CN105671390B - A kind of heat-resistant deforming magnesium alloy of calcic and neodymium and preparation method thereof - Google Patents
A kind of heat-resistant deforming magnesium alloy of calcic and neodymium and preparation method thereof Download PDFInfo
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- CN105671390B CN105671390B CN201610122638.1A CN201610122638A CN105671390B CN 105671390 B CN105671390 B CN 105671390B CN 201610122638 A CN201610122638 A CN 201610122638A CN 105671390 B CN105671390 B CN 105671390B
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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
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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
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/06—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of magnesium or alloys based thereon
Abstract
The present invention provides heat-resistant deforming magnesium alloy of a kind of calcic and neodymium and preparation method thereof；Alloying component includes Mg, Al, Ca, Nd, and each component weight/mass percentage composition is：Al：2.5~3.5 wt.%；Ca：0.30~0.60 wt.%；Nd：0.5 ~ 2.0wt.%, remaining is Mg and inevitable impurity, and total impurities are less than 0.06 wt.%.This method coordinates hot extrusion technique to realize by using compound addition alkaline earth element calcium and rear earth element nd, adds a certain amount of calcium in Mg Al systems magnesium alloy, dystectic Al can be combined into aluminium atom2Ca phases；Add rare earth neodymium, effective crystal grain thinning, while the rare-earth phase of neodymium and the aluminium formation high-temperature stable in alloy improves the intensity of material, the alloy after hot extrusion has fine and close tissue, thinner crystallite dimension, therefore at high temperature there is higher intensity ensure that certain plasticity simultaneously（Higher than 39%）.
Description
Technical field
The present invention relates to a kind of magnesium alloy, more particularly to a kind of calcic and the heat-resistant deforming magnesium alloy of neodymium and its preparation side
Method.
Background technology
With the development of society, the progress of science and technology, production and living propose higher requirement to material property.As most light
The commercial metal structural material of matter, magnesium alloy has density low, and specific strength, specific stiffness are high, and good casting property, damping property is good, electricity
Magnetic shield performance is high, it is easy to machining and it is recyclable many advantages, such as, it has also become the light-weight design such as automobile, Aero-Space and
Energy-saving preferred alloy.But the high-temperature behavior of magnesium alloy is poor, the low shortcoming of creep strength limits the further of magnesium alloy
Using.Such as conventional magnesium alloy Mg-Al based alloys（AZ systems and AM systems etc.）Although room-temperature property, corrosion resistance and die casting performance are good
It is good, but the Mg of its precipitated phasel7Al12In net distribution and fusing point is low, only 437 DEG C, be soft phase at not high temperature,
Easily softening roughening, therefore the shortcoming for causing above-mentioned serial magnesium alloy common is that high-temperature behavior is poor.It is used as structural member, its operating temperature
No more than 120 DEG C, therefore the high-temperature behavior of magnesium alloy how is improved as study hotspot in recent years.
To improve the heat resistance of magnesium alloy, alloying is a kind of effective modified method.In recent years, cheap alkaline earth element
The heat resistance that be used to improve alloy shows great potential.The thermally-stabilised of β phases in alloy can be improved by adding a small amount of Ca
Property, at the same also can significantly refining alloy microscopic structure, so as to improve synthesis mechanical property of the alloy at 100 DEG C ~ 200 DEG C
Energy.The rare earth element such as neodymium and yttrium has the effect of crystal grain thinning in the magnesium alloy, and intercrystalline strengthening can be utilized after addition, again can be with
By second-phase strength thereafter, the heat resistance of magnesium alloy is improved in terms of two.Meanwhile, as-cast structure becomes by hot-working
Shape（Extruding, rolling etc.）Afterwards, tissue is substantially refined, and casting flaw is eliminated, thus, compared with cast magnesium alloy, deformed Mg
Alloy has higher mechanical property.
By literature search, reported and changed on the basis of Mg-Al systems by compound addition alkaline earth calcium and rare earth neodymium at present
Method, patent and the application of shape magnesium alloy mechanical property apt to change and heat resistance are seldom.Simple production process, cost is not high and has
The alloy for having higher elevated temperature strength to be combined with plasticity stills need to explore.
The content of the invention
For deficiencies of the prior art, it is an object of the invention to provide a kind of calcic and the heat-resistant deforming magnesium of neodymium
Preferably alloying component is selected in high temperature 150 after alloy, the magnesium alloy materials alkaline earth calcium micro by adding and rare earth neodymium
High intensity is obtained at DEG C, while ensureing certain plasticity.
The present invention also provides a kind of preparation method of the heat-resistant deforming magnesium alloy of calcic and neodymium.
To achieve these goals, the present invention is adopted the following technical scheme that：A kind of calcic and neodymium of the present invention it is heat-resisting
Wrought magnesium alloy, is made up of Mg, Al, Ca and Nd, and the weight/mass percentage composition of its each component is：Al：2.5~3.5 wt.%；Ca：
0.30~0.60 wt.%；Nd：0.5~2.0wt.%；Remaining is Mg and inevitable impurity.Inevitably impurity is the present invention
Fe, Si etc., its total amount are less than 0.06 wt.%.
The preparation method of the heat-resistant deforming magnesium alloy of calcic and neodymium of the present invention, comprises the following steps：
A) alloy smelting and casting：Raw materials are technical pure magnesium ingot, fine aluminium ingot, Mg-30%Ca intermediate alloys, Mg-
25%Nd intermediate alloys.Cast using semi-continuous casting method.In SF6+CO2Under gas shield, magnesium ingot is put into fusion in crucible
730 ~ 750 DEG C of slag hittings are warming up to after change, fine aluminium ingot, Mg-30%Ca intermediate alloys, Mg- are added by the alloying component proportional quantity
25%Nd intermediate alloys, should preheat 15 ~ 30 minutes at 140 ~ 220 DEG C before addition, should be pressed into during addition below liquid level rapidly,
Stirring 2 ~ 5 minutes after to be melted, make composition uniform, stand 10 ~ 15 minutes；After standing is finished, dross on surface of fusant is salvaged, temperature is treated
When degree drops to 710 ~ 730 DEG C, crucible is put forward to be placed on chilling in brine bath；
B) machine：According to the size of extruder recipient by above-mentioned ingot casting sawing, railway carriage to suitable dimension；
C) homogenize：Homogenization Treatments are carried out under 440 ~ 460 DEG C of temperature conditionss, soaking time is 12 ~ 15h；
D) hot extrusion：The ingot casting and extrusion die after Homogenization Treatments are preheated 1.5 ~ 3 at 350 DEG C ~ 400 DEG C before extruding
Hour, extrusion temperature is 350 DEG C ~ 400 DEG C, and extrusion ratio is 25:1, extruding rate is 0.90 ~ 1.50m/min.
The mechanism that the present invention improves alloy heat resistance is：Alkaline earth calcium can be combined into dystectic Al with aluminium atom2Ca
Phase, the addition of rear earth element nd makes magnesium alloy cast crystal grain substantially refine, and promotes the dynamic in thermal deformation process and tie again
Crystalline substance, while forming the high-temperature stable rare-earth phase Al of Dispersed precipitate11Nd3And Al2Nd, has put forward alloy high-temp intensity, by hot extrusion
Alloy afterwards has fine and close tissue, thinner crystallite dimension, therefore intensity and plasticity with preferable alloy.
Compared with prior art, the present invention has the advantages that：
1st, alloy high-temp better performances of the invention：The microstructure of alloy is more uniform tiny, in 150 DEG C of room temperature and high temperature
Show higher intensity and elongation percentage.
2nd, cost of the present invention is relatively low：Only need to add a small amount of alkaline earth calcium and rare earth neodymium element, just can significantly improve conjunction
Golden intensity.
3rd, the present invention is simple to operate：The method only needs to once be extruded, it is not necessary to complicated processing technology, and institute
The equipment of use such as smelting furnace, heat extruder etc. are conventional common apparatus, with it is portable strong the characteristics of, be easy in industry
It is middle to realize.
Brief description of the drawings
Fig. 1 is microstructure photo-embodiment 1 of three kinds of alloys；
Fig. 2 is microstructure photo-embodiment 2 of three kinds of alloys；
Fig. 3 is microstructure photo-embodiment 3 of three kinds of alloys；
Fig. 4 is stretching engineering stress-strain curve of three kinds of alloys in room temperature；
Fig. 5 is stretching engineering stress-strain curve of three kinds of alloys at 150 DEG C.
Embodiment
The present invention is described in further detail in conjunction with specific embodiments with reference to the accompanying drawings, it should be noted that these
Embodiment is to be used to illustrate the present invention, rather than limitation of the present invention, and protection scope of the present invention is not limited to following implementation
Example.
Embodiment 1：The Mg-Al systems magnesium alloy of the rare earth neodymium of calcium containing alkaline earth of the present embodiment, by weight percentage including following
Composition：Al 2.85 wt.%, Ca 0.44 wt.%, Nd 0.62 wt.%, surplus is Mg and inevitable impurity is less than 0.06
wt.%。
Prepared by said ratio and in the following manner, the magnesium alloy with regard to the present embodiment can be obtained：
A) alloy smelting and casting：Raw materials are technical pure magnesium ingot, fine aluminium ingot, Mg-30%Ca intermediate alloys, Mg-
25%Nd intermediate alloys.Cast using semi-continuous casting method.In SF6+CO2Under gas shield, magnesium ingot is put into fusion in crucible
730 DEG C (or 740 DEG C, 750 DEG C) are warming up to after change, adds in the middle of fine aluminium ingot, Mg-30%Ca and closes by the composition proportion of embodiment 1
Gold, Mg-25%Nd intermediate alloys, are preheated 25 minutes before adding at 170 DEG C (or 140 DEG C, 210 DEG C), should be rapidly by it during addition
It is pressed into below liquid level, rear stirring to be melted 5 minutes makes composition uniform, stands 15 minutes (or 10 minutes)；After standing is finished, beat
Dross on surface of fusant is dragged for, treats that temperature drops to 710 DEG C (or 720 DEG C), crucible is put forward to be placed on chilling in brine bath；
B) machine：According to the size of extruder recipient by above-mentioned ingot casting sawing, railway carriage to suitable dimension；
C) homogenize：Homogenization Treatments are carried out under 450 DEG C of (or 440 DEG C, 460 DEG C) temperature conditionss, soaking time is
12h (or 15h)；
D) hot extrusion：By the ingot casting and extrusion die after Homogenization Treatments at 350 DEG C (or 370 DEG C, 400 DEG C) before extruding
2h (or 1.5h, 3h) is preheated, extrusion temperature is 350 DEG C (or 380 DEG C, 400 DEG C), and extrusion ratio is 25:1, extruding rate is
0.90m/min (or 1.50m/min).
Embodiment 2：The Mg-Al systems magnesium alloy of the rare earth neodymium of calcium containing alkaline earth of the present embodiment by weight percentage include below into
Point：Al 2.79 wt.%, Ca 0.39 wt.%, Nd 1.11 wt.%, surplus is Mg and inevitable impurity is less than 0.06
wt.%.Obtain the alloy smelting and casting-machining-homogenization-hot-extrusion method and the phase of embodiment 1 of the present embodiment magnesium alloy
Together, except that the composition proportion of molten alloy.
Embodiment 3：The Mg-Al systems magnesium alloy of the rare earth neodymium Han calcium containing alkaline earth of the present embodiment includes following by weight percentage
Composition：Al 2.80 wt.%, Ca 0.37 wt.%, Nd 1.76 wt.%, surplus is Mg and inevitable impurity is less than 0.06
wt.%.Obtain the alloy smelting and casting-machining-homogenization-hot-extrusion method and the phase of embodiment 1 of the present embodiment magnesium alloy
Together, except that the composition proportion of molten alloy.
Fig. 1 ~ Fig. 3 is the metallographic structure photo of extruded barses, and the metallographic structure from photo it can be found that after hot-working is put down
Equal crystallite dimension is below 5 μm, and, embodiment 1-3 average crystalline substance more uniform tiny with the increase alloy grain of Nd contents
Particle size is 4.13 μm, 2.70 μm, 2.39 μm respectively.Precipitation strength and intercrystalline strengthening cause the intensity of magnesium alloy to be improved.
Can be seen that by table 1 and Fig. 4 ~ 5, alloy (embodiment 1-3) of the invention has high intensity at 150 DEG C, and can guarantee that compared with
High plasticity.
It can be seen that, the alloy after hot extrusion has fine and close tissue, thinner crystallite dimension.By adding alkaline earth element
Calcium, plays a part of crystal grain thinning, and dystectic Al can be combined into aluminium atom2Ca phases, small and dispersed is distributed in base
In body, play a part of improving alloy heat resistance；Rear earth element nd is added, thick net distribution in matrix can be suppressed
Mg17Al12The formation of phase and the rare-earth phase (Al that high-temperature stable is formed with aluminium atom2Nd and Al11Nd3Phase), such one side energy
Dynamic recrystallization is effectively promoted, growing up for recrystal grain is hindered, obtains tiny recrystal grain；On the other hand due to
Al2Nd and Al11Nd3Mutually unique crystal structure and the combination with basal plane, in deformation process, effectively can hinder dislocation to slide
Move, so as to improve the intensity of material.Therefore, the magnesium alloy in room temperature and 150 DEG C there is higher intensity ensure that height simultaneously
Plasticity（Higher than 39%）.From table 1, alloy of the invention（Embodiment 1,2,3）Have at 150 DEG C than commercial WE43 magnesium
The higher mechanical property of alloy, yield strength ratio WE43 alloys slightly have raising, and elongation percentage is more than 5.6 times of WE43 alloys, and
Cost is lower than WE43 alloy.
Finally illustrate, the above embodiments are merely illustrative of the technical solutions of the present invention and it is unrestricted, although with reference to compared with
The present invention is described in detail good embodiment, it will be understood by those within the art that, can be to the present invention's
Technical scheme is modified or equivalent substitution, and without departing from the objective and scope of technical solution of the present invention, it all should cover
Among scope of the presently claimed invention.
Claims (1)
1. the heat-resistant deforming magnesium alloy of a kind of calcic and neodymium, it is characterised in that the magnesium alloy is main by Mg, Al, Ca, Nd group
Into Al：2.85 wt.%, Ca：0.44 wt.%, Nd：0.62wt.%, inevitable impurity is less than 0.06 wt.%；Remaining is
Mg；Or Al：2.79 wt.%, Ca：0.39 wt.%, Nd：1.11wt.%, inevitable impurity is less than 0.06wt.%, and remaining is
Mg；
Its preparation method comprises the following steps：
A) alloy smelting and casting：Raw materials are technical pure magnesium ingot, fine aluminium ingot, Mg-30%Ca intermediate alloys, Mg-25%Nd
Intermediate alloy；Cast using semi-continuous casting method；In SF6+CO2Under gas shield, magnesium ingot is put into rear liter to be melted in crucible
Temperature is added in fine aluminium ingot, Mg-30%Ca intermediate alloys, Mg-25%Nd to 730 ~ 750 DEG C of slag hittings by the alloying component proportional quantity
Between alloy, before addition should 140 ~ 220 DEG C preheat 15 ~ 30 minutes, should be pressed into during addition below liquid level rapidly, it is to be melted
Stir 2 ~ 5 minutes afterwards, make composition uniform, stand 10 ~ 15 minutes；After standing is finished, dross on surface of fusant is salvaged, treats that temperature is dropped to
At 710 ~ 730 DEG C, crucible is put forward to be placed on chilling in brine bath；
B) machine：According to the size of extruder recipient by ingot casting sawing, railway carriage to suitable dimension；
C) homogenize：Homogenization Treatments are carried out under 440 ~ 460 DEG C of temperature conditionss, soaking time is 12 ~ 15h；
D) hot extrusion：The ingot casting and extrusion die after Homogenization Treatments are preheated 1.5 ~ 3 hours at 350 DEG C ~ 400 DEG C before extruding,
Extrusion temperature is 350 DEG C ~ 400 DEG C, and extrusion ratio is 25:1, extruding rate is 0.90 ~ 1.50m/min.
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| CN106676357B (en) * | 2017-01-19 | 2018-05-04 | 重庆大学 | A kind of high plastic magnesium alloy and preparation method thereof |
| CN106702239B (en) * | 2017-01-19 | 2018-05-04 | 重庆大学 | A kind of high-yield-ratio wrought magnesium alloy and preparation method thereof |
| CN108425056A (en) * | 2018-05-03 | 2018-08-21 | 重庆大学 | A kind of room temperature high plastic magnesium alloy and preparation method thereof containing rare-earth yttrium |
| CN108950337B (en) * | 2018-08-07 | 2020-06-23 | 重庆大学 | Low-cost high-strength Mg-Zn-Y-Ce-Ca magnesium alloy and preparation method thereof |
| CN111335106B (en) * | 2020-03-25 | 2021-10-22 | 广东荣潮拓展建设有限公司 | Construction method of asphalt concrete pavement |
| CN113755732B (en) * | 2021-01-19 | 2022-08-09 | 中国科学院金属研究所 | Mg-Nd-Mn ternary heat-resistant magnesium alloy and preparation method thereof |
| CN115449682B (en) * | 2022-09-28 | 2024-04-26 | 广东汇天航空航天科技有限公司 | Rare earth and alkaline earth element compounded magnesium-based alloy and preparation method thereof |
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