CN102628214A - Carbon fiber composite material with ZnO layer electrolytically deposited on surface as well as preparation method and application thereof - Google Patents
Carbon fiber composite material with ZnO layer electrolytically deposited on surface as well as preparation method and application thereof Download PDFInfo
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- CN102628214A CN102628214A CN2012101014290A CN201210101429A CN102628214A CN 102628214 A CN102628214 A CN 102628214A CN 2012101014290 A CN2012101014290 A CN 2012101014290A CN 201210101429 A CN201210101429 A CN 201210101429A CN 102628214 A CN102628214 A CN 102628214A
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Abstract
The invention discloses a carbon fiber composite material with a ZnO layer electrochemically deposited on surface and a preparation method thereof. The ZnO layer is electrochemically deposited on the surface of a continuous carbon fiber, wherein thickness of the electrochemically deposited ZnO layer is 0.2-1.5Mum; and the preparation method thereof comprises that a high-purity metal plate is taken as a positive pole, the continuous carbon fiber oxidized by strong acid is taken as a negative pole, zinc nitrate salt is taken as main salt, electrolytic deposition is carried out under constant temperature electromagnetic stirring condition, and the thickness of the deposited layer is controlled by electrolytic deposition temperature and time. The carbon fiber composite material with the ZnO layer electrochemically deposited on the surface, prepared by the invention, has an uniform and dense ZnO layer, the thickness of the deposited layer is about 0.2-1.5Mum, and ingredient of the deposited layer is pure ZnO. The carbon fiber composite material with the ZnO layer electrochemically deposited on the surface, disclosed by the invention, has simple preparation technique, high production efficiency and high deposition quality, can be taken as wave-absorbing structural material and is expected to be a novel wave-absorbing material with high mechanical property and low density.
Description
Technical field
The invention belongs to the microwave absorbing material field, particularly a kind of carbon fiber surface electrochemical deposition ZnO layer preparation method and application.
Background technology
The axial strength of carbon fiber is high, no creep, and plurality of advantages such as fatigue durability is good, and specific heat and electric conductivity are between nonmetal and metal, and thermal coefficient of expansion is little, and resistance to chemical reagents is good, and the density of fiber is low, and is corrosion-resistant can be used as good structural wave-absorbing material.But the surface resistivity of carbon fiber still can reach 10
-3The order of magnitude of Ω cm, visible through experiment and document, when carbon fiber content is enough high; Still can produce reflection to electromagnetic wave; Thereby show shielding greater than the result who inhales ripple, and zinc oxide is a kind of room temperature energy gap 3.3eV, exciton binding energy reaches the important semiconductor functional material of 60meV; And low price has shown good performance at aspects such as opto-electronic devices.Recently, the research that traditional photoelectric material is applied in the microwave absorbing material field is more and more, and performance is excellent in microwave absorption field, and wherein ZnO is exactly one of research emphasis.Report ZnO whisker is arranged directly as microwave absorbing material in the document; ZnO mixes as microwave absorbing material with ferrite or carbonyl iron dust; ZnO mixes as microwave absorbing material with CNT, etc., these researchs all obtain good microwave assimilation effect; Therefore can conclude that ZnO is that a kind of potential excellent microwave absorbs commercial materials.Useful galvanoplastic are passed through calcining in the prior art after carbon fiber surface coats the single Metal Zn of one deck; Zn is oxidized to ZnO; Equipment that is adopted and the processing step of being taked are all comparatively complicated, because the coating poor quality of carbon fiber surface control, have problems such as oxidation is not exclusively uncontrollable.And electrochemical deposition method has characteristics such as equipment is simple, cost is low, can produce continuously are a kind of methods with applications well prospect.If at carbon fiber surface deposition layer of ZnO layer, then be expected to obtain new and effective lightweight absorbing material through electrochemical deposition method.
Summary of the invention
To above-mentioned prior art; The present invention provides a kind of carbon fiber surface electrochemical deposition ZnO layer composite and preparation method, is to deposit the ZnO layer of even compact through electrochemical deposition method at carbon fiber surface, and its technology is simple; Production efficiency is high, is fit to large-scale industrial production.The galvanoplastic that preparation method of the present invention reports in the document are compared; Equipment that the present invention adopted and step are all simpler; The coating quality of the carbon fiber surface that obtains is stable and controllable more; Can there be problems such as oxidation is not exclusively uncontrollable, prepare the ZnO sedimentary deposit at carbon fiber surface, have important research and actual application value through electrochemical deposition method.
In order to solve the problems of the technologies described above, a kind of carbon fiber surface electro-deposition of the present invention ZnO layer composite is that said electrochemical deposition ZnO layer thickness is 0.2～1.0 μ m at continuous carbon fibre surface electrochemistry deposition ZnO layer.
Further say, carbon fiber surface electro-deposition ZnO layer composite, wherein, said continuous carbon fibre is any in polyacrylonitrile-radical continuous carbon fibre, asphaltic base continuous carbon fibre and the gluing basic continuous carbon fibre.
In addition, the tow of said continuous carbon fibre be 1k, 3k, 6k, 12k, 24k and more than.
The preparation method of a kind of carbon fiber surface electro-deposition of the present invention ZnO layer may further comprise the steps:
1) be soak at room temperature 6～8h in 50%～65% the salpeter solution with continuous carbon fibre in volume fraction, the back with washed with de-ionized water to neutral; The purpose of this step is to remove carbon fiber surface impurity with strong acid, and carbon fiber surface is carried out oxidation, increases deposition table area and carbon fiber surface activity;
2) the configuration molar concentration is the zinc nitrate Zn (NO of 0.05～0.15mol/L
3)
2Electrolyte, its pH value is 5.0～6.0, and the composition of electrolyte is simple among the present invention, and its pH value is the initial value of electrolyte;
3) be that 99.99% metallic plate is an anode with purity, the continuous carbon fibre after will being handled by step 1) adopts the constant voltage deposition as negative electrode, and perfectly straight stream voltage, its voltage are 0.7～1.0V, stir electrodeposition time 5～15min down at 20-60 ℃; Electro-deposition ZnO layer thickness is controlled through electrodeposition time, guarantees that electro-deposition ZnO layer thickness is 0.2～1.5 μ m;
4) continuous carbon fibre of electrochemical deposition being accomplished is used deionized water rinsing, with the absolute ethyl alcohol flushing, uses drier again, so far, obtains the composite that carbon fiber surface is coated with 0.2～1.0 μ m electro-deposition ZnO layer.
Wherein, the metallic plate as anode is preferably pure zine plate.
A kind of carbon fiber surface electro-deposition of the present invention ZnO layer composite is as the application of structural wave-absorbing material.
Compared with prior art, the invention has the beneficial effects as follows:
The present invention provides pure ZnO carbon coated fibrous composite preparation method and application first; Material preparation is the ZnO layer that obtains even compact through electrodeposition process at carbon fiber surface; Make carbon fiber on the basis that keeps its original performance, have good impedance matching performance, method is simple; Cost is low, and the composite products quality that obtains is good.Therefore, the present invention has not only improved the impedance matching performance of carbon fiber, has increased the loss of material, more effectively improves the production efficiency and the quality of this composite, and the raising material provides a kind of simple production method simultaneously to the absorption of microwave.
Description of drawings
Fig. 1 (a) is the SEM pattern photo of embodiment 2 gained carbon fiber surface electro-deposition ZnO layer composite;
Fig. 1 (b) is the enlarged drawing of Fig. 1 (a);
Fig. 1 (c) is the SEM pattern photo of embodiment 3 gained carbon fiber surface electro-deposition ZnO layer composite;
Fig. 1 (d) is the enlarged drawing of Fig. 1 (c);
Fig. 2 is the X-ray diffractogram of embodiment 2 gained carbon fiber surface electro-deposition ZnO layer composite.
Fig. 3 (a) is the dielectric constant of embodiment 2 gained ZnO carbon coated fiber/paraffin composites (ZnO carbon coated quality of fiber mark is 30%), and wherein, ε ' is the real part of dielectric constant, ε " is the imaginary part of dielectric constant;
Fig. 3 (b) is the magnetic conductivity of embodiment 2 gained ZnO carbon coated fiber/paraffin composites (ZnO carbon coated quality of fiber mark is 30%), and wherein, μ ' is the real part of magnetic conductivity, μ " is the imaginary part of magnetic conductivity;
Fig. 3 (c) is the electromagnetic parameter and the theoretical microwave reflection loss of embodiment 2 gained ZnO carbon coated fiber/paraffin composites (ZnO carbon coated quality of fiber mark is 30%).
The specific embodiment
Below tell about detailed content of the present invention through embodiment, it is the convenience in order to understand that embodiment is provided, never be the restriction the present invention.
Embodiment 1
The polyacrylonitrile-radical continuous carbon fibre that with tow is 1k is in 50% salpeter solution after the soak at room temperature 6h oxidation processes in volume fraction; Extremely neutral with washed with de-ionized water; The purpose of this step is to remove carbon fiber surface impurity with strong acid; Carbon fiber surface is carried out oxidation, increase deposition table area and carbon fiber surface activity; Configuration electrolyte, Zn (NO
3)
2Main concentration of salt solution is 0.05mol/L, and the pH value is 5.0～6.0, is the initial value that the salting liquid hydrolysis obtains, and need not to regulate pH again; Electro-deposition is that high-purity zine plate of 99.99% is an anode with purity, with the carbon fiber after the above-mentioned oxidation processes as negative electrode, voltage 0.7V, electromagnetic agitation under 20 ℃ of conditions of bath temperature, electrodeposition time 5min; Product washes with deionized water repeatedly, cleans with absolute ethyl alcohol again, uses drier at last, so far obtains being coated with at carbon fiber surface the composite of 0.2 μ m electro-deposition ZnO layer.
Embodiment 2
The asphaltic base continuous carbon fibre that with tow is 24k is a soak at room temperature 8h oxidation processes in 65% salpeter solution in volume fraction, the back with washed with de-ionized water to neutral; Configuration electrolyte, Zn (NO
3)
2Main concentration of salt solution is 0.1mol/L, and the pH value is 5.0～6.0, is the initial value that the salting liquid hydrolysis obtains, and need not to regulate pH again.Electro-deposition is that high-purity zine plate of 99.99% is an anode with purity, and the carbon fiber after the oxidation processes is as negative electrode, voltage 1.0V, electromagnetic agitation under 60 ℃ of conditions of bath temperature, electrodeposition time 10min.Product washes with deionized water repeatedly, cleans with absolute ethyl alcohol again, uses drier at last, so far obtains being coated with at carbon fiber surface the composite of 0.5 μ m electro-deposition ZnO layer.
Embodiment 3
The gluing basic continuous carbon fibre that with tow is 6k is a soak at room temperature 7h oxidation processes in 60% salpeter solution in volume fraction.Configuration electrolyte, Zn (NO
3)
2Main concentration of salt solution is 0.15mol/L, and the pH value is 5.0～6.0, is the initial value that the salting liquid hydrolysis obtains, and need not to regulate pH again.Electro-deposition is that high-purity zine plate of 99.99% is an anode with purity, and the carbon fiber after the oxidation processes is as negative electrode, voltage 0.8V, electromagnetic agitation under 40 ℃ of conditions of bath temperature, electrodeposition time 15min.Product washes with deionized water repeatedly, cleans with absolute ethyl alcohol again, uses drier at last, so far obtains being coated with at carbon fiber surface the composite of 1.0 μ m electro-deposition ZnO layers.
Product carries out SEM, XRD and electromagnetic parameter testing.
In order to obtain test result, be that 30% ZnO carbon coated fiber mixes with paraffin that to be pressed into thickness be 2mm with mass fraction, internal diameter is 3mm, external diameter is ZnO carbon coated fiber/coaxial sample of paraffin composite of 7mm.
Test result: Fig. 1 is a SEM pattern photo, and Fig. 1 (a) is the SEM photo of embodiment 2 gained carbon fiber surface electro-deposition ZnO layer composite, and Fig. 1 (b) is the enlarged drawing of Fig. 1 (a); Fig. 1 (c) is the SEM photo of embodiment 3 gained carbon fiber surface electro-deposition ZnO layer composite, and Fig. 1 (d) is the enlarged drawing of Fig. 1 (c); Can be found out to Fig. 1 (d) by Fig. 1 (a): by the carbon fiber surface electro-deposition ZnO layer composite that preparation method of the present invention makes, electro-deposition ZnO layer is even, densification, and surface quality is high.Fig. 2 is the X-ray diffractogram (XRD figure) of embodiment 2 gained carbon fiber surface electro-deposition ZnO layer composite, and the sedimentary deposit that demonstrates carbon fiber surface through this XRD figure is ZnO, does not have other impurity phase.Fig. 3 (a) and Fig. 3 (b) are respectively the dielectric constant and the magnetic conductivity of ZnO carbon coated fiber/paraffin composite; Fig. 3 (c) is theoretical microwave reflection damage curve; (14～18GHz) all have the lossy microwave less than-10dB at high frequency region can to find out the carbon fiber surface electro-deposition ZnO layer composite that made by preparation method of the present invention; Have the maximum loss value at the 16.6GHz place, for-46.4dB, and thickness is merely 1.52mm.Can find out that carbon fiber surface electro-deposition ZnO layer composite of the present invention has excellent microwave absorbing property at high frequency region.
Although invention has been described for top combination figure; But the present invention is not limited to the above-mentioned specific embodiment, and the above-mentioned specific embodiment only is schematically, rather than restrictive; Those of ordinary skill in the art is under enlightenment of the present invention; Under the situation that does not break away from aim of the present invention, can also make a lot of distortion, these all belong within the protection of the present invention.
Claims (6)
1. a carbon fiber surface electro-deposition ZnO layer composite is characterized in that, is that said electrochemical deposition ZnO layer thickness is 0.2～1.5 μ m at continuous carbon fibre surface electrochemistry deposition ZnO layer.
2. according to the said carbon fiber surface electro-deposition of claim 1 ZnO layer composite, it is characterized in that said continuous carbon fibre is any in polyacrylonitrile-radical continuous carbon fibre, asphaltic base continuous carbon fibre and the gluing basic continuous carbon fibre.
3. according to the said carbon fiber surface electro-deposition of claim 1 ZnO layer composite, it is characterized in that, the tow of said continuous carbon fibre be 1k, 3k, 6k, 12k, 24k and more than.
4. the preparation method of a carbon fiber surface electro-deposition ZnO layer is characterized in that, may further comprise the steps:
1) be soak at room temperature 6～8h in 50%～65% the salpeter solution with continuous carbon fibre in volume fraction, with washed with de-ionized water to neutral;
2) the configuration molar concentration is the zinc nitrate electrolyte of 0.05～0.15mol/L, and its pH value is 5.0～6.0;
3) be that 99.99% metallic plate is an anode with purity, the continuous carbon fibre after will being handled by step 1) adopts the constant voltage deposition as negative electrode, and perfectly straight stream voltage, its voltage are 0.7～1.0V, stir electrodeposition time 5～15min down at 20-60 ℃;
4) continuous carbon fibre of electrochemical deposition being accomplished is used deionized water rinsing, with the absolute ethyl alcohol flushing, uses drier again, so far, obtains the composite that carbon fiber surface has 0.2～1.5 μ m electro-deposition ZnO layer.
5. according to the preparation method of the said carbon fiber surface electro-deposition of claim 4 ZnO layer, it is characterized in that, is pure zine plate as the metallic plate of anode.
6. a carbon fiber surface electro-deposition ZnO layer composite is as the application of structural wave-absorbing material.
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| CN102850652A (en) * | 2012-09-18 | 2013-01-02 | 河南工业大学 | Ternary-dielectric-filled polymer conductive composite and preparation method |
| CN105131335A (en) * | 2015-10-12 | 2015-12-09 | 中国科学院山西煤炭化学研究所 | Aminated zinc oxide nano wire-carbon fiber hybrid reinforcement and preparation method thereof |
| CN106757174A (en) * | 2017-02-23 | 2017-05-31 | 黄芃 | A kind of electro-deposition prepares the method and device of metal dust |
| CN107033544A (en) * | 2017-04-01 | 2017-08-11 | 陕西科技大学 | A kind of nano-absorbent silicon carbide fibre multi-scale reinforcing body reinforced resin based structures absorbing material and preparation method thereof |
| CN112751010A (en) * | 2019-10-31 | 2021-05-04 | 青岛海尔智能技术研发有限公司 | Double-layer coated zinc cathode, preparation method thereof, zinc-air battery and direct current water heater |
| CN114934387A (en) * | 2022-05-25 | 2022-08-23 | 中国科学院宁波材料技术与工程研究所 | High-thermal-conductivity carbon fiber and continuous preparation method |
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| CN105131335A (en) * | 2015-10-12 | 2015-12-09 | 中国科学院山西煤炭化学研究所 | Aminated zinc oxide nano wire-carbon fiber hybrid reinforcement and preparation method thereof |
| CN105131335B (en) * | 2015-10-12 | 2018-01-23 | 中国科学院山西煤炭化学研究所 | Amination zinc oxide nanowire carbon fiber hybrid reinforcement body and its preparation method |
| CN106757174A (en) * | 2017-02-23 | 2017-05-31 | 黄芃 | A kind of electro-deposition prepares the method and device of metal dust |
| CN106757174B (en) * | 2017-02-23 | 2020-08-21 | 黄芃 | Method for preparing metal powder by electrodeposition |
| CN107033544A (en) * | 2017-04-01 | 2017-08-11 | 陕西科技大学 | A kind of nano-absorbent silicon carbide fibre multi-scale reinforcing body reinforced resin based structures absorbing material and preparation method thereof |
| CN107033544B (en) * | 2017-04-01 | 2019-03-22 | 陕西科技大学 | A kind of nano-absorbent-silicon carbide fibre multi-scale reinforcing body reinforced resin based structures absorbing material and preparation method thereof |
| CN112751010A (en) * | 2019-10-31 | 2021-05-04 | 青岛海尔智能技术研发有限公司 | Double-layer coated zinc cathode, preparation method thereof, zinc-air battery and direct current water heater |
| CN114934387A (en) * | 2022-05-25 | 2022-08-23 | 中国科学院宁波材料技术与工程研究所 | High-thermal-conductivity carbon fiber and continuous preparation method |
| CN114934387B (en) * | 2022-05-25 | 2024-04-05 | 中国科学院宁波材料技术与工程研究所 | High-heat-conductivity carbon fiber and continuous preparation method |
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Application publication date: 20120808 |