CN101857935A - Method for preparing magnesium base alloy material - Google Patents

Method for preparing magnesium base alloy material Download PDF

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Publication number
CN101857935A
CN101857935A CN 201010211029 CN201010211029A CN101857935A CN 101857935 A CN101857935 A CN 101857935A CN 201010211029 CN201010211029 CN 201010211029 CN 201010211029 A CN201010211029 A CN 201010211029A CN 101857935 A CN101857935 A CN 101857935A
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magnesium
alloy
melting
preparation
component
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CN101857935B (en
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周怀营
倪成员
王仲民
颜瑞
王殿辉
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Guilin University of Electronic Technology
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Guilin University of Electronic Technology
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Abstract

The invention discloses a method for preparing a magnesium base alloy material. The atomic ratio component composition of the magnesium base alloy material is MgxM100-x, wherein in the formula, x is more than 0 and equal to or less than 90. The method comprises the following steps of: (1) casting the M component to form blocks at first and then placing the blocks on the upper part of a melting container; (2) placing fine particles of volatile magnesium raw materials on the lower part of the container; (3) introducing a protective argon gas into a furnace chamber; (4) regulating induced current power and controlling the heating rate on the upper and lower parts of the melting container to ensure that M component melting blocks on the upper part enter a melting state at first and then melting M alloy liquid flows to the lower part, performing magnetic stirring at the same time and cooling to obtain mother alloys; and (5) melting the mother alloys and preparing a crystalline magnesium alloy by using a suction casting process or preparing an amorphous magnesium alloy by using a melt spinning quenching process. The method has the advantages that: magnesium component content can change in a large range; and through the combination of the suction casting process or the melt spinning quenching process, a magnesium alloy-containing material having a uniform phase composition or a nanocrystal and amorphous magnesium alloy material can be prepared.

Description

A kind of preparation method of magnesium base alloy material
Technical field
The present invention relates to the preparation method of Magnuminium, the preparation method of the magnesium base alloy material that the molten boiling point difference of particularly a kind of each constituent element is big.
Background technology
Research and development and application along with novel magnesium alloy system such as Mg-Zn, Mg-RE, Mg-Li and polynary Magnuminium system such as Mg-Zn-Zr-Nd, Mg-Gd-Y-Zr, multicomponent is the molten big magnesium alloy preparation technology of boiling point difference receive much concern, the accurate preparation and the structure regulating of multicomponent magnesium alloy become the emphasis and the difficult point of novel magnesium alloy research and development.
Magnesium is a kind of more active metal, and molten boiling point is low, and saturation vapour pressure is big, easily loss in the fusion process, and when the second constituent element fusing point was higher, the alloy molten temperature was higher, and the loss of magnesium more is difficult to control.For the melting of magnesium alloy, relatively Chang Yong guard method has: a) add insulating covering agent, promptly spread the insulating covering agent of one deck villaumite or villiaumite on the magnesium alloy liquid level, form the very thin protective layer of one deck, but produce as HCl, Cl during solvent protection melting 2Deng the toxic gas contaminate environment, also can introduce solvent impurity simultaneously; B) gas shield adds an air chamber that seals on smelting furnace, fill in it with shielding gas such as SO 2, SF 6, make the magnesium liquid level form thick protective membrane in one deck, suppress the volatilization of magnesium.But SO 2Gas is corrosive, and taste is unpleasant, and SF 6Have the intensive Greenhouse effect, will be banned use of future by the environmental protection legislation.
In addition; many excellent specific properties of magnesium base amorphous alloy and magnesium base amorphous matrix material make it as structured material, functional materials widespread use; magnesium base amorphous preparation commonly used mainly contains methods such as thin film deposition, mechanical ball milling, and cost height, tissue odds spare, are difficult for shortcoming such as large-scale production and seriously restricted its application.
Summary of the invention
The preparation method who the purpose of this invention is to provide the big magnesium base alloy material of the molten boiling point difference of a kind of each constituent element.This processing unit is simple, and the Magnuminium composition of preparation is accurately controlled, can be used for preparing the various Magnuminiums of Mg content from low magnesium to rich magnesium relative broad range.
The technical scheme that realizes the object of the invention is:
The big Magnuminium of the molten boiling point difference of a kind of each constituent element, the atomic ratio composition of this material consists of Mg xM L00-x, 0＜x in the formula≤90, M is rare-earth metals La, Ce, Pr, Nd, rich cerium or lanthanum rich mischmetal, one or more among transition metal Co, Al, Mn, Fe, Cr, Ti, Cu, the Zr.
The preparation method of the Magnuminium that the molten boiling point difference of a kind of each constituent element is big comprises the steps:
(1) founding of M component elder generation is become piece, place the top of melting container as master alloy;
(2) volatile magnesium raw material is placed the bottom of container with fine particle, the upper and lower is done to handle at interval;
(3) in furnace chamber, charge into the protection argon gas;
(4) regulate induced current power, the heating rate of control melting container upper and lower, guarantee to place the M component frit on top to be introduced into molten state, the M alloy liquid of molten state flows into the bottom subsequently, covering is in the magnesium granules of preheat mode, magnesium granules is successively melted, simultaneously magnetic agitation from the upper strata to lower floor, make the alloy structure homogenizing, promptly make composition mother alloy accurately after the cooling.
(5) after the mother alloy fusion with step (4) gained, adopt conventional suction casting process, promptly prepare the uniform crystalline state magnesium alloy materials of phase composite; Or when 66.7≤x in the formula≤90, adopt after the fusion and get rid of the band emergency cooling process, can prepare the magnesium alloy materials of amorphousness.
Step (1), (2) described M frit are 100-500 with the average-volume ratio of magnesium granules: 1.
Handle at the described interval of step (2), promptly satisfies melting when initial, and the M frit separates with magnesium raw material but communicates.
The described protection ar pressure that charges into of step (3) is 0.5-1.5atm.
Described M component of step (4) and magnesium alloy solution temperature are controlled at 650-750 ℃.
The preparation method's of a kind of magnesium base alloy material of the present invention technical process is:
Melting M component, make big bulk, place container top → Mg to make particulate and place container bottom → induction heating M component, make it fusion, flow into Mg particulate → magnetic agitation, make composition even, cooling obtains mother alloy → fusion mother alloy, adopts and inhales casting process (or getting rid of the band emergency cooling process) preparation crystal alloy (or amorphous alloy).
Advantage of the present invention is: magnesium constituent element content can change in very wide scope, to rich magnesium alloy, particularly is applicable to the big Magnuminium of the preparation molten boiling point difference of each constituent element from low magnesium alloy; Combine with inhaling casting process, can prepare the uniform crystalline state magnesium alloy materials of phase composite; Combine with getting rid of the band emergency cooling process, can prepare that tool is nanocrystalline, the magnesium alloy materials of amorphousness.
Description of drawings
Fig. 1 is the Mg of the embodiment of the invention 1 melting 33.3Ni 66.7Alloy X-ray diffraction spectrum and standard construction database PDF#355-2227MgNi 2The contrast synoptic diagram;
Fig. 2 is the Mg of the embodiment of the invention 2 meltings 70(L A0.25Ni 0.75) 30Alloy X-ray diffraction spectrogram;
Fig. 3 is the Mg of the embodiment of the invention 2 preparations 70(La 0.25Ni 0.75) 30The back scattering figure of alloy; Wherein: a, as cast condition; B, suction casting (copper mold aperture 5.8mm); C, suction casting (copper mold aperture 4.6mm);
Fig. 4 prepares the width banded sample drawing different with thickness for getting rid of band in the embodiment of the invention 3;
Fig. 5 prepares the X-ray diffraction spectrum comparison diagram that sample and melting prepare sample for the different tape speeds that get rid of in the embodiment of the invention 3.
Embodiment:
Below in conjunction with specific embodiment the present invention is launched further description.
Below induction melting among the described embodiment all be on the development WK-IIB of photoelectricity research company limited of thing section of Chinese Academy of Sciences high-frequency induction melting equipment, to carry out.
Embodiment 1:
A kind of atom metering is than being Mg 33.3Ni 66.7The preparation method of rich magnesium single-phased alloy, comprise the steps:
(1) according to formula m M=m Total* M M/ M TotalCalculate the Ni constituent mass that melting needs, wherein m M, m TotalBe respectively M component and quality altogether, M M, M TotalBe respectively M component and molar mass altogether;
(2) the Ni frit is made in melting, places induction melting furnace top as master alloy;
(3) the magnesium raw material silica tube bottom that drawn handles of packing into, Ni frit and magnesium granules volume ratio are controlled at about 200: 1;
(4) in furnace chamber, charge into the argon gas that pressure is 0.5-1atm;
(5) regulating induction melting power is 6.8KWh -1, silica tube is placed in the load coil, and be 25 seconds total heat-up time, then at 4.0KWh -1Power is incubated 10 seconds down, assurance places the M component frit on top to be introduced into molten state, the M alloy liquid of molten state flows into the bottom subsequently, covering is in the magnesium granules of preheat mode, magnesium granules is successively melted from the upper strata to lower floor, magnetic agitation makes the alloy structure homogenizing simultaneously, promptly makes MgNi after the cooling 2Mother alloy.
(6) mother alloy is heated to complete fusion, adopt the conventional casting condensation process of inhaling, promptly on the incidental absorbing and casting device of induction melting equipment, carry out, select the cooling copper mold for use, the cooling copper mold die cavity of molten metal liquid, obtain single-phase magnesium alloy after the cooling with high pressure argon stream injection different diameter.Accompanying drawing 1 is for the X-ray diffraction spectrogram (XRD) of the single-phased alloy of this embodiment preparation, with standard construction database PDF#355-2227MgNi 2Contrast confirms that the alloy of preparation is MgNi 2Single-phased alloy shows under these processing condition, and the loss that has successfully overcome magnesium is to the accurately influence of preparation of alloy.
Embodiment 2
A kind of composition is Mg 70(La 0.25Ni 0.75) 30The preparation of rich magnesium alloy.At first calculate the quality (starting material La, Ni purity are 99.9%) of required La and Ni component, mix the back and in induction melting furnace, be smelted into LaNi master alloy frit according to the formula among the embodiment 1.LaNi alloy frit and the magnesium raw material that the is placed on silica tube top silica tube bottom that drawn handles of packing into, LaNi frit and magnesium granules volume ratio are controlled at about 150: 1, charge into the 1atm argon gas in the stove, and power setting is 6.2KWh during induction melting -1, be 25 seconds total heat-up time, then at 4.0KWh -1Power is incubated 10 seconds down, assurance places the M component frit on top to be introduced into molten state, the M alloy liquid of molten state flows into the bottom subsequently, covering is in the magnesium granules of preheat mode, magnesium granules is successively melted from the upper strata to lower floor, magnetic agitation makes the alloy structure homogenizing simultaneously, and making composition after the cooling accurately should richness magnesium mother alloy.Mother alloy is heated to complete fusion, adopt the conventional casting condensation process of inhaling, promptly on the incidental absorbing and casting device of induction melting equipment, carry out, select the cooling copper mold for use, the cooling copper mold die cavity of molten metal liquid, obtain the column magnesium alloy after the cooling with high pressure argon stream injection different diameter.Accompanying drawing 2 shows that for the X-ray diffraction spectrogram (XRD) of the rich magnesium alloy of this embodiment preparation this alloy is by Mg 2Ni, La 2Mg 17And LaMg 3Form, confirm to adopt the rich magnesium alloy composition of this prepared accurately controlled; Accompanying drawing 3 (a) is the figure of back scattering tissue topography of preparation alloy, can clearly observe three phase region, accompanying drawing 3 (b) and accompanying drawing 3 (c) are inhaled the alloy structure pattern (SEM back scattering figure) that casting obtains when should alloy being respectively 5.8mm and 4.6mm in the copper mold aperture, and enlargement ratio is 1000 times.As seen from the figure, along with reduce (corresponding speed of cooling increases) in copper mold aperture, alloy grain and phase constitution refinement phenomenon that the suction casting obtains are obvious, and the component segregation phenomenon reduces, and being evenly distributed degree improves mutually.These constitutional featuress all help the improvement of magnesium alloy over-all properties.
Embodiment 3
A kind of composition is Mg 70(La 0.22Ni 0.67Co 0.11) 30Amorphous magnesium alloy get rid of band emergency cooling process preparation method.Employing prepares the identical method of mother alloy with embodiment 2 and makes Mg 70(La 0.22Ni 0.67Co 0.11) 30Mother alloy, then with this mother alloy with the complete fusion of induction melting, alloy liquation stream is mapped on the surface of rotating metallic roller (accessory of induction melting equipment) by leting slip a remark, liquation contacts with roll surface and forms weld pool, weld pool be limited at let slip a remark and roll surface between, cooled off simultaneously and shearing action, by means of the rotation of roller, liquation is constantly proposed to form amorphous ribbon from weld pool.In the present embodiment, select copper cooling wheel disc for use, the wheel disc speed setting is in 15-30 meter per second (linear velocity of finger wheel dish outer rim), and the distance between cooling wheel disc and the nozzle is 5-15mm, obtained banded alloy thickness at 0.01-0.2mm, the width alloy strip in the 0.5-4mm scope.Accompanying drawing 4 is for getting rid of the width sample different with thickness that band prepares; Accompanying drawing 5 is the XRD figure spectrum of alloy sample.Can find out by the result, significantly nanocrystalline/non-crystal structure feature that the alloy strip of preparation has, differential thermal analysis confirms that it has thermostability preferably.

Claims (6)

1. magnesium base alloy material, it is characterized in that: the atomic ratio composition of this material consists of Mg xM 100-x, 0＜x in the formula≤90, M is rare-earth metals La, Ce, Pr, Nd, rich cerium or lanthanum rich mischmetal, one or more among transition metal Co, Al, Mn, Fe, Cr, Ti, Cu, the Zr.
2. the preparation method of the described a kind of magnesium base alloy material of claim 1 is characterized in that: comprise the steps:
(1) founding of M component elder generation is become piece, place the top of melting container as master alloy;
(2) volatile magnesium raw material is placed the bottom of container with fine particle, do between the upper and lower to handle at interval;
(3) in furnace chamber, charge into the protection argon gas;
(4) regulate induced current power, the heating rate of control melting container upper and lower, guarantee to place the M component frit on top to be introduced into molten state, the M alloy liquid of molten state flows into the bottom subsequently, covering is in the magnesium granules of preheat mode, magnesium granules is successively melted, simultaneously magnetic agitation from the upper strata to lower floor, make the alloy structure homogenizing, promptly make composition mother alloy accurately after the cooling;
(5) with the mother alloy of step (4) gained, adopt conventional suction casting process after the fusion, can prepare the uniform crystalline state magnesium alloy materials of phase composite; Or when 66.7≤x in the formula≤90, adopt after the fusion and get rid of the band emergency cooling process, can prepare the magnesium alloy materials of amorphousness.
3. preparation method according to claim 2 is characterized in that: step (1), (2) described M frit are 100-500 with the average-volume ratio of magnesium granules: 1.
4. preparation method according to claim 2 is characterized in that: the described interval of step (2) is handled and is meant that melting container satisfies melting when initial, and the M frit separates with magnesium raw material but communicates.
5. preparation method according to claim 2 is characterized in that: step (3) is described, and to charge into the protection ar pressure be 0.5-1.5atm.
6. preparation method according to claim 2 is characterized in that: described M component of step (4) and magnesium alloy solution temperature are controlled at 650-750 ℃.
CN2010102110296A 2010-06-25 2010-06-25 Method for preparing magnesium base alloy material Expired - Fee Related CN101857935B (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102876946A (en) * 2012-09-13 2013-01-16 燕山大学 Magnetic magnesium alloy and preparation method thereof
CN109852867A (en) * 2017-11-30 2019-06-07 江苏宇之源新能源科技有限公司 A kind of novel metal preform material
CN114672686A (en) * 2022-03-21 2022-06-28 华中科技大学 Preparation method of additional nano-particle reinforced cast aluminum-lithium alloy

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN2716781Y (en) * 2004-04-02 2005-08-10 福建省泉州鑫艺鸿镁业有限公司 Magnesium alloy smelting furnace

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN2716781Y (en) * 2004-04-02 2005-08-10 福建省泉州鑫艺鸿镁业有限公司 Magnesium alloy smelting furnace

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
《无机化学》 19860630 申泮文等 储氢材料新合成方法的研究 第2页第3行 1 , 2 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102876946A (en) * 2012-09-13 2013-01-16 燕山大学 Magnetic magnesium alloy and preparation method thereof
CN109852867A (en) * 2017-11-30 2019-06-07 江苏宇之源新能源科技有限公司 A kind of novel metal preform material
CN114672686A (en) * 2022-03-21 2022-06-28 华中科技大学 Preparation method of additional nano-particle reinforced cast aluminum-lithium alloy
CN114672686B (en) * 2022-03-21 2022-10-28 华中科技大学 Preparation method of additional nano-particle reinforced cast aluminum-lithium alloy

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