CN104975278B - Carbon fiber surface thermal reduction metallization copper-plating technique - Google Patents
Carbon fiber surface thermal reduction metallization copper-plating technique Download PDFInfo
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Abstract
The present invention relates to carbon fiber surface modification method technical field, a kind of carbon fiber surface thermal reduction metallization copper-plating technique is disclosed.The technique it include the step, micro- carbon containing environment of oxygen, N such as pre-treatment of carbon fiber, the preparation of pre-plating solution, dipping, thermal reduction copper facing2For protection and diluent gas, reduction temperature is 650 700 DEG C, the 50min of recovery time 40, and the pH value of plating solution is 11 ~ 12.The present invention is reduced using micro- oxygen carbon-containing atmosphere to mantoquita, with carbon fiber electroless copper compared with electro-coppering, is reduced the sensitization before copper facing, is activated this two big step, reduce AgNO3、PdCl2Deng the use of noble metal, experimental cost is reduced, pre-treatment step is simplified；Carbon fiber surface after copper facing show that carbon fiber surface has substantial amounts of copper to adhere to by XRD and EDS analyses, and has reached certain covering ratio；SEM observations are obtained, and the copper of carbon fiber surface is distributed in carbon fiber surface in superposition island.
Description
Technical field
The present invention relates to carbon fiber surface modification method technical field, specifically one kind is sharp under micro- oxygen carbon-containing atmosphere
The property being reduced at high temperature with mantoquita is to carbon fiber surface thermal reduction metallization copper-plating technique.
Background technology
PAN base carbon fibres (Carbon fiber) are by polymerization, spinning, pre-oxidation, carbonization by polyacrylonitrile fibre
Etc. fiber made from process, phosphorus content is high.It is high, swollen with excellent electrical and thermal conductivity, high specific strength, good toughness, electromagnetic shielding
The performance such as swollen coefficient is small.Carbon fiber is widely used in leading in industry, space flight, new energy etc. as reinforcement enhancing composite
Domain.
The research of carbon fiber surface metallization can promote the exploitation of carbon fiber metal based composites, and copper facing is a kind of suitable
Suitable surface metalation processing method, because copper carbon fiber and parent metal compound tense, combination is by original carbon-gold
The category way of contact is changed into the way of contact of metal-Metal, has both improved the wetability of carbon fiber and metal, carbon is solved again fine
Between dimension and matrix the problem of poor compatibility.Copper carbon fiber have simultaneously the good intensity of copper, hardness, electric conductivity, thermal conductivity and
The high specific strength of carbon fiber, than modulus of elasticity, and excellent properties such as high temperature resistant, while coating can also modifying carbon fibers surface
Microdefect.Carbon fiber surface copper coating is a lot, and conventional includes chemical plating, electroplates, ion sputtering process etc., electroless plating side
Method such as needs to be sensitized, activated at the pretreatment before Copper Plating of Carbon Fiber, uses AgNO3、PdCl2Deng noble metal so that copper facing cost
Higher, pre-treatment step is complicated；Ion sputtering requires high for sample, and level of coverage is influenceed big by material structure form.
The content of the invention
It is an object of the invention to provide a kind of carbon fiber surface thermal reduction metallization copper-plating technique, to solve in the prior art
Conventional carbon fiber surface copper electroplating method cost is high, the problem of pre-treatment step and reducing atmosphere control complicated.
In order to solve the above technical problems, the technical solution used in the present invention is：
A kind of carbon fiber surface thermal reduction metallization copper-plating technique, the technique is micro- in high temperature using mantoquita under micro- oxygen atmosphere
The property that can be reduced under oxygen atmosphere carries out copper facing to carbon fiber surface, and it comprises the following steps：
Step 1: pre-treatment of carbon fiber：From epoxy of the air calcination-oxidizing acid Combined Processing method to carbon fiber surface
Glue carries out degumming process, and pending carbon fiber sample is first carried out into 400 DEG C in resistance furnace heats after 40min, using dense
Salpeter solution ultrasound immersion roughening treatment 30min, uses distilled water washes clean, is put into 80 DEG C of conditions in thermostatic drying chamber after taking-up
Lower dry 12h；
Step 2: the preparation of pre-plating solution：With complexing agent titration supersaturation CuSO4Solution, until solution is changed into blue-tinted transparent,
Solution ph is determined, ammoniacal liquor, NaOH make pH adjusting agent；
Step 3: thermal reduction copper facing：Carbon fiber after step one pre-processes immersion is soaked repeatedly by pre-plating solution,
After drying 3 ~ 4 times, thermal reduction copper facing is carried out to the carbon fiber for scribbling pre-plating solution, atmosphere is N2+O2, N2For protection and diluent gas,
Control O2Volume percent content is 0.2-0.8%, and reduction temperature is 650-700 DEG C, recovery time 40-50min.
As a further improvement on the present invention, the pre- liquid that crosses is saturation CuSO in the step 24- complex solution, its pH
It is worth for 11-12.
As the further improvement of the present invention, the complexing agent main component in the step 2 is NH4HCO3 。
As the further improvement of the present invention, the carbon fiber is in pencil before copper facing, per Shu Hanyou 1.2k root monofilament,
The principal component on surface is epoxy resin coating.
The high-performance carbon fibre that the carbon fiber material that step one of the present invention is used produces for Lanzhou carbon fibre factory, carbon is fine
Dimension is in pencil, per Shu Hanyou 1.2k root monofilament, and carbon fiber surface has principal component to be epoxy resin coating, carbon fiber performance such as table 1
It is shown.
The carbon fiber basic performance of table 1
The pre- main salt of liquid that crosses is CuSO in step 24, complexing agent NH4HCO3, mainly due to copper (II) complex ion of its formation
Property is stable, place the long period and occur without precipitation, is configuration provides basic stabilization, the uniform condition of pre-plating solution.
Orthogonal test is analyzed by the experimental result for soaking weightening ratio, as the pH of plating solution<When 11, it is unfavorable for copper facing
The progress of process, excess of ammonia water can promote copper precipitation reaction；But it is not that the higher the better for pH value, works as pH>When 13, copper facing effect
It is undesirable, be primarily due to bath pH value it is excessive when, bath portion occur natural decomposition, make the unit area in carbon fiber surface
The copper of deposition is gradually decreased, and the addition of excessive ammoniacal liquor reduces plated metal ion concentration, and plating amount of copper declines therewith, but metal
Ion complexation is influenceed very big by pH value, and under certain pH value, metal ion may be precipitated；It is true by test of many times
The pH value for being set to plating solution is 11 ~ 12.
The reduction temperature of technique of the present invention is 650-700 DEG C.
Beneficial effects of the present invention are：
（1）The present invention is reduced using micro- oxygen carbon-containing atmosphere to mantoquita, with carbon fiber electroless copper compared with electro-coppering
Compared with reducing the sensitization before copper facing, activate this two big step, reduce AgNO3、PdCl2Deng the use of noble metal, reality is reduced
Cost is tested, pre-treatment step is simplified；
（2）The optimization preplating formula of liquid of the present invention is supersaturation CuSO4Complex solution, its pH is 11 ~ 12, in 650-
Preferable copper facing effect can be realized by carrying out reduction to carbon fiber surface within being incubated 1 hour at 700 DEG C；
（3）The present invention use micro- oxygen environment, it is to avoid technique step is played using hydrogen technological operation and requires height, may be gone out
Existing dangerous the problem of；
（4）The present invention uses NH4HCO3As complexing agent, compared with ammoniacal liquor, with simple to operate, ammonium concentration is big, can
Control the characteristics of scope is big；
（5）Carbon fiber surface after technique copper facing of the present invention is analyzed by XRD and EDS to be drawn, carbon fiber surface
Copper adheres to, and reaches higher covering ratio；SEM observations are obtained, and copper plate is uniformly distributed in carbon fiber surface.
Brief description of the drawings
Fig. 1 is the flow chart of technique of the present invention；
Fig. 2 is the XRD on carbon fiber samples surface after copper facing；
Fig. 3 is the SEM figures of carbon fiber samples after copper facing；
Fig. 4 is the EDS energy spectrum diagrams of carbon fiber samples after copper facing；
Fig. 5 is carbon fiber surface shape appearance figure before copper facing（A left side is before removing glue, the right side is after removing glue；）
Fig. 6 is carbon fiber surface shape appearance figure after copper facing.
Embodiment
The present invention and its advantage are described further below in conjunction with the accompanying drawings.
A kind of carbon fiber surface thermal reduction metallization copper-plating technique, the technique is gone back under micro- oxygen carbon-containing atmosphere using mantoquita
The property of originality gas reduction carries out copper facing to carbon fiber surface, and carbon fiber is in pencil before copper facing, per Shu Hanyou 1.2k root lists
Silk, the principal component on surface is epoxy resin coating, and it comprises the following steps：
Step 1: pre-treatment of carbon fiber：Carbon fiber surface is carried out from air calcination-oxidizing acid compounding method
Degumming process, first carries out 400 DEG C by pending carbon fiber sample in resistance furnace and heats after 40min, molten using concentrated nitric acid
Liquid ultrasound immersion roughening treatment 30min, uses distilled water washes clean, is put into thermostatic drying chamber under the conditions of 80 DEG C and dries after taking-up
12h；
Step 2: the preparation of pre-plating solution：Oversaturated CuSO is titrated with complexing agent A4Solution, until solution is changed into blue saturating
Bright, ammoniacal liquor makees pH adjusting agent；The solution ph of plating solution is 11 ~ 12；
Step 3: thermal reduction copper facing：Carbon fiber after step one pre-processes immersion is soaked repeatedly by pre-plating solution,
After drying 3 ~ 4 times, thermal reduction copper facing is carried out to the carbon fiber for scribbling pre-plating solution, atmosphere is N2+O2, N2For protection and diluent gas,
Control O2Volume percent content is 0.2-0.8%, and reduction temperature is 670-720 DEG C, recovery time 30-50min.
Process chart described in the present embodiment is as shown in Figure 1.
（1）XRD analysis
D8 Advance type diffractometer diffraction analysis is utilized to resulting sample, as seen from Figure 2 in three angles
The characteristic peak of copper on (43.52,50.78,74.48) position corresponds to (111) of cubic system copper, (200), (220) respectively
Face, peak value and standard PDF cards are very identical；Other peaks of material containing Cu are had no in spectrogram, it can be deduced that on carbon fiber surface
Only exist the copper existed in elemental copper form, it was demonstrated that reduction is complete.
（2）EDS is analyzed
The composition composition of coating is analyzed using EDS, Surface scan is carried out to copper carbon fiber.Experimental facilities is that JSM-5600 is cold
Field emission type ESEM, resolution ratio is 131.7ev（Thermn companies of the U.S.）, Fig. 3, Fig. 4 and table 2 are resulting coating
EDS electronic images and profiling results.
The EDS experimental datas of table 2
It can be seen that occurring in that stronger copper peak in element collection of illustrative plates from Fig. 3, Fig. 4, show the main member on carbon fiber top layer
Plain composition is copper；It can be seen that carbon fiber surface obtains one kind after hot thermal reduction from the percentage table of constituent content mass ratio
Copper content reaches as high as the 63.35% of material surface element gross mass in the surface of low-carbon high-copper, the data of table 2, illustrates copper component
Certain overlay capacity is formd in carbon fiber surface.
（3）Morphology analysis
Used in Morphology analysis is the SJSM-6701F cold field emission type ESEMs of Optical Co., Ltd of JEOL, its
Resolution ratio is 1.0nm (15kv), 2.2nm (1kv), after the non-removing glue of gained, removing glue and after copper facing carbon fiber surface pattern as point
Not as shown in Figure 5, Figure 6；
By sample comparative analysis, gluing carbon fiber surface it is smooth, gully texture is very shallow, and subregion texture disappears,
Carbon fiber surface is in gully shape after removing photoresist, and gully clean mark, surface is presented coarse, there is concavo-convex defect pattern；Carbon is fine after copper facing
There are a large amount of particles Cu superpositions in dimension table face, fiber surface is covered by copper substantially.
Technique of the present invention has carbon fiber surface by adjusting the measures such as solution ph, reduction temperature, soaking time
What is imitated plates metallic copper, reduces the step of being pre-processed before copper facing, reduces production cost.
Claims (4)
- The copper-plating technique 1. a kind of carbon fiber surface thermal reduction is metallized, it is characterised in that：The technique utilizes copper under micro- oxygen atmosphere The property that salt is reduced in the carbon containing environment of micro- oxygen at high temperature carries out copper facing to carbon fiber surface, and it comprises the following steps：Step 1: pre-treatment of carbon fiber：Carbon fiber surface is entered from air calcination method-oxidizing acid processing compounding method Row degumming process, first carries out 400 DEG C by pending carbon fiber sample in resistance furnace and heats after 40min, utilize concentrated nitric acid Solution ultrasound immersion roughening treatment 30min, uses distilled water washes clean, is put into thermostatic drying chamber under the conditions of 80 DEG C and does after taking-up Dry 12h；Step 2: the preparation of pre-plating solution：With complexing agent titration supersaturation CuSO4Solution, until solution is changed into blue-tinted transparent, is determined Solution ph, pH adjusting agent is made with ammoniacal liquor, NaOH；Step 3: thermal reduction copper facing：Carbon fiber after step one pre-processes immersion is soaked repeatedly by pre-plating solution, dried After 3 ~ 4 times, thermal reduction copper facing is carried out to the carbon fiber for scribbling pre-plating solution, atmosphere is by N2+O2Constitute, N2For protection and diluent gas, Control O2Volume percent content is in 0.2-1.8%, and temperature is 650 ~ 700 DEG C, and the recovery time is controlled between 30 ~ 50min.
- The copper-plating technique 2. carbon fiber surface thermal reduction according to claim 1 is metallized, it is characterised in that：The step 2 In the pre- liquid that crosses for supersaturation CuSO4- complex solution, its pH value is 11-12.
- The copper-plating technique 3. carbon fiber surface thermal reduction according to claim 1 or 2 is metallized, it is characterised in that：The step Complexing agent in rapid two is NH4HCO3。
- The copper-plating technique 4. carbon fiber surface thermal reduction according to claim 3 is metallized, it is characterised in that：The carbon fiber It is in pencil before copper facing, per Shu Hanyou 1.2k root monofilament, surface principal component is epoxy resin coating.
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| CN106498456A (en) * | 2016-11-21 | 2017-03-15 | 江苏梦得新材料科技有限公司 | A kind of carbon fiber surface copper-plating technique |
| CN106744902B (en) * | 2017-02-22 | 2019-03-22 | 盐城工学院 | A kind of preparation method of Ni-coated graphite alkene |
| CN109943870A (en) * | 2017-12-21 | 2019-06-28 | 宜兴市宜泰碳纤维织造有限公司 | A kind of carbon fiber surface copper plating process |
| CN109955556A (en) * | 2017-12-25 | 2019-07-02 | 宜兴市宜泰碳纤维织造有限公司 | A kind of three-dimensional thin preparation method for compiling precast body of surface modified carbon web tire composite ceramic |
| RU2698809C1 (en) * | 2018-05-31 | 2019-08-30 | Общество с ограниченной ответственностью "Межотраслевой инжиниринговый центр МГТУ им. Н.Э. Баумана" (ООО "МИЦ МГТУ им. Н.Э. Баумана") | Method of producing composite material based on carbon fibers |
| CN115821340A (en) * | 2022-12-08 | 2023-03-21 | 山东大学 | Preparation method of high-conductivity and high-strength copper-plated carbon fiber |
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| JPS5669335A (en) * | 1979-11-09 | 1981-06-10 | Hitachi Ltd | Carbon fiber composite metal |
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| CN101058866A (en) * | 2007-05-25 | 2007-10-24 | 东北大学 | Method for preparing Al-base composite material |
| CN102226276A (en) * | 2011-06-13 | 2011-10-26 | 重庆大学 | Method of nickel-copper-phosphor ternary alloy plating on carbon fiber surface |
| CN103484842A (en) * | 2013-09-11 | 2014-01-01 | 昆山市万丰制衣有限责任公司 | Copper plating process for surface of carbon fiber |
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