CN106834846A - A kind of multicomponent heat-resistant corrosion-resistant magnesium alloy and preparation method - Google Patents

A kind of multicomponent heat-resistant corrosion-resistant magnesium alloy and preparation method Download PDF

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CN106834846A
CN106834846A CN201611206714.3A CN201611206714A CN106834846A CN 106834846 A CN106834846 A CN 106834846A CN 201611206714 A CN201611206714 A CN 201611206714A CN 106834846 A CN106834846 A CN 106834846A
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alloy
resistant
corrosion
magnesium alloy
heat
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CN106834846B (en
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刘国军
王慧远
查敏
王珵
杨治政
罗丹
荣建
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Jilin University
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Jilin University
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    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C23/00Alloys based on magnesium
    • C22C23/02Alloys based on magnesium with aluminium as the next major constituent
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C1/00Making alloys
    • C22C1/02Making alloys by melting
    • C22C1/03Making alloys by melting using master alloys

Abstract

The invention discloses a kind of multicomponent heat-resistant corrosion-resistant magnesium alloy and preparation method, alloy includes by percentage to the quality:5.8~7.8%Al, 2.2~3.2%Sn, 0.2~1.0%Zn, 0.2~2.0%RE, 0.1~0.3%Mn, remainder are the impurity of Mg and inevitable total amount≤0.2%.Tin, neodymium and/or samarium is added to form refractory grain phase Nd in magnalium base material5Sn3And Sm5Sn3, and refractory grain phase is further refined by the addition of zinc, improve strong plasticity, heat resistance and the corrosion resistance of alloy;Remaining tin is combined generation Mg with magnesium simultaneously2Sn, further improves alloy property;Addition manganese reduce impurity element harm, improve alloy corrosion resistance, by adjusting element between proportioning obtain heat-proof corrosion-resistant magnesium alloy.

Description

A kind of multicomponent heat-resistant corrosion-resistant magnesium alloy and preparation method
Technical field
The present invention relates to light metal material and metallurgical technology field.It is more particularly related to a kind of multicomponent heat-resistant Cast magnesium alloy and preparation method thereof.
Background technology
As energy scarcity and problem of environmental pollution increasingly sharpen, field of traffic lightweight unavoidably, as environment Friendly light material causes extensive concern.Magnesium alloy as current applicable most light metal structure material, with compared with Specific strength high and specific stiffness, good diamagnetic interference, excellent damping characteristics, high-termal conductivity and easily recovery etc. are excellent Point, has significant application in the field such as Aero-Space, facilities for transport and communication manufacture, household electrical appliances instrument, telecommunications, biomedicine Value and huge application prospect, it has also become one of metal material of 21 century most development potentiality.So far, it is existing Commercial magnesium alloy still based on the Mg-Al systems magnesium alloy of AZ91, AM50, accounts for the 90% of magnesium alloy total amount.
The Mg of Mg-Al systems magnesium alloy17Al12Crystal boundary is mainly mutually distributed in divorsed eutectic web form, alloy is degrading Decay resistance and elevated temperature strength.Therefore, vast researcher is from design of alloy (alloying) and is heat-treated (at T6 Reason) etc. aspect Mg-Al systems magnesium alloy is conducted a research, it is intended to improve its mechanical property and decay resistance.
The stacking fault energy of magnesium can be reduced in appropriate Sn addition Mg-Al magnesium alloys and then be advantageously implemented superplasticity, while With certain solid solution strengthening effect;When but the content of Sn is higher, large-sized Mg2Sn is gathered in crystal boundary and reduces alloy Performance;Single addition Sn improves unobvious to the corrosion resisting property of alloy.Effect of the RE elements in Mg-Al magnesium alloys is mainly logical Cross the mechanical property to form Al-RE phases and improve alloy by being heat-treated, but Al-RE phases easily alloy crystal boundary be enriched with into And size is larger, the precipitation strength effect of alloy is reduced.Zn elements are one of alloy elements for commonly using in magnesium alloy, mainly For improving the mechanical property of alloy, but, low-alloyed corrosion resisting property can drop in the addition of excessive Zn.The addition of Mn elements can To reduce the damaging effect of Impurity Fe, while in the Al-Mn compounds and Mg of crystal boundary generation17Al12Compare, it is easier to Passivation, improves the corrosion resisting property of magnesium alloy.It is indicated above, it is difficult to realize to have in single addition alloying element to Mg-Al alloys The magnesium alloy of the heat-proof corrosion-resistant of certain mechanical property.Majority research lays particular emphasis on the formation of Al-RE phases and is modified, and does not consider Alloying element tin forms dystectic second phase with neodymium or samarium, these dystectic second heat resistances for mutually contributing to alloy Improve.
Chinese patent " a kind of cast Mg alloy with high strength and its melting method "【Application number:200810230077.2】It is open A kind of cast Mg alloy with high strength, the weight/mass percentage composition of its each composition is respectively:Gd:8.1~11.5%, Y:1.0 ~4.5%, RE:0.01~3.0%, Zn:0.01~0.2%, Mn:0~0.18%, Zr≤1.0%, and (Gd+Y+RE)≤ 15.5%;Mg and impurity:Surplus, the content of rare earth of the alloy is high, and by adding the further refining alloy of alloy element Zr Crystallite dimension, improve alloy preparation cost, the alloy does not contain relatively inexpensive alloy element Al and Sn.
Chinese patent " a kind of high-strength heat-resistant magnesium alloy and its method of smelting "【Application number:200610112622.9】It is public A kind of high-strength heat-resistant magnesium alloy is opened, its component content is:Y be 4.5~10wt%, Gd be 0~8wt%, Dy be 0~ 5wt%, Tb are 0~5wt%, and Ho is 0~5wt%, and Er is 0~5wt%, and Tm is 0~5wt%, and Nd is 2~4.5wt%, and Sm is 0~3.5wt%, remaining is Mg, and the alloy can be as wrought magnesium alloy, it is also possible to used as casting.The alloy contains height The rare earth of content increased alloy preparation cost, without alloy element Al, Zn, Sn and Mn, while also not carrying out the resistance to of correlation The detection of corrosion energy.
Chinese patent " a kind of heat-proof magnesium-base rare earth alloy and preparation method thereof "【Application number:200610131696.7】Propose Alloy composition and percentage by weight be:6~8%Gd, 1~5%R, 0.3~0.6%Zr, impurity element Ni, Cu, Fe, Si and The total amount of Al is not more than 0.05%, and remaining is Mg;Constituting formula is:Mg- (6~8%) Gd- (1~5%) R- (0.3~0.6%) Zr.Wherein, R represents Nd or Sm or MY or Dy or Ho or Er;Content of rare earth scope control in the alloy is 7%~13%.Should The content of rare earth of alloy is higher, increased alloy preparation cost, at the same substantial amounts of rare-earth phase increased alloy subsequent heat treatment into This, the alloy does not have addition element Al, Zn, Sn and Mn.
Chinese patent " a kind of Mg-Sn-Al wrought magnesium alloy and preparation method thereof "【Application number:CN201310071667.6】 Disclose its raw material components and weight/mass percentage composition is:Industrial pure tin:4.00%~10.00%;Commercial-purity aluminium:1.00%~ 6.00%;Manganese:0.01%~1.00%;Remaining is pure magnesium and inevitable impurity, the pure magnesium, commercial-purity aluminium And industrial pure tin purity is all more than 99%;Zinc purity is more than 99.5%;Manganese is in the form of 4% magnesium manganese intermediate alloy Addition.The Sn contents of the alloy are higher, used as wrought magnesium alloy, without addition rare earth element.
Patent 201110032706.1 discloses a kind of high-toughness heat-resistant corrosion-resistant rare earth magnesium alloy and preparation method thereof, its matter Measuring percentage composition is:The aluminium of 3-6%;The manganese of 0.2-0.5%, the rare earth of 1.0-2.5%, the antimony of 0.6-1.2%, 0.3-0.8% Cadmium, remaining is magnesium, and described rare earth is commercialization cerium-rich mischmetal (RE), described commercialization cerium-rich mischmetal (RE) Element composition mass percent be:The lanthanum (La) of 25-35%, the cerium (Ce) of 60-72%, the praseodymium (Pr) of 3-8%, 0-3% Neodymium (Nd).Preparation method:It is mixed gas protected in the SF6+CO2 that volume fraction is 0.5% by the alloy material of said ratio After magnesium is melted in crucible under melting condition, at 660-680 DEG C, to be closed in the middle of commercial-purity aluminium, aluminium manganese intermediate alloy, Mg-RE Golden form adds alloy element, after furnace charge to be added is completely dissolved into alloy molten solution, temperature is raised, then by industrial star antimony With pure cadmium by bell jar press-in alloy molten solution, being uniformly mixed and continuing to heat up, the refining of refining agent refining magnesium alloys liquid is added, Poured into a mould after standing, obtain this product.Advantage:Improve the obdurability and room temperature and mechanical behavior under high temperature of alloy;Make the tough of alloy Property, heat-resisting and corrosion resisting property be higher than existing AE systems magnesium alloy.
The content of the invention
It is an object of the present invention to provide a kind of magnesium alloy, tin, neodymium and/or samarium is added to form high-melting-point in magnalium base material Particle phase Nd5Sn3And Sm5Sn3, and refractory grain phase is further refined by the addition of zinc, improve the strong plasticity of alloy, resistance to Hot and corrosion resistance, and the proportioning adjusted between element obtains heat-proof corrosion-resistant magnesium alloy.
It is a still further object of the present invention to provide a kind of preparation method of magnesium alloy, when control argon gas flow velocity, blowing argon gas The parameters such as melt temperature, the time of blowing argon gas and blowing argon gas head mixing speed in the melt, are at utmost reduced in organizing The content of slag, and then be conducive to improving alloy property.
In order to realize these purposes of the invention and further advantage, there is provided a kind of multicomponent heat-resistant corrosion-resistant magnesium alloy, Include by percentage to the quality:5.8~7.8%Al, 2.2~3.2%Sn, 0.2~1.0%Zn, 0.2~2.0%RE, 0.1~ 0.3%Mn, remainder is the impurity of Mg and inevitable total amount≤0.2%.
Preferably, the RE is Nd and/or Sm.
Preferably, Si≤0.1% in the impurity.
Preferably, including:7.0~7.8%Al, 2.5~3.0%Sn, 0.5~1.0%Zn, 0.8~1.6%RE, 0.1 ~0.3%Mn, remainder is the impurity of Mg and inevitable total amount≤0.2%.
Preferably, the RE is 0.6~1.4%Nd and/or 0.3~0.6%Sm.
The purpose of the present invention is also realized by a kind of preparation method of multicomponent heat-resistant corrosion-resistant magnesium alloy, including following step Suddenly:
Raw material preheating;
Protective atmosphere is passed through in smelting furnace, magnesium ingot is put into and is heated to being completely melt, aluminium ingot, zinc are added at 670~690 DEG C Ingot and tin slab, are completely dissolved and are warming up to 700~720 DEG C after stirring, and sequentially add and closed in the middle of Mg-Mn intermediate alloys, Mg-Sm Gold, Mg-Nd intermediate alloys, then being warming up to 730~750 DEG C makes alloy melt composition uniform, then be cooled to 680~700 DEG C and to Blowing argon gas are refined 1~5 minute in melt, and the alloy melt after skimming stands 10~30 minutes in 720~750 DEG C of insulations, will close Golden melt is cast in the mould that preheating temperature is 200~300 DEG C;
Casting is put into the electric furnace for be connected with protective atmosphere carries out solution treatment, small in 410~430 DEG C of insulations 18~24 When, then with stove with the rate of heat addition of 10~20 DEG C/min be warming up to 500~540 DEG C and be incubated 1~3 hour, then quench into water In;
Casting after solution treatment is put into aging oven, 175~240 DEG C is warming up to and is incubated 36~84 hours, Then take out air cooling.
Preferably, purity >=99.99% of magnesium ingot, purity >=99.99% of aluminium ingot, purity >=99.99% of zinc ingot metal, Purity >=99.99% of tin slab, impurity content≤0.1% of Mg-Nd, Mg-Sm and Mg-Mn intermediate alloy.
Preferably, the protective atmosphere in alloy casting step is SF6And CO2Mixed gas, the SF6And CO2Gas The volume ratio of body is 1:90~110.
Preferably, the argon gas flow velocity of the refining is 5-20 ml/mins.
Preferably, the raw material preheating includes:Raw material are placed 0.5~1 hour in being put into 90~135 DEG C of baking oven.
The present invention at least includes following beneficial effect:
1st, design of alloy principle of the invention is multi-element alloyed, rather than a certain alloying element is used alone.Such as, In Mg-Al-Sn alloys, that preferentially form is Mg2Sn phases, but after rare earth (RE) element is added, due between Sn, RE Electronegative defference then preferentially forms RE compared with big between Sn, Mg5Sn3Phase rather than Mg2Sn phases, remaining part Sn and Mg reacts life Into Mg2Sn phases;Because the content of the alloying element Sn and RE that are added in alloy is less, the second phase size of generation is smaller, works as conjunction After gold element Zn is added, RE5Sn3Phase and Mg2Sn meets and further refined, and more disperse is distributed in crystal boundary, is follow-up Solution treatment and Ageing Treatment provide the second phase size guarantee, correspondingly improve the heat resistance and corrosion resistance of alloy Energy.The addition of Mn elements further improves the corrosion resisting property of alloy.
2nd, the second phase RE5Sn3And Mg2Sn has refined Mg17Al12Phase, when alloy graining, the second phase RE5Sn3And Mg2Sn is excellent Prior to Mg17Al12Generated in grain boundaries, then large scale, continuous Mg17Al12Cannot mutually be formed in crystal boundary, when alloy is carried out During effect treatment, be conducive to Mg17Al12The small size of phase is separated out, and then improves intensity, heat resistance and the corrosion resisting property of alloy.Together On, the addition of Zn elements so that this effect is more obvious.
3rd, in alloy preparation method, the especially blowing argon gas refinement step in casting method, it is therefore an objective to remove alloy melt In slag, melt temperature, the time of blowing argon gas and blowing argon gas head when its argon gas flow velocity, blowing argon gas stirring speed in the melt The content of slag in as-cast microstructure when the parameters such as degree determine alloy graining, suitable technological parameter is conducive at utmost The content of slag in tissue is reduced, and then is conducive to improving alloy property;Such as:Argon gas flow velocity is too fast, then make the further oxygen of alloy Change, or argon gas flow velocity is excessively slow, the slag for having remnants is stayed in alloy structure, and both are all unfavorable for the microstructure of alloy, is disliked Intensity, heat resistance and the corrosion resisting property of alloy are changed.The temperature of solution treatment and Ageing Treatment, time in alloy preparation method The isoparametric effect that preferably further ensure that precipitation strength.
By multi-element alloyed composition design, the phase of high temperature second for obtaining Dispersed precipitate during alloy graining is realized Solution strengthening, refined crystalline strengthening and second-phase strength;Further by heat treatment, ageing strengthening is realized, improve alloy Heat resistance, while significantly improving the corrosion resisting property of alloy.
Further advantage of the invention, target and feature embody part by following explanation, and part will also be by this The research and practice of invention and be understood by the person skilled in the art.
Brief description of the drawings
Fig. 1 is the precipitated phase shape appearance figure of multicomponent heat-resistant corrosion-resistant magnesium alloy of the invention.
Specific embodiment
The present invention is described in further detail below in conjunction with the accompanying drawings, to make those skilled in the art with reference to specification text Word can be implemented according to this.
It should be appreciated that it is used herein such as " have ", "comprising" and " including " term do not allot one or many The presence or addition of individual other elements or its combination.
The invention provides a kind of multicomponent heat-resistant corrosion-resistant magnesium alloy, include by percentage to the quality:5.8~7.8%Al, 2.2~3.2%Sn, 0.2~1.0%Zn, 0.2~2.0%RE, 0.1~0.3%Mn, remainder is for Mg and inevitably The impurity of total amount≤0.2%, wherein, the RE is the mixing of Nd or Sm or Nd and Sm, Si≤0.1% in the impurity.
In another embodiment, the multicomponent heat-resistant corrosion-resistant magnesium alloy includes:7.0~7.8%Al, 2.5~3.0%Sn, 0.5~1.0%Zn, 0.8~1.6%RE, 0.1~0.3%Mn, remainder are Mg and inevitable total amount≤0.2% Impurity, wherein, the RE is 0.5~1.0%Nd and/or 0.3~0.6%Sm, Si≤0.1% in the impurity.
Mg alloy heat-proof corrosion-resistant performance optimization process is:
1st, Mg-Al alloy substrates
Aluminium element is added in magnesium to lift the solid solution strengthening effect of alloy, when the quality of Al and Mg is 1:11~15.5 energy The casting character and decay resistance of magnesium alloy are enough improved, alloy lightweight is realized.But Mg17Al12Mutually it is degrading the corrosion resistant of alloy Corrosion energy and elevated temperature strength.
2nd, Mg-Al-Sn alloys:
Addition element Sn in Mg-Al alloy substrates, wherein, based on quality Al:Mg:Sn=1:11~15.5:0.38~ 0.41, Sn, Al is co-doped with being conducive to the improvement of plasticity.
The mass fraction proportioning of the Mg-Al-Sn alloys of table one
Embodiment Mg (wt%) Al (wt%) Sn (wt%)
1 91.48 6.0 2.4
2 90.77 6.5 2.6
3 90.06 7.0 2.8
4 89.35 7.5 3
5 88.62 8.0 3.2
The alloy that embodiment 1-5 is obtained carries out tensile test at room temperature, high temperature (175 DEG C) tension test and the full leaching examination of corrosion Test, wherein, the test data of decay resistance is according to homogeneous corrosion total immersion test side of GB10124-1988 metal materials laboratory What method was obtained, and result of the test is summarized in table two.
The mass fraction proportioning of the Mg-Al-Sn alloys of table two
From table two, as Sn contents increase to 3.0% by 2.4%, the normal temperature of alloy, high temperature tensile properties and anti-corrosion Performance is improved, but increases to 3.2%, and the mechanical performance of alloy declines on the contrary.Reason is as follows:Mg-Al-Sn alloys are compared with Mg- The crystal grain of Al alloys is further refined, and because diffusion velocities of the Sn in Mg is slow, being not easy to overaging causes precipitated phase brilliant Grain length is big, because in alloy melt process of setting, part Sn preferentially combines to form the Mg of high-melting-point Dispersed precipitate with Mg2Sn Phase, this mutually can be used as divorsed eutectic Mg17Al12Mutually heterogeneous forming core core, can play solution strengthening, Refining Mg Alloy crystal grain and Refinement Mg17Al12The effect of phase, when alloy high-temp deforms, additionally it is possible to hinder the motion of dislocation, improves the elevated temperature strength of alloy With plasticity.When Sn constituent contents are high, the Mg of formation2Sn meets roughening, produces the effect of isolating to matrix and then reduces alloy Mechanical property.
3rd, Mg-Al-Sn-RE alloys:
Addition element RE in Mg-Al-Sn alloys, experiment is as shown in the table,:
The orthogonal test condition of table three
The orthogonal test table of table four
A B C D
6 A(1) B(1) C(1) D(1)
7 A(1) B(2) C(2) D(2)
8 A(1) B(3) C(3) D(3)
9 A(1) B(4) C(4) D(4)
10 A(2) B(1) C(2) D(3)
11 A(2) B(2) C(1) D(4)
12 A(2) B(3) C(4) D(1)
13 A(2) B(4) C(3) D(2)
14 A(3) B(1) C(3) D(4)
15 A(3) B(2) C(4) D(3)
16 A(3) B(3) C(1) D(2)
17 A(3) B(4) C(2) D(1)
18 A(4) B(1) C(4) D(2)
19 A(4) B(2) C(3) D(1)
20 A(4) B(3) C(2) D(4)
21 A(4) B(4) C(1) D(3)
The magnesium alloy of embodiment 6-21 different ratios in table four is tested, test event include tensile test at room temperature, High temperature (175 DEG C) tension test and corrosion total immersion test, wherein, the test data of decay resistance is according to GB10124-1988 gold Category material testing laboratory's homogeneous corrosion total immersion test method is obtained.
The performance test summary sheet of table five
Range analysis is carried out to orthogonal test high temperature tensile strength and corrosion resisting property, analyze data collects and table six.
The range analysis data summarization of table six
It is Mg-Al-Sn-RE in C3A1D2B4, i.e. alloy for the optimal proportion of high-temperature mechanical property from table six Mass fraction is 7.7%Al, 2.1%Sn, 1.2%RE (0.8%Nd and 0.4%Sm), and remainder is for Mg and inevitably The impurity of total amount≤0.2%.A certain amount of rare earth element is added, when alloying element Sn and RE (Nd and Sm) adds alloy to melt jointly During body, due between the TiFe_xM_y alloy of the TiFe_xM_y alloy much smaller than Sn and Mg and Sn, Nd, Sm and Mg of Sn and RE (Nd and Sm) compound Electronegativity relation, Sn preferentially combines to form RE with RE (Nd and Sm)5Sn3Second phase of high-melting-point Dispersed precipitate, rest Sn Mg is combined to form with Mg2The part of Sn phases and Sn is solid-solution in magnesium alloy substrate, coordinates Sn that alloy is substantially improved using Nd, Sm high Warm nature energy, and proportioning is adjusted, the RE of formation5Sn3Meet enhancing aging hardening effect, alloy high-temp performance is substantially improved not only to be had Effect ground improves alloy casting character, and RE5Sn3Formation both reduce Mg17Al12The content of phase, alloy structure is refined, made Mg17Al12Small and dispersed fractions distribution is mutually able to, the high-temperature behavior of alloy is improve.Rear earth element nd, samarium and lanthanum, cerium and praseodymium phase Than invigoration effect in the magnesium alloy is stronger, but the addition of high content rare earth element can improve the cost of magnesium alloy, excessive RE5Sn3Aggregation of meeting is roughened, and is harmful to the mechanical property of alloy.
Visible by deck watch six, table two, addition rare earth element can have a certain upgrade to the decay resistance of alloy, but It is that influence is limited.
3、Mg-Al-Sn-RE-Zn
On the basis of Mg-Al-Sn-RE alloy optimal proportion mass fractions are, a certain amount of Zn is added, by orthogonal examination Discussion Zn is tested to alloy mechanical performance and refinement RE5Sn3The effect of phase:
The orthogonal test condition of table seven
The orthogonal test table of table eight
A B C D E
6 A(1) B(1) C(1) D(1) E(1)
7 A(1) B(2) C(2) D(2) E(2)
8 A(1) B(3) C(3) D(3) E(3)
9 A(1) B(4) C(4) D(4) E(4)
10 A(2) B(1) C(2) D(4) E(3)
11 A(2) B(2) C(1) D(3) E(4)
12 A(2) B(3) C(4) D(2) E(1)
13 A(2) B(4) C(3) D(1) E(2)
14 A(3) B(1) C(3) D(2) E(4)
15 A(3) B(2) C(1) D(1) E(3)
16 A(3) B(3) C(4) D(4) E(2)
17 A(3) B(4) C(2) D(3) E(1)
18 A(4) B(1) C(4) D(3) E(2)
19 A(4) B(2) C(3) D(4) E(1)
20 A(4) B(3) C(2) D(1) E(4)
21 A(4) B(4) C(1) D(2) E(3)
The magnesium alloy of embodiment 6-21 different ratios in table four is tested, test event include tensile test at room temperature, High temperature (175 DEG C) tension test and corrosion total immersion test, wherein, the test data of decay resistance is according to GB10124-1988 gold Category material testing laboratory's homogeneous corrosion total immersion test method is obtained.
The performance test summary sheet of table nine
The contrast table five of table nine is visible, and Zn is added and the mechanical performance under normal temperature, the high temperature of alloy is all increased, to alloy Decay resistance lifted.
The range analysis data summarization of table ten
As table nine and table ten are visible, for the mechanical performance for improving alloy, optimum combination is C3D4A2E2B4, because: 1. the addition of Zn can refine RE5Sn3Phase, electron-microscope scanning is scanned to sample and shows that in Fig. 1, alloy grain is refined; 2. also there is solution strengthening effect, alloy mechanical performance is improved;The optimal proportion C3A1D2B4 of comparative example 6-21, it is seen then that Zn is by refining RE5Sn3Phase, makes Sm exceed element S n, mechanicalness of the lifting rare earth element to alloy on alloy mechanical performance influence The influence of energy.It is further that the corrosion resisting property for improving alloy is optimal to be combined as:A1B2D1C1F2, it is seen then that in Mg- Al-Sn-RE-Zn alloys, mechanical performance and corrosion resisting property can not get both, be ensure alloy while excellent mechanical performance, Also there is corrosion resisting property higher, Mn is added in Mg-Al-Sn-RE-Zn alloys.
4th, Mg-Al-Sn-RE-Zn-Mn alloys:
On the basis of the optimal machinery proportioning of Mg-Al-Sn-RE-Zn alloys, Mg contents are reduced, addition Mn improves alloy Decay resistance, refers to table 11.
Table 11 adds the alloy corrosion resistance energy test data summary sheet of manganese
As shown in table 11, addition manganese can improve the corrosion resisting property of alloy, by contrast table nine, when Mn contents are 0.1- The corrosion resisting property of alloy can be significantly improved when 0.3%, Mn elements can reduce the easy corrosion energy of Fe elements in impurity, but content mistake Gao Shihui has a certain impact to the high-temperature behavior of alloy, and preferably mass fraction is 0.2%.
It is visible above, add tin, neodymium and/or samarium to form refractory grain phase Nd in magnalium base material5Sn3With Sm5Sn3, and refractory grain phase is further refined by the addition of zinc, improve strong plasticity, heat resistance and the corrosion resistance of alloy;Together When remaining tin combined with magnesium and generated Mg2Sn, further improves alloy property;Addition manganese reduces the harm of impurity element, improves and closes Gold corrosion resistance, by adjusting element between proportioning obtain heat-proof corrosion-resistant magnesium alloy, as quality proportioning 7.7%Al, 2.3%Sn, 0.8%Zn, 1.4%RE (wherein 0.8%Nd, 0.4%Sm), 0.2%Mn, the impurity of inevitable total amount 0.16% and residue Mg when, obtain the Mg alloys with good mechanical properties and corrosion resisting property.
The invention also discloses a kind of multicomponent heat-resistant corrosion-resistant magnesium alloy preparation method, comprise the following steps:
1) raw material prepares
Weighed by the chemical composition and mass percent of design alloy and closed in the middle of pure magnesium, fine aluminium, pure zinc, pure tin, Mg-Nd Gold, Mg-Sm intermediate alloys, Mg-Mn intermediate alloys are used as raw material;Wherein, the purity of purity >=99.99% of magnesium ingot, aluminium ingot >=99.99%, purity >=99.99% of zinc ingot metal, purity >=99.99% of tin slab, Mg-Nd, Mg-Sm and Mg-Mn intermediate alloy Impurity content≤0.1%.
Above-mentioned each component raw material are put into 90~135 DEG C of baking oven and are preheated 0.5~1 hour;
2) alloy casting
First, it is 1 pure magnesium ingot to be put into and be passed through volume ratio:90~110 SF6And CO2In hybrid protection gas, gas is protected It is heated to being completely melt in the smelting furnace of atmosphere, aluminium ingot, zinc ingot metal, tin slab is added at 670~690 DEG C, treats that alloy is completely dissolved and fills After dividing stirring, 700~720 DEG C are warming up to, sequentially add Mg-Mn intermediate alloys, Mg-Sm intermediate alloys, Mg-Nd intermediate alloys, 730~750 DEG C are warming up to, are stirred after after added alloy material all fusing, make alloy melt composition uniform, then be cooled to 680~700 DEG C and to blowing argon gas in melt, wherein, argon gas is by anhydrous CaCl2Dry high-purity argon gas (>=99.99%), Argon gas flow velocity is 5-20 ml/mins, and refining is skimmed after 1~5 minute, and then alloy melt stands 10 in 720~750 DEG C of insulations ~30 minutes, alloy melt is cast in the fine copper mould or cast iron die that preheating temperature is 200~300 DEG C.
3) solution treatment T6
It is 1 casting to be put into and is connected with volume ratio:90~110 SF6And CO2In the electric furnace of hybrid protection gas, 410~ 430 DEG C be incubated 18~24 hours, then with stove with the rate of heat addition of 10~20 DEG C/min be warming up to 500~540 DEG C and insulation 1~ 3 hours, in water of then quenching.
4) Ageing Treatment
Casting after solution treatment is put into aging oven, 175~240 DEG C is warming up to and is incubated 36~84 hours, Air cooling is then taken out, high-strength temperature-resistant corrosion-resistant magnesium alloy is obtained.
Embodiment 25
According to mass fraction be 7.3%Al, 3.0%Sn, 0.8%Zn, 1.2%RE (0.8%Nd and 0.4%Sm) and 0.2% Mn, the impurity remaining as Mg and inevitable total amount≤0.2% carries out dispensing, and dispensing is put into 120 DEG C of baking oven , then be put into pure magnesium ingot in electrical crucible, in SF by baking 50 minutes6:CO2Volume ratio is 1:It has been heated under 100 protection 680 DEG C are warming up to after running down, fine aluminium, pure zinc, pure tin is added, aluminium alloy is sufficiently stirred for after dissolving, Mg- is added at 700 DEG C Nd, Mg-Sm and Mg-Mn intermediate alloy, alloy are sufficiently stirred for aluminium alloy after being completely melt, being cooled to 680 DEG C carries out argon gas refining 2 Minute, surface scum is dragged for, argon gas flow velocity is 8 ml/mins, then rise to 745 DEG C of standings and be cast to 200 DEG C of cast irons after 20 minutes Mould;Casting is put into again is connected with the electric furnace of dry high purity nitrogen atmosphere, 20 hours are incubated at 420 DEG C, then with stove with every The rate of heat addition of 10 DEG C of minute is warming up to 510 DEG C and is incubated 3 hours, in water of then quenching;Then by the casting after solution treatment It is put into 225 DEG C of aging oven and is incubated 72 hours, then take out air cooling, obtains the excellent anti-corrosion magnesium of polynary high-strength temperature-resistant Alloy.
Magnesium alloy obtained in embodiment 25 is tested, test event includes tensile test at room temperature, (175 DEG C) drawings of high temperature Experiment and corrosion total immersion test are stretched, its corrosion resisting property is 2.679 (mm/a), and obtained alloy has excellent heat-proof corrosion-resistant Energy.
Embodiment 26
According to mass fraction be 7.3%Al, 3.0%Sn, 0.8%Zn, 1.2%RE (0.8%Nd and 0.4%Sm) and 0.2% Mn, the impurity remaining as Mg and inevitable total amount≤0.2% carries out dispensing, and dispensing is put into 120 DEG C of baking oven , then be put into pure magnesium ingot in electrical crucible, in SF by baking 50 minutes6:CO2Volume ratio is 1:It has been heated under 100 protection 680 DEG C are warming up to after running down, fine aluminium, pure zinc, pure tin is added, aluminium alloy is sufficiently stirred for after dissolving, Mg- is added at 710 DEG C Nd, Mg-Sm and Mg-Mn intermediate alloy, alloy are sufficiently stirred for aluminium alloy after being completely melt, being cooled to 690 DEG C carries out argon gas refining 3 Minute, surface scum is dragged for, argon gas flow velocity is 15 ml/mins, then rise to 745 DEG C of standings and be cast to 200 DEG C of castings after 20 minutes Swage has;Casting is put into again is connected with the electric furnace of dry high purity nitrogen atmosphere, 420 DEG C be incubated 20 hours, then with stove with 15 DEG C per minute of the rate of heat addition is warming up to 520 DEG C and is incubated 2 hours, in water of then quenching;Then by the casting after solution treatment Part is put into 240 DEG C of aging oven and is incubated 72 hours, then takes out air cooling, enters to obtain excellent polynary high-strength temperature-resistant resistance to Erosion magnesium alloy.
Embodiment 27
According to mass fraction be 7.3%Al, 3.0%Sn, 0.8%Zn, 1.2%RE (0.8%Nd and 0.4%Sm) and 0.2% Mn, the impurity remaining as Mg and inevitable total amount≤0.2% carries out dispensing, and dispensing is put into 120 DEG C of baking oven , then be put into pure magnesium ingot in electrical crucible, in SF by baking 50 minutes6:CO2Volume ratio is 1:It has been heated under 100 protection 680 DEG C are warming up to after running down, fine aluminium, pure zinc, pure tin is added, aluminium alloy is sufficiently stirred for after dissolving, Mg- is added at 720 DEG C Nd, Mg-Sm and Mg-Mn intermediate alloy, alloy are sufficiently stirred for aluminium alloy after being completely melt, being cooled to 700 DEG C carries out argon gas refining 5 Minute, surface scum is dragged for, argon gas flow velocity is 20 ml/mins, then rise to 745 DEG C of standings and be cast to 200 DEG C of castings after 20 minutes Swage has;Casting is put into again is connected with the electric furnace of dry high purity nitrogen atmosphere, 420 DEG C be incubated 20 hours, then with stove with 15 DEG C per minute of the rate of heat addition is warming up to 520 DEG C and is incubated 2 hours, in water of then quenching;Then by the casting after solution treatment Part is put into 180 DEG C of aging oven and is incubated 84 hours, then takes out air cooling, enters to obtain excellent polynary high-strength temperature-resistant resistance to Erosion magnesium alloy.
Blowing argon gas refinement step in the preparation method of magnesium alloy of the invention, especially casting method, controls argon gas stream The parameters such as melt temperature, the time of blowing argon gas and blowing argon gas head mixing speed in the melt when speed, blowing argon gas, suitably Technological parameter is conducive at utmost reducing the content of slag in tissue, it is therefore an objective to remove the slag in alloy melt, which determines conjunction The content of slag in as-cast microstructure during gold solidification, and then be conducive to improving alloy property.In alloy preparation method at solid solution Temperature, the time isoparametric effect that preferably further ensure that precipitation strength of reason and Ageing Treatment.
Although embodiment of the present invention is disclosed as above, it is not restricted to listed in specification and implementation method With.It can be applied to various suitable the field of the invention completely.For those skilled in the art, can be easily Realize other modification.Therefore under the universal limited without departing substantially from claim and equivalency range, the present invention is not limited In specific details and shown here as the legend with description.

Claims (10)

1. a kind of multicomponent heat-resistant corrosion-resistant magnesium alloy, it is characterised in that include by percentage to the quality:
5.8~7.8%Al, 2.2~3.2%Sn, 0.2~1.0%Zn, 0.2~2.0%RE, 0.1~0.3%Mn, remainder It is Mg and the impurity of inevitable total amount≤0.2%.
2. multicomponent heat-resistant corrosion-resistant magnesium alloy as claimed in claim 1, it is characterised in that the RE is Nd and/or Sm.
3. multicomponent heat-resistant corrosion-resistant magnesium alloy as claimed in claim 2, it is characterised in that Si≤0.1% in the impurity.
4. multicomponent heat-resistant corrosion-resistant magnesium alloy as claimed in claim 3, it is characterised in that including:7.0~7.8%Al, 2.5~ 3.0%Sn, 0.5~1.0%Zn, 0.8~1.6%RE, 0.1~0.3%Mn, remainder be Mg and inevitable total amount≤ 0.2% impurity.
5. multicomponent heat-resistant corrosion-resistant magnesium alloy as claimed in claim 3, it is characterised in that the RE be 0.6~1.4%Nd and/ Or 0.3~0.6%Sm.
6. a kind of preparation method of multicomponent heat-resistant corrosion-resistant magnesium alloy, prepares polynary resistance to as any one of claim 1-5 Hot corrosion-resistant magnesium alloy, it is characterised in that including:
Protective atmosphere is passed through in smelting furnace, magnesium ingot is put into and is heated to being completely melt, 670~690 DEG C add aluminium ingots, zinc ingot metal and Tin slab, is completely dissolved and is warming up to 700~720 DEG C after stirring, sequentially add Mg-Mn intermediate alloys, Mg-Sm intermediate alloys, Mg-Nd intermediate alloys, then being warming up to 730~750 DEG C makes alloy melt composition uniform, then it is cooled to 680~700 DEG C and to melt Interior blowing argon gas are refined 1~5 minute, and the alloy melt after skimming stands 10~30 minutes in 720~750 DEG C of insulations, and alloy is melted Body is cast in the mould that preheating temperature is 200~300 DEG C;
Casting is put into the electric furnace for be connected with protective atmosphere carries out solution treatment, and 18~24 hours are incubated at 410~430 DEG C, Then with stove with the rate of heat addition of 10~20 DEG C/min be warming up to 500~540 DEG C and be incubated 1~3 hour, in water of then quenching;
Casting after solution treatment is put into aging oven, 175~240 DEG C is warming up to and is incubated 36~84 hours, then Take out air cooling.
7. the preparation method of multicomponent heat-resistant corrosion-resistant magnesium alloy according to claim 6, it is characterised in that:The purity of magnesium ingot >= 99.99%th, purity >=99.99% of aluminium ingot, purity >=99.99% of zinc ingot metal, purity >=99.99% of tin slab, Mg-Nd, Mg- Impurity content≤0.1% of Sm and Mg-Mn intermediate alloys.
8. the preparation method of multicomponent heat-resistant corrosion-resistant magnesium alloy according to claim 7, it is characterised in that:Alloy casting step In protective atmosphere be SF6And CO2Mixed gas, the SF6And CO2The volume ratio of gas is 1:90~110.
9. the preparation method of multicomponent heat-resistant corrosion-resistant magnesium alloy according to claim 8, it is characterised in that the argon of the refining Gas velocity is 5-20 ml/mins.
10. the preparation method of multicomponent heat-resistant corrosion-resistant magnesium alloy according to claim 8, it is characterised in that also including raw material Preheating:Raw material are put into 90~135 DEG C of baking oven and are placed 0.5~1 hour.
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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108707800A (en) * 2018-08-09 2018-10-26 吉林大学 Low content of rare earth magnesium alloy materials of a kind of high-strength plasticity and preparation method thereof
CN108977710A (en) * 2018-07-23 2018-12-11 上海交通大学 A kind of extrusion casint magnesium alloy materials and preparation method thereof
CN110229983A (en) * 2019-06-21 2019-09-13 中信戴卡股份有限公司 A kind of magnesium alloy and preparation method thereof
TWI679004B (en) * 2019-06-20 2019-12-11 廷鑫興業股份有限公司 Easy-to-screw compression magnesium alloy screw having double screw threads
CN111254333A (en) * 2020-04-02 2020-06-09 吉林大学 Multi-element high-strength corrosion-resistant wrought magnesium alloy and preparation method thereof
CN111270118A (en) * 2020-03-19 2020-06-12 上海交通大学 Corrosion-resistant ternary magnesium alloy and preparation method thereof
CN112522560A (en) * 2020-12-02 2021-03-19 太原科技大学 Magnesium alloy with corrosion resistance and preparation method thereof
CN113005346A (en) * 2021-02-23 2021-06-22 吉林大学 Corrosion-resistant fast extrusion magnesium alloy and preparation method thereof

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102242298A (en) * 2011-07-04 2011-11-16 四川大学 Al and Zn strengthened Mg-Sn-RE-based high-toughness heat-resistant magnesium alloy
CN102965555A (en) * 2012-11-13 2013-03-13 宁波杭州湾新区珠峰企业管理服务有限公司 Corrosion-resistant magnesium alloy and preparation method thereof
CN103695741A (en) * 2013-12-16 2014-04-02 中国科学院金属研究所 Mg-Zn-Al-Sn-Mn series magnesium alloy and preparation method thereof
CN103924142A (en) * 2014-05-09 2014-07-16 重庆大学 Magnesium alloy and preparing method thereof
CN104561716A (en) * 2015-02-04 2015-04-29 威海万丰镁业科技发展有限公司 Magnesium alloy and preparation method thereof
KR101680041B1 (en) * 2015-05-21 2016-11-28 한국기계연구원 Wrought magnesium alloy having high ductility and high toughness and method for preparing the same
KR20160136832A (en) * 2015-05-21 2016-11-30 한국기계연구원 High strength wrought magnesium alloys and method for manufacturing the same

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102242298A (en) * 2011-07-04 2011-11-16 四川大学 Al and Zn strengthened Mg-Sn-RE-based high-toughness heat-resistant magnesium alloy
CN102965555A (en) * 2012-11-13 2013-03-13 宁波杭州湾新区珠峰企业管理服务有限公司 Corrosion-resistant magnesium alloy and preparation method thereof
CN103695741A (en) * 2013-12-16 2014-04-02 中国科学院金属研究所 Mg-Zn-Al-Sn-Mn series magnesium alloy and preparation method thereof
CN103924142A (en) * 2014-05-09 2014-07-16 重庆大学 Magnesium alloy and preparing method thereof
CN104561716A (en) * 2015-02-04 2015-04-29 威海万丰镁业科技发展有限公司 Magnesium alloy and preparation method thereof
KR101680041B1 (en) * 2015-05-21 2016-11-28 한국기계연구원 Wrought magnesium alloy having high ductility and high toughness and method for preparing the same
KR20160136832A (en) * 2015-05-21 2016-11-30 한국기계연구원 High strength wrought magnesium alloys and method for manufacturing the same

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
刘国军等: "Mg-5Sn系镁合金研究进展", 《热加工工艺》 *

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108977710A (en) * 2018-07-23 2018-12-11 上海交通大学 A kind of extrusion casint magnesium alloy materials and preparation method thereof
CN108707800A (en) * 2018-08-09 2018-10-26 吉林大学 Low content of rare earth magnesium alloy materials of a kind of high-strength plasticity and preparation method thereof
CN108707800B (en) * 2018-08-09 2020-03-20 吉林大学 Magnesium alloy material with high strength and plasticity and low rare earth content and preparation method thereof
TWI679004B (en) * 2019-06-20 2019-12-11 廷鑫興業股份有限公司 Easy-to-screw compression magnesium alloy screw having double screw threads
CN110229983A (en) * 2019-06-21 2019-09-13 中信戴卡股份有限公司 A kind of magnesium alloy and preparation method thereof
US11041230B2 (en) 2019-06-21 2021-06-22 Citic Dicastal Co., Ltd Magnesium alloy and preparation method thereof
CN111270118A (en) * 2020-03-19 2020-06-12 上海交通大学 Corrosion-resistant ternary magnesium alloy and preparation method thereof
CN111254333A (en) * 2020-04-02 2020-06-09 吉林大学 Multi-element high-strength corrosion-resistant wrought magnesium alloy and preparation method thereof
CN112522560A (en) * 2020-12-02 2021-03-19 太原科技大学 Magnesium alloy with corrosion resistance and preparation method thereof
CN113005346A (en) * 2021-02-23 2021-06-22 吉林大学 Corrosion-resistant fast extrusion magnesium alloy and preparation method thereof

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