crystallization and the compact structure are promoted, and the hardness of the composite coating is improved.
Example 3: this example is based on example 1, but differs therefrom in that the duty ratio in S2 is changed to a range of 0.2 to 1.0, and the microhardness HV of the plating layer is as shown in fig. 2 below;
the relationship between the pulse duty ratio and the microhardness of the coating is shown in fig. 2, and the change trend is similar to that shown in fig. 1, and the microhardness is increased and then decreased along with the increase of the duty ratio. The reason for analysis is that the change is mainly attributed to that the change of the duty ratio influences the crystallization process and the compounding amount of the nano particles in the composite coating, and further influences the strengthening effect of the particles and the compactness of the composite coating. The duty ratio is small, the conduction time is short, the stop time is long, ions consumed in the stop time can be effectively supplemented and recovered, the concentration gradient is weakened, and the continuity and the stability of the crystallization process are maintained. After the duty ratio is increased, the plating speed is accelerated, and the limit time required for coating the particles is shortened. In addition, the high peak current density prompts the codeposition process to be carried out under the condition of larger cathode overpotential, and the nano particles are easy to be attached and embedded in the composite coating, so that the composite quantity is increased. However, if the duty ratio is increased to a certain degree, the effect is equal to the direct current effect, and the continuously carried co-deposition process may cause concentration polarization due to the blockage of diffusion mass transfer and convection mass transfer, so that the composite coating structure is weakened, the composite amount of the nano particles is reduced, and the microhardness is reduced macroscopically.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (6)
1. A technology for depositing inner holes of fine micropores with large depth-diameter ratio is characterized by comprising the following steps:
s1, before electroplating, the prepared composite electroplating solution is subjected to low-current activated carbon adsorption impurity removal and electrolysis impurity removal;
s2, stabilizing the pH value of the composite electroplating solution to 2-5, controlling the concentration of the nano-slurry to 50-150 g/L and the main salt to be nickel sulfamate 380-450 g/L, then electroplating, using the surface treated electrolytic nickel plate as an anode and the surface treated stainless steel plate as a cathode, and electroplating the nanocrystalline coating by adopting a single pulse electrodeposition process, wherein the electrodeposition time is 2-4 h, and the pulse current density is 6.0-8.0A/dm2The duty ratio is 35-65%, the period is 1-2 ms, the electrodeposition temperature is 55-65 ℃, the stirring speed is 200-400 r/min, and the ultrasonic power is constant at 350W.
2. The inner hole deposition technology of a fine micro-hole with a large depth-diameter ratio as claimed in claim 1, wherein: the nano-slurry is high-purity nano-slurry particles subjected to impurity removal and wetting treatment.
3. The inner hole deposition technology of a fine micro-hole with a large depth-diameter ratio as claimed in claim 1, wherein: the slow-release acid for adjusting the pH value in the composite electroplating liquid is boric acid.
4. The inner hole deposition technology of a fine micro-hole with a large depth-diameter ratio as claimed in claim 1, wherein: the composite electroplating solution also comprises 0.01-0.05g/L of anionic surfactant sodium dodecyl sulfate as a wetting agent.
5. The inner hole deposition technology of a fine micro-hole with a large depth-diameter ratio as claimed in claim 1, wherein: the purity of the electrolytic nickel plate for the anode is more than 99.99%, the electrode spacing between the anode and the cathode is 5-10 cm, the specification is 10cm x 0.2 cm, and the area ratio of the anode to the cathode is more than or equal to 6: 1.
6. the inner hole deposition technology of a fine micro-hole with a large depth-diameter ratio as claimed in claim 1, wherein: and sequentially polishing the cathode stainless steel to a mirror surface effect through metallographic abrasive paper, placing the cathode stainless steel into 80 ℃ alkaline solution for ultrasonic treatment for 10-12 min to remove dirt and oil, then placing the base body subjected to oil removal treatment into 80 ℃ deionized water for ultrasonic treatment for 2min to remove the alkaline solution remained on the surface of the stainless steel base body, and finally placing the base body into dilute sulfuric acid solution for ultrasonic oscillation for 60-80 s to perform rust removal and surface activation treatment.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202110501705.1A CN113215631A (en) | 2021-05-08 | 2021-05-08 | Inner hole deposition technology for fine micropores with large depth-diameter ratio |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202110501705.1A CN113215631A (en) | 2021-05-08 | 2021-05-08 | Inner hole deposition technology for fine micropores with large depth-diameter ratio |
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6200450B1 (en) * | 1998-03-30 | 2001-03-13 | Wen Hua Hui | Method and apparatus for depositing Ni-Fe-W-P alloys |
| CN102002748A (en) * | 2010-12-09 | 2011-04-06 | 大连大学 | Method for preparing ferromagnetic nano composite material with pulse-ultrasound electrodeposition |
| CN107326405A (en) * | 2017-06-23 | 2017-11-07 | 安庆市枞江汽车部件制造有限公司 | A kind of electroplating surface processing technology of car belt buckle |
| CN108207090A (en) * | 2017-12-29 | 2018-06-26 | 广州兴森快捷电路科技有限公司 | The production method of printed circuit board |
| CN108221012A (en) * | 2018-01-03 | 2018-06-29 | 西北工业大学 | A kind of Fe-Ni/ZrO2The electro-deposition preparation method of nanocomposite |
| CN111334827A (en) * | 2020-03-13 | 2020-06-26 | 河海大学 | Ultrasonic-assisted nano cerium oxide doped Ni-W-TiN composite coating and preparation method thereof |
-
2021
- 2021-05-08 CN CN202110501705.1A patent/CN113215631A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6200450B1 (en) * | 1998-03-30 | 2001-03-13 | Wen Hua Hui | Method and apparatus for depositing Ni-Fe-W-P alloys |
| CN102002748A (en) * | 2010-12-09 | 2011-04-06 | 大连大学 | Method for preparing ferromagnetic nano composite material with pulse-ultrasound electrodeposition |
| CN107326405A (en) * | 2017-06-23 | 2017-11-07 | 安庆市枞江汽车部件制造有限公司 | A kind of electroplating surface processing technology of car belt buckle |
| CN108207090A (en) * | 2017-12-29 | 2018-06-26 | 广州兴森快捷电路科技有限公司 | The production method of printed circuit board |
| CN108221012A (en) * | 2018-01-03 | 2018-06-29 | 西北工业大学 | A kind of Fe-Ni/ZrO2The electro-deposition preparation method of nanocomposite |
| CN111334827A (en) * | 2020-03-13 | 2020-06-26 | 河海大学 | Ultrasonic-assisted nano cerium oxide doped Ni-W-TiN composite coating and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 夏法锋等: "《机械零件表面沉积纳米镀层及测试技术》", 31 May 2011 * |
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