CN111647901A - Black hole liquid and preparation method and use method thereof - Google Patents
Black hole liquid and preparation method and use method thereof Download PDFInfo
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- CN111647901A CN111647901A CN202010410347.9A CN202010410347A CN111647901A CN 111647901 A CN111647901 A CN 111647901A CN 202010410347 A CN202010410347 A CN 202010410347A CN 111647901 A CN111647901 A CN 111647901A
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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: the preparation method comprises the steps of taking a graphite plate as an anode, taking a titanium plate or the graphite plate as a cathode, taking water or ammonia water as electrolyte, carrying out electrolysis, 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 a black hole liquid and a preparation method and a using method thereof.
Background
The black hole is a technology for uniformly depositing conductive carbon black/graphite on the hole wall to form a conductive layer. And directly electroplating copper after the black hole is formed, so that hole metallization is realized. The appearance of the black hole technology is a challenge to the traditional electroless copper Plating (PTH), and the biggest characteristic of the black hole technology is to replace the traditional electroless copper plating process and realize hole metallization by utilizing a conductive carbon black/graphite layer formed by physical action so as to provide a conductive base for electroplating. The whole black hole processing time only needs dozens 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 number of control factors is reduced as compared with PTH, and the number of medicines used is reduced, there is also a great advantage in convenience of operation and maintenance. More importantly, the black hole technology is environment-friendly, does not contain pollutants such as formaldehyde, heavy metals, complexing agents and the like, and reduces the sewage treatment cost, which is particularly important on the economic premise that the environment control is greatly enhanced and the sustainable development is promoted in our country.
At present, black hole liquid (such as CN106535505A, CN104562115A, US5015339, US5389270, P4724005A and the like) adopted by a direct electroplating process for the metallization of holes of a printed circuit board is suspension liquid which takes water as a dispersion medium and carbon black/graphite particles as a conductive matrix, and the use performance of the black hole liquid is seriously influenced because the suspension liquid is unstable and easy to generate coagulation due to poor hydrophilicity of the carbon black/graphite. In order to improve the stability of the dispersion, a surfactant is usually added, and the surfactant is adsorbed on the surface of the carbon black/graphite by physical action, so that the balance of adsorption and desorption exists, and the desorption of the surfactant can cause the carbon black/graphite particles to be re-aggregated and settled during the storage period, so that the problem of suspension stability cannot be fundamentally solved. Meanwhile, the conductivity of the conductive layer is also reduced because the surfactant is mixed in the conductive layer behind the black hole.
Disclosure of Invention
The present invention is directed to solving at least one of the problems of 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 high conductivity.
The technical purpose of the invention is realized by the following technical scheme:
a preparation method of black hole liquid comprises the following steps: the preparation method comprises the steps of taking a graphite plate as an anode, taking a titanium plate or the graphite plate as a cathode, taking water or ammonia water as electrolyte, carrying out electrolysis, adding a reducing agent, and stirring.
Preferably, the concentration of the ammonia water is 0.1-2 mol/L.
Preferably, the graphite plate as the anode is characterized in that: ash contentLess than or equal to 50ppm, and the volume density is 1.5-20g/cm3The granularity is less than 500 mu m.
Preferably, the electrolysis conditions are as follows: the voltage is 6-60V, and the current density is 10-300mA/cm2The electrolysis time is 8-168 h.
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, an amino acid, succinic acid, lactic acid, and citric acid.
Preferably, the addition amount of the reducing agent in the electrolyte is 0.1 to 10 g/L.
Preferably, the distance between the anode and the cathode is 5-10 mm.
The invention also aims to provide the black hole liquid prepared by the preparation method.
The 3 rd purpose of the invention is to provide a use method of the 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 to 90 s.
Preferably, the drying temperature is 40-100 ℃.
The invention has the beneficial effects that:
(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 and adding a surfactant.
(2) The black hole liquid has super-strong stability, and does not generate sedimentation after being placed for more than one year. In the oxidation and electrolysis process of the graphite plate, graphite flakes and graphene oxide are continuously generated, the graphite flakes are wrapped by the graphene oxide to form hydrophilic negative charge colloid, the graphene oxide and the graphite nanoplatelets belong to a flaky structure, and van der Waals force between the graphene oxide and the graphite nanoplatelets is strong, so that the graphene oxide is difficult to desorb on the surfaces of the graphite nanoplatelets, and the colloid formed by the graphene oxide and the graphite nanoplatelets is very stable in water.
(3) In the use process of the black hole liquid, the finally formed conductive layer is complete and smooth. The black hole liquid prepared by the invention does not use any surfactant, so that bubbles are not generated in the using process and are the main reason for generating faults, and secondly, the granularity of the graphite flake is concentrated between 100 and 300nm, and the formed conductive layer has small roughness and high flatness.
(4) In the use process of the black hole liquid, the finally formed conductive layer has high conductivity. The black hole liquid prepared by the invention does not use any surfactant, so that the conductive layer formed in the using process is free from surfactant inclusion, and higher conductivity can be obtained.
Detailed Description
The present invention will be further described with reference to the following specific examples.
Example 1:
a preparation method of black hole liquid comprises the following steps: taking a graphite plate with the thickness of 80mm, the length of 700mm and the width of 700mm as an anode, wherein the ash content is 50ppm, and the volume density is 1.5g/cm3The granularity is 300 um; a titanium plate with the thickness of 10mm, the length of 700mm and the width of 700mm is taken as a cathode; the distance between the graphite plate and the titanium plate is 5 mm; the electrolyte is ultrapure water with the resistivity larger than 18M omega; the power supply is rectified DC power supply, and during electrolysis, the voltage is 6-60V, and the current density is 10-40mA/cm2After electrolyzing for 168 hours, the electrolysis was stopped, and 2g/L citric acid was added thereto and dissolved by stirring to obtain a black hole solution A.
Example 2:
a preparation method of black hole liquid comprises the following steps: taking a graphite plate with the thickness of 80mm, the length of 700mm and the width of 700mm as an anode, wherein the ash content of the graphite plate is 45ppm, and the volume density of the graphite plate is 2g/cm3The granularity is 300 um; a titanium plate with the thickness of 10mm, the length of 700mm and the width of 700mm is taken as a cathode; the distance between the graphite plate and the titanium plate is 5 mm; the electrolyte is 0.1mol/L ammonia water solution; the power supply is rectified DC power supply, and during electrolysis, the voltage is 6-60V, and the current density is 60mA/cm2After the electrolysis was carried out for 96 hours, the electrolysis was stopped, and 1g/L glyoxylic acid was added thereto and stirred to obtain a black well solution B.
Example 3:
a preparation method of black hole liquid comprises the following steps: taking a graphite plate with the thickness of 80mm, the length of 700mm and the width of 700mm as an anode, wherein the ash content of the graphite plate is 20ppm, and the volume density of the graphite plate is 2.3g/cm3The granularity is 300 um; a titanium plate with the thickness of 10mm, the length of 700mm and the width of 700mm is taken as a cathode; the distance between the graphite plate and the titanium plate is 5 mm; the electrolyte is ultrapure water with the resistivity larger than 18M omega; the power supply is rectified DC power supply, and during electrolysis, the voltage is 6-60V, and the current density is 10-200mA/cm2After 24 hours of electrolysis, the electrolysis was stopped, and 1g/L glucose was added thereto and stirred to obtain a black pore solution C.
Example 4:
a preparation method of black hole liquid comprises the following steps: taking a graphite plate with the thickness of 80mm, the length of 700mm and the width of 700mm as an anode, the ash content of the graphite plate is 30ppm, and the volume density of the graphite plate is 2.3g/cm3The granularity is 400 um; a titanium plate with the thickness of 10mm, the length of 700mm and the width of 700mm is taken as a cathode; the distance between the graphite plate and the titanium plate is 5 mm; the electrolyte is 1mol/L ammonia water solution; the power supply is rectified DC power supply, and during electrolysis, the voltage is 6-60V, and the current density is 150mA/cm2After 24 hours of electrolysis, the electrolysis was stopped, and 2g/L of amino acid was added thereto and stirred to obtain a black hole solution D.
Example 5:
a preparation method of black hole liquid comprises the following steps: taking a graphite plate with the thickness of 80mm, the length of 700mm and the width of 700mm as an anode, wherein the ash content is 50ppm, and the volume density is 2.2g/cm3The granularity is 350 um; a titanium plate with the thickness of 10mm, the length of 700mm and the width of 700mm is taken as a cathode; the distance between the graphite plate and the titanium plate is 5 mm; the electrolyte is 2mol/L ammonia water solution; the power supply is a pulse power supply, and the current density is controlled at 250mA/cm during electrolysis2And the frequency is 10kHz, after the electrolysis is carried out for 12 hours, the electrolysis is stopped, and 1g/L malic acid is added and stirred to obtain black pore liquid E.
Example 6:
a preparation method of black hole liquid comprises the following steps: the stone with the thickness of 80mm, the length of 700mm and the width of 700mm is usedThe ink plate was the anode, and had an ash content of 20ppm and a bulk density of 2.0g/cm3The granularity is 350 um; a titanium plate with the thickness of 10mm, the length of 700mm and the width of 700mm is taken as a cathode; the distance between the graphite plate and the titanium plate is 10 mm; the electrolyte is ultrapure water with the resistivity larger than 18M omega; the power supply is rectified DC power supply, and during electrolysis, the voltage is 6-60V, and the current density is 10-300mA/cm2After electrolysis for 18 hours, the electrolysis was stopped, and 0.5g/L of hydrazine was added thereto and stirred to obtain a black pore liquid F.
Example 7:
a preparation method of black hole liquid comprises the following steps: taking a graphite plate with the thickness of 80mm, the length of 700mm and the width of 700mm as an anode, wherein the ash content of the graphite plate is 45ppm, and the volume density of the graphite plate is 1.8g/cm3The granularity is 400 um; a titanium plate with the thickness of 10mm, the length of 700mm and the width of 700mm is taken as a cathode; the distance between the graphite plate and the titanium plate is 10 mm; the electrolyte is 1mol/L ammonia water solution; the power supply is rectified direct current power supply, and the current density is 300mA/cm during electrolysis2After 8 hours of electrolysis, the electrolysis was stopped, and 1G/L vitamin C was added thereto and stirred to obtain a black hole solution G.
Example 8:
a use method of black hole liquid comprises the following steps: and (2) soaking the laminated printed circuit board in the black hole liquid A for 40s at 25 ℃ so that graphite flakes wrapped by graphene oxide in the black hole liquid A are adsorbed on the wall of the through hole on the laminated printed circuit board, and after the black hole treatment is finished, drying the laminated printed circuit board 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 to form a conductive layer A.
Example 9:
a use method of black hole liquid comprises the following steps: and (2) soaking the laminated printed circuit board in the black hole liquid B for 40s at 25 ℃ to enable graphite flakes wrapped by graphene oxide in the black hole liquid B to be adsorbed on the wall of the through hole on the laminated printed circuit board, and after the black hole treatment is finished, drying the laminated printed circuit board at 60 ℃ to enable the graphene oxide on the wall of the through hole on the laminated printed circuit board to be reduced into reduced graphene oxide by glyoxylic acid and enable carbon on the wall of the through hole to be solidified to form a conducting layer B.
Example 10:
a use method of black hole liquid comprises the following steps: and (2) soaking the laminated printed circuit board in the black hole liquid C for 40s at 25 ℃ so that graphite flakes wrapped by graphene oxide in the black hole liquid C are adsorbed on the wall of the through hole on the laminated printed circuit board, and after the black hole treatment is finished, drying the laminated printed circuit board at 70 ℃ so that the graphene oxide on the wall of the through hole on the laminated printed circuit board is reduced into reduced graphene oxide by glucose and carbon on the wall of the through hole is solidified to form a conducting layer C.
Example 11:
a use method of black hole liquid comprises the following steps: and (2) soaking the laminated printed circuit board in the black hole liquid D for 50s at 25 ℃ to enable graphite flakes wrapped by graphene oxide in the black hole liquid D to be adsorbed on the wall of the through hole on the laminated printed circuit board, and after the black hole treatment is finished, drying the laminated printed circuit board at 85 ℃ to enable the graphene oxide on the wall of the through hole on the laminated printed circuit board to be reduced into reduced graphene oxide by amino acid and enable carbon on the wall of the through hole to be solidified to form a conducting layer D.
Example 12:
a use method of black hole liquid comprises the following steps: and (2) soaking the laminated printed circuit board in the black hole liquid E for 50s at 25 ℃ so that graphite flakes wrapped by graphene oxide in the black hole liquid E are adsorbed on the wall of the through hole on the laminated printed circuit board, and after the black hole treatment is finished, drying the laminated printed circuit board at 85 ℃ so that the graphene oxide on the wall of the through hole on the laminated printed circuit board is reduced into reduced graphene by malic acid and carbon on the wall of the through hole is solidified to form a conducting layer E.
Example 13:
a use method of black hole liquid comprises the following steps: and (2) soaking the laminated printed circuit board in the black hole liquid F for 50s at 25 ℃ to enable graphite flakes wrapped by graphene oxide in the black hole liquid F to be adsorbed on the wall of the through hole on the laminated printed circuit board, and after the black hole treatment is finished, drying the laminated printed circuit board at 45 ℃ to enable the graphene oxide on the wall of the through hole on the laminated printed circuit board to be reduced into reduced graphene oxide by hydrazine and enable carbon on the wall of the through hole to be solidified to form a conducting layer F.
Example 14:
a use method of black hole liquid comprises the following steps: and (2) soaking the laminated printed circuit board in the black hole liquid G for 50s at 25 ℃ to enable graphite flakes 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 after the black hole treatment is finished, drying the laminated printed circuit board at 45 ℃ to enable the graphene oxide on the wall of the through hole on the laminated printed circuit board to be reduced into reduced graphene oxide by vitamin C and enable carbon on the wall of the through hole to be solidified to form a conducting layer G.
Test example:
and (3) stability testing: the black well solutions of examples 1 to 7 were collected and left to stand for 1 year, and then the solutions were observed for sedimentation, and the results are shown in Table 1.
Table 1: stability test results for black pore liquid
And (3) conductivity test: the conductive layers of examples 8-14 were taken and tested for conductivity, and the results are shown in Table 2.
Table 2: conductivity test results of conductive layer
As can be seen from Table 1, the black hole liquid of the invention has excellent stability, and the black hole liquid can not be settled after being naturally placed for 1 year; as shown in Table 2, the conductivity of the finally formed conductive layer in the use process of the black hole liquid of the present invention is above 50S/cm, and can reach 58.1S/cm at most, which indicates that the black hole liquid has strong conductivity.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. A preparation method of black hole liquid is characterized by comprising the following steps: the method comprises the following steps: the preparation method comprises the steps of taking a graphite plate as an anode, taking a titanium plate or the graphite plate as a cathode, taking water or ammonia water as electrolyte, carrying out electrolysis, adding a reducing agent, and stirring.
2. The method for preparing a black hole liquid according to claim 1, wherein: the concentration of the ammonia water is 0.1-2 mol/L.
3. The method for preparing a black hole liquid according to claim 1, wherein: the graphite plate as the anode is characterized in that: ash content is less than or equal to 50ppm, and volume density is 1.5-20g/cm3The granularity is less than 500 mu m.
4. The method for preparing a black hole liquid according to claim 1, wherein: the conditions of the electrolysis are as follows: the voltage is 6-60V, and the current density is 10-300mA/cm2The electrolysis time is 8-168 h.
5. The method for preparing a black hole liquid according to claim 1, wherein: the reducing agent comprises at least one of hydrogen bromide, hydrogen iodide, sodium borohydride, vitamin C, hydrazine, malic acid, glyoxylic acid, ethylene glycol, glucose, chitosan, amino acids, succinic acid, lactic acid and citric acid.
6. The method for preparing a black hole liquid according to claim 5, wherein: the addition amount of the reducing agent in the electrolyte is 0.1-10 g/L.
7. A black hole liquid is characterized in that: prepared by the preparation method of any one of claims 1 to 6.
8. The use method of the black hole liquid is characterized by comprising the following steps: dipping the laminated printed circuit board into the black hole liquid of claim 7 at 25-35 ℃, and taking out and drying the laminated printed circuit board.
9. The method of using a black hole fluid as claimed in claim 8, wherein: the immersion time is 20-90 s.
10. The method of using a black hole fluid as claimed in claim 8, wherein: the drying temperature is 40-100 ℃.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
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| 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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2020
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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 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
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