CN103710738B - A kind of composite film preparation method improving Mg-based hydrogen storage surface corrosion resistance performance - Google Patents
A kind of composite film preparation method improving Mg-based hydrogen storage surface corrosion resistance performance Download PDFInfo
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- CN103710738B CN103710738B CN201310744535.5A CN201310744535A CN103710738B CN 103710738 B CN103710738 B CN 103710738B CN 201310744535 A CN201310744535 A CN 201310744535A CN 103710738 B CN103710738 B CN 103710738B
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Abstract
Improve a composite film preparation method for Mg-based hydrogen storage surface corrosion resistance performance, the present invention relates to the method improving Mg-based hydrogen storage surface corrosion resistance performance.The present invention play solve existing Mg-based hydrogen storage surface recombination rete system each method exist obtain the less problem of amplitude that membranous layer corrosion resistance can improve.Method: one, pre-treatment; Two, anodic oxidation; Three, cathode electrodeposition, the composite film of the Mg-based hydrogen storage surface corrosion resistance performance that is namely improved.The present invention can significantly improve the solidity to corrosion of magnesium and alloy thereof, and technique is simple, and cost is lower, easily realizes industrialization, for Mg-based hydrogen storage widespread use in actual production life provides technical guarantee.The present invention is used for a kind of composite film preparation method improving Mg-based hydrogen storage surface corrosion resistance performance.
Description
Technical field
The present invention relates to the method improving Mg-based hydrogen storage surface corrosion resistance performance.
Background technology
Magnesium elements is rich content in the earth's crust, and it is little that magnesium and alloy thereof have density, and specific tenacity is high, and Young's modulus is large waits excellent performance, is ideal structural metallic materials, is widely used in the every field such as Aeronautics and Astronautics, traffic, machinery, medical treatment.But magnesium self is very active, and chemical property is extremely unstable, in use very easily occurs to interact with surrounding medium and corrosion failure occurs, greatly limit magnesium and the widespread use of alloy in more areas thereof.Therefore improve the corrosion resistance nature of magnesium and alloy thereof, and then control its erosion rate and be very important.Surfacecti proteon is the important means realizing magnesium and alloy high corrosion resistance thereof.Compound protective film has inside and outside double membrane structure: internal layer adopts anodizing technology preparation, and this layer and matrix have good combination, and the formation that this layer of coarse surface tissue is subsequent film simultaneously provides vantage point.The method at present both at home and abroad adopting compounding technology to prepare coating on magnesium and alloy thereof also has report, but institute to obtain the amplitude that membranous layer corrosion resistance can improve less, the pitting potential processing rear material improve only about about 1V.
In sum, there is institute and obtain the less problem of amplitude that membranous layer corrosion resistance can improve in existing Mg-based hydrogen storage surface recombination Film preparation method, the pitting potential processing material afterwards improve only about about 1V.
Summary of the invention
The present invention to solve existing Mg-based hydrogen storage surface recombination Film preparation method exist obtain the less problem of amplitude that membranous layer corrosion resistance can improve, and provide a kind of composite film preparation method improving Mg-based hydrogen storage surface corrosion resistance performance.
Improve a composite film preparation method for Mg-based hydrogen storage surface corrosion resistance performance, specifically carry out according to following steps:
One, pre-treatment: use 1500 order sand paper that magnesium plate is carried out grinding process, obtain the magnesium plate after polishing, then under ultrasonic frequency is 25KHz ~ 130KHz, the magnesium plate after polishing is put into dehydrated alcohol and carries out ultrasonic cleaning 5min ~ 15min, and cold wind dries up, obtain pretreated magnesium plate;
Two, anodic oxidation: with pretreated magnesium plate for negative electrode and anode, magnesium plate negative electrode and magnesium plate anode are put into electrolytic solution I, then be the voltage of power supply at the additional 20V ~ 100V in electrolyzer two ends with direct supply, and 5min ~ 60min is oxidized under voltage is 20V ~ 100V, obtain the magnesium plate after anodic oxidation; The solute of the electrolytic solution I described in step 2 is non-magnesium metal-salt and magnesium salts, solvent is dehydrated alcohol, and non-magnesium metal salt concentrations is 0.01mol/L ~ 0.1mol/L in described electrolytic solution I, in described electrolytic solution I, magnesium salt concentrations is 0.001mol/L ~ 0.05mol/L;
Three, cathode electrodeposition: with the magnesium plate after anodic oxidation be negative electrode, with graphite cake for anode, magnesium plate negative electrode after anodic oxidation and graphite sheet anode are put into electrolytic solution II, then with direct supply or the pulse power for power supply is at the voltage of the additional 20V ~ 100V in electrolyzer two ends, and under voltage is 20V ~ 100V, deposit 5min ~ 60min, the composite film of the magnesium plate surface corrosion resistance performance that is namely improved; The solute of the electrolytic solution II described in step 3 is Ca (NO
3)
2and organic acid, solvent is dehydrated alcohol, and Ca (NO in described electrolytic solution II
3)
2concentration is 0.01mol/L ~ 0.1mol/L, and in described electrolytic solution II, organic acid concentration is 0.001mol/L ~ 0.2mol/L.
The invention has the beneficial effects as follows: the present invention can significantly improve the solidity to corrosion of Mg-based hydrogen storage, pitting potential brings up to 2.01V from original-1.61V, improves 3.62V, and corrosion electric current density reduces about two orders of magnitude.Technique is simple, and cost is lower, easily realizes industrialization, for Mg-based hydrogen storage widespread use in actual production life provides technical guarantee.
The present invention is used for a kind of composite film preparation method improving Mg-based hydrogen storage surface corrosion resistance performance.
Accompanying drawing explanation
Fig. 1 is the change curve of pure magnesium corrosive nature before and after embodiment coating composite film; 1 is the polarization curve of pure magnesium; 2 for applying the polarization curve of composite film magnesium.
Embodiment
Technical solution of the present invention is not limited to following cited embodiment, also comprises the arbitrary combination between each embodiment.
Embodiment one: a kind of composite film preparation method improving Mg-based hydrogen storage surface corrosion resistance performance described in present embodiment, specifically carry out according to following steps:
One, pre-treatment: use 1500 order sand paper that magnesium plate is carried out grinding process, obtain the magnesium plate after polishing, then under ultrasonic frequency is 25KHz ~ 130KHz, the magnesium plate after polishing is put into dehydrated alcohol and carries out ultrasonic cleaning 5min ~ 15min, and cold wind dries up, obtain pretreated magnesium plate;
Two, anodic oxidation: with pretreated magnesium plate for negative electrode and anode, magnesium plate negative electrode and magnesium plate anode are put into electrolytic solution I, then be the voltage of power supply at the additional 20V ~ 100V in electrolyzer two ends with direct supply, and 5min ~ 60min is oxidized under voltage is 20V ~ 100V, obtain the magnesium plate after anodic oxidation; The solute of the electrolytic solution I described in step 2 is non-magnesium metal-salt and magnesium salts, solvent is dehydrated alcohol, and non-magnesium metal salt concentrations is 0.01mol/L ~ 0.1mol/L in described electrolytic solution I, in described electrolytic solution I, magnesium salt concentrations is 0.001mol/L ~ 0.05mol/L;
Three, cathode electrodeposition: with the magnesium plate after anodic oxidation be negative electrode, with graphite cake for anode, magnesium plate negative electrode after anodic oxidation and graphite sheet anode are put into electrolytic solution II, then with direct supply or the pulse power for power supply is at the voltage of the additional 20V ~ 100V in electrolyzer two ends, and under voltage is 20V ~ 100V, deposit 5min ~ 60min, the composite film of the magnesium plate surface corrosion resistance performance that is namely improved; The solute of the electrolytic solution II described in step 3 is Ca (NO
3)
2and organic acid, solvent is dehydrated alcohol, and Ca (NO in described electrolytic solution II
3)
2concentration is 0.01mol/L ~ 0.1mol/L, and in described electrolytic solution II, organic acid concentration is 0.001mol/L ~ 0.2mol/L.
The beneficial effect of present embodiment is: present embodiment can significantly improve the solidity to corrosion of magnesium and alloy thereof, and pitting potential brings up to 2.01V from original-1.61V, improves 3.62V, and corrosion electric current density reduces about two orders of magnitude.Technique is simple, and cost is lower, easily realizes industrialization, for Mg-based hydrogen storage widespread use in actual production life provides technical guarantee.
Embodiment two: present embodiment and embodiment one unlike: the magnesium plate described in step one is pure magnesium plate or magnesium alloy plate.Other is identical with embodiment one.
Embodiment three: one of present embodiment and embodiment one or two unlike: the non-magnesium metal-salt described in step 2 is Ca (NO
3)
2, Zn (NO
3)
2, CaCl
2or FeCl
3.Other is identical with embodiment one or two.
Embodiment four: one of present embodiment and embodiment one to three unlike: the magnesium salts described in step 2 is Mg (NO
3)
2or MgCl
2.Other is identical with embodiment one to three.
Embodiment five: one of present embodiment and embodiment one to four unlike: the organic acid described in step 3 is TETRADECONIC ACID, palmitic acid or stearic acid.Other is identical with embodiment one to four.
Embodiment six: one of present embodiment and embodiment one to five unlike: the pulse power dutycycle described in step 3 is 1% ~ 50%.Other is identical with embodiment one to five.
Following examples are adopted to verify beneficial effect of the present invention:
Embodiment:
A kind of composite film preparation method improving Mg-based hydrogen storage surface corrosion resistance performance described in the present embodiment, specifically carries out according to following steps:
One, pre-treatment: use 1500 order sand paper that pure magnesium plate is carried out grinding process, obtain the pure magnesium plate after polishing, then under ultrasonic frequency is 40KHz, the pure magnesium plate after polishing is put into dehydrated alcohol and carries out ultrasonic cleaning 10min, and cold wind dries up, obtain pretreated pure magnesium plate;
Two, anodic oxidation: with pretreated pure magnesium plate for negative electrode and anode, pure magnesium plate negative electrode and pure magnesium plate anode are put into electrolytic solution I, then be the voltage of power supply at the additional 100V in electrolyzer two ends with direct supply, and 10min is oxidized under voltage is 100V, obtain the pure magnesium plate after anodic oxidation; The solute of the electrolytic solution I described in step 2 is Ca (NO
3)
2with Mg (NO
3)
2, solvent is dehydrated alcohol, and Ca (NO in described electrolytic solution I
3)
2concentration is 0.045mol/L, Mg (NO in described electrolytic solution I
3)
2concentration is 0.005mol/L;
Three, cathode electrodeposition: with the pure magnesium plate after anodic oxidation be negative electrode, with graphite cake for anode, pure magnesium plate negative electrode after anodic oxidation and graphite sheet anode are put into electrolytic solution II, then be the voltage of power supply at the additional 100V in electrolyzer two ends with direct supply, and under voltage is 100V, deposit 30min, the composite film of the magnesium surface corrosion resisting property that is namely improved; The solute of the electrolytic solution II described in step 3 is Ca (NO
3)
2and stearic acid, solvent is dehydrated alcohol, and Ca (NO in described electrolytic solution II
3)
2concentration is 0.05mol/L, and in described electrolytic solution II, stearic acid concentration is 0.05mol/L.
The present embodiment utilizes polarization curve to test the change curve of pure magnesium corrosive nature before and after coating composite film as shown in Figure 1; 1 is the polarization curve of pure magnesium; 2 for applying the polarization curve of composite film magnesium; The test environment of polarization curve is simulated body fluid (37 DEG C).Show in figure, when corrosion potential is in more among a small circle during change, the corrosion current of matrix magnesium sharply increases, and material is damaged at short notice.Obvious passivation region has been there is in anodic polarization curves through applying pure magnesium after composite film, and larger between passivation region.Pitting potential brings up to 2.01V from original-1.61V, and corrosion electric current density reduces about two orders of magnitude.This composite film visible has increased substantially the corrosion resistance nature of magnesium.
Claims (5)
1. improve a composite film preparation method for Mg-based hydrogen storage surface corrosion resistance performance, it is characterized in that a kind of composite film preparation method improving Mg-based hydrogen storage surface corrosion resistance performance carries out according to following steps:
One, pre-treatment: use 1500 order sand paper that magnesium plate is carried out grinding process, obtain the magnesium plate after polishing, then under ultrasonic frequency is 25KHz ~ 130KHz, the magnesium plate after polishing is put into dehydrated alcohol and carries out ultrasonic cleaning 5min ~ 15min, and cold wind dries up, obtain pretreated magnesium plate;
Two, anodic oxidation: with pretreated magnesium plate for negative electrode and anode, magnesium plate negative electrode and magnesium plate anode are put into electrolytic solution I, then be the voltage of power supply at the additional 20V ~ 100V in electrolyzer two ends with direct supply, and 5min ~ 60min is oxidized under voltage is 20V ~ 100V, obtain the magnesium plate after anodic oxidation; The solute of the electrolytic solution I described in step 2 is non-magnesium metal-salt and magnesium salts, solvent is dehydrated alcohol, and non-magnesium metal salt concentrations is 0.01mol/L ~ 0.1mol/L in described electrolytic solution I, in described electrolytic solution I, magnesium salt concentrations is 0.001mol/L ~ 0.05mol/L;
Three, cathode electrodeposition: with the magnesium plate after anodic oxidation be negative electrode, with graphite cake for anode, magnesium plate negative electrode after anodic oxidation and graphite sheet anode are put into electrolytic solution II, then with direct supply or the pulse power for power supply is at the voltage of the additional 20V ~ 100V in electrolyzer two ends, and under voltage is 20V ~ 100V, deposit 5min ~ 60min, the composite film of the magnesium plate surface corrosion resistance performance that is namely improved; The solute of the electrolytic solution II described in step 3 is Ca (NO
3)
2and organic acid, solvent is dehydrated alcohol, and Ca (NO in described electrolytic solution II
3)
2concentration is 0.01mol/L ~ 0.1mol/L, and in described electrolytic solution II, organic acid concentration is 0.001mol/L ~ 0.2mol/L;
Organic acid described in step 3 is TETRADECONIC ACID, palmitic acid or stearic acid.
2. a kind of composite film preparation method improving Mg-based hydrogen storage surface corrosion resistance performance according to claim 1, is characterized in that the magnesium plate described in step one is pure magnesium plate or magnesium alloy plate.
3. a kind of composite film preparation method improving Mg-based hydrogen storage surface corrosion resistance performance according to claim 1, is characterized in that the non-magnesium metal-salt described in step 2 is Ca (NO
3)
2, Zn (NO
3)
2, CaCl
2or FeCl
3.
4. a kind of composite film preparation method improving Mg-based hydrogen storage surface corrosion resistance performance according to claim 1, is characterized in that the magnesium salts described in step 2 is Mg (NO
3)
2or MgCl
2.
5. a kind of composite film preparation method improving Mg-based hydrogen storage surface corrosion resistance performance according to claim 1, is characterized in that the pulse power dutycycle described in step 3 is 1% ~ 50%.
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| CN104313664B (en) * | 2014-09-30 | 2017-05-17 | 扬州大学 | Surface treatment method for rare earth magnesium alloy product |
| CN104711572B (en) * | 2015-01-26 | 2017-04-19 | 北方工业大学 | Production method of magnesium alloy phosphate/fatty acid salt composite super-hydrophobic corrosion resistant membrane |
| CN106757251A (en) * | 2017-01-18 | 2017-05-31 | 东南大学 | A kind of preparation method of Mg alloy surface composite coating |
| CN108624931A (en) * | 2018-04-04 | 2018-10-09 | 上海交通大学 | A kind of phosphorus calcium zinc stone coating and preparation method thereof of pure magnesium and Mg alloy surface |
| CN109295488B (en) * | 2018-09-29 | 2020-08-11 | 广东省生物工程研究所（广州甘蔗糖业研究所） | Magnetic composite oxide ceramic membrane with self-sealing hole structure and preparation method thereof |
| CN112522750A (en) * | 2020-12-12 | 2021-03-19 | 山西农业大学 | Preparation method of coating for improving surface corrosion resistance of 65Mn steel |
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| JP2000345370A (en) * | 1999-06-07 | 2000-12-12 | Ueda Alumite Kogyo Kk | Surface treatment of magnesium or magnesium alloy |
| CN101709496A (en) * | 2009-11-30 | 2010-05-19 | 郑州大学 | Micro-arc oxidation-electrodeposition preparation method of magnesium-based bioactive coating |
| CN102268711A (en) * | 2011-06-22 | 2011-12-07 | 沈阳理工大学 | Method for preparing biological composite coating on surface of magnesium-based material |
| CN103272287A (en) * | 2013-05-24 | 2013-09-04 | 华南理工大学 | Biological medical degradable material and preparation method thereof |
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Patent Citations (5)
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|---|---|---|---|---|
| JP2000345370A (en) * | 1999-06-07 | 2000-12-12 | Ueda Alumite Kogyo Kk | Surface treatment of magnesium or magnesium alloy |
| CN101709496A (en) * | 2009-11-30 | 2010-05-19 | 郑州大学 | Micro-arc oxidation-electrodeposition preparation method of magnesium-based bioactive coating |
| CN102268711A (en) * | 2011-06-22 | 2011-12-07 | 沈阳理工大学 | Method for preparing biological composite coating on surface of magnesium-based material |
| CN103272287A (en) * | 2013-05-24 | 2013-09-04 | 华南理工大学 | Biological medical degradable material and preparation method thereof |
| CN103272284A (en) * | 2013-05-24 | 2013-09-04 | 华南理工大学 | Biological medical controllable all-degradable material and preparation method thereof |
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