CN108265187A - Reduce the method that crystal grain is significantly roughened in magnesium-rare earth alloy higher temperature solid solution - Google Patents

Reduce the method that crystal grain is significantly roughened in magnesium-rare earth alloy higher temperature solid solution Download PDF

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Publication number
CN108265187A
CN108265187A CN201711379244.5A CN201711379244A CN108265187A CN 108265187 A CN108265187 A CN 108265187A CN 201711379244 A CN201711379244 A CN 201711379244A CN 108265187 A CN108265187 A CN 108265187A
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China
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magnesium
rare earth
alloy
solid solution
earth alloy
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CN201711379244.5A
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CN108265187B (en
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付彭怀
王丹
周逸源
彭立明
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SHANGHAI LIGHT ALLOY NET FORMING NATIONAL ENGINEERING RESEARCH CENTER Co Ltd
Zhangjiagang Magnesium Valley Hub Manufacturing Co Ltd
Shanghai Jiaotong University
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SHANGHAI LIGHT ALLOY NET FORMING NATIONAL ENGINEERING RESEARCH CENTER Co Ltd
Zhangjiagang Magnesium Valley Hub Manufacturing Co Ltd
Shanghai Jiaotong University
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    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C1/00Making non-ferrous alloys
    • C22C1/02Making non-ferrous alloys by melting
    • C22C1/03Making non-ferrous alloys by melting using master alloys
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C23/00Alloys based on magnesium
    • C22C23/06Alloys based on magnesium with a rare earth metal as the next major constituent
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22FCHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/06Changing 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 invention discloses the solutions that crystallite dimension in a kind of magnesium-rare earth alloy higher temperature solid solution is significantly roughened.Rare earth element ce of the concrete scheme to add 0.6~1.2 mass percent in magnesium-rare earth alloy.Rare earth element ce is added in magnesium-rare earth alloy, Mg Ce phases can be formed in grain boundaries in casting process.During high temperature solid solution, Mg Ce phases cannot be solid-solution in matrix completely, can be pinned at the migration that crystal boundary under high temperature is prevented on crystal boundary, play the role of that crystal grain is hindered significantly to be roughened.

Description

Reduce the method that crystal grain is significantly roughened in magnesium-rare earth alloy higher temperature solid solution
Technical field
The present invention relates to a kind of heat treatment optimization method in structural metallic materials field, specifically, referring to one kind The solution that crystallite dimension is significantly roughened in magnesium-rare earth alloy higher temperature solid solution, i.e., it is a kind of to prevent at magnesium-rare earth alloy solid solution The method that crystal grain is significantly roughened during reason.
Background technology
As most light structural metallic materials, magnesium alloy has many advantages, such as that specific strength, specific stiffness are high, and damping property is good, extensively Applied to aerospace, traffic, 3C fields etc..Mg-Gd-Y systems exist in recent years due to having good room temperature intensity and heat resistance Aerospace field has been widely used, such as the VW103Z alloys in the national standards of 2016 editions:Mg‐10Gd‐3Y‐Zr (wt.%) alloy.But during the higher temperature solid solution of this kind of alloy after casting, the crystallite dimension inside alloy would generally be shown It writes roughening or local anomaly roughening, crystallite dimension is grown up to 100~200 μm, even more by 30~60 μm under original cast state Greatly.Crystallite dimension roughening cause alloy T6 handle after intensity and plasticity be less than the temperature-room type plasticity of standard value, particularly alloy, usually Only between 1.5~2.5%, it is difficult to meet requirement of the high-quality magnesium alloy component to plasticity, seriously limit Mg-Gd-Y alloys Extensive use.This kind of alloy includes:《High-strength heat-resisting magnesium alloy and preparation method thereof》(the patent No.: CN200510025251.6 it is) disclosed:Mg- (6~15) Gd- (1~6) Y- (0.35~0.8) Zr- (0~1.5) Ca magnesium rare earth closes Gold;《High-strength heat-resistant rare earth magnesium alloy》(the patent No.:CN200610031169.9 it is) disclosed:Mg- (2~10) Gd- (3~12) Y Magnesium-rare earth alloy;《A kind of magnesium alloy and preparation method thereof》(the patent No.:CN200610144003.8 it is) disclosed:Mg- (7~11) Gd- (2~5) Y- (0~1.0) Zn- (0.3~0.6) Zr magnesium-rare earth alloys etc..Routine business magnesium-rare earth alloy WE43 (Mg-4Y- 2Nd-1RE, wt.%), there is also similar problems for the magnesium-rare earth alloys such as WE54, Chinese trade mark ZM6 (Mg-Nd-Zn-Zr):Casting exists The notable roughening of crystallite dimension causes material temperature-room type plasticity low during solution treatment, the unusual coarsening harm of local grain size Bigger.
Invention content
For the problem of grain coarsening, the present invention is few by adding in the alloy in the higher temperature solid solution of magnesium-rare earth alloy The Ce elements of amount form Mg-Ce phases, since maximum solid solution degrees of the Ce in Mg is relatively low, in height in the grain boundaries of magnesium-rare earth alloy Mg-Ce phases cannot be solid-solution in matrix completely during temperature solid solution, and crystal boundary under high temperature is prevented so as to be pinned on crystal boundary Migration plays the role of that crystal grain is prevented significantly to be roughened.
The present invention is achieved by the following technical solutions:
The method that crystal grain is significantly roughened in magnesium-rare earth alloy higher temperature solid solution is reduced the present invention provides a kind of, including Following steps:After the magnesium-rare earth alloy is melted, Ce elements, magnesium after refining, standing and casting are added at 700~740 DEG C The weight percent of Ce elements is 0.6~1.2% in rare earth alloy.
Preferably, the addition form of the Ce elements is Mg-Ce intermediate alloys.
Preferably, the magnesium-rare earth alloy is selected from Mg-10Gd-3Y-Zr alloys, Mg-3Nd-0.2Zn-Zr alloys In one kind.
The alloying element that the present invention is significantly roughened using Ce as crystal grain in prevention magnesium-rare earth alloy higher temperature solid solution, it is main If since maximum solid solution degree of the Ce elements in Mg is 0.52wt%, the eutectic temperature of Mg-Ce is 593 DEG C, and Ce is in magnesium rare earth It can be functioned as follows during alloy graining and follow-up solution treatment:
(1) in process of setting:The rare earth elements such as Ce and Gd, Y, Nd (RE) and Mg form Mg-RE chemical combination in process of setting Object, since conventional coagulation process is a nonequilibrium process, Ce elements can more be evenly distributed in Mg-RE compounds it In, i.e., Mg-Ce eutectic phases can be with the eutectic phases symbiosis such as Mg-Gd, Mg-Y, Mg-Nd.
(2) during solution treatment:Since maximum solid solution degree of the elements such as Gd, Y, Nd in Mg is larger, conventional magnesium rare earth The constituent contents such as Gd, Y, Nd are below its maximum solid solution degree in alloy, during solution treatment, these rare earth elements gradually from It is dissolved into magnesium matrix in Mg-RE compounds, finally the only remaining Mg-Ce phases for being located at crystal boundary;Ce also has certain in Mg Solid solubility compares rounding, tiny in the Mg-Ce phase shapes after part is dissolved.The tiny Mg-Ce phases of shape rounding can be While hindering grain coarsening, its negative effect to material temperature-room type plasticity is reduced.
Compared with prior art, the present invention has following advantageous effect:
After 0.6~1.2wt.%Ce being added in conventional magnesium-rare earth alloy, crystal grain ruler during alloy high-temp solution treatment Very little roughening rate Δ is less than 20%:Δ=(d-d0)/d0, average grain sizes of the wherein d for magnesium-rare earth alloy after solution treatment, d0 Average grain size for magnesium-rare earth alloy before solution treatment.
Description of the drawings
Upon reading the detailed description of non-limiting embodiments with reference to the following drawings, other feature of the invention, Objects and advantages will become more apparent upon:
Fig. 1 is the microscopic structure (500 ×) after 525 DEG C × 12h solution treatment:(a)VW103Z;(b)VW103Z+1.2Ce.
Specific embodiment
With reference to specific embodiment, the present invention is described in detail.Following embodiment will be helpful to the technology of this field Personnel further understand the present invention, but the invention is not limited in any way.It should be pointed out that the ordinary skill to this field For personnel, without departing from the inventive concept of the premise, various modifications and improvements can be made.These belong to the present invention Protection domain.
Embodiment 1
It is significantly thick that the present embodiment is related to crystal grain in Mg-10Gd-3Y-Zr (wt.%) alloy (VW103Z) higher temperature solid solution The solution of change.In Mg-10Gd-3Y-Zr magnesium-rare earth alloy fusion-casting process, Ce elements are added at 700~740 DEG C, so It is refined afterwards according to the melt treatment of conventional magnesium-rare earth alloy, quiescence in high temperature, last gravitational casting molding, magnesium after casting The weight percent of Ce elements is 1.2% in rare earth alloy.Alloy is obtained modified using conventional fusion-cast technique gravitational casting Then magnesium-rare earth alloy Mg-10Gd-3Y-1.2Ce-Zr is carried out using the 525 DEG C × 12h of conventional solid solution technique of VW103Z alloys Solution treatment, shown in microscopic structure Fig. 1 after solid solution, alloy (crystallite dimension roughening rate Δ is 120%) phase with being not added with Ce Than (Fig. 1 a), VW103Z (Fig. 1 b) alloy grain for adding Ce is more tiny, and solution treatment process crystallite dimension roughening rate Δ is only It is 5.6%.
Embodiment 2
The present embodiment is related to grain coarsening in Mg-3Nd-0.2Zn-Zr (wt.%) alloy (EZ30Z) higher temperature solid solution Solution.In Mg-3Nd-0.2Zn-Zr magnesium-rare earth alloy fusion-casting process, Ce elements are added at 700~740 DEG C, then Melt treatment according to conventional magnesium-rare earth alloy is refined, quiescence in high temperature, and last gravitational casting molding, magnesium is dilute after casting The weight percent of Ce elements is 0.6% in native alloy.Alloy obtains modified magnesium using conventional fusion-cast technique gravitational casting Then rare earth alloy Mg-3Nd-0.2Zn-0.6Ce-Zr is consolidated using the 540 DEG C × 16h of conventional solid solution technique of EZ30Z alloys Molten processing compared with the alloy (crystallite dimension roughening rate Δ is 60%) for being not added with Ce, adds the EZ30Z alloy grains of Ce more Tiny, solution treatment process crystallite dimension roughening rate Δ is only 15.4%.
Embodiment 3
The present embodiment is related to grain coarsening in Mg-3Nd-0.2Zn-Zr (wt.%) alloy (EZ30Z) higher temperature solid solution Solution.In Mg-3Nd-0.2Zn-Zr magnesium-rare earth alloy fusion-casting process, Ce elements are added at 700~740 DEG C, then Melt treatment according to conventional magnesium-rare earth alloy is refined, quiescence in high temperature, and last gravitational casting molding, magnesium is dilute after casting The weight percent of Ce elements is 0.7% in native alloy.Alloy obtains modified magnesium using conventional fusion-cast technique gravitational casting Then rare earth alloy Mg-3Nd-0.2Zn-0.7Ce-Zr is consolidated using the 540 DEG C × 16h of conventional solid solution technique of EZ30Z alloys Molten processing compared with the alloy (crystallite dimension roughening rate Δ is 60%) for being not added with Ce, adds the EZ30Z alloy grains of Ce more Tiny, solution treatment process crystallite dimension roughening rate Δ is only 13.2%.
Embodiment 4
The present embodiment is related to grain coarsening in Mg-3Nd-0.2Zn-Zr (wt.%) alloy (EZ30Z) higher temperature solid solution Solution.In Mg-3Nd-0.2Zn-Zr magnesium-rare earth alloy fusion-casting process, Ce elements are added at 700~740 DEG C, then Melt treatment according to conventional magnesium-rare earth alloy is refined, quiescence in high temperature, and last gravitational casting molding, magnesium is dilute after casting The weight percent of Ce elements is 0.8% in native alloy.Alloy obtains modified magnesium using conventional fusion-cast technique gravitational casting Then rare earth alloy Mg-3Nd-0.2Zn-0.8Ce-Zr is consolidated using the 540 DEG C × 16h of conventional solid solution technique of EZ30Z alloys Molten processing compared with the alloy (crystallite dimension roughening rate Δ is 60%) for being not added with Ce, adds the EZ30Z alloy grains of Ce more Tiny, solution treatment process crystallite dimension roughening rate Δ is only 11.6%.
Embodiment 5
The present embodiment is related to grain coarsening in Mg-3Nd-0.2Zn-Zr (wt.%) alloy (EZ30Z) higher temperature solid solution Solution.Ce elements are added at 700~740 DEG C in Mg-3Nd-0.2Zn-Zr magnesium-rare earth alloy fusion-casting process, are then pressed The melt treatment of more solito magnesium-rare earth alloy is refined, quiescence in high temperature, last gravitational casting molding, magnesium rare earth after casting The weight percent of Ce elements is 0.9% in alloy.It is dilute that alloy using conventional fusion-cast technique gravitational casting obtains modified magnesium Then native alloy Mg-3Nd-0.2Zn-0.9Ce-Zr is dissolved using the 540 DEG C × 16h of conventional solid solution technique of EZ30Z alloys Processing compared with the alloy (crystallite dimension roughening rate Δ is 60%) for being not added with Ce, adds the EZ30Z alloy grains more refinement of Ce Small, solution treatment process crystallite dimension roughening rate Δ is only 10.8%.
Embodiment 6
The present embodiment is related to grain coarsening in Mg-3Nd-0.2Zn-Zr (wt.%) alloy (EZ30Z) higher temperature solid solution Solution.In Mg-3Nd-0.2Zn-Zr magnesium-rare earth alloy fusion-casting process, Ce elements are added at 700~740 DEG C, then Melt treatment according to conventional magnesium-rare earth alloy is refined, quiescence in high temperature, and last gravitational casting molding, magnesium is dilute after casting The weight percent of Ce elements is 1.0% in native alloy.Alloy obtains modified magnesium using conventional fusion-cast technique gravitational casting Then rare earth alloy Mg-3Nd-0.2Zn-1.0Ce-Zr is consolidated using the 540 DEG C × 16h of conventional solid solution technique of EZ30Z alloys Molten processing compared with the alloy (crystallite dimension roughening rate Δ is 60%) for being not added with Ce, adds the EZ30Z alloy grains of Ce more Tiny, solution treatment process crystallite dimension roughening rate Δ is only 7.8%.
Embodiment 7
The present embodiment is related to grain coarsening in Mg-3Nd-0.2Zn-Zr (wt.%) alloy (EZ30Z) higher temperature solid solution Solution.In Mg-3Nd-0.2Zn-Zr magnesium-rare earth alloy fusion-casting process, Ce elements are added at 700~740 DEG C, then Melt treatment according to conventional magnesium-rare earth alloy is refined, quiescence in high temperature, and last gravitational casting molding, magnesium is dilute after casting The weight percent of Ce elements is 1.1% in native alloy.Alloy obtains modified magnesium using conventional fusion-cast technique gravitational casting Then rare earth alloy Mg-3Nd-0.2Zn-1.1Ce-Zr is consolidated using the 540 DEG C × 16h of conventional solid solution technique of EZ30Z alloys Molten processing compared with the alloy (crystallite dimension roughening rate Δ is 60%) for being not added with Ce, adds the EZ30Z alloy grains of Ce more Tiny, solution treatment process crystallite dimension roughening rate Δ is only 6.8%.
Comparative example 1
The present embodiment is related to grain coarsening in Mg-3Nd-0.2Zn-Zr (wt.%) alloy (EZ30Z) higher temperature solid solution Solution.In Mg-3Nd-0.2Zn-Zr magnesium-rare earth alloy fusion-casting process, Ce elements are added at 700~740 DEG C, then Melt treatment according to conventional magnesium-rare earth alloy is refined, quiescence in high temperature, and last gravitational casting molding, magnesium is dilute after casting The weight percent of Ce elements is 0.5% in native alloy.Alloy obtains modified magnesium using conventional fusion-cast technique gravitational casting Then rare earth alloy Mg-3Nd-0.2Zn-0.5Ce-Zr is consolidated using the 540 DEG C × 16h of conventional solid solution technique of EZ30Z alloys Molten processing compared with the alloy (crystallite dimension roughening rate Δ is 60%) for being not added with Ce, adds the EZ30Z alloy grains of Ce more Tiny, solution treatment process crystallite dimension roughening rate Δ is 47%, and improvement result is not notable.
Comparative example 2
The present embodiment is related to grain coarsening in Mg-3Nd-0.2Zn-Zr (wt.%) alloy (EZ30Z) higher temperature solid solution Solution.In Mg-3Nd-0.2Zn-Zr magnesium-rare earth alloy fusion-casting process, Ce elements are added at 700~740 DEG C, then Melt treatment according to conventional magnesium-rare earth alloy is refined, quiescence in high temperature, and last gravitational casting molding, magnesium is dilute after casting The weight percent of Ce elements is 1.5% in native alloy.Alloy obtains modified magnesium using conventional fusion-cast technique gravitational casting Then rare earth alloy Mg-3Nd-0.2Zn-1.5Ce-Zr is consolidated using the 540 DEG C × 16h of conventional solid solution technique of EZ30Z alloys Molten processing compared with the alloy (crystallite dimension roughening rate Δ is 60%) for being not added with Ce, adds the EZ30Z alloy grains of Ce more Tiny, solution treatment process crystallite dimension roughening rate Δ is only 6.5%.Although the addition of 1.5%Ce can play prevention solid solution The effect of grain coarsening in the process, but the addition of Ce at this time is that the negative effect of temperature-room type plasticity is extremely highlighted to material, is prolonged Stretch rate decline>20%.
Specific embodiments of the present invention are described above.It is to be appreciated that the invention is not limited in above-mentioned Particular implementation, those skilled in the art can make various deformations or amendments within the scope of the claims, this not shadow Ring the substantive content of the present invention.

Claims (3)

1. a kind of reduce the method that crystal grain is significantly roughened in magnesium-rare earth alloy higher temperature solid solution, which is characterized in that including as follows Step:After the magnesium-rare earth alloy is melted, Ce elements are added at 700~740 DEG C, after refining, standing and casting, magnesium rare earth The weight percent of Ce elements is 0.6~1.2% in alloy.
2. the method that crystal grain is significantly roughened in magnesium-rare earth alloy higher temperature solid solution, feature are reduced as described in claim 1 It is, the addition form of the Ce elements is Mg-Ce intermediate alloys.
3. the method that crystal grain is significantly roughened in magnesium-rare earth alloy higher temperature solid solution, feature are reduced as described in claim 1 It is, the one kind of the magnesium-rare earth alloy in Mg-10Gd-3Y-Zr alloys, Mg-3Nd-0.2Zn-Zr alloys.
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101270430A (en) * 2008-02-19 2008-09-24 重庆大学 Magnesium-zincium-manganese based magnesium alloy containing cerium
CN101760683A (en) * 2008-12-24 2010-06-30 沈阳铸造研究所 High-strength casting magnesium alloy and melting method thereof
CN102134672A (en) * 2011-03-22 2011-07-27 南昌大学 Mg-Al-Mn-xCe rare earth die cast magnesium alloy
CN103667755A (en) * 2012-09-21 2014-03-26 上海航天精密机械研究所 Rare earth-magnesium alloy smelting and purifying method
CN104498797A (en) * 2014-12-31 2015-04-08 上海交通大学 High-strength casting magnesium alloy with low hot cracking tendency and preparation method for high-strength casting magnesium alloy

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101270430A (en) * 2008-02-19 2008-09-24 重庆大学 Magnesium-zincium-manganese based magnesium alloy containing cerium
CN101760683A (en) * 2008-12-24 2010-06-30 沈阳铸造研究所 High-strength casting magnesium alloy and melting method thereof
CN102134672A (en) * 2011-03-22 2011-07-27 南昌大学 Mg-Al-Mn-xCe rare earth die cast magnesium alloy
CN103667755A (en) * 2012-09-21 2014-03-26 上海航天精密机械研究所 Rare earth-magnesium alloy smelting and purifying method
CN104498797A (en) * 2014-12-31 2015-04-08 上海交通大学 High-strength casting magnesium alloy with low hot cracking tendency and preparation method for high-strength casting magnesium alloy

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