CN111647901B - Black hole liquid and preparation method and application method thereof - Google Patents
Black hole liquid and preparation method and application method thereof Download PDFInfo
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- CN111647901B CN111647901B CN202010410347.9A CN202010410347A CN111647901B CN 111647901 B CN111647901 B CN 111647901B CN 202010410347 A CN202010410347 A CN 202010410347A CN 111647901 B CN111647901 B CN 111647901B
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- black hole
- hole liquid
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/184—Preparation
- C01B32/19—Preparation by exfoliation
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/20—Graphite
- C01B32/21—After-treatment
- C01B32/22—Intercalation
- C01B32/225—Expansion; Exfoliation
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
- H05K3/18—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material
Abstract
The invention discloses a preparation method of black hole liquid, which comprises the following steps: and (3) electrolyzing by taking a graphite plate as an anode, taking a titanium plate or a graphite plate as a cathode and taking water or ammonia water as electrolyte, and then adding a reducing agent and stirring. The black hole liquid prepared by the method can be stably stored for more than one year without sedimentation, and the finally formed conductive layer has stronger conductivity.
Description
Technical Field
The invention relates to the technical field of printed circuit board manufacturing, in particular to black hole liquid and a preparation method and a use method thereof.
Background
Black holes are a technique of uniformly depositing conductive carbon black/graphite on the walls of holes to form a conductive layer. The black holes can be directly electroplated with copper, thereby realizing hole metallization. The advent of black hole technology has been challenging to conventional electroless copper (PTH) processes, and its biggest feature is that instead of conventional electroless copper plating processes, hole metallization is achieved with a physically formed conductive carbon black/graphite layer, thereby providing a conductive substrate for electroplating. The whole black hole processing time only needs tens of minutes, and compared with the PTH processing time, the processing time is greatly shortened, and the production efficiency is improved. On the other hand, since the process is simple, the control factor is reduced compared with PTH, and the number of used drugs is reduced, it is also advantageous in terms of convenience in operation and maintenance. More important is that the black hole technology is environment-friendly, does not contain formaldehyde, heavy metal, complexing agent and other pollutants, and reduces the sewage treatment cost, which is particularly important under the economic premise that the environment control is greatly enhanced and the sustainable development is promoted in our country.
At present, a black hole liquid (such as CN106535505A, CN104562115A, US5015339, US5389270, P4724005A and the like) adopted in a printed circuit board hole metallization direct electroplating process is a suspension liquid which takes water as a dispersion medium and carbon black/graphite particles as a conductive matrix, and the suspension liquid is unstable due to poor hydrophilicity of the carbon black/graphite, so that coagulation is easy to occur, and the service performance of the black hole liquid is seriously influenced. In order to improve the stability of the dispersion, a method of adding a surfactant is generally adopted, and as the surfactant is adsorbed on the surface of carbon black/graphite by physical action, the equilibrium of adsorption and desorption exists, and the desorption of the surfactant can lead to the reagglomeration and sedimentation of carbon black/graphite particles during the storage period, so that the problem of the stability of the suspension cannot be fundamentally solved. Meanwhile, as the surfactant is mixed in the conductive layer behind the black holes, the conductivity of the conductive layer is reduced.
Disclosure of Invention
The present invention aims to solve at least one of the technical problems existing in the prior art. Therefore, a first object of the present invention is to provide a method for preparing a black hole liquid, which can be stably stored for more than one year without sedimentation, and the finally formed conductive layer has a strong conductivity.
The technical aim of the invention is realized by the following technical scheme:
the preparation method of the black hole liquid comprises the following steps: and (3) electrolyzing by taking a graphite plate as an anode, taking a titanium plate or a graphite plate as a cathode and taking water or ammonia water as electrolyte, and then adding a reducing agent and stirring.
Preferably, the concentration of the ammonia water is 0.1-2mol/L.
Preferably, the graphite sheet as the anode is characterized by: ash content less than or equal to 50ppm and volume density of 1.5-20g/cm 3 The granularity is less than 500 mu m.
Preferably, the conditions of the electrolysis are: voltage of 6-60V and current density of 10-300mA/cm 2 The electrolysis time is 8-168h.
Preferably, the reducing agent includes at least one of hydrogen bromide, hydrogen iodide, sodium borohydride, vitamin C, hydrazine, malic acid, glyoxylic acid, ethylene glycol, glucose, chitosan, amino acid, succinic acid, lactic acid, and citric acid.
Preferably, the addition amount of the reducing agent in the electrolyte is 0.1-10g/L.
Preferably, the spacing between the anode and the cathode is 5-10mm.
The invention also aims to provide a black hole liquid which is prepared by the preparation method.
The invention provides a method for using black hole liquid, which comprises the following steps: and (3) at the temperature of 25-35 ℃, putting the laminated printed circuit board into the black hole liquid for dipping, and taking out and drying the laminated printed circuit board.
Preferably, the time of the impregnation is 20-90s.
Preferably, the temperature of the drying is 40-100 ℃.
The beneficial effects of the invention are as follows:
(1) The preparation method of the black hole liquid has the advantages of simple process, convenient operation and environmental protection. In the preparation process of the black hole liquid for the printed circuit board, the stable nano black hole liquid can be obtained without grinding or adding a surfactant.
(2) The black hole liquid has super stability and can not be settled after being placed for more than one year. In the oxidation electrolysis process of the graphite plate, graphite sheets and graphene oxide are continuously generated, the graphene oxide wraps the graphite sheets to form hydrophilic negative-charge colloid, the graphene oxide and the nano-graphite sheets belong to lamellar structures, van der Waals force between the graphene oxide and the nano-graphite sheets is strong, so that the graphene oxide is difficult to desorb on the surface of the nano-graphite sheets, and the colloid formed by the graphene oxide is very stable in water.
(3) In the using process of the black hole liquid, the finally formed conductive layer is complete and flat. The black hole liquid prepared by the invention does not use any surfactant, so that bubbles are not generated in the use process, and are the main cause of faults, and secondly, the granularity of graphite flakes is concentrated between 100 and 300nm, so that the formed conductive layer has small roughness and high flatness.
(4) In the use process of the black hole liquid, the conductivity of the finally formed conductive layer is high. The black hole liquid prepared by the invention does not use any surfactant, so that the conductive layer formed in the use process is free from surfactant inclusion, and higher conductivity can be obtained.
Detailed Description
The invention will be further illustrated with reference to specific examples.
Example 1:
the preparation method of the black hole liquid comprises the following steps: at a thickness of 80Graphite plate with length of 700mm and width of 700mm is used as anode, ash content of 50ppm and volume density of 1.5g/cm 3 The granularity is 300um; a titanium plate with the thickness of 10mm, the length of 700mm and the width of 700mm is used as a cathode; the spacing between the graphite plate and the titanium plate is 5mm; the electrolyte is ultrapure water with resistivity greater than 18MΩ; the power supply is a rectification direct current power supply, and has voltage of 6-60V and current density of 10-40mA/cm during electrolysis 2 After 168 hours of electrolysis, the electrolysis was stopped, and 2g/L of citric acid was added thereto and dissolved with stirring to obtain black hole solution A.
Example 2:
the preparation method of the black hole liquid comprises the following steps: graphite plate with thickness of 80mm, length of 700mm and width of 700mm is used as anode, ash content of 45ppm and volume density of 2g/cm 3 The granularity is 300um; a titanium plate with the thickness of 10mm, the length of 700mm and the width of 700mm is used as a cathode; the spacing between the graphite plate and the titanium plate is 5mm; the electrolyte is 0.1mol/L ammonia water solution; the power supply is a rectification direct current power supply, and has voltage of 6-60V and current density of 60mA/cm during electrolysis 2 After electrolysis for 96 hours, the electrolysis was stopped, and 1g/L glyoxylic acid was added and stirred to obtain black hole solution B.
Example 3:
the preparation method of the black hole liquid comprises the following steps: graphite plate with thickness of 80mm, length of 700mm and width of 700mm is used as anode, ash content of 20ppm and volume density of 2.3g/cm 3 The granularity is 300um; a titanium plate with the thickness of 10mm, the length of 700mm and the width of 700mm is used as a cathode; the spacing between the graphite plate and the titanium plate is 5mm; the electrolyte is ultrapure water with resistivity greater than 18MΩ; the power supply is a rectification direct current power supply, and has voltage of 6-60V and current density of 10-200mA/cm during electrolysis 2 After electrolysis for 24 hours, the electrolysis was stopped, and 1g/L glucose was added thereto and stirred to obtain a black hole solution C.
Example 4:
the preparation method of the black hole liquid comprises the following steps: graphite plate with thickness of 80mm, length of 700mm and width of 700mm is used as anode, ash content of 30ppm and volume density of 2.3g/cm 3 The granularity is 400um; with a thickness of 10mm and a length of 700mmA titanium plate with the width of 700mm is used as a cathode; the spacing between the graphite plate and the titanium plate is 5mm; the electrolyte is 1mol/L ammonia water solution; the power supply is a rectification direct current power supply, and has voltage of 6-60V and current density of 150mA/cm during electrolysis 2 After electrolysis for 24 hours, the electrolysis was stopped, and 2g/L of amino acid was added and stirred to obtain a black-hole solution D.
Example 5:
the preparation method of the black hole liquid comprises the following steps: graphite plate with thickness of 80mm, length of 700mm and width of 700mm is used as anode, ash content of 50ppm and volume density of 2.2g/cm 3 The granularity is 350um; a titanium plate with the thickness of 10mm, the length of 700mm and the width of 700mm is used as a cathode; the spacing between the graphite plate and the titanium plate is 5mm; the electrolyte is 2mol/L ammonia water solution; the power supply is pulse power supply, and the current density is controlled at 250mA/cm during electrolysis 2 After electrolysis for 12 hours at a frequency of 10kHz, the electrolysis was stopped, and 1g/L malic acid was added and stirred to obtain a black hole solution E.
Example 6:
the preparation method of the black hole liquid comprises the following steps: graphite plate with thickness of 80mm, length of 700mm and width of 700mm is used as anode, ash content of 20ppm and volume density of 2.0g/cm 3 The granularity is 350um; a titanium plate with the thickness of 10mm, the length of 700mm and the width of 700mm is used as a cathode; the interval between the graphite plate and the titanium plate is 10mm; the electrolyte is ultrapure water with resistivity greater than 18MΩ; the power supply is a rectification direct current power supply, and has voltage of 6-60V and current density of 10-300mA/cm during electrolysis 2 After electrolysis for 18 hours, the electrolysis was stopped, and 0.5g/L of hydrazine was added and stirred to obtain a black-hole solution F.
Example 7:
the preparation method of the black hole liquid comprises the following steps: graphite plate with thickness of 80mm, length of 700mm and width of 700mm is used as anode, ash content of 45ppm and volume density of 1.8g/cm 3 The granularity is 400um; a titanium plate with the thickness of 10mm, the length of 700mm and the width of 700mm is used as a cathode; the interval between the graphite plate and the titanium plate is 10mm; the electrolyte is 1mol/L ammonia water solution; the power supply is a rectifying DC power supply, and the current density is 300mA/cm during electrolysis 2 After electrolysis for 8 hours, stopping electrolysis, adding 1G/L vitamin C and stirring to obtain black hole liquid G.
Example 8:
the application method of the black hole liquid comprises the following steps: the laminated printed circuit board is placed into the black hole liquid A at 25 ℃ for soaking for 40 seconds, so that graphite sheets wrapped by graphene oxide in the black hole liquid A are adsorbed on the wall of a through hole on the laminated printed circuit board, after the black hole treatment is carried out, the laminated printed circuit board needs to be dried at 80 ℃ so that the graphene oxide on the wall of the through hole on the laminated printed circuit board is reduced by citric acid and carbon on the wall of the through hole is solidified, and a conductive layer A is formed.
Example 9:
the application method of the black hole liquid comprises the following steps: and immersing the laminated printed circuit board in the black hole liquid B at 25 ℃ for 40 seconds to enable graphite sheets wrapped by graphene oxide in the black hole liquid B to be adsorbed on the wall of the through holes on the laminated printed circuit board, and drying the laminated printed circuit board at 60 ℃ after the black hole treatment is finished, so that the graphene oxide on the wall of the through holes on the laminated printed circuit board is reduced into reduced graphene oxide by glyoxylic acid and carbon on the wall of the through holes is solidified to form the conductive layer B.
Example 10:
the application method of the black hole liquid comprises the following steps: and immersing the laminated printed circuit board in the black hole liquid C at 25 ℃ for 40 seconds to enable graphite sheets wrapped by graphene oxide in the black hole liquid C to be adsorbed on the wall of the through holes on the laminated printed circuit board, and drying the laminated printed circuit board at 70 ℃ after the black hole treatment is carried out, so that the graphene oxide on the wall of the through holes on the laminated printed circuit board is reduced into reduced graphene oxide by glucose and carbon on the wall of the through holes is solidified to form the conductive layer C.
Example 11:
the application method of the black hole liquid comprises the following steps: and immersing the laminated printed circuit board in the black hole liquid D at 25 ℃ for 50 seconds to enable graphite sheets wrapped by graphene oxide in the black hole liquid D to be adsorbed on the wall of the through holes on the laminated printed circuit board, and drying the laminated printed circuit board at 85 ℃ after the black hole treatment is finished, so that the graphene oxide on the wall of the through holes on the laminated printed circuit board is reduced into reduced graphene oxide by amino acid and carbon on the wall of the through holes is solidified to form the conductive layer D.
Example 12:
the application method of the black hole liquid comprises the following steps: and immersing the laminated printed circuit board in the black hole liquid E at 25 ℃ for 50 seconds to enable graphite sheets wrapped by graphene oxide in the black hole liquid E to be adsorbed on the wall of the through holes on the laminated printed circuit board, and drying the laminated printed circuit board at 85 ℃ after the black hole treatment is finished, so that the graphene oxide on the wall of the through holes on the laminated printed circuit board is reduced into reduced graphene by malic acid and carbon on the wall of the through holes is solidified to form the conductive layer E.
Example 13:
the application method of the black hole liquid comprises the following steps: and immersing the laminated printed circuit board in the black hole liquid F at 25 ℃ for 50 seconds to enable graphite sheets wrapped by graphene oxide in the black hole liquid F to be adsorbed on the wall of the through holes on the laminated printed circuit board, and drying the laminated printed circuit board at 45 ℃ after the black hole treatment is finished, so that the graphene oxide on the wall of the through holes on the laminated printed circuit board is reduced into reduced graphene oxide by hydrazine and carbon on the wall of the through holes is solidified to form the conductive layer F.
Example 14:
the application method of the black hole liquid comprises the following steps: and immersing the laminated printed circuit board in the black hole liquid G at 25 ℃ for 50 seconds to enable graphite sheets wrapped by graphene oxide in the black hole liquid G to be adsorbed on the wall of the through hole on the laminated printed circuit board, and drying the laminated printed circuit board at 45 ℃ after the black hole treatment is finished, so that the graphene oxide on the wall of the through hole on the laminated printed circuit board is reduced to reduced graphene oxide by vitamin C and carbon on the wall of the through hole is solidified to form the conductive layer G.
Test example:
stability test: the black hole liquid in examples 1 to 7 was taken and left for 1 year naturally, and then the solution was observed for sedimentation, and the results are shown in Table 1.
Table 1: results of stability test of Black hole liquid
Conductivity test: the conductive layers of examples 8 to 14 were tested for conductivity and the results are shown in Table 2.
Table 2: conductive layer conductivity test results
As shown in Table 1, the black hole liquid of the invention has excellent stability, and can not be settled after being naturally placed for 1 year; as shown in Table 2, the conductivity of the finally formed conductive layer is above 50S/cm in the use process of the black hole liquid provided by the invention, and the highest conductivity can reach 58.1S/cm, which shows that the black hole liquid has stronger conductivity.
The above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above examples, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principle of the present invention should be made in the equivalent manner, and the embodiments are included in the protection scope of the present invention.
Claims (8)
1. A preparation method of black hole liquid is characterized in that: the method comprises the following steps: the method comprises the steps of taking a graphite plate as an anode, taking a titanium plate or a graphite plate as a cathode, taking water or ammonia water as electrolyte, carrying out electrolysis, adding a reducing agent, and stirring to obtain the electrolyte, wherein the reducing agent comprises at least one of hydrogen bromide, hydrogen iodide, sodium borohydride, vitamin C, hydrazine, malic acid, glyoxylic acid, glycol, glucose, chitosan, amino acid, succinic acid, lactic acid and citric acid, and the adding amount of the reducing agent in the electrolyte is 0.1-10g/L.
2. The method for preparing the black hole liquid according to claim 1, wherein the method comprises the following steps: the concentration of the ammonia water is 0.1-2mol/L.
3. The method for preparing the black hole liquid according to claim 1, wherein the method comprises the following steps: the graphite sheet as anode is characterized by: ash content less than or equal to 50ppm and volume density of 1.5-20g/cm 3 The granularity is less than 500 mu m.
4. The method for preparing the black hole liquid according to claim 1, wherein the method comprises the following steps: the conditions of the electrolysis are as follows: voltage of 6-60V and current density of 10-300mA/cm 2 The electrolysis time is 8-168h.
5. A black hole liquid is characterized in that: prepared by the preparation method of any one of claims 1 to 4.
6. The application method of the black hole liquid is characterized by comprising the following steps of: the laminated printed circuit board is put into the black hole liquid according to claim 5 for dipping at the temperature of 25-35 ℃, and then the laminated printed circuit board is taken out and dried.
7. The method for using the black hole liquid according to claim 6, wherein: the time of the soaking is 20-90s.
8. The method for using the black hole liquid according to claim 6, wherein: the temperature of the drying is 40-100 ℃.
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| CN113207243A (en) * | 2021-05-08 | 2021-08-03 | 电子科技大学中山学院 | Preparation and application method of black hole liquid |
| CN115594171A (en) * | 2022-07-29 | 2023-01-13 | 广东利尔化学有限公司（Cn） | Carbon pore process nano graphite dispersion liquid and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2162905A1 (en) * | 1993-05-17 | 1994-11-24 | Charles Edwin Thorn | Carbon compositions and processes for preparing a non-conductive substrate for electroplating |
| CN104562115A (en) * | 2014-07-04 | 2015-04-29 | 广东丹邦科技有限公司 | Black hole liquid for printed circuit board and preparation method of black hole liquid |
| CN104831307A (en) * | 2015-05-13 | 2015-08-12 | 东南大学 | Preparation method of micro/nano graphene sheet |
| CN106535505A (en) * | 2016-11-23 | 2017-03-22 | 昆山尚宇电子科技有限公司 | Black hole solution for manufacturing printed board |
| CN108323036A (en) * | 2018-02-10 | 2018-07-24 | 深圳市祥盛兴科技有限公司 | A kind of blank hole liquid and black holes chemical industry skill |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2162905A1 (en) * | 1993-05-17 | 1994-11-24 | Charles Edwin Thorn | Carbon compositions and processes for preparing a non-conductive substrate for electroplating |
| CN104562115A (en) * | 2014-07-04 | 2015-04-29 | 广东丹邦科技有限公司 | Black hole liquid for printed circuit board and preparation method of black hole liquid |
| CN104831307A (en) * | 2015-05-13 | 2015-08-12 | 东南大学 | Preparation method of micro/nano graphene sheet |
| CN106535505A (en) * | 2016-11-23 | 2017-03-22 | 昆山尚宇电子科技有限公司 | Black hole solution for manufacturing printed board |
| CN108323036A (en) * | 2018-02-10 | 2018-07-24 | 深圳市祥盛兴科技有限公司 | A kind of blank hole liquid and black holes chemical industry skill |
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