CN104178784A - Preparation method of metal surface copper-nickel alloy - Google Patents
Preparation method of metal surface copper-nickel alloy Download PDFInfo
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- CN104178784A CN104178784A CN201410403253.3A CN201410403253A CN104178784A CN 104178784 A CN104178784 A CN 104178784A CN 201410403253 A CN201410403253 A CN 201410403253A CN 104178784 A CN104178784 A CN 104178784A
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- cupronickel
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Abstract
The invention discloses a preparation method of a metal surface copper-nickel alloy, which comprises the following steps: (1) metal surface pretreatment; (2) solution preparation; (3) constant-current deposition of copper-nickel alloy; and (4) surface heat treatment. The preparation method has the advantages of simple process, controllable temperature and components, low cost, high efficiency, no pollution and no risk. The electrochemical testing proves that the copper-nickel alloy film has better corrosion resistance than the metal bare sample. The copper-nickel alloy has the advantages of low heat treatment temperature, short holding time and more compact and uniform film; and the electrochemical testing proves that the corrosion resistance is further enhanced.
Description
Technical field
The present invention relates to aseptic technic field, metallic surface, relate in particular to the preparation method of a kind of metallic surface cupronickel.
Background technology
Metallic corrosion is the ubiquitous a kind of spontaneous phenomenon of nature, is that metallic substance and surrounding environment chemistry or electrochemical effect occur and destroyed phenomenon.The direct economic loss producing due to metallic corrosion every year accounts for 3% left and right of gross national product, and therefore, corrosion of metal and protection are related to the Sustainable development of whole national economy.Ball surface area is taken up an area more than 70% in ocean, reasonably develops oceanic resources and is day by day subject to people's attention.In seawater, contain the chlorion that easily causes corrosion, iron and steel, aluminium, the equal seawater corrosion resistance not of many engineering metal materials such as stainless steel even.These external these materials, and also can form marine biofouling on the surface of the non-metallic material such as timber, glass.Copper is seawater corrosion resistance not only, and the cupric ion dissolving in water has germicidal action, can prevent marine biofouling.Thereby copper and copper alloy is material very important in the industry of ocean, especially cupronickel, the parent who is subject to people because of its more anti-corrosion characteristic relies, widespread use in desalinator, offshore oil production gas production platform and other seashore and submarine facility.But the main adding elements nickel in cupronickel is a kind of rare strategic materials, expensive.Direct large batch of use cupronickel cost is large, and cost is high and limited the widespread use of cupronickel.Therefore the preparation method who seeks a kind of simple and effective cupronickel protective membrane just seems particularly important.
The preparation method of cupronickel mainly contains mechanical alloying method, reduction method, supersonic method, powder metallurgic method, the hot method of hydrothermal/solvent, quiet high pressure synthesis method etc. at present.These synthetic methods, although can successfully synthesize cupronickel, its major part of preparing is the powder of cupronickel.And the application of these methods has larger shortcoming.Equipment component more complicated, needed temperature is high, and environment is harsh; Part be consume energy larger.
Galvanostatic deposition is rather well received a kind of technology recent years; galvanostatic deposition is to pass to constant current in containing the solution that is deposited metal ion; positively charged positively charged ion is discharged on negative electrode; obtain a kind of electro-deposition techniques of target product; and the research of preparing cupronickel protective film by galvanostatic deposition is also in the starting stage; in addition the generation that galvanic deposit defect is exactly hydrogen makes rete occur hole to a certain degree, has greatly limited its application in engineering.The metal of the cupronickel having deposited is processed in vacuum oven to insulation for some time and can be eliminated fully the hole in rete, make rete finer and close evenly, strengthen its anti-corrosion characteristic and play the provide protection to metallic matrix.
Galvanostatic method is prepared cupronickel its unique advantage.First, can form the film that one deck mixes in metal target or miscellaneous part surface, target compound is protected fully.Secondly, he can not be subject to the restriction of target compound shape.The 3rd, efficiency is high, and cost is low, and equipment is simple, easy to operate, environment friendly and pollution-free.The 4th, by the component that regulates deposition current can realize cupronickel, control.
The cupronickel protective film of formation of deposits can get rid of through follow-up surface vacuum thermal treatment the hole being trapped in rete, and further makes rete evenly fine and close, improves the corrosion resisting property of rete.
Summary of the invention
The invention provides the preparation method of a kind of metallic surface cupronickel.
The present invention adopts following technical scheme:
The preparation method's of metallic surface of the present invention cupronickel concrete steps are as follows:
(1) pretreatment of metal surface:
Polished with abrasive paper for metallograph in metallic surface, then use metallic phase polisher milling polishing, then use solvent cleaning oil removing, finally with scolding tin, be welded on copper conductor, making electrode, to put dry place standby;
(2) solution preparation:
Nickel source, Tong Yuan, tensio-active agent and complexing agent are mixed, and the mol ratio of nickel source, Tong Yuan, tensio-active agent and complexing agent is 0.3～0.9:0.03～0.1:1 * 10
-5～6 * 10
-5: 0.25～0.4,, obtain mixing solutions, then regulate pH to 2-6,
(3) galvanostatic deposition cupronickel:
Take saturated calomel electrode as reference electrode, platinum electrode is to electrode, and metal electrode prepared by step (1) is negative electrode, and the solution of the step (2) of take preparation is electrolytic solution, film forming under the continuous current of-8mA～-35mA, obtains having the cupronickel of different components;
(4) surface heat is processed:
Metal vacuum heat treatment at 200～800 ℃ by step (3) deposited copper nickelalloy, can obtain metallic surface of the present invention cupronickel.
In step (1), polish successively with the abrasive paper for metallograph by different meshes in preferable alloy surface, and after polishing, oil removing is cleaned, and makes electrode standby.
In step (2), described nickel source is single nickel salt, nickelous chloride, nickelous nitrate, described copper source is copper sulfate, cupric chloride, cupric nitrate, described tensio-active agent is Sodium palmityl sulfate, Sodium dodecylbenzene sulfonate, stearic acid, described complexing agent is Trisodium Citrate, boric acid, disodium ethylene diamine tetraacetate or lactic acid, a kind of in citric acid.
In step (4), preferably by metal sintering at 500 ℃ of step (3) deposited copper nickelalloy, insulation 30min.
Because the sedimentation potential of copper and mickel differs larger, by adding complexing agent to regulate both sedimentation potentials that the possibility of its codeposition is increased, under suitable deposition current, realize the codeposition of copper nickel and prepare cupronickel film.Galvanic deposit is inevasible is that the generation of hydrogen is trapped in metallic surface, increases the compactness uniformity coefficient of rete by follow-up vacuum heat treatment.
Positively effect of the present invention is as follows:
(1) preparation method of metallic surface of the present invention cupronickel is simple, and component and temperature are adjustable.Cost is low, and efficiency is high, pollution-free non-hazardous advantage.By electro-chemical test, its anticorrosion properties are better than bare metal sample.
(2) cupronickel that prepared by the present invention sintered heat insulating in vacuum stove,, soaking time is short, makes rete finer and close evenly, and by electro-chemical test, its erosion resistance is greatly improved.
Accompanying drawing explanation
Fig. 1 is the XRD figure spectrum of the metallic surface cupronickel of the embodiment of the present invention 1 preparation.
Fig. 2 is the electrokinetic potential polarization curve of the metallic surface cupronickel of the embodiment of the present invention 1 preparation.
Fig. 3 is the electrochemical impedance spectrogram of the metallic surface cupronickel of the embodiment of the present invention 1 preparation.
Fig. 4 is the Bode figure of the metallic surface cupronickel of the embodiment of the present invention 1 preparation.
Fig. 2,3,4 condition are 500 ℃-CuNi.
Fig. 5 is the scanning electron microscope (SEM) photograph of the metallic surface cupronickel of the embodiment of the present invention 1 preparation;
A is post-depositional cupronickel, and b is the cupronickel of embodiment 1 vacuum heat treatment.
Embodiment
The following examples are to describe in further detail of the present invention.
Embodiment 1 bronze medal matrix surface galvanostatic technique deposited copper nickelalloy.
1) pretreatment of metal surface.Polish successively with the abrasive paper for metallograph of different meshes in metallic surface, after polishing, oil removing is cleaned, and makes electrode standby.
2) obtain solution: single nickel salt 0.3M, copper sulfate 0.06M, tensio-active agent Sodium dodecylbenzene sulfonate 0.01g, complexing of metal ion agent Trisodium Citrate 0.10M.
3) galvanostatic deposition cupronickel.Take saturated calomel electrode respectively as reference electrode, and platinum electrode is to electrode, and copper electrode is negative electrode ,-10mA and-15mA under film forming 900s.
4) vacuum heat treatment makes its densification.Sintering at 500 ℃, insulation 30min, makes it finer and close, improves performance.
5) material phase analysis.Made sample is carried out to XRD test, discovery has all obtained pure cupronickel under these two electric currents, and the ratio of cupronickel can be read by testing spectrogram, under wherein-10mA, be Cu0.81Ni0.19, the size that can control thus deposition current for Cu0.70Ni0.30. under-15mA obtains the easily cupronickel of control of component.(as Fig. 1)
6) electro-chemical test.Carry out electrokinetic potential polarization curve and electrochemical impedance collection of illustrative plates (EIS) test, adopt three-electrode system, reference electrode is saturated calomel electrode, to electrode, is platinum electrode, working electrode is copper matrix, and electro-chemical test corrosive medium used is 3.5%wt.NaCl neutral electrolyte solution.
Test result as shown in Figure 2,3, 4, Fig. 2,3,4 condition are 500 ℃-CuNi, from Fig. 2 electrokinetic potential polarization curve, find out, compare with the cupronickel rete of naked sample and deposition, the corrosion potential of the copper matrix of modifying through cupronickel moves to right, corrosion current significantly declines, and after the lower sintered heat insulating of 500 degree, corrosion potential further moves to right again on upper basis, has shown good anti-corrosion characteristic.As seen from Figure 3, the shape of the electrochemical impedance spectrogram of modified copper sample and undressed copper sample do not have very big difference, and this just shows, the chemical substance of modification does not change the character of copper matrix.But galvanostatic deposition cupronickel film, half circular diameter in Nyquist figure increases, and after thermal treatment, half circular diameter increases again, has significantly improved the corrosion resistance of copper sample, and this is consistent with electrokinetic potential polarization test result.From the Bode figure of Fig. 4, can find out, the cupronickel film low-frequency impedance mould value making exceeds 1 order of magnitude than naked sample, and the cupronickel that deposition is obtained carries out after sintered heat insulating, and the resistance value of low frequency range has had again larger lifting on the basis of previous step.
7) Analysis of Surface Topography: the cupronickel depositing under p-8mA carries out scanning electron microscopic observation.Result as shown in Figure 5, is the cupronickel under amplifying 10000 times, and what a showed is post-depositional cupronickel, and what b showed is the cupronickel after embodiment 1 preparation vacuum heat treatment.Post-depositional is rice kernel shape, and finer and close evenly after thermal treatment, on original basis, rete is finer and close, even, there is no space, and this just can effectively stop the immersion of corrosive medium, improves the corrosion resisting property of rete.
Although illustrated and described embodiments of the invention, for the ordinary skill in the art, be appreciated that without departing from the principles and spirit of the present invention and can carry out multiple variation, modification, replacement and modification to these embodiment, scope of the present invention is limited by claims and equivalent thereof.
Claims (8)
1. a preparation method for metallic surface cupronickel, is characterized in that: the concrete steps of described method are as follows:
(1) pretreatment of metal surface:
Polished with abrasive paper for metallograph in metallic surface, then use metallic phase polisher milling polishing, then use solvent cleaning oil removing, finally with scolding tin, be welded on copper conductor, making electrode, to put dry place standby;
(2) solution preparation:
Nickel source, Tong Yuan, tensio-active agent and complexing agent are mixed, and the mol ratio of nickel source, Tong Yuan, tensio-active agent and complexing agent is 0.3～0.9:0.03～0.1:1 * 10
-5～6 * 10
-5: 0.25～0.4, obtain mixing solutions;
(3) galvanostatic deposition cupronickel:
Take saturated calomel electrode as reference electrode, platinum electrode is to electrode, and metal electrode prepared by step (1) is negative electrode, and the solution of the step (2) of take preparation is electrolytic solution, film forming under the continuous current of-8mA～-35mA, obtains having the cupronickel of different components;
(4) surface heat is processed:
By metal thermal treatment at 200～800 ℃ of step (3) deposited copper nickelalloy, insulation, can obtain metallic surface of the present invention cupronickel.
2. the preparation method of metallic surface as claimed in claim 1 cupronickel, is characterized in that: in step (1), polish successively with the abrasive paper for metallograph of different meshes in metallic surface, and after polishing, oil removing is cleaned, and makes electrode standby.
3. the preparation method of metallic surface as claimed in claim 1 cupronickel, is characterized in that: in step (1), described metal is aluminium and aluminium alloy, copper and copper alloy, magnesium and magnesium alloy, carbon steel and stainless steel.
4. the preparation method of metallic surface as claimed in claim 1 cupronickel, is characterized in that: in step (2), described nickel source is single nickel salt, nickelous chloride or nickelous nitrate, and described copper source is copper sulfate, cupric chloride or cupric nitrate.
5. the preparation method of metallic surface as claimed in claim 1 cupronickel, is characterized in that: in step (2), described tensio-active agent is Sodium palmityl sulfate, Sodium dodecylbenzene sulfonate or stearic acid.
6. the preparation method of metallic surface as claimed in claim 1 cupronickel, is characterized in that: in step (2), described complexing agent is Trisodium Citrate, boric acid, disodium ethylene diamine tetraacetate or lactic acid, a kind of in citric acid.
7. the preparation method of metallic surface as claimed in claim 1 cupronickel, is characterized in that: in step (2), mixing solutions regulates pH with sodium hydroxide, is adjusted to 2-6.
8. the preparation method of metallic surface as claimed in claim 1 cupronickel, is characterized in that: in step (4), preferably by metal vacuum heat treatment at 500 ℃ of step (3) deposited copper nickelalloy.
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104651890A (en) * | 2015-02-27 | 2015-05-27 | 黑龙江科技大学 | Preparation method of low-cost high-corrosion-resistance Monel metal coating |
| CN104819930A (en) * | 2015-05-05 | 2015-08-05 | 中国兵器科学研究院宁波分院 | Metal surface protective layer corrosion test method |
| CN105018986A (en) * | 2015-08-11 | 2015-11-04 | 江苏金曼科技有限责任公司 | Cyanide-free and phosphorus-free alloy bottoming liquid |
| CN105506686A (en) * | 2015-12-23 | 2016-04-20 | 苏州市金星工艺镀饰有限公司 | Electroplating method for decorative nickel-copper-gold ternary alloy electroplating bath |
| CN106676594A (en) * | 2016-06-10 | 2017-05-17 | 太原工业学院 | Low-cost cyanide-free copper-zinc-tin alloy electroplating solution and copper-zinc-tin alloy electroplating technology thereof |
| CN108950671A (en) * | 2018-09-25 | 2018-12-07 | 湖南工业大学 | A kind of stainless base steel corrosion-proof wear coating structure and its preparation method and application |
| CN109252066A (en) * | 2017-07-12 | 2019-01-22 | 钟表制作有限公司 | The timepiece formed by nonmagnetic binary CuNi alloy |
| CN109957820A (en) * | 2017-12-25 | 2019-07-02 | 丹阳市延陵镇度越五金厂 | A kind of handware electroplating process for surface |
| CN110396707A (en) * | 2019-08-31 | 2019-11-01 | 嘉兴巧蕊贸易有限公司 | A kind of Zn-nSiO of durability2The super-hydrophobic oleophobic material of corronil is electroplated |
| CN110607541A (en) * | 2019-08-17 | 2019-12-24 | 山东理工大学 | Copper-nickel composite electrode for electric spark machining of diamond and preparation method thereof |
| CN114196992A (en) * | 2021-11-29 | 2022-03-18 | 哈尔滨工业大学 | Ni-Al alloy component and electrodeposition incremental forming method thereof |
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104651890A (en) * | 2015-02-27 | 2015-05-27 | 黑龙江科技大学 | Preparation method of low-cost high-corrosion-resistance Monel metal coating |
| CN104819930A (en) * | 2015-05-05 | 2015-08-05 | 中国兵器科学研究院宁波分院 | Metal surface protective layer corrosion test method |
| CN105018986A (en) * | 2015-08-11 | 2015-11-04 | 江苏金曼科技有限责任公司 | Cyanide-free and phosphorus-free alloy bottoming liquid |
| CN105506686A (en) * | 2015-12-23 | 2016-04-20 | 苏州市金星工艺镀饰有限公司 | Electroplating method for decorative nickel-copper-gold ternary alloy electroplating bath |
| CN106676594A (en) * | 2016-06-10 | 2017-05-17 | 太原工业学院 | Low-cost cyanide-free copper-zinc-tin alloy electroplating solution and copper-zinc-tin alloy electroplating technology thereof |
| CN109252066A (en) * | 2017-07-12 | 2019-01-22 | 钟表制作有限公司 | The timepiece formed by nonmagnetic binary CuNi alloy |
| CN109957820A (en) * | 2017-12-25 | 2019-07-02 | 丹阳市延陵镇度越五金厂 | A kind of handware electroplating process for surface |
| CN108950671A (en) * | 2018-09-25 | 2018-12-07 | 湖南工业大学 | A kind of stainless base steel corrosion-proof wear coating structure and its preparation method and application |
| CN108950671B (en) * | 2018-09-25 | 2023-12-01 | 湖南工业大学 | Stainless steel-based corrosion-resistant and wear-resistant coating structure and preparation method and application thereof |
| CN110607541A (en) * | 2019-08-17 | 2019-12-24 | 山东理工大学 | Copper-nickel composite electrode for electric spark machining of diamond and preparation method thereof |
| CN110396707A (en) * | 2019-08-31 | 2019-11-01 | 嘉兴巧蕊贸易有限公司 | A kind of Zn-nSiO of durability2The super-hydrophobic oleophobic material of corronil is electroplated |
| CN110396707B (en) * | 2019-08-31 | 2021-06-18 | 哈工大泰州创新科技研究院有限公司 | Durable Zn-nSiO2Super-hydrophobic and oleophobic material for electroplating copper-nickel alloy |
| CN114196992A (en) * | 2021-11-29 | 2022-03-18 | 哈尔滨工业大学 | Ni-Al alloy component and electrodeposition incremental forming method thereof |
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