CN106756371A - A kind of corrosion-resistant magnesium alloy high - Google Patents
A kind of corrosion-resistant magnesium alloy high Download PDFInfo
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- CN106756371A CN106756371A CN201710080020.8A CN201710080020A CN106756371A CN 106756371 A CN106756371 A CN 106756371A CN 201710080020 A CN201710080020 A CN 201710080020A CN 106756371 A CN106756371 A CN 106756371A
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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 corrosion-resistant magnesium alloy high, belong to metal material field.The corrosion-resistant magnesium alloy high, as mass fraction, the composition of the magnesium alloy is：Sc 2 5%, Mn 0.5 1%, Zr 0.5 1%, balance of Mg and inevitable impurity.The corrosion-resistant magnesium alloy high that the present invention is developed, which are added Sc elements, finds that Sc constituent contents are bigger by the OCP for testing heterogeneity, and current potential is raised, and corrosion tendency reduces, thus the decline of corrosion reaction driving force.The present invention is added after appropriate 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 appropriate Sc elements, and the species and ratio of rational proportion other alloying elements, the corrosive nature of magnesium alloy materials is further improved by the synergy of alloying element, a kind of corrosion-resistant magnesium alloy high of the new systems of Mg Sc Mn Zr is successfully developed.
Description
Technical field
The present invention relates to a kind of corrosion-resistant magnesium alloy high, belong to metal material field.
Background technology
The corrosion of material is very universal in production and living, often causes spillage of material, pattern change, mechanical property to move back
Change etc. so that load-carrying construction part cannot meet normal use demand.Material corrosion generality, spontaneity, continuation, non-thread
The characteristics of property, complexity so that the material failure caused by corrosion is often difficult to Accurate Prediction, so as to cause the huge of lives and properties
Big loss.Such as 1985, Japanese frame Boeing-747 aircraft was crashed due to the aging fracture of the stress corrosion 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 of China, bullet train, manned space flight, deep-sea early warning and detection, near space vehicle, repeat
The high speed development in the Important Project such as earth to orbit and return transportation system field, the demand to high combination property lightweighting materials is increasingly compeled
Cut.Magnesium is the structural metallic materials of current most lightweight, and its proportion is approximately the 2/3 of aluminium, the 1/4 of steel, be described as can loss of weight, energy-conservation,
" the 21 century green engineering material " of speed-raising.In the past, magnesium alloy was because low strength, deformability are weak, inflammable, decay resistance
The shortcomings of difference, limits its range of application, but the research and development of high strength rare earth magnesium alloy achieve major progress in recent years, and its is exhausted
Intensity is had been able to more than 500MPa, so as to expand its application in Important Project field significantly.
Deeply the corrosion mechanism of understanding magnesium alloy is to develop premise and the basis of corrosion-resistant magnesium alloy high.PH-Electric Potential Graph
（Pourbaix phasors）It is thermodynamically to weigh the important criterion that can corrosion occur, is also prediction material corrosion performance, analysis
The important tool of material corrosion mechanism.With the pH-Electric Potential Graph of pure magnesium（Fig. 1）As a example by, 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, from for thermodynamics, corrosion will not occur, i.e., magnesium metal can be with stable existence；Then mean in the region of magnesium ion
Magnesium to tend to ionic condition presence, that is, corrode；And in the region of magnesium hydroxide, although magnesium is not in the form of simple substance
In the presence of, but due to generate magnesium hydroxide can stable existence, it is attached to magnesium surface and can to a certain extent prevent corruption
The continuation of erosion occurs, that is, generate passivation layer, is conducive to the raising of decay resistance.As can be seen here, Pourbaix phasors are point
The powerful tool of analysis Corrosion Thermodynamics tendency.Although having had more than 70 kinds of pH-Electric Potential Graphs of common metal has all passed through real
Test is drawn surely, but it is still unknown to be directed to the pH-Electric Potential Graph of alloy especially magnesium alloy system, is needed badly by high-volume
Calculating or experiment come it is perfect.
The defect that current corrosion resistance of magnesium alloy can be differed from is not solved still well.Therefore, how by effective
Magnesium alloy formula design and develop, improve the decay resistance of magnesium alloy, be still arduous and urgent task.
The content of the invention
The present invention develops a kind of Mg-Sc- of new system for the technical problem of existing Corrosion Behaviors of Magnesium Alloys poor performance
Mn-Zr corrosion-resistant magnesium alloys high.The corrosion-resistant magnesium alloy high developed of the present invention, from reducing corrosion reaction driving force, suppress anode and
Cathode reaction these three aspect carried out the improvement of corrosive nature, obtained comparing high purity magnesium（99.95%）Corrosion rate is also low one
The material of the order of magnitude, can be applicable on the appearance member of LED and electronic product.
Realize the object of the invention and the technical scheme that uses for：A kind of corrosion-resistant magnesium alloy high, as mass fraction, the magnesium is closed
Gold composition be：Sc 2-5%, Mn 0.5-1%, Zr 0.5-1%, balance of Mg and inevitable impurity.
As one embodiment of the present invention, described corrosion-resistant magnesium alloy high, as mass fraction, the composition of the magnesium alloy
For：Sc 3%, Mn 0.8%, Zr 0.7%, balance of Mg and inevitable impurity.
As one embodiment of the present invention, described corrosion-resistant magnesium alloy high, as mass fraction, the composition of the magnesium alloy
For：Sc 5%, Mn 0.5%, Zr 0.5%, balance of Mg and inevitable impurity.
As one embodiment of the present invention, described corrosion-resistant magnesium alloy high, as mass fraction, the composition of the magnesium alloy
For：Sc 2%, Mn 1%, Zr 1%, balance of Mg and inevitable impurity.
Preferably, corrosion-resistant magnesium alloy high of the present invention is comprised the following steps：
1）Get the raw materials ready and cleared up with stove：Got the raw materials ready according to magnesium alloy component ratio, stove is cleaned up；Wherein, Sc elements are with Mg-Sc
Between alloy add, or Mn elements are added in simple substance Mg-Mn intermediate alloys form, or Zr elements are closed with the middle of pure Zr Mg-Zr
Gold is added；
2）Magnesium ingot melts：Put whole pure magnesium ingots into well formula electrical crucible, uniformly sprinkled in crucible bottom and pure magnesium ingot surface
Cosan, with crucible cover by crucible, is passed through by body SF6And N2The protective gas of composition, heat temperature raising makes whole pure magnesium ingots
It is completely melt under sulfur dioxide and the protective gas, by magnesium melt temperature control at 700 780 DEG C；
3）Add intermediate alloy：When magnesium melt temperature reaches more than 710 DEG C, by Mg-Mn intermediate alloys, 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, insulation 15
Minute, it is ensured that the intermediate alloy of addition all melts, and liquid magnesium alloy is obtained；
4）Alloy is refined：Treat that magnesium melt temperature rises to more than 730 DEG C, add the special refining agent of magnesium alloy to proceed by refining；Essence
During refining, refining spoon is immersed at the 2/3 of liquid magnesium alloy, intensely from top to bottom stirs liquid magnesium alloy until minute surface occurs in liquid level
Untill gloss；In whipping process, constantly toward spreading the special refining flux of magnesium alloy on magnesium alloy liquid level；Refining is finished, and is removed
Flux and scum silica frost on liquid level, then gently spread last layer coverture；Cool to preference temperature stand until be mingled with fully float or
Sink, finally skimmed.
Preferably, in step 4）In, the special refining agent of described magnesium alloy is：The special RJ-5 refinings of magnesium-rare earth are molten
Agent.
Preferably, in step 4）In, described coverture is：The special RJ-5 flux of magnesium-rare earth.
Compared with prior art, technological merit of the invention is：
1st, the corrosion-resistant magnesium alloy high that the present invention is developed, which are added Sc elements, is sent out by the OCP for testing heterogeneity
Existing, Sc constituent contents are bigger, and current potential is raised, and corrosion tendency reduces, thus the decline of corrosion reaction driving force, by testing electrokinetic potential
Polarization curve finds that with the addition of the Mg-Sc alloys after Sc elements, either negative electrode or anode flowpath are meaned as left avertence is moved
Addition Sc elements such that it is able to be effectively reduced corrosion driving force, but to pass through while suppress anode and cathode reaction
Experiment finds：Excessive Sc elements cause that the hydrogen-separating quantity and weight loss of magnesium alloy rise on the contrary.
2nd, the corrosion-resistant magnesium alloy high that the present invention is developed, the wherein content of Sc elements are controlled between 2-5%, improve Mg bases
The film layer volume conditions P-B ratios of the incomplete film layer in body surface face, originally Mg matrix surfaces（Pilling-bedworth Ratio）
Less than 1, i.e. film layer structure shrinkage porosite, it is impossible to Mg matrix surfaces are completely covered is added after appropriate 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.
3rd, the present invention is by adding appropriate Sc elements, and rational proportion other alloying elements species and ratio, lead to
The synergy for crossing alloying element further improves the corrosive nature of magnesium alloy materials, successfully develops a kind of Mg-Sc-Mn-
The corrosion-resistant magnesium alloy high of the new systems of Zr.
Brief description of the drawings
Fig. 1 is the pH-Electric Potential Graph of pure magnesium in the prior art.
Fig. 2 is the Thermodynamically stable state region figure 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 embodiment
The present invention is described further with reference to embodiment.
Embodiment 1
By taking 25kg as an example, according to Mg-3Sc-0.8Mn-0.7Zr proportioning as a example by, its as mass fraction, Sc 3%, Mn 0.8%, Zr
0.7%, balance of Mg and inevitable impurity, calculate the quality of intermediate alloy, are got the raw materials ready.Specifically can be by such as lower section
Method is obtained：
1）Get the raw materials ready and cleared up with stove：Got the raw materials ready according to magnesium alloy component ratio, stove is cleaned up；Wherein, Sc elements are with Mg-Sc
Between alloy add, or Mn elements are added in simple substance Mg-Mn intermediate alloys form, or Zr elements are closed with the middle of pure Zr Mg-Zr
Gold is added；
2）Magnesium ingot melts：Whole pure magnesium ingots are put into well formula electrical crucible in close mode of trying one's best, in crucible bottom and pure
Magnesium ingot surface uniformly sprinkles Cosan, with crucible cover by crucible, is passed through by body SF6And N2The protective gas of composition, heating
Heat up, whole pure magnesium ingots is completely melt under sulfur dioxide and the protective gas, by magnesium melt temperature control 700
780℃；
3）Add intermediate alloy：When magnesium melt temperature reaches more than 710 DEG C, by Mg-Mn intermediate alloys, 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, insulation 15
Minute, it is ensured that the intermediate alloy of addition all melts, and liquid magnesium alloy is obtained；
4）Alloy is refined：Treat that magnesium melt temperature rises to more than 730 DEG C, add the special refining agent of magnesium alloy to proceed by refining；Essence
During refining, refining spoon is immersed at the 2/3 of liquid magnesium alloy, intensely from top to bottom stirs liquid magnesium alloy until minute surface occurs in liquid level
Untill gloss；In whipping process, constantly toward spreading the special refining agent of magnesium alloy on magnesium alloy liquid level；Refining is finished, and removes liquid
Flux and scum silica frost on face, then gently spread last layer coverture；Cool to preference temperature stand until be mingled with fully float or under
It is heavy, finally skimmed.
Mg-3Sc-0.8Mn-0.7Zr corrosion-resistant magnesium alloy materials high manufactured in the present embodiment, its hydrogen-separating quantity is 0.8mL/cm2/
Day, weight loss is 0.6 × 10-2g/cm2/day。
Embodiment 2
By taking 25kg as an example, according to Mg-2Sc-1Mn-1Zr proportioning as a example by, its as mass fraction, Sc 2%, Mn 1%, Zr 1% are remaining
It is Mg and inevitable impurity to measure, and calculates the quality of intermediate alloy, is got the raw materials ready.Specific preparation method is with embodiment 1.
Mg-2Sc-1Mn-1Zr corrosion-resistant magnesium alloy materials high manufactured in the present embodiment, its hydrogen-separating quantity is 1.0mL/cm2/ day,
Weight loss is 0.5 × 10-2g/cm2/day。
Embodiment 3
By taking 25kg as an example, according to Mg-5Sc-0.5Mn-0.5Zr proportioning as a example by, its as mass fraction, Sc 5%, Mn 0.5%, Zr
0.5%, balance of Mg and inevitable impurity, calculate the quality of intermediate alloy, are got the raw materials ready.Specific preparation method is same
Embodiment 1.
Mg-5Sc-0.5Mn-0.5Zr corrosion-resistant magnesium alloy materials high manufactured in the present embodiment, its hydrogen-separating quantity is 0.4mL/cm2/
Day, weight loss is 1.0 × 10-2g/cm2/day。
Comparative example 1
By taking 25kg as an example, according to Mg-10Sc-0.8Mn-0.7Zr proportioning as a example by, its as mass fraction, Sc 10%, Mn 0.8%,
Zr 0.7%, balance of Mg and inevitable impurity, calculate the quality of intermediate alloy, are got the raw materials ready.Specific preparation method
With embodiment 1.
Mg-10Sc-0.8Mn-0.7Zr corrosion-resistant magnesium alloy materials high prepared by comparative example 1, its hydrogen-separating quantity is 2.6mL/cm2/
Day, weight loss is 3.1 × 10-2g/cm2/day。
Comparative example 2
By taking 25kg as an example, according to Mg-15Sc-0.8Mn-0.7Zr proportioning as a example by, its as mass fraction, Sc 15%, Mn 0.8%,
Zr 0.7%, balance of Mg and inevitable impurity, calculate the quality of intermediate alloy, are got the raw materials ready.Specific preparation method
With embodiment 1.
Mg-15Sc-0.8Mn-0.7Zr corrosion-resistant magnesium alloy materials high prepared by comparative example 1, its hydrogen-separating quantity is 3.0mL/cm2/
Day, weight loss is 3.7 × 10-2g/cm2/day。
Table 1 is embodiment 1-3, comparative example 1 and 2 is carried out liberation of hydrogen experiment and zero-G test test value, can be right by table 1
Than finding out the corrosion impact of high purity magnesium and different proportion Sc elements for magnesium alloy.Come for corrosion-resistant magnesium alloy high of the invention
Say, only adding appropriate Sc elements could improve the decay resistance of magnesium alloy, and excessive Sc elements cause magnesium alloy on the contrary
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 corrosion-resistant magnesium alloy material corrosion tests high obtained by embodiment 3, Fig. 3 exists for Mg-5Sc magnesium alloy materials
3.5% sodium chloride solution corrode 24 hours after XPS collection of illustrative plates.As shown in figure 3, can be clearly seen that in Mg-5Sc magnesium alloy materials
There is 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 form the diaphragm of stabilization densification on magnesium alloy materials surface.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%, the phases of β-Sc second can be introduced again, it is this
Second meets form micro- galvanic corrosion with Mg matrixes, so as to influence corrosion rate.
Claims (7)
1. a kind of corrosion-resistant magnesium alloy high, it is characterised in that：As mass fraction, the composition of the magnesium alloy is：Sc 2-5%, Mn
0.5-1%, Zr 0.5-1%, balance of Mg and inevitable impurity.
2. corrosion-resistant magnesium alloy high according to claim 1, it is characterised in that：As mass fraction, the composition of the magnesium alloy
For：Sc 3%, Mn 0.8%, Zr 0.7%, balance of Mg and inevitable impurity.
3. corrosion-resistant magnesium alloy high according to claim 1, it is characterised in that：As mass fraction, the composition of the magnesium alloy
For：Sc 5%, Mn 0.5%, Zr 0.5%, balance of Mg and inevitable impurity.
4. corrosion-resistant magnesium alloy high according to claim 1, it is characterised in that：As mass fraction, the composition of the magnesium alloy
For：Sc 2%, Mn 1%, Zr 1%, balance of Mg and inevitable impurity.
5. the corrosion-resistant magnesium alloy high according to any one of Claims 1 to 4, it is characterised in that：The corrosion-resistant magnesium alloy high is by such as
Lower section method is obtained：
1）Get the raw materials ready and cleared up with stove：Got the raw materials ready according to magnesium alloy component ratio, stove is cleaned up；Wherein, Sc elements are with Mg-Sc
Between alloy add, or Mn elements are added in simple substance Mg-Mn intermediate alloys form, or Zr elements are closed with the middle of pure Zr Mg-Zr
Gold is added；
2）Magnesium ingot melts：Put whole pure magnesium ingots into well formula electrical crucible, uniformly sprinkled in crucible bottom and pure magnesium ingot surface
Cosan, with crucible cover by crucible, is passed through by body SF6And N2The protective gas of composition, heat temperature raising makes whole pure magnesium ingots
It is completely melt under sulfur dioxide and the protective gas, by magnesium melt temperature control at 700 780 DEG C；
3）Add intermediate alloy：When magnesium melt temperature reaches more than 710 DEG C, by Mg-Mn intermediate alloys, 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, insulation 15
Minute, it is ensured that the intermediate alloy of addition all melts, and liquid magnesium alloy is obtained；
4）Alloy is refined：Treat that magnesium melt temperature rises to more than 730 DEG C, add the special refining agent of magnesium alloy to proceed by refining；Essence
During refining, refining spoon is immersed at the 2/3 of liquid magnesium alloy, intensely from top to bottom stirs liquid magnesium alloy until minute surface occurs in liquid level
Untill gloss；In whipping process, constantly toward spreading the special refining agent of magnesium alloy on magnesium alloy liquid level；Refining is finished, and removes liquid
Flux and scum silica frost on face, then gently spread last layer coverture；Cool to preference temperature stand until be mingled with fully float or under
It is heavy, finally skimmed.
6. corrosion-resistant magnesium alloy high according to claim 5, it is characterised in that：In step 4）In, described magnesium alloy is special
Refining agent is：The special RJ-5 refining fluxs of magnesium-rare earth.
7. corrosion-resistant magnesium alloy high according to claim 5, it is characterised in that：In step 4）In, described 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 |
Non-Patent Citations (1)
| Title |
|---|
| 温平: "《新编铸造技术数据手册》", 31 May 2012 * |
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