CN108834309B - Graphene metallization solution and preparation method and application thereof - Google Patents
Graphene metallization solution and preparation method and application thereof Download PDFInfo
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- CN108834309B CN108834309B CN201811009256.3A CN201811009256A CN108834309B CN 108834309 B CN108834309 B CN 108834309B CN 201811009256 A CN201811009256 A CN 201811009256A CN 108834309 B CN108834309 B CN 108834309B
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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
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/09—Use of materials for the conductive, e.g. metallic pattern
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/18—Processes for applying liquids or other fluent materials performed by dipping
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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
- C25D5/54—Electroplating of non-metallic surfaces
Abstract
The invention discloses a graphene metallization solution and a preparation method and application thereof, wherein the graphene metallization solution is prepared from the following raw materials in percentage by mass: 0.5-5.0% of graphene or graphene oxide; 1-3% of film-forming agent; 1-6% of a dispersant; 0.01 to 0.2 percent of anionic surfactant; alkaline solution, adjusting the pH value to 4-14; the balance being water. According to the invention, low-concentration graphene or low-oxidation-degree graphene oxide material is used as a basic conductive material, effective adsorption of graphene metallization solution on the surface or the hole wall of a non-metal substrate can be realized through simple and efficient pretreatment, a very thin film layer with reliable binding force and conductivity close to or even exceeding that of metal copper can be formed through simple drying treatment, the film layer is only a few to dozens of nanometers thick, and can be used as a bottoming conductive layer for direct copper electroplating.
Description
Technical Field
The invention relates to the field of new material synthesis and surface treatment, in particular to a graphene metallization solution and a preparation method and application thereof.
Background
With the rapid development of electronic information technology, the demands of circuit boards and various metalized products are increasing day by day. In order to realize interlayer interconnection on an electronic circuit board, holes need to be drilled on a substrate, and metallization treatment is carried out on hole walls, namely, a layer of metal or conductive material is deposited on an insulating base material and can be used as a bottom plating layer for subsequent electroplating. Hole metallization is one of the key processes for circuit board fabrication. The currently used hole metallization techniques mainly include the following:
1. chemical copper technology: the most commonly used chemical copper adopts acid-based or base-based activating solution, fluoboric acid is used as an accelerator, copper sulfate, formaldehyde, potassium sodium tartrate, ethylene diamine tetraacetic acid and sodium salt thereof, sodium hydroxide and the like are used as main raw materials of the chemical copper, dangerous goods such as cyanide, mercury chloride and the like are generally used as stabilizers, the pretreatment process is long, six treatment medicine water tanks are needed, 10-14 cleaning water are needed, most of the cleaning water needs to be heated, great fire hazard exists, and almost every circuit board factory has fire accidents of different degrees; the whole process generates a large amount of waste liquid and cleaning wastewater, the sewage treatment is difficult and complicated, and the highly toxic stabilizer contained in the main waste liquid copper precipitation liquid seriously pollutes the environment, is extremely difficult to decompose in the natural environment and is easy to accumulate to cause long-term harm. In addition, in the whole process, various dangerous chemicals (fluoboric acid, hydrochloric acid and sodium hydroxide) and oxidants (concentrated sulfuric acid and persulfate) are used, so that the pollution to the atmosphere and the indoor environment is serious, the harm to the human body is great, such as carcinogenic formaldehyde, and activators such as noble metal palladium and the like are generated, the whole process cost is relatively high, and the environmental and sewage treatment cost is very high. In addition, the chemical copper bath solution has poor stability, is sensitive to the material of a processed substrate, such as resin type, glass fiber type and the like, has poor mechanical properties of a chemical copper layer compared with an electroplating layer, and has the disadvantages of long process flow, inconvenient operation and maintenance, difficult quality control and higher running cost.
2. Black hole/conductive carbon black technology: by adopting the black hole technology of graphite or carbon black, although the use of chemicals is greatly reduced and the process time is greatly shortened, the conductivity of the carbon black or graphite is too poor, compared with the traditional chemical copper plating layer, the technology can not meet the technical standards and performance requirements of related products, the product can only be used on partial low-end hard board products or soft boards, the process is often repeated, the production efficiency is greatly reduced, and the additional time and space cost of manpower, material resources and time is increased;
3. organic conductive film/superconducting technology: the conductivity of the organic conductive film is poorer than that of a black film conductive layer formed by a black hole technology, the potential risks of aging cracking and high-temperature cracking exist in the organic conductive polymer, and performance defects or quality hidden dangers exist in both product performance requirements and technical requirements and the service life and reliability of subsequent products, so that the organic conductive film can only be used in partial low-end hard board products at present.
Other metallization processes are difficult to adapt to industrial mass production, so that the search for a metallization process technology which is environment-friendly, efficient and suitable for large-scale industrial production is particularly urgent under the situation that the current environment-friendly requirement and the technological requirement are increasingly strict. Many metallization technologies at present have the problems of high cost, complex technology, complex process flow or unsuitability for large-scale industrial production, difficult process control and the like.
Accordingly, the prior art is yet to be improved and developed.
Disclosure of Invention
In view of the defects of the prior art, the invention aims to provide a graphene metallization solution and a preparation method and application thereof, and aims to solve the problems that the existing metallization technology is expensive in cost, complex in technology, complex in process flow or not suitable for large-scale industrial production, difficult in process control and the like.
The technical scheme of the invention is as follows:
the graphene metallization solution is prepared from the following raw materials in percentage by mass:
the graphene metallization solution is characterized in that the number of layers of graphene or graphene oxide is 1-3.
The graphene metallization solution is characterized in that the sheet diameter of the graphene or the graphene oxide is 10nm-5 μm.
The graphene metallization solution is characterized in that the film forming agent is one or more of JZ, PVP, PVA and CCMS.
The graphene metallization solution is characterized in that the dispersing agent is one or more of PVP, dimethylformamide, N-methyl pyrrolidone and methyl cellosolve.
The graphene metallization solution, wherein the anionic surfactant is TxP-10, sodium dodecyl sulfate, sodium dodecyl sulfonate, carboxylate, sulfate, sulfonate and phosphate.
The graphene metallization solution is characterized in that the alkaline solution is a sodium hydroxide solution.
The invention relates to a preparation method of a graphene metallization solution, which comprises the following steps: according to the mass percentage, uniformly mixing graphene or graphene oxide, a film-forming agent, a dispersing agent, an anionic surface treating agent, an alkaline solution and water to form a stable dispersion system, and obtaining the graphene metallization solution.
The application of the graphene metallization solution is used for metallization of non-metal surfaces.
The application, wherein, the method for metalizing the non-metal surface comprises the following steps: treating the non-metallic surface in the graphene metallization solution to metalize the non-metallic surface.
Has the advantages that: according to the invention, graphene with extremely low concentration or graphene oxide material with low oxidation degree is used as a basic conductive material, effective adsorption on the surface or the hole wall of the non-metal substrate can be realized by simple pretreatment of the non-metal substrate, an extremely thin film layer with reliable binding force and conductivity close to or even exceeding that of metal copper can be formed by simple drying treatment, the film layer has the thickness of only a few to dozens of nanometers, and can be used as a bottoming conductive layer, and copper can be directly electroplated subsequently.
Detailed Description
The invention provides a graphene metallization solution and a preparation method and application thereof, and the invention is further described in detail below in order to make the purpose, technical scheme and effect of the invention clearer and more clear. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The invention provides a graphene metallization solution, which is prepared from the following raw materials in percentage by mass:
the graphene material has excellent conductivity which is far superior to that of common metal materials, and graphene oxide with low oxidation degree can be used in the invention, the conductivity of the graphene oxide is equivalent to that of copper and silver, and the conductivity of the graphene oxide partially even exceeds that of copper and silver, so that the conductive effect required by bottoming electroplating can be achieved only by a thin continuous and complete graphene film.
According to the invention, graphene with extremely low concentration or graphene oxide material with low oxidation degree is used as a basic conductive material, effective adsorption on the surface or the hole wall of the non-metal substrate can be realized by simple pretreatment of the non-metal substrate, an extremely thin film layer with reliable binding force and conductivity close to or even exceeding that of metal copper can be formed by simple drying treatment, the film layer has the thickness of only a few to dozens of nanometers (3-100nm), and can be used as a bottoming conductive layer for direct copper electroplating.
The invention adopts graphene or graphene oxide material with low oxidation degree as a basic conductive material. Preferably, the number of graphene or graphene oxide layers is 1 to 3, that is, single-layer or few-layer graphene is mainly used, and the few-layer graphene is 3 layers or less and 3 layers or less. Preferably, the sheet diameter of the graphene or graphene oxide is less than 5 micrometers, preferably 10nm-5 μm, and the appropriate sheet diameter is determined according to the minimum processing size of a processing object.
Preferably, the film-forming agent is one or more of JZ (fatty alcohol polyoxyethylene ether phosphate), PVP (polyvinylpyrrolidone), PVA (polyvinyl alcohol), CCMS (polyethylene glycol monostearate) and the like.
Preferably, the dispersant is one or more of PVP (polyvinylpyrrolidone), dimethylformamide, N-methylpyrrolidone, methylcellosolve and the like.
Preferably, the anionic surfactant is one or more of TXP-10 (potassium phenolether phosphate), sodium dodecyl sulfate, sodium dodecyl sulfonate, carboxylate, sulfate ester salt, sulfonate, phosphate ester salt and the like.
Preferably, the alkaline solution is a sodium hydroxide solution, etc., without being limited thereto.
Preferably, the water is pure water or deionized water.
The invention also provides a preparation method of the graphene metallization solution, which comprises the following steps: according to the mass percentage, uniformly mixing graphene or graphene oxide, a film-forming agent, a dispersing agent, an anionic surface treating agent, an alkaline solution and water to form a stable dispersion system, and obtaining the graphene metallization solution.
Specifically, graphene or graphene oxide is first converted into a graphene sheet-like solution having a sheet diameter of tens of nanometers to 5 micrometers according to actual needs by ultrasonic waves and a physical mechanical pulverization technique, and then mixed with a dispersant, a film-forming agent, an anionic surface treatment agent, an alkaline solution, water, and the like to form a stable dispersion system.
The invention also provides an application of the graphene metallization solution, wherein the graphene metallization solution is used for metallization of a non-metal surface. Wherein, the nonmetal can be nonmetal such as circuit board, pottery, plastic cement, glass.
The invention can adopt vertical impregnation and horizontal impregnation in practical production application, and the introduction of the vertical impregnation and the horizontal impregnation is as follows:
vertical impregnation is relatively suitable for medium and small enterprises and laboratory simulation production. The method is completed by a two-step method or a three-step method of dipping and drying and micro-etching by directly using the existing equipment of manufacturers without adding equipment. The production efficiency is not high, and the efficiency advantage of the invention cannot be exerted.
Horizontal impregnation: special matching equipment is adopted, the method is suitable for large-scale mass production of large and medium-sized enterprises, metallization treatment can be realized in a short time, and the production capacity and the product quality are greatly improved.
In view of production efficiency and quality stability, horizontal impregnation is preferred in the process of the present invention. Horizontal impregnation requires the cooperation of horizontal production equipment. The process is exemplified with a circuit board as a main template. The specific manufacturer can decide which production mode to select according to the self condition. The process flow and the process conditions of the invention are as follows:
the process flow comprises the following steps: cleaning/adjusting → secondary counter-current rinsing → graphene metallization solution treatment → air drying → micro-etching → secondary counter-current rinsing → air drying → electro-coppering/pattern transfer line manufacturing.
Cleaning/conditioning: the cleaning/conditioning solution contains surface treating agent, solvent, auxiliary agent, organic base, inorganic base, etc. The surface treatment agent is one or a mixture of more of cationic surfactant, nonionic surfactant, anionic and cationic amphoteric surfactant and the like, and can effectively wet the surface of the nonmetal substrate and clean (remove pollutants such as grease, rusty spots, fingerprints, dust, oxides and the like) through the surface treatment agent, so that the cleanness of the surface of the nonmetal substrate is ensured; meanwhile, the polar charge of the surface of the non-metal matrix can be adjusted, so that a layer of uniform cationic surfactant is adsorbed on the surface of the non-metal matrix, and the subsequent graphene metallization treatment is facilitated.
Secondary countercurrent rinsing: the degreasing agent remained on the surface of the nonmetal substrate can be effectively removed, the cleaned/adjusted nonmetal substrate surface is fully washed, and redundant residual components are washed away.
And (3) graphene metallization solution treatment: treating the non-metallic surface in the graphene metallization solution to metalize the non-metallic surface. Specifically, the nonmetal is soaked in the graphene metallization solution at the temperature of 20-50 ℃, the soaking time is 30-300 seconds, and the preferred soaking time is 60-120 seconds. In order to ensure the perforation effect, the treatment section can be additionally provided with circulating filtration, high-pressure spraying and ultrasonic equipment as assistance, so that the treatment capacity and the actual penetration effect of the solution on the walls of the deep holes and the small holes are improved.
Through the treatment procedures, the brownian motion of microparticles in the graphene metalized solution and the space effect of graphene sheet layer components are effectively adsorbed and combined with the surface of the nonmetal substrate, and the positive charge effect of cations on the surface of the nonmetal substrate and the negative charges on the surface of the graphene form opposite charge adsorption, so that a fine and uniform film layer is finally formed on the surface of the nonmetal substrate.
Microetching, namely treating the non-metal substrate by using microetching liquid for 20-40 seconds, wherein the microetching liquid is a persulfate-sulfuric acid system microetching liquid, the concentration of the persulfate is 60-100 g/L, and the concentration of the sulfuric acid is 3-5% (volume ratio).
Air drying and drying: the method is carried out by a physical method, so that the conductive film layer can be conveniently and rapidly formed.
The microetching and the subsequent processing steps are suitable for the electronic circuit board, and the process is suitable for the electronic circuit board but not limited in the field of the metallized holes of the electronic circuit board.
In the above-described steps, the following are to be explained:
1. the graphene metallization solution liquid medicine tanks are all provided with circulating stirring and filtering devices, and ultrasonic equipment is suggested to be arranged on a horizontal line;
2. the higher the temperature of the drying section is, the better the drying section temperature is (preferably 80-100 ℃), which is not only beneficial to drying the graphene to form a film, but also beneficial to improving the binding force of the film;
3. the graphene metallization solution is opened by the stock solution, analysis and adjustment are not needed, and the stock solution can be used for supplementing the liquid level in time;
4. when the graphene metallization solution chemical water tank is not produced, the circulating stirring of the graphene metallization solution chemical water tank is recommended to be kept, and the stability of the tank solution is facilitated;
5. the graphene metallization solution can be used for effectively treating different base materials such as polyimide PI, polyester resin BT, polytetrafluoroethylene PTFE resin and the like, and a special or extra treatment process is not needed;
6. the product detection in the production process can adopt the traditional backlight detection method of chemical copper and the copper plating method of a light plate.
In summary, the graphene metallization solution and the preparation method and application thereof provided by the invention adopt low-concentration graphene or low-oxidation-degree graphene oxide material as a basic conductive material, effective adsorption of the graphene metallization solution on the surface or the hole wall of a non-metal substrate can be realized through simple and efficient pretreatment, a very thin film layer with reliable bonding force and conductivity close to or even exceeding that of metal copper can be formed through simple drying treatment, the film layer is only a few to dozens of nanometers thick (3-100nm), and can be used as a bottoming conductive layer, and copper can be directly electroplated subsequently.
It is to be understood that the invention is not limited to the examples described above, but that modifications and variations may be effected thereto by those of ordinary skill in the art in light of the foregoing description, and that all such modifications and variations are intended to be within the scope of the invention as defined by the appended claims.
Claims (3)
1. The graphene metallization solution is characterized by being prepared from the following raw materials in percentage by mass:
0.5-5.0% of graphene;
1-3% of film-forming agent;
1-6% of a dispersant;
0.01 to 0.2 percent of anionic surfactant;
adjusting the pH value of the alkaline solution to 4-14;
the balance of water;
wherein the number of layers of the graphene is 1-3; the sheet diameter of the graphene is 10nm-5 mu m; the film-forming agent is one or more of fatty alcohol-polyoxyethylene ether phosphate, polyvinylpyrrolidone, polyvinyl alcohol and polyethylene glycol monostearate; the dispersant is one or more of PVP, dimethylformamide, N-methyl pyrrolidone and methyl cellosolve; the anionic surfactant is TxOne or more of P-10, sodium dodecyl sulfate, sodium dodecyl sulfonate, carboxylate, sulfate, sulfonate and phosphate; the alkaline solution is a sodium hydroxide solution; the water is pure water or deionized water.
2. A method of preparing the graphene metallization solution of claim 1, comprising the steps of: uniformly mixing graphene, a film-forming agent, a dispersing agent, an anionic surfactant, an alkaline solution and water according to the mass percentage to form a stable dispersion system, so as to obtain the graphene metallization solution; more specifically, the method comprises the following steps: graphene is changed into graphene sheet-like solution with the sheet diameter of 10 nanometers to 5 micrometers by ultrasonic and physical mechanical crushing technology, and then the graphene sheet-like solution is mixed with a dispersing agent, a film forming agent, an anionic surfactant, an alkaline solution and water to form a stable dispersion system.
3. Use of the graphene metallization solution according to claim 1 for non-metallic surface metallization; the method for metalizing the non-metal surface comprises the following steps: treating the non-metallic surface in the graphene metallization solution to metalize the non-metallic surface;
more specifically, when the method is applied, horizontal impregnation is adopted, and horizontal impregnation needs to be matched with horizontal production equipment; the specific process flow is as follows: cleaning/adjusting → secondary counter-current rinsing → graphene metallization solution treatment → air drying → micro-etching → secondary counter-current rinsing → air drying → electro-coppering/pattern transfer line manufacturing; the method comprises the following specific steps:
cleaning/conditioning: the solution for cleaning/adjusting contains surface treating agent, solvent, auxiliary agent, organic base and inorganic base; the surface treatment agent is a mixed dissolved substance of a cationic surfactant and a nonionic surfactant, the surface of the nonmetal substrate is wetted by the surface treatment agent, and grease, rusty spots, finger prints, dust and oxide pollutants are removed during cleaning, so that the cleanness of the surface of the nonmetal substrate is ensured; meanwhile, the polar charge of the surface of the non-metal matrix is adjusted, so that a layer of uniform cationic surfactant is adsorbed on the surface of the non-metal matrix, and the subsequent graphene metallization treatment is facilitated;
secondary countercurrent rinsing: removing the residual degreasing agent on the surface of the nonmetal substrate, ensuring the cleaned/adjusted nonmetal substrate surface to be fully washed by water, and washing off redundant residual components;
and (3) graphene metallization solution treatment: treating the non-metallic surface in the graphene metallization solution to metalize the non-metallic surface; specifically, soaking nonmetal in the graphene metallization solution at the temperature of 20-50 ℃ for 60-120 seconds; the treatment section is additionally provided with circulating filtration, high-pressure spraying and ultrasonic equipment as assistance, so that the treatment capacity and the actual penetration effect of the solution on the walls of the deep holes and the small holes are improved;
through the treatment procedures, effective adsorption and combination are carried out on the surface of the nonmetal substrate by Brownian motion of microparticles in the graphene metalized solution and the space effect of graphene sheet layer components, and the positive charge effect of cations on the surface of the nonmetal substrate and negative charges on the surface of the graphene form opposite charge adsorption, so that a fine and uniform film layer is finally formed on the surface of the nonmetal substrate;
microetching, namely treating the non-metal substrate by using microetching liquid for 20-40 seconds, wherein the microetching liquid is persulfate-sulfuric acid system microetching liquid, the concentration of the persulfate is 60-100 g/L, and the concentration of the sulfuric acid is 3-5% by volume ratio;
air drying and drying: the method is carried out by a physical method, so that a conductive film layer can be conveniently and rapidly formed;
in the above process, more specific requirements are:
(1) the graphene metallization solution liquid medicine tanks are all provided with circulating stirring and filtering devices, and ultrasonic equipment is arranged on a horizontal line;
(2) the temperature of the drying section is 80-100 ℃, which is not only beneficial to drying the graphene to form a film, but also beneficial to improving the binding force of the film;
(3) the graphene metallization solution is opened by the stock solution, analysis and adjustment are not needed, and the stock solution can be used for supplementing the liquid level in time;
(4) the circulation stirring of the graphene metallization solution medicine water tank is kept during production stoppage, which is beneficial to the stability of the tank liquor;
the substrate adopting the process comprises polyimide PI, polyester resin BT or polytetrafluoroethylene PTFE resin.
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| EP3656894A1 (en) * | 2018-11-25 | 2020-05-27 | Nanjing Graphene Research Institute Corporation | Method for electroplating copper on non-metallic surfaces using graphene-based ink |
| CN109811380B (en) * | 2019-03-21 | 2022-06-10 | 华侨大学 | Conductive surface treatment method before electroplating of ABS (acrylonitrile butadiene styrene) plastic |
| CN111058078B (en) * | 2019-12-30 | 2021-09-24 | 中国科学院青海盐湖研究所 | Copper foil with graphene film coated on surface and preparation method thereof |
| CN112795965B (en) * | 2020-12-29 | 2022-04-01 | 中国科学院过程工程研究所 | Graphene oxide electroplating solution and preparation method and application thereof |
| 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 |
| CN114016010A (en) * | 2021-11-05 | 2022-02-08 | 深圳市天熙科技开发有限公司 | Acidic pore-finishing agent and surface metallization treatment process method of inorganic non-metallic base material |
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| EP2785896B1 (en) * | 2011-12-02 | 2015-09-23 | Altana AG | Method for producing electrically conductive structures on non-conductive substrates and structures made in this manner |
| CN103103590A (en) * | 2013-01-08 | 2013-05-15 | 西北工业大学 | Direct-electroplating conductive liquid and preparation method thereof |
| CN103491727B (en) * | 2013-09-29 | 2016-02-24 | 哈尔滨工业大学 | Printed circuit board (PCB) graphite oxide reducing process carries out the method for hole electricity conduction |
| TWI522499B (en) * | 2014-03-19 | 2016-02-21 | Nat Univ Chung Hsing | A method of modifying the reduced graphene layer on the surface of the substrate |
| CN104562115B (en) * | 2014-07-04 | 2017-07-11 | 广东丹邦科技有限公司 | Blank hole liquid for printed circuit board and preparation method thereof |
| CN105063681A (en) * | 2015-08-28 | 2015-11-18 | 韶关硕成化工有限公司 | High-concentration carbon hole solution for PCB and preparation method thereof |
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| CN105860667B (en) * | 2016-06-03 | 2019-03-01 | 中国人民解放军国防科学技术大学 | Graphene oxide ink and its preparation method and application |
| TWI586849B (en) * | 2016-08-04 | 2017-06-11 | 國立中興大學 | A method of reducing the graphene layer of the oxidized graphene layer on the surface of the substrate and the hole wall of the aspect ratio hole and the adjusting liquid used in the method |
| TWI628989B (en) * | 2016-10-25 | 2018-07-01 | 萬億股份有限公司 | Method for forming wire and filling via of pcb |
| TWI618821B (en) * | 2017-04-21 | 2018-03-21 | 萬億股份有限公司 | Method for manufacturing traces of pcb |
| CN107903713A (en) * | 2017-11-29 | 2018-04-13 | 北京旭碳新材料科技有限公司 | Highly conductive watersoluble plumbago alkene electrically conductive ink and preparation method thereof, composition |
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| CN108425138B (en) * | 2018-05-11 | 2020-05-05 | 华侨大学 | Surface treatment method for ABS plastic electroplating |
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