CN104060280A - Aluminum alloy sacrificial anode suitable for deep sea environment and high in current efficiency - Google Patents
Aluminum alloy sacrificial anode suitable for deep sea environment and high in current efficiency Download PDFInfo
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- CN104060280A CN104060280A CN201410311844.8A CN201410311844A CN104060280A CN 104060280 A CN104060280 A CN 104060280A CN 201410311844 A CN201410311844 A CN 201410311844A CN 104060280 A CN104060280 A CN 104060280A
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Abstract
The invention belongs to the technical field of corrosion prevention, and particularly relates to an aluminum alloy sacrificial anode suitable for the deep sea environment and high in current efficiency. According to the sacrificial anode, with aluminum as the matrix, 4.0-6.0wt% of zinc, 0.020-0.030wt% of indium, 0.05-0.10wt% of tin, 0.5-1.0wt% of magnesium and 0.05-1.0wt% of titanium are added, wherein the weight percentage of iron impurities is smaller than 0.050wt%, the weight percentage of copper is smaller than 0.010wt%, and the balance is the aluminum. The sacrificial anode is manufactured in a vacuum melting mode. As is shown in tests carried out in a simulated deep sea environment, the current efficiency of the sacrificial anode is larger than 92%, the open circuit potential of the sacrificial anode ranges from -1.05 to -1.20, the activation performance is good, dissolution is uniform, and corrosion products can fall off easily. The sacrificial anode can be applied to cathode protection for metal components used in the deep sea environment.
Description
Technical field
The invention belongs to aseptic technic field, be specifically related to a kind of sacrificial aluminium alloy anode that is applicable to have in deep-marine-environment high current efficiency.
Background technology
The cathode protection method of sacrificial anode is a kind of guard method conventional in current corrosion prevention.Its ultimate principle is that sacrificial anode material and protected material are linked together; sacrificial anode material current potential is lower than protected metal; the electric current that potential difference between dependence sacrificial anode and protected metal and sacrificial anode corrosion dissolution constantly occur and provide makes protected metal generation cathodic polarization, thereby protected corrosion of metal is suppressed.The corrosion that is exactly in short anode material is accelerated, and cathode material corrosion is suppressed, is therefore called the cathode protection method of sacrificial anode.That the cathode protection method of sacrificial anode has is simple to operate, cost is low, do not need the advantages such as special messenger safeguards, is widely used in corrosion of metal protection.The preparation of sacrificial anode material is most important link in the cathode protection method of sacrificial anode.
In ocean environment, the cathode protection method of sacrificial anode is current application the most a kind of method.The advantages such as sacrificial aluminium alloy anode has resource abundance, cost is low, density is little, be easy to processing, theoretical electrical capacity is large, therefore sacrificial aluminium alloy anode is widely used in the protection of ocean structure in recent years.Data about the Performance of Sacrificial Anode Using of neritic environment are many, also announced some and be applicable to the preparation method of the sacrificial anode of neritic environment in China's GB.Deep-marine-environment has the complex conditions such as pressure is large, temperature is low, dissolved oxygen amount is low, different from neritic environment of the corrosion in deep-marine-environment.Experimental results show that the existing sacrificial anode for neritic environment exists under deep-marine-environment condition that current efficiency is lower, current potential is shuffled, it is inhomogeneous to dissolve; and the phenomenons such as corrosion product difficult drop-off, cannot meet in deep-marine-environment the effectively requirement of protection of metallic facility.
Summary of the invention
1, technical problem to be solved by this invention is to provide a kind of sacrificial anode being applicable in deep-marine-environment, solves that the existing sacrificial anode current potential for deep-sea is unstable, current efficiency is low, it is inhomogeneous to dissolve and the problem such as cost is higher.The present invention be take aluminium and is carried out microalloying as matrix; make it in the environment of deep-sea high pressure, low temperature, hypoxemia, there is higher current efficiency, stable current potential and dissolve the features such as pattern is even, corrosion product easily comes off, for deep-sea hardware provides permanently effective protection.
2, for this reason, the present invention proposes a kind of new sacrificial anode component prescription, take aluminium as matrix, add zinc, indium, tin, magnesium, titanium alloy element, form hexa-atomic alloy, concrete composition proportion: (wt%): zinc 4.0 ~ 6.0%, indium 0.020 ~ 0.030%, tin 0.05 ~ 0.10%, magnesium 0.5 ~ 1.0%, titanium 0.05 ~ 0.10%, wherein impurity iron <0.050%, copper <0.010%, surplus is aluminium.
3, this sacrificial anode adopts the technique of vacuum metling, and because the fusing point of titanium is higher, the fusing point of magnesium is lower, for preventing that the too high magnesium that causes of Heating temperature from volatilizing.So first titanium is added together with aluminium, in vacuum smelting furnace, to be smelted into titanium content be 2.5% aluminum titanium alloy, then according to composition proportion, adds vacuum smelting furnace to smelt with other each pure metal, adopts induction stirring in smelting process.Smelt its naturally cooling of end relief and obtain casting rod, finally casting rod is processed into the desired size shape of experiment.
4, the Sacrificial Anode that the present invention is prepared by microalloying is that 8Mpa, temperature be the condition of 4 ℃ under carried out continuous current test experiments to sample at pressure according to GB GB17859/1999.Operating potential in simulated deep-sea environment is between-1.05 ~-1.10V (vs, Ag/AgCl, saturated KCl solution), and electrical capacity is greater than 2600Ah/kg, and current efficiency is greater than 92%.Be uniformly dissolved, corrosion product easily comes off, and indium content is lower, and without other harmful elements, environmental pollution is less.
Embodiment
Below with reference to specific embodiment, the present invention is further explained.
Embodiment mono-: label is sample D1.
Take aluminium as matrix, add zinc, indium, tin, magnesium, titanium alloy element, form hexa-atomic alloy, concrete composition proportion: (wt%): zinc 6.0%, indium 0.020%, tin 0.05%, magnesium 0.5%, titanium 0.05%, wherein impurity iron <0.050%, copper <0.010%, surplus is aluminium.First with fine aluminium and titanium sponge smelting, going out titanium content is 2.5% aluminum titanium alloy, then according to composition proportion, adds vacuum smelting furnace to smelt aluminum titanium alloy and other each pure metal, adopts induction stirring in smelting process.Smelt and finish its naturally cooling of relief, finally obtain casting rod.Casting rod is processed into the cylinder of Φ 16 * 28mm, surfaceness is 1.6, stamps therein the threaded hole of M3 * 8mm, in order to connect wire in a plane.Then with acetone oil removing, dry, weigh, take pictures, adopt afterwards epoxy sealing two planes, retain 14cm
2working area, make the present invention's laboratory sample used.The open circuit potential of sacrificial anode in deep-marine-environment be-1.100V (vs, Ag/AgCl, saturated KCl solution), and operating potential is-1.076V (vs, Ag/AgCl, saturated KCl solution), and current efficiency is 92.56%, and electrical capacity is 2633Ah/kg.Be uniformly dissolved, corrosion product easily comes off.
Embodiment bis-: label is sample D2.
Take aluminium as matrix, add zinc, indium, tin, magnesium, titanium alloy element, form hexa-atomic alloy, concrete composition proportion: (wt%): zinc 5.8%, indium 0.025%, tin 0.05%, magnesium 1.0%, titanium 0.10%, wherein impurity iron <0.050%, copper <0.010%, surplus is aluminium.First with fine aluminium and titanium sponge smelting, going out titanium content is 2.5% aluminum titanium alloy, then according to composition proportion, adds vacuum smelting furnace to smelt aluminum titanium alloy and other each pure metal, adopts induction stirring in smelting process.Smelt and finish its naturally cooling of relief, finally obtain casting rod.Casting rod is processed into the cylinder of Φ 16 * 28mm, surfaceness is 1.6, stamps therein the threaded hole of M3 * 8mm, in order to connect wire in a plane.Then with acetone oil removing, dry, weigh, take pictures, adopt afterwards epoxy sealing two planes, retain 14cm
2working area, make the present invention's laboratory sample used.The open circuit potential of sacrificial anode in deep-marine-environment be-1.103V (vs, Ag/AgCl, saturated KCl solution), and operating potential is-1.048V (vs, Ag/AgCl, saturated KCl solution), and current efficiency is 93.75%, and electrical capacity is 2662Ah/kg.Be uniformly dissolved, corrosion product easily comes off.
Embodiment tri-: label is sample D3.
Take aluminium as matrix, add zinc, indium, tin, magnesium, titanium alloy element, form hexa-atomic alloy, concrete composition proportion: (wt%): zinc 5.6%, indium 0.020%, tin 0.10%, magnesium 0.5%, titanium 0.10%, wherein impurity iron <0.050%, copper <0.010%, surplus is aluminium.First with fine aluminium and titanium sponge smelting, going out titanium content is 2.5% aluminum titanium alloy, then according to composition proportion, adds vacuum smelting furnace to smelt aluminum titanium alloy and other each pure metal, adopts induction stirring in smelting process.Smelt and finish its naturally cooling of relief, finally obtain casting rod.Casting rod is processed into the cylinder of Φ 16 * 28mm, surfaceness is 1.6, stamps therein the threaded hole of M3 * 8mm, in order to connect wire in a plane.Then with acetone oil removing, dry, weigh, take pictures, adopt afterwards epoxy sealing two planes, retain 14cm
2working area, make the present invention's laboratory sample used.The open circuit potential of sacrificial anode in deep-marine-environment be-1.100V (vs, Ag/AgCl, saturated KCl solution), and operating potential is-1.076V (vs, Ag/AgCl, saturated KCl solution), and current efficiency is 93.02%, and electrical capacity is 2644Ah/kg.Be uniformly dissolved, corrosion product easily comes off.
In experiment, be provided with the Sacrificial Anode material of 9 groups of heterogeneities, quad alloy Al-Zn-In-Mg(1 group wherein) and quinary alloy Al-Zn-In-Sn-Mg(2 group), Al-Zn-In-Mg-Ti(2 group) be comparative group, hexa-atomic alloy A l-Zn-In-Sn-Mg-Ti is this experiment invention.
In table 1 experiment, the theoretical chemistry of each sacrificial anode forms
The chemical property contrast of 9 groups of samples in table 2 experiment
Mentality of designing of the present invention is:
Because aluminium is self-passivating metal, surface easily generates fine and close oxide film, makes its current potential than calibration, so fine aluminium can not directly be used as sacrificial anode, conventionally adopts the method for alloying to prepare that current potential is lower, the sacrificial anode of excellent property.Wherein, Al-Zn-In series sacrificial anode is current most study, a most widely used class aluminum base alloy sacrificial anode material.
The basic ideas of adding each element in the present invention in the alloying process of Sacrificial Anode are: zinc is topmost activating element.The existence of zinc can effectively reduce the current potential of sacrificial anode, simultaneously, together with the alloying element such as zinc and tin, indium, can destroy the stability of surface of pure aluminum oxide film, improves alloy active.But because the solubleness of zinc in aluminium is limited, zinc too high levels easily produces segregation, so zinc content is controlled at 4.0% ~ 6.0%.A small amount of indium can significantly improve the activity of alloy, reduces electrode potential of alloy, improves the current efficiency of sacrificial anode; But excessive indium can make alloy occur from corrosion, thereby reduces current efficiency, so the content of indium is generally no more than 0.030%.Alloying element tin is more satisfactory alloying element, can in aluminium, form sosoloid, reduces the impact of impurity elements of ferrum, copper etc., can reduce zinc and the segregation of indium in alloy simultaneously, reduces intergranular corrosion.Add magnesium can improve the electrochemistry homogeneity of metallic surface, reduce alloy from erosion rate, improve the homogeneity that surface corrosion is dissolved.When tin and magnesium acting in conjunction, also can fall low-alloyed current potential, carry heavy alloyed activation performance.A small amount of titanium, in Sacrificial Anode, produces synergy with magnesium, and the crystal grain of refining aluminum alloy, makes alloy structure more even effectively, reduces and reduces because of second-phase or the bulk crystal grain current efficiency causing that comes off.
Claims (3)
1. a sacrificial aluminium alloy anode that is applicable to have in deep-marine-environment high current efficiency; it is characterized in that, take aluminium as matrix, add zinc, indium, tin, magnesium, titanium alloy element; concrete composition proportion (wt%): zinc 4.0 ~ 6.0%; indium 0.020 ~ 0.030%, tin 0.05 ~ 0.10%, magnesium 0.5 ~ 1.0%; titanium 0.05 ~ 0.10%; impurity iron <0.050% wherein, copper <0.010%, surplus is aluminium.
2. a kind of sacrificial aluminium alloy anode that is suitable for having in deep-marine-environment high current efficiency according to claim 1; it is characterized in that; the current efficiency of described sacrificial aluminium alloy anode is more than 92%; open circuit potential is between-1.05 ~-1.20; activation performance is better; be uniformly dissolved, corrosion product easily comes off.
3. a kind of preparation method who is suitable for having in deep-marine-environment the sacrificial aluminium alloy anode of high current efficiency according to claim 1, is characterized in that, concrete preparation process is:
With fine aluminium and titanium sponge smelting, going out titanium content is 2.5% aluminum titanium alloy;
Aluminium, zinc, indium, tin, magnesium, aluminum titanium alloy are added in vacuum smelting furnace and smelted by composition proportion;
In smelting process, adopt induction stirring;
Smelting finishes rear naturally cooling and obtains casting rod, finally casting rod is processed into required shape.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105779830A (en) * | 2016-04-06 | 2016-07-20 | 中国兵器科学研究院宁波分院 | Easy-to-corrode aluminum alloy material and preparation method thereof |
| CN106350824A (en) * | 2015-07-16 | 2017-01-25 | 东北大学 | Efficient aluminum alloy sacrificial anode for deep sea, and producing method thereof |
| CN111187954A (en) * | 2020-02-27 | 2020-05-22 | 西安石油大学 | Aluminum alloy sacrificial anode material for improving water/gas interface protection effect of sewage storage tank and preparation method thereof |
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| JPS58221250A (en) * | 1982-06-15 | 1983-12-22 | Nippon Soda Co Ltd | Zinc alloy for hot dipping |
| US4917966A (en) * | 1987-02-24 | 1990-04-17 | The Ohio State University | Galvanic protection of steel with zinc alloys |
| CN102162103A (en) * | 2011-05-30 | 2011-08-24 | 天津恒仁石油设备有限公司 | Aluminum alloy sacrificial anode suitable for abyssal environment and preparation method thereof |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58221250A (en) * | 1982-06-15 | 1983-12-22 | Nippon Soda Co Ltd | Zinc alloy for hot dipping |
| US4917966A (en) * | 1987-02-24 | 1990-04-17 | The Ohio State University | Galvanic protection of steel with zinc alloys |
| CN102162103A (en) * | 2011-05-30 | 2011-08-24 | 天津恒仁石油设备有限公司 | Aluminum alloy sacrificial anode suitable for abyssal environment and preparation method thereof |
Non-Patent Citations (1)
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| 齐公台等，: "不同锡含量高温铝基牺牲阳极的电化学性能", 《材料保护》, vol. 32, no. 10, 31 October 1999 (1999-10-31) * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106350824A (en) * | 2015-07-16 | 2017-01-25 | 东北大学 | Efficient aluminum alloy sacrificial anode for deep sea, and producing method thereof |
| CN105779830A (en) * | 2016-04-06 | 2016-07-20 | 中国兵器科学研究院宁波分院 | Easy-to-corrode aluminum alloy material and preparation method thereof |
| CN111187954A (en) * | 2020-02-27 | 2020-05-22 | 西安石油大学 | Aluminum alloy sacrificial anode material for improving water/gas interface protection effect of sewage storage tank and preparation method thereof |
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