CN104762614A - High thermal conductive graphite fiber surface palladium-free electroless copper plating process - Google Patents
High thermal conductive graphite fiber surface palladium-free electroless copper plating process Download PDFInfo
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- CN104762614A CN104762614A CN201510179313.2A CN201510179313A CN104762614A CN 104762614 A CN104762614 A CN 104762614A CN 201510179313 A CN201510179313 A CN 201510179313A CN 104762614 A CN104762614 A CN 104762614A
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Abstract
The invention relates to a high thermal conductive graphite fiber surface palladium-free electroless copper plating process. The technical scheme is as follows: by using graphite fiber with banding large section or cylindrical graphite fiber as a matrix, performing pretreatment processes such as coarsening, neutralizing, sensitizing and reducing, and then performing electroless copper plating on the surface of the graphite fiber, wherein the section shape of the graphite fiber with bonding large section is similar to rectangular, or is the cylindrical graphite fiber, the width or diameter is 1-2mm, the thickness is 8-20 microns, and the length is 5-10nm; the electroless plating temperature is 40-50 DEG C, and the pH is 12-12.5. The process disclosed by the invention is simple, the metal palladium with expensive price is avoided, the cost is low, the repeatability is low, and the production period is short; the graphite fiber plating treated by using the process has the characteristics of strong binding force, and uniform and bright plating.
Description
Technical field
The invention belongs to the technical field of material surface process, be specifically related to a kind of high conductive graphite fiber surface without palladium chemical-copper-plating process.
Background technology
Metal matrix graphite fiber composite materials has the premium properties such as high-modulus, high specific strength, is with a wide range of applications in the field such as space flight and aviation, material.Filler is done with the graphite fibre of surface metalation, obtained structural composite material can use as high performance structural member in fields such as aircraft skin, automobile and engines, obtained functional composite material then utilizes the performances such as the high heat conduction of material, conduction, low-expansion coefficient and low density to be widely used in fields such as heat management, electron device package, precision optical instrument, instrument, therefore, the high performance graphite fiber of surface metalation is a kind of reinforcement of very attractive.
Metallic copper is often used as and carries out metalized modified to graphite fibre surface due to the ductility of excellence, the feature such as conductivity and low price.Electroless plating is conventional a kind of surface modifying method, and it is when passing through without extrinsic current, utilizes redox reaction, the metal ion in solution is formed a kind of coating technology of metal plating at the article surface with catalytic activity.Carry out electroless copper at graphite fibre/carbon fiber surface and have a lot of processing method, but these processing methodes need use precious metal palladium and cause the more high weak point of cost.
Summary of the invention
The object of the present invention is to provide a kind of high conductive graphite fiber surface without palladium chemical-copper-plating process, adopt the method, under the condition not using expensive palladium metal or other noble silver, utilize the autocatalysis activation performance on graphite fibre surface, can obtain and the copper coating using palladium to carry out electroless copper to compare favourably, this copper coating bonding force is strong, and the complete careful and good luster in surface, also reduces the cost of chemical-copper-plating process simultaneously.
The present invention for solving the problems of the technologies described above adopted scheme is:
A kind of high conductive graphite fiber surface is without palladium chemical-copper-plating process, this technique is that graphite fibre is directly carried out electroless copper after alligatoring, neutralization, sensitization and reduction, its chemical plating fluid comprises copper sulfate, formaldehyde, Seignette salt, 2,2 '-dipyridyl, yellow prussiate of potash and sodium hydroxide.
In such scheme, the technique of graphite fibre alligatoring adopts diluted acid to soak, and described dilute acid soln is the mixed solution of 10 ~ 40wt% dust technology and dilute sulphuric acid, and soak time is 10-30min.
In such scheme, reduce by inferior sodium phosphate.
In such scheme, the basic parameter of its electroless plating is: cupric sulfate pentahydrate 15 ~ 20g/L, Seignette salt 15 ~ 20g/L, formaldehyde 15 ~ 20ml/L, 2,2 '-dipyridyl, 3 ~ 10mg/L, yellow prussiate of potash 10 ~ 20g/L, sodium hydroxide 10 ~ 20g/L, pH value of solution 12 ~ 12.5, temperature 40 ~ 50 DEG C.
In such scheme, using the solution of 10g/L tindichloride, 40mL/L hydrochloric acid and 0.2g/L tin grain composition as sensitizing solution.
In such scheme, the width of described graphite fibre or diameter are 1 ~ 2mm, and thickness is 8 ~ 20 μm, and length is 5 ~ 10mm.
In such scheme, the thickness of coating obtained after electroless copper is 1.72 μm.
First the present invention adopts chemical method to carry out surface modification to graphite fibre, to make graphite fibre surface coarsening, increase the wetting ability on graphite fibre surface, and then the bonding force increased between graphite fibre and copper coating, graphite fibre is joined in the dilute acid soln of 10-30% and soak, make its surface presentation channel form, soak time is 10-30min; Then joined in diluted sodium hydroxide solution by the graphite fibre after alligatoring and neutralize, to neutralize the diluted acid remaining in graphite fibre surface, then cleaning is to neutral; Again the graphite fibre after reduction is joined in plating solution after irritated China and reduction and carry out electroless copper, and constantly stir, by the pH value of pH meter test plating solution, observe the change of graphite fibre surface color, graphite fibre surface reddens gradually, and have bubble to emerge, after 15min, take out graphite fibre, clean with distilled water, dry under being placed on infrared lamp, dry.
The invention has the beneficial effects as follows: use these processing condition can avoid using valuable palladium activation step, reduce process costs.Meanwhile, can form copper coating fast on graphite fibre surface, copper plating rate reaches 4.7mg/min, and thickness of coating reaches 7.2 μm, and therefore, preparation technology of the present invention is simple, and cost is lower, reproducible, with short production cycle; Different thickness of coating requirement can be met by this processing method, coating is even, glossiness good, bonding force is good.
Accompanying drawing explanation
Fig. 1 is the graphite fibre surface topography map without any process.
Fig. 2 is the surface topography map of graphite fibre after roughening treatment.
Fig. 3 is the copper coating shape appearance figure after electroless plating is carried out on graphite fibre surface.
Fig. 4 schemes with the powder X-ray RD of the graphite fibre not carrying out electroless plating after carrying out electroless plating.
Fig. 5 is the thickness of copper coating after graphite fibre Electroless copper.
Embodiment
Below in conjunction with embodiment, the invention will be further described, the restriction not to its protection domain.
In this embodiment: described graphite fibre is the banded graphite fibre in large section or cylindric graphite fibre, and its width or diameter are 1 ~ 2mm, and thickness is 8 ~ 20 μm, and length is 5 ~ 10mm.Repeat no more in embodiment.
Embodiment 1
(1) graphite fibre alligatoring: prepare 10wt% dilute sulphuric acid and 10wt% dust technology mixing dilute acid soln in beaker, added by graphite fibre in solution, after stirring 10min, filters out graphite fibre.
(2) neutralize: the diluted sodium hydroxide solution that 10wt% put into by the graphite fibre of alligatoring is neutralized, then extremely neutral with distilled water cleaning graphite fibre surface.
(3) sensitization: the sensitizing solution graphite fibre after neutralization being put into 10g/L tindichloride, 40mL/L hydrochloric acid and 0.2g/L tin grain composition, stirs 15min, more carefully cleans with distilled water, put into oven for drying.
(4) reduce: the ortho phosphorous acid sodium solution that 30g/L put into by the graphite fibre after sensitization reduces, after 5min, clean with distilled water flushing.
(5) electroless plating: the graphite fibre that early stage is handled well, the solution putting into electroless plating carries out electroless plating.Take out the graphite fibre after having plated copper, clean up with distilled water, dry under being placed on infrared lamp.Dried its pattern of rear scanning electron microscopic observation.The basic parameter of its electroless plating is as follows:
Embodiment 2
(1) graphite fibre alligatoring: prepare 20wt% dilute sulphuric acid and 20wt% dust technology mixing dilute acid soln in beaker, added by graphite fibre in solution, after stirring 10min, leaches graphite fibre.
(2) neutralize: the diluted sodium hydroxide solution that 20wt% put into by the graphite fibre of alligatoring is neutralized, then extremely neutral with distilled water cleaning graphite fibre surface.
(3) sensitization: the sensitizing solution graphite fibre after neutralization being put into 10g/L tindichloride, 40mL/L hydrochloric acid and 0.2g/L tin grain, stirs 15min, more carefully cleans with distilled water, put into oven for drying.
(4) reduce: the ortho phosphorous acid sodium solution that 30g/L put into by the graphite fibre after sensitization reduces, after 5min, clean with distilled water flushing.
(5) electroless plating: the graphite fibre that early stage is handled well, the solution putting into electroless plating carries out electroless plating.The basic parameter of its electroless plating is as follows:
Take out the graphite fibre after having plated copper, clean up with distilled water, dry under being placed on infrared lamp.To characterize before and after graphite fibre alligatoring by scanning electron microscope and the pattern of copper coating after electroless plating.
High conductive graphite fibre chemistry of the present invention is copper-plated has technique simply, the features such as cost is lower, reproducible and with short production cycle.
Claims (7)
1. one kind high conductive graphite fiber surface is without palladium chemical-copper-plating process, it is characterized in that, this technique is that graphite fibre is directly carried out electroless copper after alligatoring, neutralization, sensitization and reduction, its chemical plating fluid comprises copper sulfate, formaldehyde, Seignette salt, 2,2 '-dipyridyl, yellow prussiate of potash and sodium hydroxide.
2. high conductive graphite fiber surface according to claim 1 is without palladium chemical-copper-plating process, it is characterized in that, the technique of graphite fibre alligatoring adopts diluted acid to soak, and described dilute acid soln is the mixed solution of 10 ~ 40wt% dust technology and dilute sulphuric acid, and soak time is 10-30min.
3. high conductive graphite fiber surface according to claim 1 is without palladium chemical-copper-plating process, it is characterized in that, reduces by inferior sodium phosphate.
4. high conductive graphite fiber surface according to claim 1 is without palladium chemical-copper-plating process, it is characterized in that, the basic parameter of its electroless plating is: cupric sulfate pentahydrate 15 ~ 20g/L, Seignette salt 15 ~ 20g/L, formaldehyde 15 ~ 20ml/L, 2,2 '-dipyridyl, 3 ~ 10mg/L, yellow prussiate of potash 10 ~ 20g/L, sodium hydroxide 10 ~ 20g/L, pH value of solution 12 ~ 12.5, temperature 40 ~ 50 DEG C.
5. high conductive graphite fiber surface according to claim 1 is without palladium chemical-copper-plating process, it is characterized in that, using the solution of 10g/L tindichloride, 40mL/L hydrochloric acid and 0.2g/L tin grain composition as sensitizing solution.
6. high conductive graphite fiber surface according to claim 1 prepares without palladium chemical-copper-plating process, it is characterized in that, described graphite fibre is banded or cylindric graphite fibre, the width of described graphite fibre or diameter are 1 ~ 2mm, thickness is 8 ~ 20 μm, and length is 5 ~ 10mm.
7. high conductive graphite fiber surface according to claim 1 is without palladium chemical-copper-plating process, it is characterized in that, the thickness of coating obtained after electroless copper is 1.72 μm.
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| CN201510179313.2A CN104762614B (en) | 2015-04-15 | 2015-04-15 | A kind of high heat conduction graphite fibre surface is without palladium chemical-copper-plating process |
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| CN201510179313.2A CN104762614B (en) | 2015-04-15 | 2015-04-15 | A kind of high heat conduction graphite fibre surface is without palladium chemical-copper-plating process |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105256290A (en) * | 2015-10-08 | 2016-01-20 | 山东建筑大学 | Novel diamond plating process applied to stone cutters |
| CN109355644A (en) * | 2018-10-17 | 2019-02-19 | 武汉欣远拓尔科技有限公司 | The plating solution and its preparation method and plating method of a kind of Ni-Fe-P alloy coating |
| CN112482024A (en) * | 2020-11-26 | 2021-03-12 | 南京信息工程大学 | Preparation method of copper-plated carbon fabric electromagnetic shielding material |
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| US6320129B1 (en) * | 1999-09-21 | 2001-11-20 | Industrial Technology Research Institute | Method for making electrode of polymer composite |
| CN102586704A (en) * | 2012-03-23 | 2012-07-18 | 北京科技大学 | High thermal conductivity graphite whisker/copper composite and preparation method thereof |
| CN103726133A (en) * | 2014-01-02 | 2014-04-16 | 东华大学 | High-strength, compact and ordered porous graphene fiber and continuous preparation method thereof |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6320129B1 (en) * | 1999-09-21 | 2001-11-20 | Industrial Technology Research Institute | Method for making electrode of polymer composite |
| CN102586704A (en) * | 2012-03-23 | 2012-07-18 | 北京科技大学 | High thermal conductivity graphite whisker/copper composite and preparation method thereof |
| CN103726133A (en) * | 2014-01-02 | 2014-04-16 | 东华大学 | High-strength, compact and ordered porous graphene fiber and continuous preparation method thereof |
Non-Patent Citations (1)
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| 王彪等: "石墨表面无敏化及活化的化学镀铜法", 《表面技术》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105256290A (en) * | 2015-10-08 | 2016-01-20 | 山东建筑大学 | Novel diamond plating process applied to stone cutters |
| CN109355644A (en) * | 2018-10-17 | 2019-02-19 | 武汉欣远拓尔科技有限公司 | The plating solution and its preparation method and plating method of a kind of Ni-Fe-P alloy coating |
| CN112482024A (en) * | 2020-11-26 | 2021-03-12 | 南京信息工程大学 | Preparation method of copper-plated carbon fabric electromagnetic shielding material |
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| CN104762614B (en) | 2017-11-24 |
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