CN101638786B - High-potential sacrificial magnesium alloy anode and manufacturing method thereof - Google Patents
High-potential sacrificial magnesium alloy anode and manufacturing method thereof Download PDFInfo
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- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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- C23F13/00—Inhibiting corrosion of metals by anodic or cathodic protection
- C23F13/02—Inhibiting corrosion of metals by anodic or cathodic protection cathodic; Selection of conditions, parameters or procedures for cathodic protection, e.g. of electrical conditions
- C23F13/06—Constructional parts, or assemblies of cathodic-protection apparatus
- C23F13/08—Electrodes specially adapted for inhibiting corrosion by cathodic protection; Manufacture thereof; Conducting electric current thereto
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- C23F13/14—Material for sacrificial anodes
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Abstract
The invention provides a high-potential sacrificial magnesium alloy anode and a manufacturing method thereof. The high-potential sacrificial magnesium alloy anode comprises the following chemical components in percentage by weight: 0 to 0.4 percent of Zn, less than or equal to 0.01 percent of Al, less than or equal to 0.02 percent of Si, less than or equal to 0.05 percent of Mn, less than or equal to 0.03 percent of Fe, less than or equal to 0.003 percent of Ni, less than or equal to 0.005 percent of Cu, and the balance of Mg; besides, the potential of the high-potential sacrificial magnesium alloy anode is more than -1.70 volts, and the current efficiency is over 50 percent. The high-potential sacrificial magnesium alloy anode has a simple manufacturing process and low cost, and has the electrical property in accordance with the prescriptions of an ASTM standard.
Description
Technical field
The present invention relates to sacrificial magnesium alloy anode, particularly a kind of novel low-cost high-potential sacrificial magnesium alloy anode.
Background technology
Corrosion of Metallic Materials spreads all over the every field of national economy, and is very huge by the direct and indirect financial loss that corrosion causes, and corrosion is also very great to the influence that environment and the eubiosis are produced.Therefore, the problem of relevant metal corrosion and protection gets more and more people's extensive concerning, and becomes an important research field of material subject.
The method that prevents metallic corrosion is a lot, and adopting electrochemical cathodic protection is one of most important method, and utilizing galvanic protection is a kind of important metallic corrosion safeguard procedures.Chemical reaction takes place when metal is immersed in the electrolytic solution easily, and according to electrochemical principle as can be known, galvanic corrosion all might take place in the different of bath composition, adhesion impurity, stress and ventilation property etc. around the metal.In electrochemical corrosion course; metal itself has formed many galvanic cells; negative electrode is served as at some position; anode is served as at other positions; in the middle of the anode region metallics enters solution; electronics by solution stream to negative electrode; and the positive ion that enters in the solution flows to cathode zone by electrolytic solution from anode, has therefore formed current circuit, causes the anodic corrosion; the galvanic protection of steel construction makes protected steel construction become negative electrode exactly; other metal that electronegativity is higher, as anode and form the loop, electronics flows to steel construction as negative electrode from anode as magnesium; make steel can not become positive ion and enter solution, steel construction just obtains protection like this.In order to reach this purpose, sacrificial anode material must have enough negative and stable current potential to guarantee to have enough driving voltages.
Because sacrificial anode has does not need additional power source, can not disturb close on metallic facility, electric current dispersive ability good, advantage such as be easy to administer and maintain, thereby in anticorrosion engineering, be used widely.Sacrificial magnesium alloy anode is one of material that metal is carried out electro-chemical protection; it is widely used in the galvanic protection of the metallic facility of water supply and sewage in soil, fresh water, seawater, the urban construction, coal gas, Sweet natural gas, heating, oil pipeline etc.; metal is played preservative activity, have broad application prospects.Compare with other sacrificial anode, sacrificial magnesium alloy anode has that little, the theoretical electrical capacity of density is big, current potential is negative, polarizability is low, and is very big to the driving voltage of iron and steel, is applicable to the protection of hardware in resistivity soil with high and the fresh water.
Sacrificial magnesium alloy anode is divided into noble potential and low potential two kinds.High-potential sacrificial magnesium alloy anode is a magnesium-manganese alloy, it is (weight percent wt%) Mn0.5-1.3% that its composition requires, Al≤0.01%, Fe≤0.01%, Ni≤0.001%, Cu≤0.01%, Si≤0.05%, all the other single foreign matter contents are no more than 0.05%, and require the open circuit potential of sacrificial magnesium alloy anode standard A STM843-1993 (2003) regulation that its electrical property satisfies the U.S. greater than-1.7V, and current efficiency is greater than 50%.The low potential sacrificial magnesium alloy anode is the magnalium zinc alloy, mainly contains AZ31 series and AZ63 series, and manganese is all had certain requirement.No matter high-potential sacrificial magnesium alloy anode still is the low potential sacrificial magnesium alloy anode, all needs to add the Mn element.High-potential sacrificial magnesium alloy anode particularly, the content of Mn even reach 0.5-1.3%.High petential magnesium alloy sacrificial anode material is to be invented by the Dow Chemical company of the U.S., and the sacrificial magnesium alloy anode standard A STM843-1993 (2003) of the U.S. drafts formulation by the said firm.The standard GB/T 17731-2004 of China is the USS that adopts.So the manganese content and the ASTM conformance to standard of high-potential sacrificial magnesium alloy anode.And manufacturer all over the world and supply commercial city are the standards that adopts with reference to the ASTM standard formulation at present, and Mn content is all had certain requirement.
Yet, when Dow Chemical company carries out high-potential sacrificial magnesium alloy anode research and development and produces, employing be the MAGNESIUM METAL of producing by electrolytic process.And the MAGNESIUM METAL that electrolytic process is produced, its iron level is very high, general between 0.08-0.4%, iron is a very deleterious metallic element in magnesium alloy, badly influence the corrosion resistance of magnesium alloy, for example when iron level drops to 0.005% by 0.01%, its erosion resistance nearly can improve about two orders of magnitude.Therefore in the preparation high-potential sacrificial magnesium alloy anode, need remove these a large amount of iron.Mn element and iron react and can produce manganeseirom, in fusion process, because the manganeseirom density that produces is bigger, can sink to the bottom of melting pot, therefore need to add the content that a large amount of manganese elements guarantees to reduce iron in the process of producing.In addition, add the stress corrosion that manganese can improve magnesium alloy.
The MAGNESIUM METAL that China produces, prepare by Pidgeon process more than 95%, its iron level is generally at (weight percent wt%) below 0.01%, in this case, whether also need to add manganese and reduce iron level? the high-potential sacrificial magnesium alloy anode production technique of China's domestic current is by adding electrolytic manganese or MnCl
2Make manganese content reach the ASTM standard of 0.5-1.3%.Because the fusing point of manganese metal is 1244 ℃ of 650 ℃ far above magnesium, need add under than higher temperature.And high temperature then can make the magnesium melt be more prone to oxidation, brings more oxide compound into, and oxide compound then can seriously reduce the current potential and the current efficiency of high-potential sacrificial magnesium alloy anode.And the easy moisture absorption of Manganous chloride tetrahydrate (MnCl2), and water vapour is abnormally dangerous to the magnesium of molten state, even the possibility of blast is arranged, and the content of nickel in the Manganous chloride tetrahydrate and iron is very high, in use can introduce new impurity.Therefore need a kind of novel magnesium alloy sacrificial anode that does not add manganese or can reach the electrical property of present ASTM prescribed by standard with other other low melting point metal replacement manganese at present.
Summary of the invention
The objective of the invention is to improve, need not add manganese and replace low-cost high-potential sacrificial magnesium alloy anode of manganese and preparation method thereof with other low melting point metal and provide a kind of at the weak point that present noble potential magnesium-manganese alloy sacrificial anode must add the manganese of 0.5-1.3% content.
High petential magnesium alloy sacrificial anode material of the present invention is only by adding current potential and the electrical property that low-melting Zn changes magnesium alloy.This product technology is easy, and cost is cheap relatively, is a kind of high-potential sacrificial magnesium alloy anode that can significantly improve the magnesium alloy chemical property.
A scheme of the present invention provides a kind of high-potential sacrificial magnesium alloy anode, the chemical ingredients of this high-potential sacrificial magnesium alloy anode (weight percent) is: Mn 0-0.5%, Al≤0.01%, Si≤0.02%, Fe≤0.03%, Ni≤0.003%, Cu≤0.005%, all the other are Mg, and the current potential of this high-potential sacrificial magnesium alloy anode is greater than-1.70V, and current efficiency is greater than 50%.
Another program of the present invention provides a kind of high-potential sacrificial magnesium alloy anode, the chemical ingredients of this high-potential sacrificial magnesium alloy anode (mass percent) is: Zn0.05%-0.4%, Al≤0.01%, Si0.02%, Mn≤0.05%, Fe≤0.03%, Ni≤0.003%, Cu≤0.005%, all the other are Mg, and the current potential of this high-potential sacrificial magnesium alloy anode is greater than-1.70V, and current efficiency is greater than 50%.
Another scheme of the present invention provides a kind of manufacture method of high-potential sacrificial magnesium alloy anode, comprising the steps: to get chemical ingredients is Al≤0.01%, Si≤0.02%, Mn≤0.05%, Fe≤0.03%, Ni≤0.003%, Cu≤0.005%, all the other are the magnesium ingot of Mg, toast preheating; Magnesium ingot after the baking preheating is put into crucible, carry out melting at 720 ℃ and make it become melt; Add manganese powders to melt at 760 ℃ afterwards so that manganese content greater than zero (0) smaller or equal to 0.5%; Control melt afterwards and carry out refining under 740 ℃ temperature, refining time is 15 minutes; Leave standstill insulation 40 minutes at 720 ℃ afterwards; And under 720 ℃ of temperature, melt is cast to coagulation forming in the mould afterwards.
Another scheme of the present invention provides a kind of manufacture method of high-potential sacrificial magnesium alloy anode, comprising the steps: to get chemical ingredients is Al≤0.01%, Si≤0.02%, Mn≤0.05%, Fe≤0.03%, Ni≤0.003%, Cu≤0.005%, all the other are the magnesium ingot of Mg, toast preheating; Magnesium ingot after the baking preheating is put into crucible, carry out melting at 720 ℃ and make it become melt; After the melting, add zinc ingot metal to melt, so that zinc content is smaller or equal to 0.4% more than or equal to 0.05% at 690-750 ℃; Afterwards, the control melt carries out refining under 740 ℃ temperature, and refining time is 10-30 minute; After refining is finished, melt temperature is controlled at 700-740 ℃, insulation was left standstill 20-60 minute; And under 700-740 ℃ of temperature, melt is cast to coagulation forming in the mould.
The advantage of this high-potential sacrificial magnesium alloy anode of the present invention is, manufacturing process is extremely simple, having changed for a long time people thinks always and must add the viewpoint that the Mn element just can be prepared the sacrificial magnesium alloy anode that meets the ASTM standard, add the more cheap zinc of cost and change into, and the current efficiency of the high-potential sacrificial magnesium alloy anode of interpolation zinc of the present invention and current potential surpass the regulation of present ASTM standard.Has more wide application prospect.
Description of drawings
Fig. 1 is the current efficiency of the pairing high-potential sacrificial magnesium alloy anode of manganese of different content.
Fig. 2 is the current efficiency of the pairing high-potential sacrificial magnesium alloy anode of zinc of different content.
Embodiment
The high-potential sacrificial magnesium alloy anode sample of the sample that does not add manganese by method preparation of the present invention, the sample that adds manganese and interpolation zinc will be specifically described below.By testing the electrical property of above-mentioned sample, show that the electrical property of the above-mentioned sample for preparing by method of the present invention all meets or exceeds the regulation of ASTM standard, especially zinciferous high-potential sacrificial magnesium alloy anode sample, its electrical property is better than the regulation of ASTM standard.
At first the high-potential sacrificial magnesium alloy anode of manganese is not added in preparation.What do not add wherein that the starting material of the high-potential sacrificial magnesium alloy anode of manganese, zinc adopt is the crude magnesium of my company's direct production, its chemical ingredients (percentage ratio wt% by weight) is: Al≤0.006%, Si≤0.0078%, Mn≤0.015%, Fe≤0.0018%, Ni≤0.0003%, Cu≤0.0015%, the single content of other impurity is not more than 0.01%, and surplus is Mg.Concrete preparation method is as follows: magnesium ingot is toasted after the preheating, put it in the crucible, melt at 720 ℃; After fusing is finished, carry out refining at 730 ℃ of control melts, refining time is 15 minutes; Leave standstill insulation 40 minutes at 720 ℃ then; Under this temperature, melt is cast to coagulation forming in the mould (for example, metal die) afterwards.Sampling is also carried out electric performance test (for example, adopting the G97 method), and test result is: current potential reaches-1.72V, and current efficiency is 55.8%.
Then, the high-potential sacrificial magnesium alloy anode of manganese is added in preparation.What the starting material of the high-potential sacrificial magnesium alloy anode of this interpolation manganese adopted is the crude magnesium of my company's direct production, its chemical ingredients (percentage ratio wt% by weight) is: Al≤0.006%, Si≤0.0078%, Mn≤0.015%, Fe≤0.0018%, Ni≤0.0003%, Cu≤0.0015%, the single content of other impurity is not more than 0.01%, and surplus is Mg.Concrete preparation method is as follows: magnesium ingot is toasted after the preheating, put it in the crucible, melt at 720 ℃; After fusing is finished, add manganese powder to melt, so that manganese content reaches 0.1% at 760 ℃; Control melt afterwards and carry out refining at 740 ℃, refining time is 15 minutes; Leave standstill insulation 40 minutes at 720 ℃ then, under this temperature, melt is cast to coagulation forming in the mould (for example metal die) afterwards.Sampling is also carried out electric performance test.Test result is: current potential reaches-1.72V, and current efficiency is 52%, as shown in Figure 1.
In addition, also having prepared manganese content is 0.5% high-potential sacrificial magnesium alloy anode.This manganese content is that the starting material of 0.5% high-potential sacrificial magnesium alloy anode are identical with the starting material of above-mentioned high-potential sacrificial magnesium alloy anode, what adopt is the crude magnesium of my company's direct production, its chemical ingredients (percentage ratio wt% by weight) is: Al≤0.006%, Si≤0.0078%, Mn≤0.015%, Fe≤0.0018%, Ni≤0.0003%, Cu≤0.0015%, the single content of other impurity is not more than 0.01%, and surplus is Mg.Its preparation method is as follows: magnesium ingot is toasted after the preheating, put it in the crucible, melt at 720 ℃; After fusing is finished, add manganese powder to melt, so that manganese content reaches 0.5% at 760 ℃; Control melt afterwards and carry out refining, refining time 15 minutes at 740 ℃; Leave standstill insulation 40 minutes at 720 ℃ then, under this temperature, melt is cast to coagulation forming in the mould afterwards.The test of electrical property is carried out in sampling.Test result is: current potential reaches-1.70V, and current efficiency is 51.4%.The high-potential sacrificial magnesium alloy anode of various manganese content (for example, manganese content is respectively 0.1%, 0.2%, 0.3%, 0.4% and 0.7%) that adopted method for preparing in addition.And the electrical property of the high-potential sacrificial magnesium alloy anode of prepared various manganese content tested, test result as shown in Figure 1, its current efficiency is all greater than 50%, and current potential all reaches-more than the 1.70V, satisfy the sacrificial magnesium alloy anode standard A STM843-1993 (2003) of the U.S..
Though the electrical property of the high petential magnesium alloy sacrifice sun of above-mentioned interpolation manganese prepared in accordance with the present invention satisfies sacrificial magnesium alloy anode standard A STM843-1993 (2003), because the fusing point of manganese is higher, the adding technology more complicated, and the manganese price is expensive.So manufacturing cost and simplified manufacturing technique in order to reduce sacrificial magnesium alloy anode, the zinc that we are lower with fusing point, price is more cheap substitutes manganese, has prepared the high-potential sacrificial magnesium alloy anode that adds zinc.The starting material of the high-potential sacrificial magnesium alloy anode of interpolation zinc are identical with above-mentioned sacrificial magnesium alloy anode, what adopt is the crude magnesium of my company's direct production, its chemical ingredients (percentage ratio wt% by weight) is: Al≤0.006%, Si≤0.0078%, Mn≤0.015%, Fe≤0.0018%, Ni≤0.0003%, Cu≤0.0015%, the single content of other impurity are not more than 0.01%, and surplus is Mg.The preparation method of high-potential sacrificial magnesium alloy anode who adds zinc is as follows: magnesium ingot is toasted after the preheating, put it in the crucible, melt at 720 ℃.After fusing is finished, add zinc ingot metal to melt, so that zinc content reaches 0.05% 690-750 ℃ (being preferably 740 ℃); Control melt afterwards and carry out refining, refining time 10-30 minute (being preferably 15 minutes) at 740 ℃; Leave standstill 20-60 minute (being preferably 40 minutes) of insulation 700-740 ℃ (being preferably 720 ℃) then, under this temperature, melt is cast to coagulation forming in the mould afterwards.Electric performance test is carried out in sampling.Test result is: current potential reaches-1.73V, and current efficiency was 61.8% (as shown in Figure 2).Can know from this test result and to find out, this zinc content is that the electrical property of 0.05% high-potential sacrificial magnesium alloy anode is better than sacrificial magnesium alloy anode standard A STM843-1993 (2003), and its current efficiency is far above the current efficiency of manganiferous sacrificial magnesium alloy anode.
In addition, the present invention also adopts with above-mentioned manufacturing zinc content is that the method for 0.05% high-potential sacrificial magnesium alloy anode identical method has been made zinc content and is respectively 0.2%, 0.4%, 0.6%, 1.0% high-potential sacrificial magnesium alloy anode, and has tested the electrical property of the different high-potential sacrificial magnesium alloy anode of these zinc content.Test result shows that the current potential of these zinciferous high-potential sacrificial magnesium alloy anodes all reaches-1.70V, and Fig. 2 shows the test result of the current efficiency of these zinciferous high-potential sacrificial magnesium alloy anodes.As shown in Figure 2, smaller or equal to 0.4% high-potential sacrificial magnesium alloy anode, its current efficiency satisfies the regulation of the sacrificial magnesium alloy anode standard A STM843-1993 (2003) of the U.S. all greater than 50% for zinc content.
In sum, the high-potential sacrificial magnesium alloy anode of manganese content 0% to 0.5% prepared in accordance with the present invention and zinc content all satisfy the electrical property of sacrificial magnesium alloy anode standard A STM843-1993 (2003) regulation of the U.S. smaller or equal to the electrical property of 0.4% high-potential sacrificial magnesium alloy anode, and compare with the existing manganiferous high-potential sacrificial magnesium alloy anode that satisfies above-mentioned standard, the low cost of manufacture and the manufacturing process of high-potential sacrificial magnesium alloy anode of the present invention are simple.
Claims (2)
1. high-potential sacrificial magnesium alloy anode, it is characterized in that, the chemical ingredients of this high-potential sacrificial magnesium alloy anode is by percentage to the quality: Zn0.05%-0.4%, Al≤0.01%, Si≤0.02%, Mn≤0.05%, Fe≤0.03%, Ni≤0.003%, Cu≤0.005%, all the other are Mg, and the current potential of this high-potential sacrificial magnesium alloy anode is greater than-1.70V, and current efficiency is greater than 50%.
2. the manufacture method of a high-potential sacrificial magnesium alloy anode comprises the steps:
Getting chemical ingredients is Al≤0.01%, Si≤0.02%, Mn≤0.05%, Fe≤0.03%, Ni≤0.003%, Cu≤0.005%, and all the other are the magnesium ingot of Mg, toast preheating;
Magnesium ingot after the baking preheating is put into crucible, carry out melting at 720 ℃ and make it become melt;
After the melting, add zinc ingot metal to melt, so that zinc content is smaller or equal to 0.4% more than or equal to 0.05 at 690-750 ℃;
Afterwards, the control melt carries out refining under 740 ℃ temperature, and refining time is 10-30 minute;
After refining is finished, melt temperature is controlled at 700-740 ℃, insulation was left standstill 20-60 minute; And
Under 700-740 ℃ of temperature, melt is cast to coagulation forming in the mould.
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| JPH09310131A (en) * | 1996-05-21 | 1997-12-02 | Sumikou Boshoku Kk | Production of magnesium alloy for voltaic anode |
| CN101225521A (en) * | 2007-01-16 | 2008-07-23 | 维恩克材料技术（北京）有限公司 | Water heater magnesium-alloy anode material having sterilization function |
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2008
- 2008-07-29 CN CN2008101408440A patent/CN101638786B/en active Active
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2009
- 2009-06-30 WO PCT/CN2009/072564 patent/WO2010012184A1/en active Application Filing
Patent Citations (3)
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|---|---|---|---|---|
| US6251240B1 (en) * | 1999-01-15 | 2001-06-26 | Korea Institute Of Science And Technology | Mg-Ca sacrificial anode |
| CN1263167A (en) * | 1999-02-08 | 2000-08-16 | 洛阳华陵镁业有限公司 | Technological process for adding manganese in magnesium-manganese sacrifical anode alloy |
| CN1718858A (en) * | 2005-07-23 | 2006-01-11 | 太原理工大学 | High petential magnesium alloy sacrificial anode material and its manufacturing method |
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| 宋永安等.高性能MAZ镁合金牺牲阳极的研究.镁合金材料及应用.2002,632-635. * |
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| CN101638786A (en) | 2010-02-03 |
| WO2010012184A1 (en) | 2010-02-04 |
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