CN102925902A - Method for controlling electrochemical performance of aluminum anode with high iron tramp content - Google Patents
Method for controlling electrochemical performance of aluminum anode with high iron tramp content Download PDFInfo
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- CN102925902A CN102925902A CN2012104219146A CN201210421914A CN102925902A CN 102925902 A CN102925902 A CN 102925902A CN 2012104219146 A CN2012104219146 A CN 2012104219146A CN 201210421914 A CN201210421914 A CN 201210421914A CN 102925902 A CN102925902 A CN 102925902A
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Abstract
The invention relates to a method for controlling the electrochemical performance of an aluminum anode with high iron tramp content. The method comprises the following steps: adding Mn and Si with proper quantity in a microalloying way to reduce the bad influence of element Fe, building an inherent proportioning relationship between Al-Zn-In system anode alloy element with high iron tramp content and impurity elements, wherein the range of the major element ingredient and the content range of impurities Cu, Fe and Si is as follows: the content of Zn is 5%-6.5%, the content of In is 0.015%-0.020%, Mn is less than or equal to 0.20%, Fe is less than or equal to 0.20%, Si is less than or equal to 0.15%, and Cu is less than or equal to 0.01%, wherein the unit is weight percentage. According to the method provided by the invention, the effective way for solving the defect of the electrochemical performance of the Al-Zn-In system anode material with high iron tramp content can be obtained. Compared with other aluminum alloy sacrificial anodes, the method can reduce the level of the applicable raw material and the requirement of Fe impurity content in large-scale production, and can lower the manufacture cost. The ternary Al-Zn-In sacrificial anode designed according to the inherent proportioning relationship is good in electrochemical performance in the laboratory conventional test and the practical simulation test.
Description
Technical field:
The present invention relates to a kind of improvement technology of sacrificial aluminium alloy anode, be specially a kind of electrochemical behavior of aluminum anode in alkaline control method of high ferro foreign matter content, be applicable to the galvanic protection field of steel marine structure.
Background technology:
The advantages such as that sacrificial aluminium alloy anode has is lightweight, electrical capacity is large, cheap have obtained using more and more widely in the protection of boats and ships, maritime facilities etc.The quality of the chemical property of aluminium alloy sacrificial anode material depends primarily on kind, content, existence form and the distribution of aluminum anode interalloy element, and the performance that the content of impurity also can antianode exerts an influence.
Aluminium has enough negative current potential (standard potential for-1.66(vs.SCE)) and higher thermodynamic activity, and density is little, and it is large that electric weight occurs, and raw material is easy to get, cheap, is the ideal material of making sacrificial anode.But the passivation that fine aluminium is intrinsic, its surface generates fine and close Al easily
2O
3Film causes anode potential to raise, the steady potential pact in seawater-0.78V(vs.SCE), do not reach theoretic electropotential.In order to make the aluminium can be as a kind of electrode materials of practicality, scholar both domestic and external have carried out a large amount of research work.Research and practice shows: by adding some alloying element (such as Zn ﹑ Hg ﹑ In ﹑ Sn ﹑ Cd ﹑ Si ﹑ Mg etc.), aluminium is carried out alloying, can limit or stop the aluminium surface to form fine and close continuously oxide film, promote its surface active, make alloy have negative current potential and higher current efficiency.These main alloys add element according to the different mechanism of action that is risen in aluminum anode, be divided on paper two groups: depassivator and properties-correcting agent.Principal element commonly used as depassivator has: In, Hg and Sn.The characteristic that shows behind these elements and the aluminium alloying is considered to play obvious effect in the activation of aluminium sacrificial anode.Four kinds of modal properties-correcting agent are Zn, Mg, Bi, Cd.The characteristic that properties-correcting agent shows is considered to improve the performance of aluminium.
Modal impurity is iron, copper, silicon in sacrificial aluminium alloy anode.It has been generally acknowledged that these impurity are the actual capacitances that are harmful to and can reduce aluminium sacrificial anode, therefore in the production process of aluminum anode, extremely emphasize to use the rafifinal raw material.Exist inevitably the impurity such as Fe, Cu, Si in the commercial-purity aluminium raw material, the performance that these impurity have been proved to be aluminum anode is harmful to, and particularly Fe and Cu have remarkably influenced to electropotential and the current efficiency of aluminum anode.Iron is as impurity antianode performance, and especially the antianode electrical capacity has very adverse influence.Fe is the main segregation phase that corrosion microbattery negative electrode is provided for it mutually, and this is that this inclusion is negative electrode with respect to the matrix of aluminium owing to formed the inclusion of intermetallic compound.Because the minute corrosive cell that these inclusiones form has significantly reduced the electrical capacity of anode.Also be to eliminate these impurity to the impact of electrochemical behavior of aluminum anode in alkaline so improve a main aspect of electrochemical behavior of aluminum anode in alkaline.Can be by adding alloying elements, make itself and Fe and Cu form compound, thereby mask their original negative interactions, or add some elements and can improve its microtexture, make the disadvantageous effect of the elements such as Fe, Cu, Si be reduced to minimum level, thereby improve the chemical property of aluminum anode.The element that adds at present mainly contains Mn, Bi, Co etc.
Antianode, the metal cost proportion in the whole cost of anode is maximum.Raw-material selection should be satisfied the content of impurity, also wants the reduce material rate and reduces cost.Change along with iron contamination content (GB/T1196-2002) in the present domestic aluminum raw material, Variation Features according to aluminum current raw material iron contamination, the electrochemical behavior of aluminum anode in alkaline control method that needs a kind of high ferro foreign matter content of exploitation, purpose is that acquisition is a kind of efficient, cheaply the Al-Zn-In series sacrificial anode.
Summary of the invention:
The object of the invention is to overcome the shortcoming of prior art, a kind of electrochemical behavior of aluminum anode in alkaline control method of high ferro foreign matter content is provided.It is alloy sacrificial anode electrochemical performance adverse effect to Al-Zn-In that the method adopts the alloying proportioning of suitable material to reduce high Fe content impurity.
In order to realize the foregoing invention purpose, technical scheme of the present invention is: take GB Al-Zn-In-(Cd) sacrificial aluminium alloy anode prescription as the basis, according to up-to-date domestic raw material standard optimal alloy elemental range, the disadvantageous effect that adds an amount of Mn and Si impurity reduction element of Fe by microalloying, the Al-Zn-In that has set up a kind of high ferro foreign matter content is the inherent proportion relation between anode alloy element and impurity element, its principal element composition range and impurity Cu, Fe, the content range of Si is (following all be weight percentage): the content of Zn is 5%～6.5%, the content of In is 0.015%～0.020%, Mn≤0.20%; Fe≤0.20%; Si≤0.15%; Cu≤0.01% because the fusing point of Mn and Si is higher, needs during melting to add with the form of Al-Mn alloy and Al-Si alloy.
The ternary Al-Zn-In sacrificial anode designed according to above-mentioned inherent proportion relation all shows good chemical property in testing laboratory's conventionally test and real extra large simulation test: open circuit potential≤-1.115V, operating potential-1.050～-1.110V between, actual capacitance 〉=2600A.h/kg.
Al-Zn-In aluminum alloy anode of the present invention to steel plate under water average cathodic protection potential remain on-0.95V(SCE) about.
By the inventive method, the high ferro that achieves a solution foreign matter content Al-Zn-In is the deteriorated effective way of anode material chemical property.The Fe element is detrimental impurity, and the increase of its content can cause the Efficiency Decreasing of anode, and current potential is shuffled, the inhomogeneous even generation intergranular corrosion of erosion profile; Zn unit have an optimum addition range, and in this scope, the Zn element can play and make that current potential is negative to be moved, and improves the effect of dissolving situation; The content of In element also must be controlled in the suitable scope, current potential is born moved, and improves the surface dissolution situation of anode; Mn is as alloying element, when Fe content≤0.20%, can improve the current efficiency of anode and make that operating potential is negative to be moved, and the Fe too high levels then impact of Mn antianode performance is also less.Add an amount of Si element and can reduce the alloy casting defective.
Compared with prior art, the present invention has developed a kind of electrochemical behavior of aluminum anode in alkaline control method of high ferro foreign matter content, determined that efficient aluminium-zinc-indium is the optimal components scope of alloy anode principal element, can use iron level≤0.20%(% by weight) the aluminium of high ferro foreign matter content prepare, thereby obtain high-performance, aluminum alloy anode material cheaply.The inventive method can be reduced in the requirement of applicable starting material grade and Fe foreign matter content in the scale operation, further save the anode manufacturing cost, help to solve the cost of alloy and the relation between performance, solve the problem of the Fe impurity element control that runs in the actual production.
Embodiment:
Below by specific embodiment the inventive method is further elaborated:
Embodiment 1,
A kind of Al-Zn-In of high ferro foreign matter content is anode, the content range of its principal element composition range and impurity Cu, Fe, Si is (following all be weight percentage): the content of Zn is that the content of 5%～6.5%, In is 0.015%～0.020%(Mn≤0.20%; Fe≤0.20%; Si≤0.15%; Cu≤0.01%).
Because the fusing point of Mn and Si is higher, need during melting to add with the form of Al-Mn alloy and Al-Si alloy.
Embodiment 2, conventional electrochemical property test
With reference to GB GB/T17848-1999 sacrificial anode electrochemical performance testing standard the designed anode of the present invention is carried out electrochemical property test.Test(ing) medium is Qingdao Area beach natural sea-water, and reference electrode is saturated calomel electrode (SCE).
The actual chemical ingredients of melted anode adopts PE3300A type Atomic Absorption Spectroscopy AAS to analyze, and analysis ingredient and design mix are basically identical.
The continuous current test is the standard method of estimating the anode electrochemical performance, and the self-discharge experiment then more near the actual working state of anode, is therefore adopted two kinds of methods to combine and estimated the chemical property of designed anode.Test result shows, and is as shown in table 1 according to the chemical property of the designed ternary Al-Zn-In aluminum alloy anode of the inherent proportion relation of the alloying element of inventing and impurity element:
The chemical property of table 1.Al-Zn-In aluminum alloy anode
Aluminium sacrificial anode is carried out to the galvanic protection simulation test of carbon steel in embodiment 3, real sea, Qingdao
The corrosion electrochemistry performances such as the protection potential of mensuration anode, generation electric current, surface dissolution pattern, corrosion rate are determined galvanic protection effects such as protected structural defence rates.
Test materials: sacrificial anode
Al+5～6.5%Zn+0.015～0.020%In
Starting material: Al ingot: Fe≤0.20%, Si≤0.10%, Cu≤0.01%, Mn≤0.20%
Cathode material: Q235B steel plate
Test method: test is with reference to GB6384-86 boats and ships and the oceanographic engineering sea water corrosion test method of metallic substance in natural surroundings, GB/T15748-95 marine metal material galvanizing corrosion test method; GB/T 3855-99 seagoing vessel Sacrificial Anode Protection Design and installation;
Test specification: the sacrificial anode sample is 80 * 20 * 5mm, is of a size of 40 * 20 * 5mm, and the specification of Q235B steel is 200 * 200 * 2.5mm, and the galvanic protection ratio of cathodic to anodic area is about 40:1.
The simulation test experiment cycle is three months.
Test-results shows (table 2): (1) anode surface dissolving morphology change: dissolving evenly.(2) anode material is to the cathodic protection potential of steel: steel plate underwater cathode protection average potential remains on-0.95V(SCE).
The galvanic protection performance of table 2.Al-Zn-In aluminum alloy anode
Claims (3)
1. the electrochemical behavior of aluminum anode in alkaline control method of a high ferro foreign matter content, it is characterized in that: the disadvantageous effect that adds Mn and Si impurity reduction element of Fe by microalloying, the Al-Zn-In that has set up a kind of high ferro foreign matter content is the inherent proportion relation between anode alloy element and impurity element, the content range of its principal element composition range and impurity Cu, Fe, Si is: the content of Zn is 5%～6.5%, the content of In is 0.015%～0.020%, Mn≤0.20%, Fe≤0.20%, Si≤0.15%, Cu≤0.01%, more than all be weight percentage; Need during melting to add Mn and Si with the form of Al-Mn alloy and Al-Si alloy.
2. the electrochemical behavior of aluminum anode in alkaline control method of a kind of high ferro foreign matter content according to claim 1, it is characterized in that: the chemical property of Al-Zn-In aluminum alloy anode is: open circuit potential≤-1.115V, operating potential-1.050～-1.110V between, actual capacitance 〉=2600A.h/kg.
3. the electrochemical behavior of aluminum anode in alkaline control method of a kind of high ferro foreign matter content according to claim 1 is characterized in that: the Al-Zn-In aluminum alloy anode to steel plate under water average cathodic protection potential remain on-0.95V.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106637231A (en) * | 2016-10-18 | 2017-05-10 | 青岛双瑞海洋环境工程股份有限公司 | Aluminum alloy anode suitable for high-resistivity environment and preparation method thereof |
| CN108808007A (en) * | 2018-06-01 | 2018-11-13 | 安徽工业大学 | A kind of preparation method of the aluminium-air cell anode material of high Fe content |
| CN109244442A (en) * | 2018-08-08 | 2019-01-18 | 中南大学 | A kind of porous anodized aluminum and aluminium-air cell |
| CN113621857A (en) * | 2021-10-11 | 2021-11-09 | 山东裕航特种合金装备有限公司 | Preparation method and application of aluminum alloy sacrificial anode |
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| CN102154651A (en) * | 2011-03-30 | 2011-08-17 | 李振国 | Sacrificial anode for deep sea environment and manufacturing method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102154651A (en) * | 2011-03-30 | 2011-08-17 | 李振国 | Sacrificial anode for deep sea environment and manufacturing method thereof |
Non-Patent Citations (1)
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| 马景灵: "微合金化铝基阳极材料的组织与性能", 《兰州理工大学博士学位论文》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106637231A (en) * | 2016-10-18 | 2017-05-10 | 青岛双瑞海洋环境工程股份有限公司 | Aluminum alloy anode suitable for high-resistivity environment and preparation method thereof |
| CN108808007A (en) * | 2018-06-01 | 2018-11-13 | 安徽工业大学 | A kind of preparation method of the aluminium-air cell anode material of high Fe content |
| CN109244442A (en) * | 2018-08-08 | 2019-01-18 | 中南大学 | A kind of porous anodized aluminum and aluminium-air cell |
| CN113621857A (en) * | 2021-10-11 | 2021-11-09 | 山东裕航特种合金装备有限公司 | Preparation method and application of aluminum alloy sacrificial anode |
| CN113621857B (en) * | 2021-10-11 | 2021-12-21 | 山东裕航特种合金装备有限公司 | Preparation method and application of aluminum alloy sacrificial anode |
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Application publication date: 20130213 |