CN106756371B - A kind of high corrosion-resistant magnesium alloy - Google Patents
A kind of high corrosion-resistant magnesium alloy Download PDFInfo
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- CN106756371B CN106756371B CN201710080020.8A CN201710080020A CN106756371B CN 106756371 B CN106756371 B CN 106756371B CN 201710080020 A CN201710080020 A CN 201710080020A CN 106756371 B CN106756371 B CN 106756371B
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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
- C22C23/06—Alloys based on magnesium with a rare earth metal as the next major constituent
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
- C22C1/03—Making non-ferrous alloys by melting using master alloys
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/06—Making non-ferrous alloys with the use of special agents for refining or deoxidising
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Abstract
The present invention relates to a kind of high corrosion-resistant magnesium alloys, belong to metal material field.The high corrosion-resistant magnesium alloy, as mass fraction, the ingredient of the magnesium alloy is：Sc 2-5%, Mn 0.5-1%, Zr 0.5-1%, surplus are Mg and inevitable impurity.The high corrosion-resistant magnesium alloy that the present invention is developed, which are added Sc elements, and the open circuit potential by testing heterogeneity finds that Sc constituent contents are bigger, and current potential increases, and corrosion tendency reduces, thus corrosion reaction driving force declines.The present invention is added after suitable Sc elements, can form Sc2O3With Mg (OH)2Hybrid films so that Mg matrix surface film layers are finer and close, and the corrosion rate of high purity magnesium is greatly reduced.The present invention is by adding suitable Sc elements, and the type and ratio of other alloying elements of rational proportion, the corrosive nature that magnesium alloy materials are further improved by the synergistic effect of alloying element successfully develops a kind of high corrosion-resistant magnesium alloy of Mg-Sc-Mn-Zr systems.
Description
Technical field
The present invention relates to a kind of high corrosion-resistant magnesium alloys, belong to metal material field.
Background technology
The corrosion of material is very universal in production and living, and spillage of material, pattern change, mechanical property is often caused to move back
Change etc. so that load-carrying construction component cannot be satisfied normal use demand.It is material corrosion generality, spontaneity, duration, non-thread
The characteristics of property, complexity so that material failure is often difficult to Accurate Prediction caused by corrosion, so as to cause the huge of lives and properties
Big loss.Such as 1985, a Japanese frame Boeing-747 aircraft was crashed due to the stress corrosion aging fracture of component, is caused more than 500
People is wrecked.The corrosion of material also brings huge economic loss to national economy.
With the big aircraft in China, bullet train, manned space flight, deep-sea early warning and detection, near space vehicle, repeat
The high speed development in the Important Projects such as earth to orbit and return transportation system field, the demand to high combination property lightweighting materials are increasingly compeled
It cuts.Magnesium is the structural metallic materials of current most lightweight, and proportion is approximately the 1/4 of the 2/3 of aluminium, steel, be known as can loss of weight, it is energy saving,
" the 21 century green engineering material " of speed-raising.In the past, magnesium alloy due to low strength, deformability is weak, inflammable, corrosion resistance
The shortcomings of poor, limits its scope of application, but the research and development of high strength rare earth magnesium alloy achieve major progress in recent years, absolutely
Intensity is had been able to more than 500MPa, to expand its application in Important Project field significantly.
Deeply the corrosion mechanism of understanding magnesium alloy is to develop the premise and basis of high corrosion-resistant magnesium alloy.PH-Electric Potential Graph
（Pourbaix phasors）It is the important criterion thermodynamically weighed corrosion and can occurred, and prediction material corrosion performance, analysis
The important tool of material corrosion mechanism.With the pH-Electric Potential Graph of pure magnesium（Fig. 1）For, be broadly divided into figure magnesium metal, magnesium ion,
Three regions of magnesium hydroxide, have corresponded to stabilized metal area, corrosion region and passivation region, as shown in Figure 2 respectively.It is being labeled as magnesium metal
Region, for thermodynamics, corrosion will not occur, i.e., magnesium metal can be stabilized；It then means in the region of magnesium ion
It magnesium to tend to exist with ionic condition, that is, corrodes；And in the region of magnesium hydroxide, although magnesium is not in the form of simple substance
In the presence of, but since the magnesium hydroxide of generation can be stabilized, corruption can be prevented to a certain extent by being attached to magnesium surface
Erosion continues to occur, that is, generates passivation layer, be conducive to the raising of corrosion resistance.It can be seen that Pourbaix phasors are point
Analyse the powerful tool of Corrosion Thermodynamics tendency.Although the pH-Electric Potential Graph for having had more than 70 kinds of common metals has all passed through reality
Test is drawn surely, but is still unknown for the pH-Electric Potential Graph of alloy especially magnesium alloy system, and there is an urgent need for pass through high-volume
Calculating or experiment come it is perfect.
The defect that corrosion resistance of magnesium alloy can be poor at present is not well solved still.Therefore, how by effective
Magnesium alloy formula design and exploitation, improve the corrosion resistance of magnesium alloy, be still arduous and urgent task.
Invention content
The present invention is directed to the technical issues of existing Corrosion Behaviors of Magnesium Alloys poor performance, develops a kind of Mg-Sc-Mn-Zr of system
High corrosion-resistant magnesium alloy.The high corrosion-resistant magnesium alloy that the present invention is developed, from reducing, corrosion reaction driving force, inhibition anode and cathode are anti-
It answers these three aspects to carry out the improvement of corrosive nature, has obtained comparing high purity magnesium（99.95%）Corrosion rate also order of magnitude lower
Material, can be applicable on the appearance member of LED and electronic product.
Realize the object of the invention and the technical solution that uses for：A kind of high corrosion-resistant magnesium alloy, as mass fraction, the magnesium close
Gold ingredient be：Sc 2-5%, Mn 0.5-1%, Zr 0.5-1%, surplus are Mg and inevitable impurity.
As a preferred embodiment of the present invention, the high corrosion-resistant magnesium alloy, as mass fraction, the ingredient of the magnesium alloy
For：Sc 3%, Mn 0.8%, Zr 0.7%, surplus are Mg and inevitable impurity.
As a preferred embodiment of the present invention, the high corrosion-resistant magnesium alloy, as mass fraction, the ingredient of the magnesium alloy
For：Sc 5%, Mn 0.5%, Zr 0.5%, surplus are Mg and inevitable impurity.
As a preferred embodiment of the present invention, the high corrosion-resistant magnesium alloy, as mass fraction, the ingredient of the magnesium alloy
For：Sc 2%, Mn 1%, Zr 1%, surplus are Mg and inevitable impurity.
Preferably, high corrosion-resistant magnesium alloy of the present invention comprises the following steps：
1）Stock and stove cleaning：It is stocked up according to magnesium alloy component ratio, stove cleans up；Wherein, Sc elements are with Mg-
Sc intermediate alloys are added, and Mn elements are added in the form of simple substance or Mg-Mn intermediate alloys, and Zr elements are in pure Zr or Mg-Zr
Between alloy be added；
2）Magnesium ingot melts：Put whole pure magnesium ingots into well formula electrical crucible, it is uniform in crucible bottom and pure magnesium ingot surface
Cosan is sprinkled, with crucible cover by crucible, is passed through by body SF6And N2The protective gas of composition, heat temperature raising make all pure
Magnesium ingot is completely melt under sulfur dioxide and the protective gas, and magnesium melt temperature is controlled at 700 780 DEG C；
3）Intermediate alloy is added：When magnesium melt temperature reaches 710 DEG C or more, by after drying Mg-Mn intermediate alloys,
Mg-Zr intermediate alloys are added in magnesium melt, and magnesium melt is warming up to 750 DEG C, and Mg-Sc intermediate alloys are added in magnesium melt,
Heat preservation 15 minutes ensures that the intermediate alloy being added all melts, liquid magnesium alloy is made；
4）Alloy refines：It waits for that magnesium melt temperature rises to 730 DEG C or more, the special refining agent of magnesium alloy is added and proceeds by essence
Refining；In refining process, refining spoon immerses at the 2/3 of liquid magnesium alloy, intensely from top to bottom stirs liquid magnesium alloy until liquid level goes out
Until existing bright luster；In whipping process, constantly toward spreading the special refining flux of magnesium alloy on magnesium alloy liquid level；It has refined
Finish, removes the flux and dross on liquid level, then gently spread last layer coverture；Preference temperature is cooled to stand until being mingled with fully
It floats or sinks, finally skim.
Preferably, in step 4）In, the special refining agent of the magnesium alloy is：The special RJ-5 refinings of magnesium-rare earth are molten
Agent.
Preferably, in step 4）In, the coverture is：The special RJ-5 flux of magnesium-rare earth.
Compared with prior art, technological merit of the invention is：
1, the high corrosion-resistant magnesium alloy that the present invention is developed, which are added Sc elements, by the open circuit electricity for testing heterogeneity
Position finds that Sc constituent contents are bigger, and current potential increases, and corrosion tendency reduces, thus corrosion reaction driving force declines, dynamic by testing
Potential polarization curve is found, is added to the Mg-Sc alloys after Sc elements, and either cathode or anode flowpath picture left avertence is moved,
Mean that adding Sc elements can inhibit anode and cathode to react simultaneously, so as to be effectively reduced corrosion driving force, still
It is found through experiments that：Excessive Sc elements make the hydrogen-separating quantity of magnesium alloy and weight loss rise instead.
2, the high corrosion-resistant magnesium alloy that the present invention is developed, the wherein content of Sc elements control between 2-5%, improve Mg bases
The incomplete film layer in body surface face, originally the film layer volume conditions P-B ratios of Mg matrix surfaces（Pilling-bedworth Ratio）
Less than 1, i.e. film layer structure shrinkage porosite can not be completely covered Mg matrix surfaces, be added after suitable Sc elements, can form Sc2O3With
Mg(OH)2Hybrid films so that Mg matrix surface film layers are finer and close, and the corrosion rate of high purity magnesium is greatly reduced.
3, the present invention is by adding suitable Sc elements, and the type and ratio of rational proportion other alloying elements, leads to
The synergistic effect for crossing alloying element further improves the corrosive nature of magnesium alloy materials, successfully develops a kind of Mg-Sc-Mn-
The high corrosion-resistant magnesium alloy of Zr systems.
Description of the drawings
Fig. 1 is the pH-Electric Potential Graph of pure magnesium in the prior art.
Fig. 2 is the thermodynamic stability administrative division map of pure magnesium in the prior art.
Fig. 3 is XPS figure of the Mg-5Sc magnesium alloy materials obtained by embodiment 3 after 3.5% sodium chloride solution corrodes 24 hours
Spectrum.
Specific implementation mode
The present invention is described further with reference to embodiment.
Embodiment 1
By taking 25kg as an example, for being matched according to Mg-3Sc-0.8Mn-0.7Zr, as mass fraction, Sc 3%, Mn
0.8%, Zr 0.7%, surplus are Mg and inevitable impurity, calculate the quality of intermediate alloy, stock up.Specifically may be used
It comprises the following steps：
1）Stock and stove cleaning：It is stocked up according to magnesium alloy component ratio, stove cleans up；Wherein, Sc elements are with Mg-
Sc intermediate alloys are added, and Mn elements are added in the form of simple substance or Mg-Mn intermediate alloys, and Zr elements are in pure Zr or Mg-Zr
Between alloy be added；
2）Magnesium ingot melts：Whole pure magnesium ingots are put into well formula electrical crucible in a manner of close as possible, in crucible bottom
Cosan is uniformly sprinkled with pure magnesium ingot surface, with crucible cover by crucible, is passed through by body SF6And N2The protective gas of composition,
Heat temperature raising makes whole pure magnesium ingots be completely melt under sulfur dioxide and the protective gas, and the control of magnesium melt temperature is existed
700〜780℃；
3）Intermediate alloy is added：When magnesium melt temperature reaches 710 DEG C or more, by after drying Mg-Mn intermediate alloys,
Mg-Zr intermediate alloys are added in magnesium melt, and magnesium melt is warming up to 750 DEG C, and Mg-Sc intermediate alloys are added in magnesium melt,
Heat preservation 15 minutes ensures that the intermediate alloy being added all melts, liquid magnesium alloy is made；
4）Alloy refines：It waits for that magnesium melt temperature rises to 730 DEG C or more, the special refining agent of magnesium alloy is added and proceeds by essence
Refining；In refining process, refining spoon immerses at the 2/3 of liquid magnesium alloy, intensely from top to bottom stirs liquid magnesium alloy until liquid level goes out
Until existing bright luster；In whipping process, constantly toward spreading the special refining agent of magnesium alloy on magnesium alloy liquid level；Refining finishes,
The flux and dross on liquid level are removed, then gently spreads last layer coverture；Preference temperature is cooled to stand until being mingled on fully
Floating or sinking, finally skims.
Mg-3Sc-0.8Mn-0.7Zr high corrosion-resistant magnesium alloys material manufactured in the present embodiment, hydrogen-separating quantity 0.8mL/cm2/
Day, weight loss are 0.6 × 10-2g/cm2/day。
Embodiment 2
By taking 25kg as an example, for being matched according to Mg-2Sc-1Mn-1Zr, as mass fraction, Sc 2%, Mn 1%, Zr
1%, surplus is Mg and inevitable impurity, calculates the quality of intermediate alloy, stocks up.Specific preparation method is the same as real
Apply example 1.
Mg-2Sc-1Mn-1Zr high corrosion-resistant magnesium alloys material manufactured in the present embodiment, hydrogen-separating quantity 1.0mL/cm2/ day,
Weight loss is 0.5 × 10-2g/cm2/day。
Embodiment 3
By taking 25kg as an example, for being matched according to Mg-5Sc-0.5Mn-0.5Zr, as mass fraction, Sc 5%, Mn
0.5%, Zr 0.5%, surplus are Mg and inevitable impurity, calculate the quality of intermediate alloy, stock up.Specific system
Preparation Method is the same as embodiment 1.
Mg-5Sc-0.5Mn-0.5Zr high corrosion-resistant magnesium alloys material manufactured in the present embodiment, hydrogen-separating quantity 0.4mL/cm2/
Day, weight loss are 1.0 × 10-2g/cm2/day。
Comparative example 1
By taking 25kg as an example, for being matched according to Mg-10Sc-0.8Mn-0.7Zr, as mass fraction, Sc 10%, Mn
0.8%, Zr 0.7%, surplus are Mg and inevitable impurity, calculate the quality of intermediate alloy, stock up.Specific system
Preparation Method is the same as embodiment 1.
Mg-10Sc-0.8Mn-0.7Zr high corrosion-resistant magnesium alloy materials prepared by comparative example 1, hydrogen-separating quantity 2.6mL/cm2/
Day, weight loss are 3.1 × 10-2g/cm2/day。
Comparative example 2
By taking 25kg as an example, for being matched according to Mg-15Sc-0.8Mn-0.7Zr, as mass fraction, Sc 15%, Mn
0.8%, Zr 0.7%, surplus are Mg and inevitable impurity, calculate the quality of intermediate alloy, stock up.Specific system
Preparation Method is the same as embodiment 1.
Mg-15Sc-0.8Mn-0.7Zr high corrosion-resistant magnesium alloy materials prepared by comparative example 1, hydrogen-separating quantity 3.0mL/cm2/
Day, weight loss are 3.7 × 10-2g/cm2/day。
The liberation of hydrogen experiment and zero-G test test value that table 1 is embodiment 1-3, comparative example 1 and 2 carries out, can be right by table 1
Than finding out the corrosion impact of high purity magnesium and different proportion Sc elements for magnesium alloy.The high corrosion-resistant magnesium alloy of the present invention is come
It says, the corrosion resistance of magnesium alloy could be improved by only adding suitable Sc elements, and excessive Sc elements make magnesium alloy instead
Hydrogen-separating quantity and weight loss rise.
Table 1
| Alloying component | HP Mg | Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative example 1 | Comparative example 2 |
| Hydrogen-separating quantity（mL/cm2/day） | 7.4 | 0.8 | 1.0 | 0.4 | 2.6 | 3.0 |
| Weight loss（×10-2g/cm2/day） | 7.1 | 0.6 | 0.5 | 1.0 | 3.1 | 3.7 |
To the Mg-Sc high corrosion-resistant magnesium alloy material corrosions test obtained by embodiment 3, Fig. 3 is Mg-5Sc magnesium alloy materials
XPS collection of illustrative plates after 3.5% sodium chloride solution corrodes 24 hours.As shown in figure 3, can be clearly seen that in Mg-5Sc magnesium alloys
There are Sc and Mg elements in material surface corrosion product, illustrate to contain Sc in film layer2O3With Mg (OH)2Two kinds of blending constituents.
The present invention is exactly based on Sc2O3With Mg (OH)2Mixed membranous layer is formed on magnesium alloy materials surface, when Sc contents are more than
When 2%, P-B ratios are more than 1, can be formed on magnesium alloy materials surface and stablize fine and close protective film.And when Sc contents are less than 2%, no
Effective mixed membranous layer can be formed, protective effect is not had；When Sc contents are more than 5%, and the second phases of β-Sc can be introduced, it is this
Second meets forms micro- galvanic corrosion with Mg matrixes, to influence corrosion rate.
Claims (6)
1. a kind of high corrosion-resistant magnesium alloy, it is characterised in that：As mass fraction, the ingredient of the magnesium alloy is：Sc 2-5%, Mn
0.5-1%, Zr 0.5-1%, surplus are Mg and inevitable impurity；
The high corrosion-resistant magnesium alloy comprises the following steps：
1）Stock and stove cleaning：It is stocked up according to magnesium alloy component ratio, stove cleans up；Wherein, Sc elements are in Mg-Sc
Between alloy be added, Zr elements are added with conjunction among pure Zr or Mg-Zr in Mn elements in the form of simple substance either Mg-Mn intermediate alloys
Gold is added；
2）Magnesium ingot melts：It puts whole pure magnesium ingots into well formula electrical crucible, is uniformly sprinkled in crucible bottom and pure magnesium ingot surface
Cosan is passed through with crucible cover by crucible by SF6And N2The protective gas of composition, heat temperature raising make whole pure magnesium ingots exist
It is completely melt under sulfur dioxide and the protective gas, magnesium melt temperature is controlled at 700 780 DEG C；
3）Intermediate alloy is added：When magnesium melt temperature reaches 710 DEG C or more, by Mg-Mn intermediate alloys, the Mg-Zr after drying
Intermediate alloy is added in magnesium melt, and magnesium melt is warming up to 750 DEG C, and Mg-Sc intermediate alloys are added in magnesium melt, heat preservation 15
Minute, ensure that the intermediate alloy being added all melts, liquid magnesium alloy is made；
4）Alloy refines：It waits for that magnesium melt temperature rises to 730 DEG C or more, the special refining agent of magnesium alloy is added and proceeds by refining；Essence
During refining, refining spoon immerses at the 2/3 of liquid magnesium alloy, intensely from top to bottom stirs liquid magnesium alloy until minute surface occurs in liquid level
Until gloss；In whipping process, constantly toward spreading the special refining agent of magnesium alloy on magnesium alloy liquid level；Refining finishes, and removes liquid
Flux on face and dross, then gently spread last layer coverture；Cool to preference temperature stand until be mingled with fully float or under
It is heavy, finally skim.
2. high corrosion-resistant magnesium alloy according to claim 1, it is characterised in that：As mass fraction, the ingredient of the magnesium alloy
For：Sc 3%, Mn 0.8%, Zr 0.7%, surplus are Mg and inevitable impurity.
3. high corrosion-resistant magnesium alloy according to claim 1, it is characterised in that：As mass fraction, the ingredient of the magnesium alloy
For：Sc 5%, Mn 0.5%, Zr 0.5%, surplus are Mg and inevitable impurity.
4. high corrosion-resistant magnesium alloy according to claim 1, it is characterised in that：As mass fraction, the ingredient of the magnesium alloy
For：Sc 2%, Mn 1%, Zr 1%, surplus are Mg and inevitable impurity.
5. high corrosion-resistant magnesium alloy according to claim 1, it is characterised in that：In step 4）In, the magnesium alloy is special
Refining agent is：The special RJ-5 refining fluxes of magnesium-rare earth.
6. high corrosion-resistant magnesium alloy according to claim 1, it is characterised in that：In step 4）In, the coverture is：It is dilute
The native special RJ-5 flux of magnesium alloy.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015111035A1 (en) * | 2014-01-23 | 2015-07-30 | Dead Sea Magnesium Ltd. | High performance creep resistant magnesium alloys |
| CN104846246A (en) * | 2015-05-29 | 2015-08-19 | 苏州慧驰轻合金精密成型科技有限公司 | Novel die-casting rare earth Mg alloy with high thermal conductivity and preparation method of novel die-casting rare earth Mg alloy |
| CN105088037A (en) * | 2015-08-28 | 2015-11-25 | 上海交通大学 | Mg-RE-Mn-series multi-element magnesium alloy and preparation method thereof |
| CN105177384A (en) * | 2015-08-28 | 2015-12-23 | 上海交通大学 | Mg-RE-Zr system multielement magnesium alloy and preparation method thereof |
| CN105525178A (en) * | 2014-10-22 | 2016-04-27 | 上海交通大学深圳研究院 | High-thermal-conductivity die-castable Mg-Y-Zr series multielement magnesium alloy and preparation method thereof |
-
2017
- 2017-02-15 CN CN201710080020.8A patent/CN106756371B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015111035A1 (en) * | 2014-01-23 | 2015-07-30 | Dead Sea Magnesium Ltd. | High performance creep resistant magnesium alloys |
| CN105525178A (en) * | 2014-10-22 | 2016-04-27 | 上海交通大学深圳研究院 | High-thermal-conductivity die-castable Mg-Y-Zr series multielement magnesium alloy and preparation method thereof |
| CN104846246A (en) * | 2015-05-29 | 2015-08-19 | 苏州慧驰轻合金精密成型科技有限公司 | Novel die-casting rare earth Mg alloy with high thermal conductivity and preparation method of novel die-casting rare earth Mg alloy |
| CN105088037A (en) * | 2015-08-28 | 2015-11-25 | 上海交通大学 | Mg-RE-Mn-series multi-element magnesium alloy and preparation method thereof |
| CN105177384A (en) * | 2015-08-28 | 2015-12-23 | 上海交通大学 | Mg-RE-Zr system multielement magnesium alloy and preparation method thereof |
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