阅读说明：本技术 一种提高复合材料腐蚀性能的方法 (A method of improving composite material corrosive nature ) 是由 舒佰坡 王宁 雷运 杨平 易健宏 谢明 于 2019-09-19 设计创作，主要内容包括：本发明公开一种提高复合材料腐蚀性能的方法,属于金属材料加工技术领域。本发明所述方法采用交流脉冲电沉积法,以铜片为阴极,在电沉积过程中加入磁力搅拌,间歇引入超声波,使碳纳米管均匀分布；本发明所述方法制备过程简单,所用仪器是常见的恒温水浴锅,脉冲电源,磁力搅拌,超声波等,获得的材料相比于纯镍材料耐腐蚀性能有较大提高。(The present invention discloses a kind of method for improving composite material corrosive nature, belongs to metal material processing technical field.Magnetic agitation is added using copper sheet as cathode using alternating-current pulse electrodeposition process in the method for the invention in electrodeposition process, is introduced intermittently into ultrasonic wave, is uniformly distributed carbon nanotube；The method of the invention preparation process is simple, and instrument is common thermostat water bath, and the material of the pulse power, magnetic agitation, ultrasonic wave etc., acquisition improves a lot compared to pure nickel material corrosion resistance.)

1. a kind of method for improving composite material corrosive nature, which is characterized in that specifically includes the following steps:

(1) carbon nanotube is pre-processed, is then added in plating solution in the ratio of 0.3 ~ 1g/L, it is spare；

(2) cathode anode is pre-processed, it is spare；

(3) ultrasonic wave is introduced in electrodeposition process intermittent:, will be equipped with plating solution, cathode and anode before plating starts Container is put into the water-bath that temperature is 45 DEG C ~ 50 DEG C and keeps the temperature, and keeps temperature uniformly, after powering on, using pulse current It is deposited on cathode plate, entire plating procedure parameter remains unchanged；Electric current is adjusted, 30 ~ 60min of magnetic agitation plating is introduced, is closed Magnetic agitation is closed, 30 ~ 60min of ultrasonic wave plating is introduced, primary common plating and a ultrasonic wave plating are a circulation, circulation 96 ~ 192 times；

(4) sample clean obtained by step (3) completely dries up afterwards, removes cathode plate, obtains after the 30min that anneals at 150 ~ 200 DEG C Carbon nano-tube reinforced metal-matrix composite material with layer structure.

2. the method according to claim 1 for improving composite material corrosive nature, it is characterised in that: carbon nanotube carries out pre- Treatment process are as follows: carbon nanotube is placed in H₂SO₄And HNO₃In mixed solution, 15 ~ 30min, 50 ~ 70 DEG C of water-baths are stirred by ultrasonic After 3 ~ 5h of middle acidification, distillation is dried after being washed to PH=7.

3. the method according to claim 1 for improving composite material corrosive nature, it is characterised in that: nickel-plating liquid is watt type Nickel-plating liquid or indium sulfamate bath nickel-plating liquid.

4. the method according to claim 3 for improving composite material corrosive nature, it is characterised in that: indium sulfamate bath Nickel-plating liquid, specific ingredient are as follows: Ni(NH₂SO₃)₂·4H₂O 300 ~ 400g/L, NiCl₂·6H₂O 10 ~ 20g/L, H₃BO₃ 20~ 50g/L, C₁₂H₂₅OSO₂Na 0.5 ~ 1g/L, C₃₆H₇₀O₁₉0.2 ~ 0.5g/L, pH value are 4 ~ 5.

5. the method according to claim 3 for improving composite material corrosive nature, it is characterised in that: watt type nickel-plating liquid, Specific ingredient are as follows: NiSO₄·7H₂O 300 ~ 400g/L, NiCl₂·6H₂O 40 ~ 50g/L, H₃BO₃30 ~ 40g/L, C₁₂H₂₅OSO₂Na 0.5 ~ 1g/L, C₃₆H₇₀O₁₉0.2 ~ 0.5g/L, pH value are 2 ~ 5.

6. the method according to claim 1 for improving composite material corrosive nature, it is characterised in that: institute in (2) in step Stating cathode is copper sheet or stainless steel substrates etc., is polished before plating its surface, is cleaned and pickling processes, wherein the thickness of copper sheet Degree is 0.25mm ~ 0.30mm.

7. the method according to claim 1 for improving composite material corrosive nature, it is characterised in that: institute in (2) in step Stating anode is pure nickel, carries out polishing and cleaning treatment to its surface before plating, and wherein the purity of nickel is >=99.99%.

8. the method according to claim 1 for improving composite material corrosive nature, it is characterised in that: in step (3): positive Current density is 1A/dm², reverse current density 0.5A/dm², the positive working time is 100ms, and the reverse operation time is 10ms, magnetic agitation speed 800r/min, ultrasonic power are 60 ~ 240W, and ultrasonic frequency is 20 ~ 60KHz.

Technical field

The present invention relates to a kind of methods for improving composite material corrosive nature, belong to metal material processing technical field.

Background technique

Carbon nanotube, due to the bind mode of its distinctive coaxial nested structure and C=C, has received people since it is found Extensive concern.The intensity, hardness, friction and abrasion of metal can be improved in reinforcement material using carbon nanotube as metal Energy, corrosive nature and thermal stability etc., are a kind of ideal reinforcements.Carbon nano-tube reinforced metal-matrix composite material is nearly ten A kind of advanced composite material to grow up for several years all has applications well potentiality in every field.

For at present, the preparation process of carbon nano-tube reinforced metal-matrix composite material is more difficult and complicated.Carbon nanotube Draw ratio it is very high, easily form the aggregate mutually wound, to ensure the functional of obtained metal-base composites, It needs to carry out carbon pipe into certain processing during the preparation process, mitigates its reunion degree, it is made to be evenly distributed in the base.In mistake In the more than ten years gone, domestic and foreign scholars have carried out a large amount of explorations to the preparation method of carbon nano-tube reinforced metal-matrix composite material And research, it is primarily present following a few major class: powder metallurgic method, casting, electricity-chemical deposition etc. at present.The present invention is directed to logical Cross the carbon nanotube enhancing nickel-base composite material that electrodeposition process preparation has good corrosion resistance.

Summary of the invention

The purpose of the present invention is to provide a kind of method for improving composite material corrosive nature, this method utilizes electro-deposition work Skill is replaced using positive back pulse, and using pure nickel as anode, copper sheet is that cathode carries out electro-deposition；Ultrasonic wave is utilized in electrodeposition process Alternate treatment forms the layer structure of one layer of big crystal grain, one layer of little crystal grain；The rubbing action of magnetic agitation simultaneously, ultrasonic wave Cavitation makes carbon nanotube dispersion more evenly；This method makes while preparing carbon nanotube enhancing nickel-base composite material The corrosive nature of composite material has greatly improved, specifically includes the following steps:

(1) carbon nanotube is pre-processed, is then added in plating solution in the ratio of 0.3 ~ 1g/L, it is spare.

(2) cathode anode is pre-processed, it is spare.

(3) ultrasonic wave is introduced in electrodeposition process intermittent: before plating starts, plating solution, cathode and sun will be housed The container of pole is put into the water-bath that temperature is 45 DEG C ~ 50 DEG C and keeps the temperature, and keeps temperature uniformly, after powering on, using pulse Electric current deposits on cathode plate, and entire plating procedure parameter remains unchanged；Adjusting electric current, introducing magnetic agitation plating 30 ~ 60min closes magnetic agitation, introduces 30 ~ 60min of ultrasonic wave plating, and primary common plating and a ultrasonic wave plating are one Circulation recycles 96 ~ 192 times.

(4) sample clean obtained by step (3) completely dries up afterwards, removes cathode plate, after the 30min that anneals at 150 ~ 200 DEG C Obtain the carbon nano-tube reinforced metal-matrix composite material with layer structure.

Preferably, carbon nanotube of the present invention carries out preprocessing process are as follows: carbon nanotube is placed in H₂SO₄And HNO₃It is mixed Close (H in solution₂SO₄And HNO₃Volume ratio be 3:1), 15 ~ 30min is stirred by ultrasonic, after being acidified 3 ~ 5h in 50 ~ 70 DEG C of water-baths, Distillation is dried after being washed to PH=7.

Preferably, plating solution of the present invention is indium sulfamate bath or watt type nickel-plating liquid, wherein sulfamate The specific ingredient of system nickel plating bath are as follows: Ni(NH₂SO₃)₂·4H₂O 300 ~ 400g/L, NiCl₂·6H₂O 10 ~ 20g/L, H₃BO₃ 20~ 50g/L, C₁₂H₂₅OSO₂Na 0.5 ~ 1g/L, C₃₆H₇₀O₁₉ 0.2 ~ 0.5g/L, pH value are 4 ~ 5；The watt specific ingredient of type nickel plating bath Are as follows: NiSO₄·7H₂O 300 ~ 400g/L, NiCl₂·6H₂O 40 ~ 50g/L, H₃BO₃30 ~ 40g/L, C₁₂H₂₅OSO₂Na 0.5~ 1g/L, C₃₆H₇₀O₁₉ 0.2~0.5g/L

Preferably, cathode described in (2) is copper sheet or stainless steel substrates etc. in step of the present invention, before plating to its surface into Row polishing cleaning and pickling processes, wherein copper sheet with a thickness of 0.25mm ~ 0.30mm.

Preferably, anode described in (2) is pure nickel in step of the present invention, is carried out at polishing and cleaning before plating to its surface It manages, wherein purity >=99.99% of pure nickel.

Preferably, forward current density is 1A/dm during copper sheet deposition nickel in step (3)², reverse current density is 0.5A/dm², the positive working time is 100ms, and the reverse operation time is 10ms, and magnetic agitation speed is 500 ~ 800r/min, is surpassed Acoustical power is 60 ~ 240W, and ultrasonic frequency is 20 ~ 60KHz.

Agents useful for same of the present invention is that analysis is pure, and plating solution is configured using deionized water.

The invention has the benefit that

In the plating process, carbon nanotube limits the growth of nickel crystallite in nickel crystallite edge distribution to the method for the invention, so that Crystal grain is tiny；It is carried out simultaneously using the pulse power of positive and negative alternate, in reverse current work, cathode dissolution, cathode surface is dense Degree is got higher, and particulate nucleation energy reduces, and nucleation point increases, so that crystal grain refinement；After introducing ultrasonic wave, the cavitation of ultrasonic wave is made With carbon nanotube being made to be evenly distributed, and it will lead to crystal grain refinement, therefore form one layer of big crystal grain, the knot of one layer of little crystal grain Structure；Since the crystal grain of composite material is more tiny, it is easy to be passivated by dynamics in etchant solution, so that material more corrosion resistant Erosion.

Detailed description of the invention

Fig. 1 compares for the polarization curve of layer structure composite material made from each embodiment and pure nickel.

Fig. 2 is the Nyquist impedance comparison of layer structure composite material and pure nickel made from each embodiment.

Specific embodiment

With reference to the accompanying drawings and detailed description, the invention will be further described, but protection scope of the present invention is simultaneously It is not limited to the content.