CN109811382B - Application of graphene oxide conductive paste in black hole direct electroplating - Google Patents
Application of graphene oxide conductive paste in black hole direct electroplating Download PDFInfo
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Abstract
The invention discloses an application of graphene oxide conductive paste in black hole direct electroplating, which comprises the steps of preparing the graphene oxide conductive paste and using the prepared graphene oxide conductive paste to perform black hole direct electroplating. According to the invention, graphene oxide is modified to enable the surface of the graphene oxide to contain isocyanate groups, so that the graphene oxide conductive paste has very high fluidity and film-forming property, the attached graphene oxide compact layer has stable continuity, the strength of the compact layer can be enhanced while the conductive capability is increased, micro cracks or fractures are not easy to occur when an electroplating plate deforms, and the service life of the conductive plate is prolonged; compared with the existing black hole direct electroplating process, the process steps of black hole direct electroplating by using the graphene oxide conductive paste are greatly simplified, the whole electroplating process can be completed by only repeating one-time coating, the operation is simple, and the yield is high.
Description
Technical Field
The invention relates to a black hole direct electroplating technology, in particular to application of graphene oxide conductive paste in black hole direct electroplating.
Background
The technology of metallization of printed circuit board (PCB, FPC) hole is one of the key of the technology of manufacturing printed circuit board, people have used the method of chemical copper deposition (PTH) for a long time, but PTH solution contains various chemicals which harm the ecological environment, such as EDTA, NTA, EDTP and formaldehyde which is easy to cause cancer, the waste water treatment is complicated, and the cost is high. In addition, the stability of the PTH solution is poor, and the analysis and maintenance of the solution are complex; meanwhile, the mechanical property of the PTH copper plating layer is poor, and the process flow is complicated, so that a new hole metallization technology is always searched in the industry, and the black hole direct electroplating technology is produced under the background.
The black hole direct electroplating technology is to dip-coat fine graphite or carbon black coating (black hole liquid) on the hole wall to form a conductive layer, and then to carry out direct electroplating. The key technology is the composition of black hole solution components. Firstly, fine graphite or carbon black powder is uniformly dispersed in a medium, namely deionized water, and a surfactant in the solution is utilized to keep the graphite or carbon black suspension liquid which is uniform in solution stable, and the graphite or carbon black suspension liquid also has good wetting property, so that the graphite or carbon black can be fully adsorbed on the surface of the pore wall of a nonconductor to form a uniform, fine and firmly combined conducting layer. The raw materials of the black hole direct electroplating technology do not contain harmful substances such as EDTA (ethylene diamine tetraacetic acid), EDTP (ethylene-propylene-terephthalate) and formaldehyde which can cause cancers, and the like which are difficult to decompose, so that the environmental pollution is small, the wastewater treatment is simple, and the treatment cost is reduced; the process is shortened, the production efficiency is obviously improved, the black hole process only needs 16 minutes, and is only 1/3 of the PTH process time; the black hole process is easy to control, the operation is simple, the analysis, maintenance and adjustment of the solution are simple, and the comprehensive economic cost is greatly reduced compared with the chemical copper deposition (PTH).
The core of the black hole direct electroplating technology is black hole liquid, the black hole liquid is black solution formed by fine carbon black or graphite with extremely strong electric conduction capability, the black hole liquid has good stability, no hydrogen is separated out in the adsorption process of the copper-clad plate after drilling is completed, the black hole liquid is in physical property in the adsorption process, no chemical reaction occurs, the phenomenon that other components are consumed due to the chemical reaction does not exist, the solution does not need to be analyzed and adjusted, the black hole liquid can be completely supplemented according to the loss reduction of actual production, and the working stability of the black hole liquid is ensured.
The main component of the existing black hole liquid is small-particle carbon black or graphite, a compact layer needs to be formed on an electroplating plate to have conductivity, if the density of a conductive layer is insufficient or a gap exists, the conductivity of the conductive layer can be greatly reduced, and once the electroplating plate is slightly deformed, the conductive layer can be slightly cracked or even broken, so that a circuit board cannot be used.
Although the steps of the black hole direct electroplating technology are greatly shortened compared with the steps of the chemical copper deposition process, the black hole direct electroplating technology has multiple steps, the steps of coating, cold and hot air drying, micro etching and the like need to be repeated, the operation of each step needs to be strictly controlled, and the electroplating failure can be caused by the error of any step, so that the yield is reduced, and the cost is increased.
Disclosure of Invention
The invention provides an application of graphene oxide conductive paste in black hole direct electroplating, aiming at the problems that the existing black hole direct electroplating technology has multiple steps and strict requirements on compactness of a conductive layer.
The technical scheme for solving the technical problems is as follows: the application of the graphene oxide conductive paste in black hole direct electroplating comprises the steps of preparing the graphene oxide conductive paste and using the prepared graphene oxide conductive paste to perform black hole direct electroplating, and is characterized by comprising the following steps of:
A. preparation of graphene oxide conductive paste
A1) Preparing graphite oxide powder: immersing 10g of natural crystalline flake graphite into a mixed acid of 100mL of concentrated sulfuric acid and 20mL of concentrated nitric acid, immersing for 12-18h at normal temperature, filtering, washing a filter cake with deionized water until the pH value of a washing liquid is 6-7, then placing the filter cake in a vacuum drying oven, and drying for 4-6h at 60-70 ℃ to obtain graphite oxide powder;
A2) modified graphite oxide: soaking graphite oxide powder in hydrazine hydrate for 8-10h at normal temperature, filtering after soaking, washing a filter cake with deionized water, and drying in a drying oven for 4h at 60 ℃ to prepare a graphene oxide microchip containing carboxyl and hydroxyl;
A3) preparing graphene oxide conductive slurry: placing the graphene oxide microchip obtained in the step A2) into DMSO (dimethyl sulfoxide), performing ultrasonic oscillation for 1h, transferring to a water bath kettle at the temperature of 80-85 ℃, adding 100g of diisocyanate, stirring and reacting for 4-6h at the temperature of 60-65 ℃, filtering, washing for 2-3 times by using dichloromethane, drying at the temperature of 45-50 ℃, then placing into a silane coupling agent for soaking for 6-8h, filtering, washing for 3-5 times by using deionized water, then placing into an organic amine aqueous solution, stirring and reacting for 5h at the temperature of 40-60 ℃ to prepare a suspension, performing high-speed shearing and grinding on the suspension by using a colloid mill for 1-2h at normal temperature, wherein the rotating speed of the colloid mill is 10000r/min, finally filtering the ground black suspension by using 120 meshes and 325 meshes in sequence, and ultrasonically dispersing the filtrate for 0.5-2h by using 20Hz to prepare graphene oxide conductive slurry;
B. black hole direct electroplating using graphene oxide conductive paste
B1) Cleaning: placing the electroplating plate in a cleaning solution at 60-70 ℃ for 3-5min, taking out and cleaning with deionized water;
B2) hole trimming: placing the cleaned electroplating plate in a pore-forming agent at 60-70 ℃ for 3-5min, taking out and drying with cold air;
B3) coating: immersing the electroplated board with the whole hole into the graphene oxide conductive slurry at room temperature for 3-5min, taking out, drying by hot air, immersing into the graphene oxide conductive slurry again for 3-5min, taking out, and drying by hot air again;
B4) micro-etching: immersing the coated electroplating plate into a microetching solution for 2min at room temperature, taking out, cleaning with deionized water, and air-drying;
B5) copper electroplating: and carrying out copper plating operation on the surface of the electroplated plate subjected to the microetching to obtain the graphene oxide conductive paste black hole electroplated plate.
Wherein the diisocyanate in step A3) is MDI or HDI; the organic amine is tetraethylenepentamine, triethylene tetramine or triethanolamine, and the concentration of the aqueous solution of the organic amine is 5wt% -15 wt%.
The invention has the beneficial effects that:
1) the graphene oxide provided by the invention has the advantages that carbon atoms are in a hexagonal ring shape, the resistivity is low, the electron migration speed is very high, the conductivity is good, and the electroplating efficiency is improved;
2) the graphene oxide is stable in performance, and can prevent the occurrence of a coagulation phenomenon without circular stirring in a static state, and the graphene oxide is used for electroplating, so that no hydrogen is separated out in the adsorption process of the copper-clad plate after drilling is finished, and a solid guarantee is provided for improving the interlayer interconnection quality of the printed board;
3) the graphene oxide is applied to the black hole liquid electroplating technology, chemical reaction does not occur in the adsorption process, the phenomenon that other components are consumed due to the chemical reaction does not exist, the solution does not need to be analyzed and adjusted, and new liquid can be supplemented completely according to the loss of actual production;
4) according to the invention, graphene oxide is modified to enable the surface of the graphene oxide to contain isocyanate groups, so that the graphene oxide conductive paste has very high fluidity and film-forming property, the compatibility of the graphene oxide and an electroplating plate is increased, negative charges on the graphene oxide can be attracted with positive charges on holes of a circuit board, and thus the graphene oxide is stably attached to the holes of the circuit board to form conductive metal holes, and the time and cost are saved for subsequent electroplating work;
5) according to the invention, linear graphene oxide is adopted to replace carbon black or graphite of particles for black hole direct electroplating, the attached graphene oxide compact layer has stable continuity, the strength of the compact layer can be enhanced while the conductive capability is increased, micro cracks or fracture are not easy to occur when an electroplating plate is deformed, and the service life of the conductive plate is prolonged;
6) because the graphene oxide conductive paste prepared by the method has good film forming property, compared with the existing black hole direct electroplating process, the process steps of performing black hole direct electroplating by using the graphene oxide conductive paste are greatly simplified, the consumption of the conductive paste is small, the whole electroplating process can be completed by only repeating one-time coating, the operation is simple, and the yield is high;
7) the graphene oxide provided by the invention has good stability, the electroplating bath solution does not need to be replaced within one year, the working hours are saved, the water and electricity are saved, the material consumption is reduced, the discharge amount of wastewater is effectively controlled, the bath solution does not contain harmful substances, the environmental pollution is small, the wastewater treatment is simple, and the cost is reduced.
Drawings
Fig. 1 to 3 are transmission electron micrographs of graphene oxide prepared according to the present invention;
FIG. 4 is a scanning electron microscope image of the copper plating front surface of the electroplated panel prepared by the present invention using the graphene oxide conductive paste for black hole direct electroplating.
Detailed Description
The present invention is described below with reference to examples, which are provided for illustration only and are not intended to limit the scope of the present invention.
Example 1
The application of the graphene oxide conductive paste in the black hole direct electroplating comprises the steps of preparing the graphene oxide conductive paste and using the prepared graphene oxide conductive paste to perform the black hole direct electroplating, wherein the steps are as follows:
A. preparation of graphene oxide conductive paste
A1) Preparing graphite oxide powder: immersing 10g of natural crystalline flake graphite into a mixed acid of 100mL of concentrated sulfuric acid and 20mL of concentrated nitric acid, immersing for 12h at normal temperature, filtering, washing a filter cake with deionized water until the pH value of a washing liquid is between 6 and 7, then placing the filter cake in a vacuum drying oven, and drying for 4h at 70 ℃ to obtain graphite oxide powder;
A2) modified graphite oxide: soaking graphite oxide powder in hydrazine hydrate for 10h at normal temperature, filtering after soaking, washing a filter cake with deionized water, and drying in a drying oven at 60 ℃ for 4h to prepare a graphene oxide microchip containing carboxyl and hydroxyl;
A3) preparing graphene oxide conductive slurry: placing the graphene oxide microchip obtained in the step A2) into DMSO (dimethyl sulfoxide), ultrasonically oscillating for 1h, transferring to a water bath kettle at 85 ℃, adding 100g of diisocyanate MDI, stirring and reacting for 6h at 60 ℃, filtering, washing with dichloromethane for 2-3 times, drying at 50 ℃, then placing into a silane coupling agent for soaking for 6h, filtering, washing with deionized water for 3-5 times, then placing into an aqueous solution of 5wt% tetraethylenepentamine, stirring and reacting for 5h at 40 ℃ to obtain a suspension, carrying out high-speed shearing and grinding on the suspension for 2h by using a colloid mill at normal temperature, wherein the rotating speed of the colloid mill is 10000r/min, finally filtering the ground black suspension by using 120 meshes and 325 meshes in sequence, and ultrasonically dispersing the filtrate for 20Hz for 0.5h to obtain graphene oxide conductive slurry;
B. black hole direct electroplating using graphene oxide conductive paste
B1) Cleaning: placing the electroplating plate in a cleaning solution at 60 ℃ for 5min, taking out and cleaning with deionized water;
B2) hole trimming: placing the cleaned electroplating plate in a pore-forming agent at 70 ℃ for 3min, taking out and drying by cold air;
B3) coating: immersing the electroplated board with the whole hole into the graphene oxide conductive slurry for 5min at room temperature, taking out, drying by hot air, immersing into the graphene oxide conductive slurry for 3min, taking out, and drying by hot air again;
B4) micro-etching: immersing the coated electroplating plate into a microetching solution for 2min at room temperature, taking out, cleaning with deionized water, and air-drying;
B5) copper electroplating: and carrying out copper plating operation on the surface of the electroplated plate subjected to the microetching to obtain the graphene oxide conductive paste black hole electroplated plate.
Example 2
The application of the graphene oxide conductive paste in the black hole direct electroplating comprises the steps of preparing the graphene oxide conductive paste and using the prepared graphene oxide conductive paste to perform the black hole direct electroplating, wherein the steps are as follows:
A. preparation of graphene oxide conductive paste
A1) Preparing graphite oxide powder: immersing 10g of natural crystalline flake graphite into a mixed acid of 100mL of concentrated sulfuric acid and 20mL of concentrated nitric acid, immersing for 16h at normal temperature, filtering, washing a filter cake with deionized water until the pH value of a washing liquid is between 6 and 7, then placing the filter cake in a vacuum drying oven, and drying for 5h at 65 ℃ to obtain graphite oxide powder;
A2) modified graphite oxide: soaking graphite oxide powder in hydrazine hydrate for 9h at normal temperature, filtering after soaking, washing a filter cake with deionized water, and drying in a drying oven for 4h at 60 ℃ to prepare a graphene oxide microchip containing carboxyl and hydroxyl;
A3) preparing graphene oxide conductive slurry: placing the graphene oxide microchip obtained in the step A2) into DMSO (dimethyl sulfoxide), ultrasonically oscillating for 1h, transferring to a water bath kettle at 85 ℃, adding 100g of diisocyanate MDI, stirring and reacting for 4h at 60 ℃, filtering, washing with dichloromethane for 2-3 times, drying at 50 ℃, then placing into a silane coupling agent for soaking for 6-8h, filtering, washing with deionized water for 3-5 times, then placing into a 10 wt% triethylene tetramine aqueous solution, stirring and reacting for 5h at 50 ℃ to obtain a suspension, carrying out high-speed shearing and grinding on the suspension by using a colloid mill for 1.5h at normal temperature, wherein the rotation speed of the colloid mill is 10000r/min, finally filtering the ground black suspension by using 120 meshes and 325 meshes in sequence, and ultrasonically dispersing the filtrate for 1h to obtain graphene oxide slurry;
B. black hole direct electroplating using graphene oxide conductive paste
B1) Cleaning: placing the electroplating plate in 65 deg.C cleaning solution for 4min, taking out, and cleaning with deionized water;
B2) hole trimming: placing the cleaned electroplating plate in a pore-forming agent at 65 ℃ for 4min, taking out and drying by using cold air;
B3) coating: immersing the electroplated board with the whole hole into the graphene oxide conductive slurry for 4min at room temperature, taking out, drying by hot air, immersing into the graphene oxide conductive slurry for 4min, taking out, and drying by hot air again;
B4) micro-etching: immersing the coated electroplating plate into a microetching solution for 2min at room temperature, taking out, cleaning with deionized water, and air-drying;
B5) copper electroplating: and carrying out copper plating operation on the surface of the electroplated plate subjected to the microetching to obtain the graphene oxide conductive paste black hole electroplated plate.
Example 3
The application of the graphene oxide conductive paste in the black hole direct electroplating comprises the steps of preparing the graphene oxide conductive paste and using the prepared graphene oxide conductive paste to perform the black hole direct electroplating, wherein the steps are as follows:
A. preparation of graphene oxide conductive paste
A1) Preparing graphite oxide powder: immersing 10g of natural crystalline flake graphite into a mixed acid of 100mL of concentrated sulfuric acid and 20mL of concentrated nitric acid, immersing for 18h at normal temperature, filtering, washing a filter cake with deionized water until the pH value of a washing liquid is between 6 and 7, then placing the filter cake in a vacuum drying oven, and drying for 6h at 60 ℃ to obtain graphite oxide powder;
A2) modified graphite oxide: soaking graphite oxide powder in hydrazine hydrate for 8 hours at normal temperature, filtering after soaking, washing a filter cake with deionized water, and drying in a drying oven at 60 ℃ for 4 hours to prepare a graphene oxide microchip containing carboxyl and hydroxyl;
A3) preparing graphene oxide conductive slurry: placing the graphene oxide microchip obtained in the step A2) into DMSO (dimethyl sulfoxide), ultrasonically oscillating for 1h, transferring to a 80 ℃ water bath, adding 100g of diisocyanate HDI, stirring and reacting for 4h at 65 ℃, filtering, washing with dichloromethane for 2-3 times, drying at 45 ℃, then placing into a silane coupling agent for soaking for 8h, filtering, washing with deionized water for 3-5 times, placing into a 15wt% triethanolamine aqueous solution, stirring and reacting for 5h at 60 ℃, preparing a suspension, carrying out high-speed shearing and grinding on the suspension for 1h with a colloid mill at normal temperature, wherein the rotation speed of the colloid mill is 10000r/min, finally sequentially filtering the ground black suspension by 120 meshes and 325 meshes, and ultrasonically dispersing the filtrate for 2h at 20Hz to prepare graphene oxide conductive slurry;
B. black hole direct electroplating using graphene oxide conductive paste
B1) Cleaning: placing the electroplating plate in a cleaning solution at 70 ℃ for 3min, taking out and cleaning with deionized water;
B2) hole trimming: placing the cleaned electroplating plate in a pore-forming agent at 60 ℃ for 5min, taking out and drying by cold air;
B3) coating: immersing the electroplated board with the whole hole into the graphene oxide conductive slurry at room temperature for 3min, taking out, drying by hot air, immersing into the graphene oxide conductive slurry again for 5min, taking out, and drying by hot air again;
B4) micro-etching: immersing the coated electroplating plate into a microetching solution for 2min at room temperature, taking out, cleaning with deionized water, and air-drying;
B5) copper electroplating: and carrying out copper plating operation on the surface of the electroplated plate subjected to the microetching to obtain the graphene oxide conductive paste black hole electroplated plate.
Fig. 1-3 are transmission electron micrographs of graphene oxide prepared according to the present invention, from which it can be seen that the graphene oxide has a complete structure after being modified; fig. 4 is a scanning electron microscope image of the copper plating front surface of the electroplating plate prepared by directly electroplating black holes with the graphene oxide conductive paste, wherein the graphene oxide has a complete structure and obvious orientation, so that the dense layer has strong mechanical properties and good conductivity.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (2)
1. The application of the graphene oxide conductive paste in black hole direct electroplating comprises the steps of preparing the graphene oxide conductive paste and using the prepared graphene oxide conductive paste to perform black hole direct electroplating, and is characterized by comprising the following steps of:
A. preparation of graphene oxide conductive paste
A1) Preparing graphite oxide powder: immersing 10g of natural crystalline flake graphite into a mixed acid of 100ml of concentrated sulfuric acid and 20ml of concentrated nitric acid, immersing for 12-18h at normal temperature, filtering, washing a filter cake with deionized water until the pH value of a washing liquid is 6-7, then placing the filter cake in a vacuum drying oven, and drying for 4-6h at 60-70 ℃ to obtain graphite oxide powder;
A2) modified graphite oxide: soaking graphite oxide powder in hydrazine hydrate for 8-10h at normal temperature, filtering after soaking, washing a filter cake with deionized water, and drying in a drying oven for 4h at 60 ℃ to prepare a graphene oxide microchip containing carboxyl and hydroxyl;
A3) preparing graphene oxide conductive slurry: placing the graphene oxide micro-sheet obtained in the step A2) into DMSO (dimethyl sulfoxide), performing ultrasonic oscillation for 1h, transferring to a water bath kettle at the temperature of 80-85 ℃, adding 100g of MDI (diphenyl diisocyanate) or HDI, stirring and reacting for 4-6h at the temperature of 60-65 ℃, filtering, washing for 2-3 times by using dichloromethane, drying at the temperature of 45-50 ℃, then placing into a silane coupling agent for soaking for 6-8h, filtering, washing for 3-5 times by using deionized water, then placing into an aqueous solution of organic amine, stirring and reacting for 5h at the temperature of 40-60 ℃ to prepare a suspension, performing high-speed shearing and grinding on the suspension by using a colloid mill for 1-2h at normal temperature, wherein the rotating speed of the colloid mill is 10000r/min, finally filtering the ground black suspension by using 120 meshes and 325 meshes in sequence, and performing ultrasonic dispersion on the filtrate for 0.5-2h by;
B. black hole direct electroplating using graphene oxide conductive paste
B1) Cleaning: placing the electroplating plate in a cleaning solution at 60-70 ℃ for 3-5min, taking out and cleaning with deionized water;
B2) hole trimming: placing the cleaned electroplating plate in a pore-forming agent at 60-70 ℃ for 3-5min, taking out and drying with cold air;
B3) coating: immersing the electroplated board with the whole hole into the graphene oxide conductive slurry at room temperature for 3-5min, taking out, drying by hot air, immersing into the graphene oxide conductive slurry again for 3-5min, taking out, and drying by hot air again;
B4) micro-etching: immersing the coated electroplating plate into a microetching solution for 2min at room temperature, taking out, cleaning with deionized water, and air-drying;
B5) copper electroplating: and carrying out copper plating operation on the surface of the electroplated plate subjected to the microetching to obtain the graphene oxide conductive paste black hole electroplated plate.
2. The application of the graphene oxide conductive paste in black hole direct electroplating according to claim 1, wherein the organic amine in step A3) is tetraethylenepentamine, triethylene tetramine or triethanolamine, and the concentration of the aqueous solution of the organic amine is 5wt% -15 wt%.
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Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1562738A (en) * | 2004-04-15 | 2005-01-12 | 上海交通大学 | Functional nano carbon tubes possessing isocyanate radical on its surface and preparation method |
| CN101394712A (en) * | 2007-09-21 | 2009-03-25 | 清华大学 | Hole blackening solution and preparation thereof |
| CN102424381A (en) * | 2011-09-09 | 2012-04-25 | 中国科学院苏州纳米技术与纳米仿生研究所 | Graphene oxide reducing method |
| CN103491727A (en) * | 2013-09-29 | 2014-01-01 | 哈尔滨工业大学 | Method using printed circuit board graphite oxide reduction method to carry out hole conductivity |
| CN103608288A (en) * | 2011-11-30 | 2014-02-26 | 积水化学工业株式会社 | Functional-group-modified carbon material, and method for producing same |
| CN103839605A (en) * | 2014-02-26 | 2014-06-04 | 华中科技大学 | Electrocondution slurry and preparation method and application of electrocondution slurry |
| KR20170098341A (en) * | 2016-02-19 | 2017-08-30 | 전자부품연구원 | Heating composition having graphene oxide and heater using the same |
| 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 |
| CN108962425A (en) * | 2018-08-02 | 2018-12-07 | 佛山腾鲤新能源科技有限公司 | A kind of preparation method of graphene conductive slurry |
| CN108963255A (en) * | 2018-06-01 | 2018-12-07 | 湖南国盛石墨科技有限公司 | A kind of preparation method of the conduction liquid of containing graphene |
| CN109243671A (en) * | 2018-11-29 | 2019-01-18 | 圣盟（廊坊）新材料研究院有限公司 | A kind of preparation method of graphene composite conductive slurry |
-
2019
- 2019-03-28 CN CN201910244507.4A patent/CN109811382B/en active Active
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1562738A (en) * | 2004-04-15 | 2005-01-12 | 上海交通大学 | Functional nano carbon tubes possessing isocyanate radical on its surface and preparation method |
| CN101394712A (en) * | 2007-09-21 | 2009-03-25 | 清华大学 | Hole blackening solution and preparation thereof |
| CN102424381A (en) * | 2011-09-09 | 2012-04-25 | 中国科学院苏州纳米技术与纳米仿生研究所 | Graphene oxide reducing method |
| CN103608288A (en) * | 2011-11-30 | 2014-02-26 | 积水化学工业株式会社 | Functional-group-modified carbon material, and method for producing same |
| CN103491727A (en) * | 2013-09-29 | 2014-01-01 | 哈尔滨工业大学 | Method using printed circuit board graphite oxide reduction method to carry out hole conductivity |
| CN103839605A (en) * | 2014-02-26 | 2014-06-04 | 华中科技大学 | Electrocondution slurry and preparation method and application of electrocondution slurry |
| KR20170098341A (en) * | 2016-02-19 | 2017-08-30 | 전자부품연구원 | Heating composition having graphene oxide and heater using the same |
| 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 |
| CN108963255A (en) * | 2018-06-01 | 2018-12-07 | 湖南国盛石墨科技有限公司 | A kind of preparation method of the conduction liquid of containing graphene |
| CN108962425A (en) * | 2018-08-02 | 2018-12-07 | 佛山腾鲤新能源科技有限公司 | A kind of preparation method of graphene conductive slurry |
| CN109243671A (en) * | 2018-11-29 | 2019-01-18 | 圣盟（廊坊）新材料研究院有限公司 | A kind of preparation method of graphene composite conductive slurry |
Non-Patent Citations (2)
| Title |
|---|
| Diisocyanate modified graphene oxide network structure: steric effect of diisocyanates on bimolecular cross-linking degree;Uttam Saha et al;《J Nanopart Res》;20140419;2404第1-21页 * |
| 甲苯二异氰酸酯插层改性氧化石墨烯;李晓萱 等;《化工新型材料》;20140430(第4期);第81-83页 * |
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