CN104762614B - A kind of high heat conduction graphite fibre surface is without palladium chemical-copper-plating process - Google Patents
A kind of high heat conduction graphite fibre surface is without palladium chemical-copper-plating process Download PDFInfo
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- CN104762614B CN104762614B CN201510179313.2A CN201510179313A CN104762614B CN 104762614 B CN104762614 B CN 104762614B CN 201510179313 A CN201510179313 A CN 201510179313A CN 104762614 B CN104762614 B CN 104762614B
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- graphite fibre
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- heat conduction
- high heat
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Abstract
The present invention relates to a kind of high heat conduction graphite fibre surface without palladium chemical-copper-plating process.Its technical scheme is：Heavy in section banding graphite fibre or cylindric graphite fibre are used as matrix, after the pre-treating technology such as being roughened, neutralized, being sensitized and being reduced, then on graphite fibre surface carries out electroless copper.The cross sectional shape of described heavy in section banding graphite fibre is approximately rectangle, or is cylindric graphite fibre, its width or a diameter of 1~2mm, and thickness is 8~20 μm, and length is 5~10mm；Described chemical plating temperature is 40~50 DEG C, and pH is 12~12.5.Present invention process is simple, avoids using expensive Metal Palladium, cost is relatively low, reproducible, with short production cycle；The graphite fibre coating handled with the process has the characteristics of adhesion is strong, coating is uniformly bright.
Description
Technical field
The invention belongs to the technical field of material surface processing, and in particular to a kind of high heat conduction graphite fibre surface is without palladium
Learn copper-plating technique.
Background technology
Metal Substrate graphite fiber composite materials have the premium properties such as high-modulus, high specific strength, in space flight and aviation, material etc.
Field is with a wide range of applications.Filler is done with the graphite fibre of surface metalation, and obtained structural composite material can be
The fields such as aircraft skin, automobile and engine use as high performance structural member, prepared by functional composite material then utilize material
The performances such as high heat conduction, conduction, low-expansion coefficient and the low-density of material are in heat management, electron device package, precision optical instrument, instrument
The fields such as table are widely used, and therefore, the high performance graphite fiber of surface metalation is a kind of reinforcement of very attractive.
Metallic copper due to excellent ductility, electric conductivity and it is cheap the features such as be often used as to graphite fibre surface
Carry out metalized modified.Chemical plating is a kind of conventional surface modifying method, and it in the case of, is utilized without extrinsic current
Redox reaction, the metal ion in solution is formed to a kind of plating of the coat of metal in the object surface with catalytic activity
Technology.Electroless copper many processes, but these processes need to use are carried out in graphite fibre/carbon fiber surface
Precious metal palladium and the weak point such as cause cost higher.
The content of the invention
It is an object of the invention to provide a kind of high heat conduction graphite fibre surface without palladium chemical-copper-plating process, using the party
Method, under conditions of without using expensive Metal Palladium or other noble silvers, lived using the self-catalysis on graphite fibre surface
Change performance, the copper coating with being compared favourably using palladium progress electroless copper can be obtained, the copper coating adhesion is strong, and surface is completely thin
Cause and good luster, while also reduce the cost of chemical-copper-plating process.
The present invention is that scheme is used by solving above-mentioned technical problem：
A kind of high heat conduction graphite fibre surface without palladium chemical-copper-plating process, the technique be by graphite fibre by roughening, in
With, sensitization and reduction after directly carry out electroless copper, its chemical plating fluid include copper sulphate, formaldehyde, sodium potassium tartrate tetrahydrate, 2,2 '-join
Pyridine, potassium ferrocyanide and sodium hydroxide.
In such scheme, the technique of graphite fibre roughening is soaked using diluted acid, and the dilute acid soln is 10~40wt%
The mixed liquor of dust technology and dilute sulfuric acid, soak time 10-30min.
In such scheme, reduced with sodium hypophosphite.
In such scheme, the basic parameter of its chemical plating is：15~20g/L of cupric sulfate pentahydrate, sodium potassium tartrate tetrahydrate 15~
20g/L, 15~20ml/L of formaldehyde, 2,2 '-bipyridyl, 3~10mg/L, 10~20g/L of potassium ferrocyanide, sodium hydroxide 10~
20g/L, pH value of solution 12~12.5,40~50 DEG C of temperature.
In such scheme, sensitization is used as using the solution that 10g/L stannous chloride, 40mL/L hydrochloric acid and 0.2g/L tin grains form
Liquid.
In such scheme, the width of described graphite fibre or a diameter of 1~2mm, thickness are 8~20 μm, length 5
~10mm.
In such scheme, the thickness of coating obtained after electroless copper is 1.72 μm.
The present invention carries out surface modification using chemical method to graphite fibre first, so that graphite fibre surface coarsening, increase
The hydrophily on graphite fibre surface, and then increase the adhesion between graphite fibre and copper coating, graphite fibre is added to 10-
Soaked in 30% dilute acid soln, make its surface that channel form, soak time 10-30min be presented；Then by the graphite after roughening
Fiber is added in diluted sodium hydroxide solution and neutralized, and the diluted acid on graphite fibre surface is remained in neutralize, then clean to
It is neutral；The graphite fibre after reduction is added in plating solution again after allergy China and reduction and carries out electroless copper, and constantly
Stirring, the pH value of plating solution to be tested with pH meter, observe the change of graphite fibre surface color, graphite fibre surface gradually reddens, and
There is bubble to emerge, after 15min, take out graphite fibre, cleaned with distilled water, be placed under infrared lamp and dry, drying.
The beneficial effects of the invention are as follows：It can avoid using valuable palladium activation step using the process conditions, reduce technique
Cost.Meanwhile copper coating can be quickly formed on graphite fibre surface, copper plating rate reaches 4.7mg/min, and thickness of coating reaches
7.2 μm, therefore, preparation technology of the present invention is simple, and cost is relatively low, reproducible, with short production cycle；It can be expired with the process
The different thickness of coating requirements of foot, coating is uniform, glossiness is good, adhesion is good.
Brief description of the drawings
Fig. 1 is the graphite fibre surface topography map without any processing.
Fig. 2 is surface topography map of the graphite fibre after roughening treatment.
Fig. 3 is that graphite fibre surface carries out the copper coating shape appearance figure after chemical plating.
Fig. 4 be carry out chemical plating after with do not carry out chemical plating graphite fibre powder xrd pattern.
Fig. 5 is the thickness of copper coating after graphite fibre Electroless copper.
Embodiment
With reference to embodiment, the invention will be further described, not to the limitation of its protection domain.
In this embodiment：Described graphite fibre is that heavy in section banding graphite fibre or cylindric graphite are fine
Dimension, its width or a diameter of 1~2mm, thickness are 8~20 μm, and length is 5~10mm.Repeated no more in embodiment.
Embodiment 1
(1) graphite fibre is roughened：10wt% dilute sulfuric acids and 10wt% dust technology mixing dilute acid solns are prepared in beaker,
Graphite fibre is added in solution, after stirring 10min, filters out graphite fibre.
(2) neutralize：The diluted sodium hydroxide solution that the graphite fibre of roughening is put into 10wt% is neutralized, then with distillation
Water cleans graphite fibre surface to neutrality.
(3) it is sensitized：Graphite fibre after neutralization is put into 10g/L stannous chloride, 40mL/L hydrochloric acid and 0.2g/L tin grain groups
Into sensitizing solution in, stir 15min, then carefully cleaned with distilled water, be put into oven for drying.
(4) reduce：The ortho phosphorous acid sodium solution that graphite fibre after sensitization is put into 30g/L is reduced, after 5min, with steaming
Distilled water is rinsed well.
(5) chemical plating：The graphite fibre handled well early stage, it is put into the solution of chemical plating and carries out chemical plating.Taking-up is plated
Graphite fibre after copper, is cleaned up with distilled water, is placed under infrared lamp and is dried.With its shape of scanning electron microscopic observation after dried
Looks.The basic parameter of its chemical plating is as follows：
Embodiment 2
(1) graphite fibre is roughened：20wt% dilute sulfuric acids and 20wt% dust technology mixing dilute acid solns are prepared in beaker,
Graphite fibre is added in solution, after stirring 10min, filters out graphite fibre.
(2) neutralize：The diluted sodium hydroxide solution that the graphite fibre of roughening is put into 20wt% is neutralized, then with distillation
Water cleans graphite fibre surface to neutrality.
(3) it is sensitized：Graphite fibre after neutralization is put into 10g/L stannous chloride, 40mL/L hydrochloric acid and 0.2g/L tin grains
In sensitizing solution, 15min is stirred, then is carefully cleaned with distilled water, is put into oven for drying.
(4) reduce：The ortho phosphorous acid sodium solution that graphite fibre after sensitization is put into 30g/L is reduced, after 5min, with steaming
Distilled water is rinsed well.
(5) chemical plating：The graphite fibre handled well early stage, it is put into the solution of chemical plating and carries out chemical plating.Its chemical plating
Basic parameter it is as follows：
The graphite fibre after copper has been plated in taking-up, is cleaned up with distilled water, is placed under infrared lamp and dries.With ESEM table
Levy the pattern that graphite fibre is roughened copper coating after front and rear and chemical plating.
The present invention high heat conduction graphite fibre electroless copper have technique it is simple, cost is relatively low, it is reproducible and production
The features such as cycle is short.
Claims (5)
1. a kind of high heat conduction graphite fibre surface is without palladium chemical-copper-plating process, it is characterised in that the technique is to pass through graphite fibre
Electroless copper is directly carried out after crossing roughening, neutralization, sensitization and reduction, its chemical plating fluid includes copper sulphate, formaldehyde, potassium tartrate
Sodium, 2,2 '-bipyridyl, potassium ferrocyanide and sodium hydroxide, the basic parameter of the chemical plating are：The g/ of cupric sulfate pentahydrate 15 ~ 20
L, the g/L of sodium potassium tartrate tetrahydrate 15 ~ 20, the ml/L of formaldehyde 15 ~ 20, the mg/L of 2,2 '-bipyridyl 3 ~ 10, the g/ of potassium ferrocyanide 10 ~ 20
L, the g/L of sodium hydroxide 10 ~ 20, the pH value of solution 12 ~ 12.5 of chemical plating fluid, 40 ~ 50 DEG C of temperature, described graphite fibre are banding
Or cylindric graphite fibre, the width of described graphite fibre or a diameter of 1 ~ 2 mm, thickness be 8 ~ 20 μm, length be 5 ~
10 mm。
2. high heat conduction graphite fibre surface according to claim 1 is without palladium chemical-copper-plating process, it is characterised in that graphite is fine
The technique for tieing up roughening is soaked using diluted acid, and the dilute acid soln is the mixed liquor of 10 ~ 40wt% dust technologies and dilute sulfuric acid, is soaked
Time is 10-30 min.
3. high heat conduction graphite fibre surface according to claim 1 is without palladium chemical-copper-plating process, it is characterised in that sub- with time
Sodium phosphate is reduced.
4. high heat conduction graphite fibre surface according to claim 1 is without palladium chemical-copper-plating process, it is characterised in that with 10
The solution of g/L stannous chloride, 40 mL/L hydrochloric acid and 0.2 g/L tin grain composition is as sensitizing solution.
5. high heat conduction graphite fibre surface according to claim 1 is without palladium chemical-copper-plating process, it is characterised in that chemical plating
The thickness of coating obtained after copper is 1.72 μm.
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| Application Number | Priority Date | Filing Date | Title |
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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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| CN104762614B true CN104762614B (en) | 2017-11-24 |
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| CN105256290B (en) * | 2015-10-08 | 2018-01-19 | 山东建筑大学 | A kind of novel diamond plating technic applied to stone cutter tool |
| CN109355644B (en) * | 2018-10-17 | 2020-07-28 | 武汉欣远拓尔科技有限公司 | Plating solution of nickel-iron-phosphorus alloy plating layer and preparation method and plating method thereof |
| CN112482024B (en) * | 2020-11-26 | 2022-09-23 | 南京信息工程大学 | Preparation method of copper-plated carbon fabric electromagnetic shielding material |
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| CN102586704B (en) * | 2012-03-23 | 2013-08-07 | 北京科技大学 | Preparation method of high thermal conductivity graphite whisker/copper composite |
| CN103726133B (en) * | 2014-01-02 | 2016-04-06 | 东华大学 | High strength, compact neat porous graphene fiber and continuous production method thereof |
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