CN101148767B - Aluminum-zinc-indium series sacrificial anode material - Google Patents
Aluminum-zinc-indium series sacrificial anode material Download PDFInfo
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- CN101148767B CN101148767B CN2007101898638A CN200710189863A CN101148767B CN 101148767 B CN101148767 B CN 101148767B CN 2007101898638 A CN2007101898638 A CN 2007101898638A CN 200710189863 A CN200710189863 A CN 200710189863A CN 101148767 B CN101148767 B CN 101148767B
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Abstract
The present invention belongs to the field of metal corrosion preventing technology and is especially one kind of Al-Zn-In sacrificial anode material comprising Zn 3.0-5.0 wt%, In 0.02-0.03 wt%, Mg 1.0 wt%, Ti 0.05-0.07 wt%, Si 0.08-0.10 wt%, impurity less than 0.15 wt% and Al for the rest. The Al-Zn-In sacrificial anode material prepared through an argon protected inductive smelting process has excellent chemoelectric performance, current efficiency higher than 92 %, practical electric capacity greater than 2650 A.hr/kg and homogeneous surface dissolving. It possesses high protecting performance on steel member operating in water environment or water-containing environment.
Description
Technical field
The invention belongs to the metal corrosion and protection field; be specifically related to a kind of aluminum-zinc-indium series sacrificial anode material, this aluminum-zinc-indium series sacrificial anode material can be implemented protection to being applied to the aqueous solution (fresh water, seawater, lake water, river) or containing the steel and iron member (boats and ships, offshore production drilling unit, oil transportation gas transmission circulating water pipeline, bridge, underground communication cable etc.) of working in the aqueous environment (as earth, seabeach etc.).
Background technology
Metallic corrosion is one of principal mode of hardware and component damage, and the galvanic anode protection method is to use one of anti-corrosion method very widely now.This method is that protected metal (negative electrode) is linked to each other with the metal (anode) more negative than its current potential; two kinds of metals are in the same electrolyte (soil, seawater, natural water etc.), by means of the electric current that has big potential difference and the continuous active dissolution of sacrificial anode material to be produced between sacrificial anode material and the protected metal protected metal are carried out cathodic polarization and reach the purpose that suppresses metallic corrosion.Sacrificial protection since its have do not need additional power source and personal management, do not disturb the adjacent metal facility, the electric current dispersive ability is good, equipment simple, easy construction, do not need often to safeguard advantage such as detection, so present this method application is very extensive.The main performance index of sacrificial anode material has: the actual capacitance height is that unit mass output electric weight is big; The current efficiency height; Dissolution evenness is good; Cheap; Nontoxic.
Sacrificial anode material commonly used at present has Magnuminium, zinc base alloy and aluminium alloy.Aluminum alloy anode material research starting is than later, but development rapidly, and main because aluminium alloy has particular performances: the actual capacitance of aluminium alloy is that the unit mass discharge capacity is 3.6 times of zinc base alloy, 1.5 times of Magnuminium.But as its year consumption of sacrificial anode material is 1/3 of zinc base alloy, Magnuminium anodic 1/2.In addition, aluminium alloy density is less, current efficiency is higher, it is placed in the middle, cheap and easy to get to drive current potential, is the maximum metallic element of content in the earth's crust, and is nuisanceless again, so become sacrificial anode material the most suitable in the periodictable.Yet fine aluminium can cause the passivation of aluminium at its fine and close hydrous oxide of surface formation in the aqueous solution, so fine aluminium can not be used as sacrificial anode material.In order to eliminate the oxide film on aluminium surface, adopt alloying process usually, promptly in aluminium, add alloying elements such as zinc, indium, mercury, tin.The representative aluminium alloy sacrificial anode material of having succeeded in developing and having used has Al-Zn-Hg system, Al-Zn-Sn system, and Al-Zn-In system, but in actual applications, these anode materials all exist weak point.As Al-Zn-Hg is that anode contains small amount of mercury, and toxicity is bigger, and such alloy bans use of both at home and abroad at present.Al-Zn-Sn is an anodic current efficiency only about 50%, and uses its chemical property also will further reduce for a long time, and this type of sacrificial anode material also seldom uses at present.
Nowadays most widely used is that Al-Zn-In is an alloy, as the Al-2.5Zn-0.02In alloy sacrificial anode material patent of applications such as Japanese Sakano, current efficiency 〉=84%, actual capacitance 〉=2400Ahkg
-1Domestic and international most of researchist is to be to change component content on the alloy basis and add alloying element to improve the current efficiency and the actual capacitance of material at Al-Zn-In.Yoshino etc. add Sn in the Al-Zn-In anode, current efficiency 〉=85%, actual capacitance 〉=2400Ahkg
-1GavalumIII (Al-3Zn-0.015In-0.1Si) the alloy sacrificial anode material patent of U.S. DOW (Dow) company application, current efficiency 〉=86%, actual capacitance 〉=2500Ahkg
-1China Chongqing non-ferrous metal institute is also to do a lot aspect the alloy at Al-Zn-In, has applied for Al-4Zn-0.03In-0.05Sn-0.5Mg alloy patent, current efficiency 〉=85%, actual capacitance 〉=2400Ahkg
-1These researchs and patent all are by selecting chemical properties such as suitable element alloyed current efficiency that improves aluminium alloy and actual capacitance.But current efficiency is not high on the one hand for above these researchs and the related material of patent, all about 85%; On the other hand, the electrical capacity of these materials is not high yet, and is purpose with the current efficiency that improves material mainly all, the surface dissolution situation when having ignored anode material work.Anode material is when work, and corrosion surface usually presents roughness, dissolves inhomogeneous.This concavo-convex uneven dissolution can shorten the work-ing life of anode material greatly.
Summary of the invention
The present invention seeks to propose a kind of aluminum-zinc-indium series sacrificial anode material, improve aluminium alloy sacrificial anode material chemical property (current efficiency by microalloying, actual capacitance), and improve its surface dissolution homogeneity, thereby when reducing the sacrificial anode material actual amount, improve its utilization ratio.
The present invention adds magnesium, titanium and the element silicon of trace based on the Al-Zn-In sacrificial anode material, and purpose is to improve the chemical property of Al-Zn-In series sacrificial anode material and improve its surface dissolution homogeneity.Major ingredient is: be raw material with aluminium, add element zinc (Zn), indium (In), also added magnesium (Mg), titanium (Ti), silicon (Si) element, add element weight percent be: Zn:3.0～5.0%; In:0.02～0.03%; Mg:1.0%; Ti:0.05～0.07%; Si:0.08～0.10%; Foreign matter content≤0.15%.
This anode adopts induction melting, uses argon shield, also available other melting method; with required aluminium ingot; zinc ingot metal, indium grain, magnesium ingot; the titanium ingot; silicon single crystal is put into crucible, and heating crucible limit, limit rotates automatically, and molten metal is mixed; tapping casting, then with the ingot casting that is cast in 500～550 ℃ of anneal.Can obtain operating potential stable (1.0～-1.1V (SCE)), current efficiency height (〉=92%), actual capacitance height (〉=2650Ahkg-
1), the uniform high-performance aluminium alloy sacrificial anode material of surface dissolution.
The present invention considers with the chemical property that improves the Al-Zn-In sacrificial anode material and improves its dissolution evenness from the microalloying aspect: add Trace Silicon, titanium and magnesium the Al-Zn-In alloy.Impurity element iron in the aluminium alloy is dissolved in aluminum substrate hardly, be present in the aluminum substrate but be big bulk with the form of iron content second phase, this phase current potential calibration causing aluminum anode causes current efficiency to reduce from corrosion, and big block iron phase causes that also the alloy surface dissolving is inhomogeneous.In the Al-Zn-In alloy, add Trace Silicon, be because silicon and iron can be preferential in conjunction with form siliceous and iron second mutually, this phase current potential is than not siliceous second negative mutually of iron content, the corrosion certainly that can slow down aluminum anode, thereby raising anodic current efficiency; Adding trace amount of titanium and magnesium can refinement aluminium alloy crystal grain, titanium in aluminium alloy easily with aluminium formation TiAl
3Intermetallic compound, magnesium can form Mg in alloy
2Al
3, MgZn
2And Mg
2The Si intermetallic compound, dystectic TiAl
3And Mg
2The Si compound has the effect of crystal grain thinning, Mg
2Al
3And MgZn
2Compound has dissolved activation as the second relative alloy.The add-on of these micro alloying elements if add-on is few, does not have due effect within certain scope, if add-on is big, form the second bigger phase of a large amount of shapes, reduces current efficiency and makes the dissolution evenness variation.The current efficiency and the actual capacitance of alloy can be obviously improved by microalloying, the surface dissolution homogeneity of alloy can also be improved.
Aluminum alloy anode material of the present invention is compared with existing Al-Zn-In anode material, summarize to get up to have the following advantages: (1) has prepared a kind of novel aluminum alloy sacrificial anode material, activation performance is good, reaches the zone of reasonableness (1.0～-1.1V (SCE)) of protection potential; (2) novel sacrificial anode material has added micro-silicon, magnesium and titanium elements, slows down the harmful effect of impurity element iron, refinement alloy grain, improved the current efficiency and the actual capacitance of aluminum anode; (3) anode material has obviously improved the anodic chemical property and has improved tissue by microalloying, and its current efficiency reaches more than 92%, and actual capacitance reaches 2650Ahkg
-1More than.It is evenly functional that the aluminum alloy anode material performance of the present invention preparation all is better than the anode material performance, particularly surface dissolution of prior art for preparing, and have good practical function in application.
Embodiment
Embodiment 1:
Each composition weight percent of aluminum-zinc-indium series sacrificial anode material is: Zn:3.0%; In:0.025%; Mg:1.0%; Ti:0.06%; Si:0.08%; All the other are aluminium, foreign matter content≤0.15%.The required composition of melting is put into ZGJL0.01-40-4 induction melting furnace crucible; granular composition is wrapped up by aluminium foil; charge into argon gas; crucible is heated to 760 ± 5 ℃ of insulation 5～6min under argon shield; crucible rotates automatically during insulation; in preheating cast iron mould, pour into pole (150 ℃ of preheating 0.5h of cast iron mould); take out behind the cooling 0.5h; the ingot casting that is cast into is put into SX-4-40 molding box formula resistance furnace slowly be warming up to 550 ℃ with 5 ℃/min speed; insulation 4h; cool to room temperature with the furnace, make aluminium alloy sacrificial anode material.The anode material of preparation is used the chemical property of CHI660C electrochemical workstation beta alloy according to the electrochemical property test method of GT/T4948-2002 standard code.This alloy current efficiency is 92.6%, and actual capacitance is 2652Ahkg
-1, surface dissolution is even, and corrosion product easily comes off.Concrete electrochemical properties sees Table 1.
Embodiment 2:
Each composition weight percent of aluminum-zinc-indium series sacrificial anode material is: Zn:5.0%; In:0.02%; Mg:1.0%; Ti:0.05%; Si:0.10%; All the other are aluminium, foreign matter content≤0.15%.The required composition of melting is put into ZGJL0.01-40-4 induction melting furnace crucible; granular composition is wrapped up by aluminium foil; charge into argon gas; crucible is heated to 760 ± 5 ℃ of insulation 5～6min under argon shield; crucible rotates automatically during insulation; in preheating cast iron mould, pour into pole (150 ℃ of preheating 0.5h of cast iron mould); take out behind the cooling 0.5h; the ingot casting that is cast into is put into SX-4-40 molding box formula resistance furnace slowly be warming up to 510 ℃ with 5 ℃/min speed; insulation 8h; cool to room temperature with the furnace, make aluminium alloy sacrificial anode material.To the anode material of preparation according to the electrochemical property test method of GT/T4948-2002 standard code with CHI660C electrochemical workstation beta alloy chemical property.This alloy current efficiency is 94.5%, and actual capacitance is 2705Ahkg
-1, surface dissolution is even, and corrosion product easily comes off.Concrete electrochemical properties sees Table 1.
Embodiment 3:
Each composition weight percent of aluminum-zinc-indium series sacrificial anode material is: Zn:4.0%; In:0.03%; Mg:1.0%; Ti:0.07%; Si:0.09%; All the other are aluminium, foreign matter content≤0.15%.The required composition of melting is put into ZGJL0.01-40-4 induction melting furnace crucible; granular composition is wrapped up by aluminium foil; charge into argon gas; crucible is heated to 760 ± 5 ℃ of insulation 5～6min under argon shield; crucible rotates automatically during insulation; in preheating cast iron mould, pour into pole (150 ℃ of preheating 0.5h of cast iron mould); take out behind the cooling 0.5h; the ingot casting that is cast into is put into SX-4-40 molding box formula resistance furnace slowly be warming up to 500 ℃ with 5 ℃/min speed; insulation 10h; cool to room temperature with the furnace, make aluminium alloy sacrificial anode material.To the anode material of preparation according to the electrochemical property test method of GT/T4948-2002 standard code with CHI660C electrochemical workstation beta alloy chemical property.This alloy current efficiency is 93.8%, and actual capacitance is 2679Ahkg
-1, surface dissolution is even, and corrosion product easily comes off.Concrete electrochemical properties sees Table 1.
Embodiment 4:
Each composition weight percent of aluminum-zinc-indium series sacrificial anode material is: Zn:3.5%; In:0.025%; Mg:1.0%; Ti:0.06%; Si:0.10%; All the other are aluminium, foreign matter content≤0.15%.The required composition of melting is put into ZGJL0.01-40-4 induction melting furnace crucible; granular composition is wrapped up by aluminium foil; charge into argon gas; crucible is heated to 760 ± 5 ℃ of insulation 5～6min under argon shield; crucible rotates automatically during insulation; in preheating cast iron mould, pour into pole (150 ℃ of preheating 0.5h of cast iron mould); take out behind the cooling 0.5h; the ingot casting that is cast into is put into SX-4-40 molding box formula resistance furnace slowly be warming up to 530 ℃ with 5 ℃/min speed; insulation 6h; cool to room temperature with the furnace, make aluminium alloy sacrificial anode material.The anode material of preparation is used the chemical property of CHI660C electrochemical workstation beta alloy according to the electrochemical property test method of GT/T4948-2002 standard code.This alloy current efficiency is 93.2%, and actual capacitance is 2661Ahkg
-1, surface dissolution is even, and corrosion product easily comes off.Concrete electrochemical properties sees Table 1.
By above embodiment as can be seen, aluminum-zinc-indium series sacrificial anode material of the present invention has high current efficiency and actual capacitance really, and the alloy surface dissolving evenly.
The chemical property of table 1 aluminum-zinc-indium series sacrificial anode material
| Anode material | Open circuit potential/V (SCE) | Operating potential/V (SCE) | Current efficiency/% | Actual capacitance/Ahkg -1 | The surface dissolution situation |
| Embodiment 1 | -1.070 | -1.062～-1.068 | 92.6. | 2652 | Dissolving is even, and corrosion product comes off automatically |
| Embodiment 2 | -1.075 | -1.065～-1.07 | 94.5 | 2705 | Dissolving is even, and corrosion product comes off automatically |
| Embodiment 3 | -1.073 | -1.063～-1.067 | 93.8 | 2679 | Dissolving is even, and corrosion product comes off automatically |
| Embodiment 4 | -1.072 | -1.063～-1.069 | 93.2 | 2661 | Dissolving is even, and corrosion product comes off automatically |
Claims (2)
1. aluminum-zinc-indium series sacrificial anode material, its major ingredient is: be raw material with aluminium, add element zinc, indium, it is characterized in that wherein also having added magnesium, titanium and element silicon; Add element weight percent be: zinc 3.0～3.5%, indium: 0.025～0.03%, magnesium: titanium 1.0%: 0.06～0.07%, silicon: 0.08～0.09%, foreign matter content≤0.15%.
2. aluminum-zinc-indium series sacrificial anode material according to claim 1 is characterized in that: major ingredient is an aluminium, and the weight percent that adds element is: zinc 3.0%, indium 0.025%, magnesium 1.0%, titanium 0.06%, silicon 0.08%.
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| CN101693999B (en) * | 2009-09-07 | 2011-02-09 | 河南科技大学 | Aluminum-zinc-tin system sacrificial anode material and preparation method thereof |
| CN102154651A (en) * | 2011-03-30 | 2011-08-17 | 李振国 | Sacrificial anode for deep sea environment and manufacturing method thereof |
| CN103088347B (en) * | 2012-12-27 | 2015-10-21 | 中国石油集团川庆钻探工程有限公司 | Storage tank coil pipe aluminium alloy sacrificial anode material and preparation method thereof |
| CN103792181A (en) * | 2013-11-08 | 2014-05-14 | 燕山大学 | Constant-current dissolution method for evaluating negative electrode protection performance of zinc-rich coating |
| CN106350824A (en) * | 2015-07-16 | 2017-01-25 | 东北大学 | Efficient aluminum alloy sacrificial anode for deep sea, and producing method thereof |
| CN105648445A (en) * | 2016-01-07 | 2016-06-08 | 广西大学 | Aluminum-zinc-indium-erbium sacrificial anode and preparation method thereof |
| CN108707909A (en) * | 2018-05-29 | 2018-10-26 | 中国科学院海洋研究所 | A kind of abyssal environment seven yuan of line aluminium alloy sacrificial anode materials and preparation method thereof |
| CN109781792B (en) * | 2019-03-12 | 2022-05-31 | 安徽工业大学 | Method for representing electrochemical activity of aluminum anode material through conductivity |
| WO2023167960A1 (en) * | 2022-03-04 | 2023-09-07 | Battelle Memorial Institute | Indium zinc-based alloy anodes forming porous structure for aqueous zinc batteries |
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