CN106555090B - Seawater pipeline large-scale low potential magnesium alloy sacrificial anode material and preparation method thereof - Google Patents
Seawater pipeline large-scale low potential magnesium alloy sacrificial anode material and preparation method thereof Download PDFInfo
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- CN106555090B CN106555090B CN201611019011.XA CN201611019011A CN106555090B CN 106555090 B CN106555090 B CN 106555090B CN 201611019011 A CN201611019011 A CN 201611019011A CN 106555090 B CN106555090 B CN 106555090B
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- magnesium alloy
- anode material
- ingot
- sacrificial anode
- low potential
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C23/00—Alloys based on magnesium
- C22C23/02—Alloys based on magnesium with aluminium as the next major constituent
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
- B22D21/00—Casting non-ferrous metals or metallic compounds so far as their metallurgical properties are of importance for the casting procedure; Selection of compositions therefor
- B22D21/002—Castings of light metals
- B22D21/007—Castings of light metals with low melting point, e.g. Al 659 degrees C, Mg 650 degrees C
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
- B22D21/00—Casting non-ferrous metals or metallic compounds so far as their metallurgical properties are of importance for the casting procedure; Selection of compositions therefor
- B22D21/02—Casting exceedingly oxidisable non-ferrous metals, e.g. in inert atmosphere
- B22D21/04—Casting aluminium or magnesium
-
- C—CHEMISTRY; METALLURGY
- 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
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- 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
- C23F13/12—Electrodes characterised by the material
- C23F13/14—Material for sacrificial anodes
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
- F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
- F16L58/00—Protection of pipes or pipe fittings against corrosion or incrustation
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- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- General Engineering & Computer Science (AREA)
- Prevention Of Electric Corrosion (AREA)
Abstract
A kind of seawater pipeline large-scale low potential magnesium alloy sacrificial anode material and preparation method thereof, the invention belongs to technical field of magnesium alloy material, it can solve impurity element in magnesium alloy anode in the prior art and, to the service life of sacrificial anode material and the adverse effect of utilization rate, include the component of following mass fraction：Al：5.1%~6.9%、Zn：2.2%~3.9%、Mn：0.1% ~ 2.5%, impurity element S i, Fe, Cu and Ni content ＜ 0.015%, rest part Mg.After magnesium ingot, aluminium ingot, zinc ingot metal, manganese chloride heating fusing are stirred evenly, under SF6 gas shields, using top pouring type low pressure direct casting system in 650 ~ 680 DEG C of casting magnesium alloy anodes, progress epoxy-based lacquers application processing.The present invention makes magnesium alloy sacrificial anode material consume uniform, service efficiency height, and the service life extends.
Description
Technical field
The invention belongs to technical field of magnesium alloy material, and in particular to a kind of seawater pipeline is sacrificial with large-scale low potential magnesium alloy
Domestic animal anode material and preparation method thereof.
Background technology
As national economic development strategy from land turns to ocean, offshore oil, the construction of natural gas fields emerge rapidly.Due to tight
Cruel marine corrosion environment, marine corrosion are always the key subjects for perplexing marine petroleum development.Corrosion not only causes material
Waste, forces stop work and production due to plant maintenance, is more seriously that oil, gas leakage is caused to cause catastrophic thing due to corrosion
Therefore.
Protective potential range -0.8 ~ -0.95V of national regulation steel in the seawater（Ag/AgCl）, protecting current density 30
~ 50%, when less than protection point position lower limit, steel cannot be effectively protected.Seawater pipeline with anode be generally aluminium anodes or
Zinc anode.The capacitance of aluminium anodes is big, up to 2970Ah/kg, potential range -0.97 ~ -1.12V（Ag/AgCl）.Zinc anode
Capacitance it is big, up to 780Ah/kg, potential range is in -1.12V（Ag/AgCl）Left and right.
But aluminium anodes and zinc anode, all than heavier, large-scale anode, which is put into pipeline, to be needed to increase many manpower and object
Power.And magnesium alloy is most light metal material, chemical property is also preferable, is commonly used for sacrificial anode material, and equipment is filled
The cathode put is protected, to extend the service life of cathode material.The capacitance of magnesium alloy is more than 1210 Ah/kg, current potential
1.51 ~ -1.53V of range（Ag/AgCl）, more than 55% current efficiency.But ordinary magnesium alloy all containing a certain amount of Si, Fe, Cu and
The impurity elements such as Ni, and these element current potentials are higher, easily cause parasitic corrosion, make the reduction of magnesium alloy anode corrosion efficiency, this
A little elements are reacted with magnesium is distributed in crystal boundary with web form, easily forms micro cell with magnesium matrix, accelerates sacrificial anode material
Consumption, and make anode consumption uneven, influence the service life and utilization rate of sacrificial anode material.
Invention content
The present invention is in order to solve in magnesium alloy anode in the prior art impurity element to the service life of sacrificial anode material
With the adverse effect of utilization rate, a kind of large-scale low potential magnesium alloy sacrificial anode material of seawater pipeline and its preparation side are provided
Method.
The present invention adopts the following technical scheme that realization：
A kind of large-scale low potential magnesium alloy sacrificial anode material of seawater pipeline, includes the component of following mass fraction：Al
：5.1%~6.9%、Zn ：2.2%~3.9%、Mn ：0.1% ~ 2.5%, impurity element S i, Fe, Cu and Ni content ＜ 0.015%, remaining
Part is Mg.
A kind of seawater pipeline preparation method of large-scale low potential magnesium alloy sacrificial anode material, includes the following steps：
（1）Magnesium ingot, aluminium ingot, zinc ingot metal and manganese chloride are preheated respectively；
（2）Magnesium ingot in crucible is heated to fusing, then adds in aluminium ingot, zinc ingot metal, after zinc ingot metal and aluminium ingot melt, stirring is equal
It is even, 10 ~ 20min of mixing time；
（3）700-740 DEG C is warming up to, manganese chloride is added in, treats its fusing, stir evenly, 5 ~ 15min of mixing time；
（4）10 ~ 20min of refining is carried out after slagging-off, stands 40 ~ 80min, 725 ~ 755 DEG C of refining temperature；
（5）In SF6Under gas shield, using top pouring type low pressure direct casting system in 650 ~ 680 DEG C of casting magnesium alloy sun
Pole；
（6）Magnesium alloy anode is subjected to epoxy-based lacquers application processing.
Content >=99% of magnesium in magnesium ingot described in the first step, content >=99% of aluminium in aluminium ingot, the content of zinc in the zinc ingot metal
≥99%。
Preheating temperature described in the first step is 250-300 DEG C.
10 ~ 30 DEG C of the epoxy-based lacquers application temperature, application humidity 60-85RH, 120-200 μm of application thickness.
The seawater pipeline is with 3 ~ 5 times that the size of large-scale low potential sacrificial magnesium alloy anode is common anode, weight
Be 5 times of common anode and more than.
Beneficial effects of the present invention are as follows：
（1）Sacrificial magnesium alloy anode of the present invention can substitute the seawater aluminium anodes and zinc anode originally used；
（2）For Corrosion Behaviors of Magnesium Alloys it is very fast the problem of, according to the different proportioning of alloy, reduce some impurity elements, from
And reduce parasitic corrosion, consuming magnesium alloy sacrificial anode material, uniform, service efficiency is high, long lifespan；
（3）Stock utilization can be improved, and reduce internal defect in cast using low pressure casting, casting is improved and prepare effect
Rate；
（4）Using epoxy-based lacquers application, the corrosion resistance of the anode material further improved closes so as to increase the magnesium
Usage time of the gold anode material in briny environment；
（5）The preparation flow of magnesium alloy materials is simple, easy to operate.
Specific embodiment
Embodiment 1, the large-scale low potential magnesium alloy sacrificial anode material of a kind of seawater pipeline, including following mass fraction
Component：Al 5.1%, Zn 2.2%, Mn 0.1%, impurity element S i, Fe, Cu and Ni content are respectively less than 0.015%, and rest part is
Mg。
A kind of seawater pipeline preparation method of large-scale low potential magnesium alloy sacrificial anode material, includes the following steps（1）
Magnesium ingot, aluminium ingot, zinc ingot metal and manganese chloride are distinguished into 250 DEG C of preheatings；
（2）Magnesium ingot in crucible is heated to fusing, then adds in aluminium ingot, zinc ingot metal, until zinc ingot metal and aluminium ingot fusing, stirring are equal
It is even, mixing time 10min；
（3）700 DEG C are warming up to, manganese chloride is added in, treats its fusing, stir evenly, mixing time 5min；
（4）Refining 10min is carried out after slagging-off, stands 40min, 725 DEG C of refining temperature；
（5）In SF6Under gas shield, using low pressure direct casting system 650 DEG C cast magnesium alloy anodes, obtain magnesium conjunction
Golden sacrificial anode；
（6）Magnesium alloy sacrificial anode material is subjected to epoxy-based lacquers application processing.10 DEG C of epoxy-based lacquers application temperature, application is wet
Spend 60RH, 120 μm of application thickness.
The obtained seawater pipeline of the present embodiment is common anode with large-scale low potential magnesium alloy sacrificial anode material size
3 times, weight is 5 times of common anode.
Embodiment 2, the large-scale low potential magnesium alloy sacrificial anode material of a kind of seawater pipeline, including following mass fraction
Component：Al 5.5%, Zn 2.9%, Mn 1.2%, impurity element S i, Fe, Cu and Ni content are respectively less than 0.015%, and rest part is
Mg。
A kind of seawater pipeline preparation method of large-scale low potential magnesium alloy sacrificial anode material, includes the following steps：
（1）Magnesium ingot, aluminium ingot, zinc ingot metal and manganese chloride are distinguished into 270 DEG C of preheatings；
（2）Magnesium ingot in crucible is heated to fusing, then adds in aluminium ingot, zinc ingot metal, until zinc ingot metal and aluminium ingot fusing, stirring are equal
It is even, mixing time 12min；
（3）720 DEG C are warming up to, manganese chloride is added in, treats its fusing, stir evenly, mixing time 8min；
（4）Refining 12min is carried out after slagging-off, stands 50min, 730 DEG C of refining temperature；
（5）In SF6Under gas shield, using low pressure direct casting system 660 DEG C cast magnesium alloy anodes, obtain magnesium conjunction
Golden sacrificial anode；
（6）Magnesium alloy sacrificial anode material is subjected to epoxy-based lacquers application processing, 15 DEG C of epoxy-based lacquers application temperature, application is wet
Spend 65RH, 150 μm of application thickness.
The obtained seawater pipeline of the present embodiment is common anode with large-scale low potential magnesium alloy sacrificial anode material size
3.2 times, weight is 5.5 times of common anode.
Embodiment 3, the large-scale low potential magnesium alloy sacrificial anode material of a kind of seawater pipeline, including following mass fraction
Component：Al 6.0%, Zn 3.1%, Mn 1.5%, impurity element S i, Fe, Cu and Ni content are respectively less than 0.015%, and rest part is
Mg。
A kind of seawater pipeline preparation method of large-scale low potential magnesium alloy sacrificial anode material, includes the following steps：
（1）By magnesium ingot, aluminium ingot, zinc ingot metal and manganese chloride respectively in 280 DEG C of preheatings；
（2）Magnesium ingot in crucible is heated to fusing, then adds in aluminium ingot, zinc ingot metal, until zinc ingot metal and aluminium ingot fusing, stirring are equal
It is even, mixing time 15min；
（3）730 DEG C are warming up to, manganese chloride is added in, treats its fusing, stir evenly, mixing time 10min；
（4）Refining 15min is carried out after slagging-off, stands 60min, 740 DEG C of refining temperature；
（5）In SF6Under gas shield, using top pouring type low pressure direct casting system 670 DEG C cast magnesium alloy anodes, obtain
To sacrificial magnesium alloy anode；
（6）By sacrificial anode material carry out epoxy-based lacquers application processing, 20 DEG C of epoxy-based lacquers application temperature, application humidity 75RH,
180 μm of application thickness.
The obtained seawater pipeline of the present embodiment is common anode with large-scale low potential magnesium alloy sacrificial anode material size
4 times, weight is 6.2 times of common anode.
Embodiment 4, the large-scale low potential magnesium alloy sacrificial anode material of a kind of seawater pipeline, including following mass fraction
Component：Al 6.9%, Zn 3.9%, Mn2.5%, impurity element S i, Fe, Cu and Ni content are respectively less than 0.015%, and rest part is
Mg。
A kind of seawater pipeline preparation method of large-scale low potential magnesium alloy sacrificial anode material, includes the following steps：
（1）By magnesium ingot, aluminium ingot, zinc ingot metal and manganese chloride respectively in 300 DEG C of preheatings；
（2）Magnesium ingot in crucible is heated to fusing, then adds in aluminium ingot, zinc ingot metal, until zinc ingot metal and aluminium ingot fusing, stirring are equal
It is even, mixing time 20min；
（3）740 DEG C are warming up to, manganese chloride is added in, treats its fusing, stir evenly, mixing time 15min；
（4）Refining 20min is carried out after slagging-off, stands 80min, 755 DEG C of refining temperature；
（5）In SF6Under gas shield, using top pouring type low pressure direct casting system 680 DEG C cast magnesium alloy anodes, obtain
To sacrificial magnesium alloy anode；
（6）By sacrificial anode material carry out epoxy-based lacquers application processing, 30 DEG C of epoxy-based lacquers application temperature, application humidity 85RH,
200 μm of application thickness.
The obtained seawater pipeline of the present embodiment is common anode with large-scale low potential magnesium alloy sacrificial anode material size
5 times, weight is 7.5 times of common anode.
Comparative example 1, the AZ31B anodes B1 bought on the market.
Comparative example 2, the AZ63B anodes B2 bought on the market.
The sacrificial magnesium alloy anode prepared in above-described embodiment 1-4 and B1-B2 are detected it according to 24488 methods of GB/T
Unit for electrical property parameters result；Its corrosion resistance is detected, and according to GB/T 6461 according to 10125 neutral salt spray test methods of GB/T
Method carries out Corrosion protection grade.Testing result is as in the table below.
It can be seen from Table 1 that electrical performance indexes of sacrificial magnesium alloy anode produced within the scope of the present invention and anti-corrosion
Performance is substantially better than Conventional alloys anode, and sacrificial magnesium alloy anode electrical performance indexes produced outside the scope of the present invention are then relatively low,
Meanwhile the electrical property result of sacrificial magnesium alloy anode obtained and corrosion resistance are then more excellent in the preferred range, because
And its use scope is expanded significantly, extend service life.
The preferred embodiment of the present invention has been described above in detail, but the present invention is not limited to the tools in the above embodiment
Body details within the scope of the technical concept of the present invention, can carry out a variety of simple variants, these letters to technical scheme of the present invention
Monotropic type all belongs to the scope of protection of the present invention.
It is further to note that each specific technical characteristic described in above-mentioned specific embodiment, in not lance
In the case of shield, can be combined by any suitable means, in order to avoid unnecessary repetition, the present invention to it is various can
The combination of energy no longer separately illustrates.
In addition, various embodiments of the present invention can be combined randomly, without departing from this hair
Bright thought, it should also be regarded as the disclosure of the present invention.
Claims (5)
1. a kind of large-scale low potential magnesium alloy sacrificial anode material of seawater pipeline, it is characterised in that：Including following mass fraction
Component：Al ：5.1%~6.9%、Zn ：2.2%~3.9%、Mn ：0.1% ~ 2.5%, impurity element S i, Fe, Cu and Ni content ＜
0.015%, rest part Mg, unit for electrical property parameters are：Open circuit potential is 1.538-1.547-V, current efficiency 57.48%-
59.32%, capacitance 1290.73-1315.93Ah/kg, Corrosion protection grade reach 8 grades and more than.
2. a kind of seawater pipeline as described in claim 1 preparation method of large-scale low potential magnesium alloy sacrificial anode material,
It is characterized in that：Include the following steps：
（1）Magnesium ingot, aluminium ingot, zinc ingot metal and manganese chloride are preheated respectively；
（2）Magnesium ingot in crucible is heated to fusing, aluminium ingot, zinc ingot metal is then added in, after zinc ingot metal and aluminium ingot melt, stirs evenly, stir
Mix 10 ~ 20min of time；
（3）700-740 DEG C is warming up to, manganese chloride is added in, treats its fusing, stir evenly, 5 ~ 15min of mixing time；
（4）10 ~ 20min of refining is carried out after slagging-off, stands 40 ~ 80min, 725 ~ 755 DEG C of refining temperature；
（5）In SF6Under gas shield, using top pouring type low pressure direct casting system in 650 ~ 680 DEG C of casting magnesium alloy anodes；
（6）Magnesium alloy anode is subjected to epoxy-based lacquers application processing.
3. a kind of seawater pipeline according to claim 2 preparation side of large-scale low potential magnesium alloy sacrificial anode material
Method, it is characterised in that：Content >=99% of magnesium in magnesium ingot described in the first step, content >=99% of aluminium in aluminium ingot, zinc in the zinc ingot metal
Content >=99%.
4. a kind of seawater pipeline according to claim 2 preparation side of large-scale low potential magnesium alloy sacrificial anode material
Method, it is characterised in that：Preheating temperature described in the first step is 250-300 DEG C.
5. a kind of seawater pipeline according to claim 2 preparation side of large-scale low potential magnesium alloy sacrificial anode material
Method, it is characterised in that：10 ~ 30 DEG C of epoxy-based lacquers application temperature described in 6th step, application humidity 60-85RH, application thickness 120-200
μm。
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108441729A (en) * | 2018-03-28 | 2018-08-24 | 武汉中原长江科技发展有限公司 | A kind of magnesium-alloy anode material and preparation method thereof |
| CN109943852A (en) * | 2019-05-10 | 2019-06-28 | 光钰科技（临沂）有限公司 | A kind of preparation method delaying sacrificial magnesium alloy anode corrosion rate |
| CN113122852A (en) * | 2021-04-25 | 2021-07-16 | 浙江钰烯腐蚀控制股份有限公司 | Preparation method of magnesium-aluminum composite anode and magnesium-aluminum composite anode |
| CN113930650A (en) * | 2021-10-25 | 2022-01-14 | 芜湖美的厨卫电器制造有限公司 | Sn-containing magnesium alloy sacrificial anode and preparation method and application thereof |
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| DE102006055024A1 (en) * | 2006-11-22 | 2008-05-29 | Daimler Ag | Procedure for protecting exhaust line-/exhaust system from corrosion, by subjecting components of the exhaust system with cathodic protection by transcrystalline stress corrosion, and coating the component with electrochemical base coat |
| CN101768745A (en) * | 2010-03-05 | 2010-07-07 | 陕西电力科学研究院 | Magnesium sacrificial anode with high current efficiency and preparation method thereof |
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