CN106834846B - 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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CN106834846B
CN106834846B CN201611206714.3A CN201611206714A CN106834846B CN 106834846 B CN106834846 B CN 106834846B CN 201611206714 A CN201611206714 A CN 201611206714A CN 106834846 B CN106834846 B CN 106834846B
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alloy
resistant
corrosion
heat
temperature
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CN106834846A (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 alloys and preparation method, alloy to 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 are the impurity of Mg and inevitable total amount≤0.2%.Tin, neodymium and/or samarium are added in magnalium base material and forms refractory grain phase Nd5Sn3And 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 with magnesium simultaneously generates Mg2Sn further improves alloy property;The harm that manganese reduces impurity element is added, the corrosion resistance of alloy is improved, heat-proof corrosion-resistant magnesium alloy is obtained by adjusting the proportioning between element.

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 fields.It is more particularly related to a kind of multicomponent heat-resistant Cast magnesium alloy and preparation method thereof.
Background technology
As energy shortages and problem of environmental pollution are increasingly sharpened, field of traffic lightweight is inevitable, as environment Friendly light material causes extensive concern.Magnesium alloy as current applicable most light metal structure material, have compared with High specific strength and specific stiffness, good diamagnetic interference, excellent damping characteristics, high-termal conductivity and easily recycling etc. are excellent Point has significant application in the fields such as aerospace, facilities for transport and communication manufacture, household electrical appliances instrument, telecommunications, biomedicine Value and huge application prospect, it has also become one of the metal material of 21 century most development potentiality.So far, existing Commercial magnesium alloy still based on the Mg-Al systems magnesium alloy of AZ91, AM50, accounts for about 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, is degrading alloy Corrosion resistance and elevated temperature strength.For this purpose, vast researcher is from design of alloy (alloying) and is heat-treated (from T6 Reason) etc. conduct a research to Mg-Al systems magnesium alloy, it is intended to improve its mechanical property and corrosion resistance.
The stacking fault energy of magnesium can be reduced in suitable Sn additions Mg-Al magnesium alloys and then is advantageously implemented superplasticity, simultaneously With certain solid solution strengthening effect;But the content of Sn it is higher when, large-sized Mg2Sn, which is gathered in crystal boundary, 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 to form Al-RE phases and improve the mechanical property of alloy by being heat-treated, but Al-RE phases easily alloy crystal boundary be enriched with into And size is larger, reduces the precipitation strength effect of alloy.Zn elements are one of common alloy elements in magnesium alloy, mainly For improving the mechanical property of alloy, still, 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 the Al-Mn compounds and Mg generated in crystal boundary17Al12It compares, 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 properties.Majority research lays particular emphasis on the formation and modification of Al-RE phases, does not consider Alloying element tin forms dystectic second phase with neodymium or samarium, these dystectic second phases contribute to the heat resistance of 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 mass percentage of each composition are 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:The content of rare earth of surplus, the alloy is high, and by adding the further refining alloy of alloy element Zr Crystallite dimension, improve alloy manufacturing cost, the alloy do 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, 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, which can be used as wrought magnesium alloy, can also be used as casting use.The alloy contains height The rare earth of content increases alloy manufacturing cost, relevant resistance to without carrying out without alloy element Al, Zn, Sn and Mn, while also 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】It proposes Composition of alloy and weight percent 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%, remaining is Mg;Forming general 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%.It should The content of rare earth of alloy is higher, increases alloy manufacturing cost, at the same a large amount of rare-earth phase increase alloy subsequent heat treatment at This, which 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】 It discloses its raw material components and mass percentage 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 99% or more;Zinc purity is 99.5% or more;Manganese is in the form of 4% magnesium manganese intermediate alloy Addition.The Sn contents of the alloy are higher, are used as wrought magnesium alloy, do not add rare earth element.
Patent 201110032706.1 discloses a kind of high-toughness heat-resistant corrosion-resistant rare earth magnesium alloy and preparation method thereof, 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, the rare earth be commercialization cerium-rich mischmetal (RE), the 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:By the alloy material of said ratio, the SF6+CO2 for being 0.5% in volume fraction is mixed gas protected After melting magnesium in crucible under melting condition, at 660-680 DEG C, to be closed among commercial-purity aluminium, aluminium manganese intermediate alloy, Mg-RE Golden form is added alloy element and increases temperature after furnace charge to be added is completely dissolved into alloy molten solution, then by industrial star antimony With pure cadmium by bell jar indentation alloy molten solution, being uniformly mixed and continuing to heat up, addition refining agent refining magnesium alloys liquid refining, It is poured into a mould after standing, obtains this product.Advantage:The obdurability and room temperature and mechanical behavior under high temperature of raising alloy;Make the tough of alloy Property, heat-resisting and corrosion resisting property be higher than existing AE systems magnesium alloy.
Invention content
It is an object of the present invention to provide a kind of magnesium alloys, and tin, neodymium and/or samarium are added in magnalium base material and forms high-melting-point Particle phase Nd5Sn3And Sm5Sn3, and refractory grain phase is further refined by the addition of zinc, improves the strong plasticity, resistance to of alloy Hot and corrosion resistance, and adjust the proportioning between element and obtain 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 mixing speed of the time of blowing argon gas and blowing argon gas head in the melt are utmostly reduced in tissue The content of slag, and then be conducive to improve alloy property.
In order to realize these purposes and other advantages according to the present invention, a kind of multicomponent heat-resistant corrosion-resistant magnesium alloy is provided, 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 are 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 are 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;
It is passed through protective atmosphere in smelting furnace, be put into magnesium ingot 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 Mg-Mn intermediate alloys, close among Mg-Sm Gold, Mg-Nd intermediate alloys, then being warming up to 730~750 DEG C keeps alloy melt ingredient uniform, then be cooled to 680~700 DEG C and to Blowing argon gas refines 1~5 minute in melt, and the alloy melt after skimming keeps the temperature standing 10~30 minutes at 720~750 DEG C, will close Golden melt is cast in the mold that preheating temperature is 200~300 DEG C;
Casting is put into the electric furnace for be connected with protective atmosphere and carries out solution treatment, it is small that 18~24 are kept the temperature at 410~430 DEG C When, then 500~540 DEG C are warming up to the rate of heat addition of 10~20 DEG C/min with stove and keep the temperature 1~3 hour, then quench into water In;
Casting after solution treatment is put into aging oven, be warming up to 175~240 DEG C and keeps the temperature 36~84 hours, It then takes out air-cooled.
Preferably, purity >=99.99% of magnesium ingot, purity >=99.99% of aluminium ingot, zinc ingot metal purity >=99.99%, 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 put into 90~135 DEG C of baking oven and place 0.5~1 hour.
The present invention includes at least following advantageous effect:
1, design of alloy principle of the invention is multi-element alloyed, rather than a certain alloying element is used alone.For example, 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 react life with Mg At Mg2Sn phases;Since the content of the alloying element Sn and RE that are added in alloy are less, the second phase size of generation is smaller, works as conjunction After gold element Zn is added, RE5Sn3Phase and Mg2Sn meets and is further refined, and more disperse is distributed in crystal boundary, is follow-up Solution treatment and ageing treatment provide the guarantee of the second phase size, correspondingly improved the heat resistance and corrosion resistance of alloy Energy.The addition of Mn elements further improves the corrosion resisting property of alloy.
2, the second phase RE5Sn3And Mg2Sn has refined Mg17Al12Phase, when alloy graining, the second phase RE5Sn3And Mg2Sn is excellent Prior to Mg17Al12It is mutually generated in grain boundaries, then large scale, continuous Mg17Al12It can not mutually be formed in crystal boundary, when alloy carries out When effect processing, be conducive to Mg17Al12The small size of phase is precipitated, 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.
3, in alloy preparation method, the blowing argon gas refinement step especially in casting method, it is therefore an objective to remove alloy melt In slag, the stirring speed of the time and blowing argon gas head of melt temperature, blowing argon gas when argon gas flow velocity, blowing argon gas in the melt The content of slag, suitable technological parameter are conducive to utmostly in as-cast microstructure when the parameters such as degree determine alloy graining The content of slag in tissue is reduced, and then is conducive to improve alloy property;Such as:Argon gas flow velocity is too fast, then makes the further oxygen of alloy Change or argon gas flow velocity is excessively slow, have remaining slag and stay in alloy structure, both are all unfavorable for the microstructure of alloy, dislike The intensity, heat resistance and corrosion resisting property of alloy are changed.The temperature of solution treatment and ageing treatment, time in alloy preparation method Etc. parameters the effect that preferably further ensure that precipitation strength.
By multi-element alloyed composition design, the second phase of high temperature for obtaining Dispersed precipitate when alloy graining is realized Solution strengthening, refined crystalline strengthening and second-phase strength;Further by heat treatment, ageing strengthening is realized, alloy is improved Heat resistance, while significantly improving the corrosion resisting property of alloy.
Part is illustrated to embody by further advantage, target and the feature of the present invention by following, and part will also be by this The research and practice of invention and be understood by the person skilled in the art.
Description of the drawings
Fig. 1 is the precipitated phase shape appearance figure of the multicomponent heat-resistant corrosion-resistant magnesium alloy of the present invention.
Specific implementation mode
Present invention will be described in further detail below with reference to the accompanying drawings, to enable those skilled in the art with reference to specification text Word can be implemented according to this.
It should be appreciated that such as " having ", "comprising" and " comprising " term used herein do not allot one or more The presence or addition of a other elements or combinations thereof.
The present invention provides a kind of multicomponent heat-resistant corrosion-resistant magnesium alloys, 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:
1, Mg-Al alloy substrates
Aluminium element is added in magnesium to promote the solid solution strengthening effect of alloy, when the quality of Al and Mg is 1:11~15.5 energy The casting character and corrosion resistance for enough improving magnesium alloy, realize alloy lightweight.But Mg17Al12Mutually it is degrading the corrosion resistant of alloy Corrosion energy and elevated temperature strength.
2, Mg-Al-Sn alloys:
Addition element Sn in Mg-Al alloy substrates, wherein be based on quality Al:Mg:Sn=1:11~15.5:0.38~ 0.41, Sn, Al is co-doped with the improvement for being conducive to plasticity.
The mass fraction of one Mg-Al-Sn alloys of table matches
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 It tests, wherein the test data of corrosion resistance is according to homogeneous corrosion total immersion test side of GB10124-1988 metal materials laboratory What method obtained, and test result is summarized in table two.
The mass fraction of two Mg-Al-Sn alloys of table matches
By table two as it can be seen that as Sn contents by 2.4% increase to 3.0%, the room 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 instead.The reason is as follows that:Mg-Al-Sn alloys are compared with Mg- The crystal grain of Al alloys is further refined, and since diffusion velocities of the Sn in Mg is slow, being not easy to overaging causes precipitated phase brilliant Grain length is big, is because in alloy melt process of setting, part Sn preferentially is combined 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 Refine Mg17Al12The effect of phase, when alloy high-temp deforms, additionally it is possible to which the movement for hindering dislocation improves the elevated temperature strength of alloy With plasticity.When Sn constituent contents are high, the Mg of formation2Sn meets roughening, and alloy is thereby reduced to the matrix generation effect of isolating Mechanical property.
3, Mg-Al-Sn-RE alloys:
Addition element RE in Mg-Al-Sn alloys, experiment is as shown in the table,:
Three orthogonal test condition of table
Four orthogonal test table of table
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 corrosion resistance is according to GB10124-1988 gold Belong to what material testing laboratory's homogeneous corrosion total immersion test method obtained.
Five performance test summary sheet of table
Range analysis, analysis data summarization and table six are carried out to orthogonal test high temperature tensile strength and corrosion resisting property.
Six range analysis data summarization of table
By table six as it can be seen that being C3A1D2B4, i.e., Mg-Al-Sn-RE in alloy for the optimal proportion of high-temperature mechanical property 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, is melted when alloy is added in alloying element Sn and RE (Nd and Sm) jointly When body, between the TiFe_xM_y alloy and Sn, Nd, Sm and Mg due to Sn and the TiFe_xM_y alloy of RE (Nd and Sm) compound much smaller than Sn and Mg Electronegativity relationship, Sn preferentially with RE (Nd and Sm) combine form RE5Sn3Second phase of high-melting-point Dispersed precipitate, rest Sn It is combined to form Mg with Mg2The part of Sn phases and Sn are solid-solution in magnesium alloy substrate, and alloy height is substantially improved using Nd, Sm cooperation Sn Warm nature energy, and proportioning is adjusted, the RE of formation5Sn3Meeting enhances aging hardening effect, and alloy high-temp performance, which is substantially improved, not only to be had Effect ground improves alloy casting character, and RE5Sn3Formation both reduce Mg17Al12The content of phase has refined alloy structure, makes Mg17Al12It is mutually able to small and dispersed fractions distribution, improves the high-temperature behavior of alloy.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.
By deck watch six, table two as it can be seen that addition rare earth element can have a certain upgrade to the corrosion 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, orthogonal examination is passed through It tests and discusses Zn to alloy mechanical performance and refinement RE5Sn3The effect of phase:
Seven orthogonal test condition of table
Eight orthogonal test table of table
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 corrosion resistance is according to GB10124-1988 gold Belong to what material testing laboratory's homogeneous corrosion total immersion test method obtained.
Nine performance test summary sheet of table
Nine contrast table five of table is as it can be seen that the room temperature to alloy is added in Zn, the mechanical performance under high temperature all increases, to alloy Corrosion resistance promoted.
Ten range analysis data summarization of table
Such as table nine and table ten as it can be seen that for improve alloy mechanical performance, optimum combination C3D4A2E2B4, be because: 1. the addition of Zn can refine RE5Sn3Phase is scanned electron-microscope scanning to sample and shows that in Fig. 1, alloy grain is refined; 2. also having 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, it is more than element S n on alloy mechanical performance influence to make Sm, promotes mechanicalness of the rare earth element to alloy The influence of energy.Further, for improving, the corrosion resisting property of 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, to ensure alloy while excellent mechanical performance, Also there is higher corrosion resisting property, Mn is added in Mg-Al-Sn-RE-Zn alloys.
4, Mg-Al-Sn-RE-Zn-Mn alloys:
On the basis of Mg-Al-Sn-RE-Zn alloys optimal machinery proportioning, Mg contents are reduced, addition Mn improves alloy Corrosion 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, tin, neodymium and/or samarium formation refractory grain phase Nd are added 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 residue tin combined with magnesium generate Mg2Sn further improves alloy property;The harm that manganese reduces impurity element is added, improves and closes The corrosion resistance of gold, heat-proof corrosion-resistant magnesium alloy is obtained by adjusting the proportioning between element, 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 with good mechanical properties and corrosion resisting property Mg alloys.
The invention also discloses a kind of multicomponent heat-resistant corrosion-resistant magnesium alloy preparation methods, include the following steps:
1) raw material preparation
Pure magnesium, fine aluminium, pure zinc, pure tin, the conjunction of the centres Mg-Nd are weighed by the chemical composition and mass percent of design alloy Gold, Mg-Sm intermediate alloys, Mg-Mn intermediate alloys are 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, waits for that alloy is completely dissolved and fills After dividing stirring, 700~720 DEG C are warming up to, Mg-Mn intermediate alloys, Mg-Sm intermediate alloys, Mg-Nd intermediate alloys are sequentially added, 730~750 DEG C are warming up to, is stirred after added alloy material all fusing, keeps alloy melt ingredient uniform, then be cooled to 680~700 DEG C and the blowing argon gas into melt, wherein argon gas is to pass through anhydrous CaCl2Dry high-purity argon gas (>=99.99%), Argon gas flow velocity is 5-20 ml/mins, and refining 1~skim after five minutes, then alloy melt is kept the temperature at 720~750 DEG C stands 10 ~30 minutes, alloy melt is cast in the fine copper mold or cast iron die that preheating temperature is 200~300 DEG C.
3) solution treatment T6
It is 1 that casting, which is put into, and is connected with volume ratio:90~110 SF6And CO2In the electric furnace of hybrid protection gas, 410~ 430 DEG C keep the temperature 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 keep the temperature 1~ 3 hours, in water of then quenching.
4) ageing treatment
Casting after solution treatment is put into aging oven, be warming up to 175~240 DEG C and keeps the temperature 36~84 hours, Then take out air-cooled, acquisition high-strength temperature-resistant corrosion-resistant magnesium alloy.
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 carries out dispensing remaining as the impurity of Mg and inevitable total amount≤0.2%, and dispensing is put into 120 DEG C of baking oven Pure magnesium ingot, is then put into electrical crucible, in SF by baking 50 minutes6:CO2Volume ratio is 1:It has been heated under 100 protection It is warming up to 680 DEG C after running down, fine aluminium, pure zinc, pure tin is added, is sufficiently stirred aluminium alloy after dissolving, Mg- is added at 700 DEG C Nd, Mg-Sm and Mg-Mn intermediate alloy, alloy are sufficiently stirred aluminium alloy after being completely melt, are cooled to 680 DEG C and carry out argon gas refining 2 Minute, surface scum is removed in fishing, and argon gas flow velocity is 8 ml/mins, then rises to 745 DEG C of standings and be cast to 200 DEG C of cast irons after twenty minutes Mold;Casting is put into again in the electric furnace for being connected with dry high purity nitrogen atmosphere, 20 hours is kept the temperature 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 keeps the temperature 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 keeps the temperature 72 hours, then take out air-cooled, obtain the excellent anti-corrosion magnesium of polynary high-strength temperature-resistant Alloy.
Magnesium alloy made from embodiment 25 is tested, test event includes (175 DEG C) tensile test at room temperature, high temperature drawings Experiment and corrosion total immersion test are stretched, corrosion resisting property is 2.679 (mm/a), and alloy obtained 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 carries out dispensing remaining as the impurity of Mg and inevitable total amount≤0.2%, and dispensing is put into 120 DEG C of baking oven Pure magnesium ingot, is then put into electrical crucible, in SF by baking 50 minutes6:CO2Volume ratio is 1:It has been heated under 100 protection It is warming up to 680 DEG C after running down, fine aluminium, pure zinc, pure tin is added, is sufficiently stirred aluminium alloy after dissolving, Mg- is added at 710 DEG C Nd, Mg-Sm and Mg-Mn intermediate alloy, alloy are sufficiently stirred aluminium alloy after being completely melt, are cooled to 690 DEG C and carry out argon gas refining 3 Minute, surface scum is removed in fishing, and argon gas flow velocity is 15 ml/mins, then rises to 745 DEG C of standings and be cast to 200 DEG C of castings after twenty minutes Swage has;Casting is put into again in the electric furnace for being connected with dry high purity nitrogen atmosphere, 20 hours is kept the temperature at 420 DEG C, then with stove with 15 DEG C of the rate of heat addition per minute is warming up to 520 DEG C and keeps the temperature 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 keeps the temperature 72 hours, and it is resistance to then take out air-cooled, excellent into acquisition polynary high-strength temperature-resistant Lose 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 carries out dispensing remaining as the impurity of Mg and inevitable total amount≤0.2%, and dispensing is put into 120 DEG C of baking oven Pure magnesium ingot, is then put into electrical crucible, in SF by baking 50 minutes6:CO2Volume ratio is 1:It has been heated under 100 protection It is warming up to 680 DEG C after running down, fine aluminium, pure zinc, pure tin is added, is sufficiently stirred aluminium alloy after dissolving, Mg- is added at 720 DEG C Nd, Mg-Sm and Mg-Mn intermediate alloy, alloy are sufficiently stirred aluminium alloy after being completely melt, are cooled to 700 DEG C and carry out argon gas refining 5 Minute, surface scum is removed in fishing, and argon gas flow velocity is 20 ml/mins, then rises to 745 DEG C of standings and be cast to 200 DEG C of castings after twenty minutes Swage has;Casting is put into again in the electric furnace for being connected with dry high purity nitrogen atmosphere, 20 hours is kept the temperature at 420 DEG C, then with stove with 15 DEG C of the rate of heat addition per minute is warming up to 520 DEG C and keeps the temperature 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 keeps the temperature 84 hours, and it is resistance to then take out air-cooled, excellent into acquisition polynary high-strength temperature-resistant Lose magnesium alloy.
The preparation method of the magnesium alloy of the present invention, the blowing argon gas refinement step especially in casting method control argon gas stream The parameters such as the mixing speed of the time and blowing argon gas head of melt temperature, blowing argon gas when speed, blowing argon gas in the melt, suitably Technological parameter is conducive to utmostly reduce the content of slag in tissue, it is therefore an objective to remove the slag in alloy melt, which determine conjunctions The content of slag in as-cast microstructure when gold solidification, and then be conducive to improve alloy property.In alloy preparation method at solid solution The effect that preferably further ensure that precipitation strength of the parameters such as temperature, the time of reason and ageing treatment.
Although the embodiments of the present invention have been disclosed as above, but its is not only in the description and the implementation listed With.It can be applied to various suitable the field of the invention completely.It for those skilled in the art, can be easily Realize other modification.Therefore without departing from the general concept defined in the claims and the equivalent scope, the present invention is simultaneously unlimited In specific details and legend shown and described herein.

Claims (5)

1. a kind of preparation method of multicomponent heat-resistant corrosion-resistant magnesium alloy, prepares multicomponent heat-resistant corrosion-resistant magnesium alloy, with mass percent Meter includes:
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 For the impurity of Mg and inevitable total amount≤0.2%;
It is characterised in that it includes:
Be passed through protective atmosphere in smelting furnace, be put into magnesium ingot and be heated to being completely melt, at 670~690 DEG C be added aluminium ingot, 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 keeps alloy melt ingredient uniform, then it is cooled to 680~700 DEG C and to melt Interior blowing argon gas refines 1~5 minute, and the alloy melt after skimming keeps the temperature standing 10~30 minutes at 720~750 DEG C, and alloy is melted Body is cast in the mold that preheating temperature is 200~300 DEG C;The argon gas flow velocity is 5-20 ml/mins;
Casting is put into the electric furnace for be connected with protective atmosphere and carries out solution treatment, 18~24 hours are kept the temperature at 410~430 DEG C, Then 500~540 DEG C are warming up to the rate of heat addition of 10~20 DEG C/min with stove and keep the temperature 1~3 hour, in water of then quenching;
Casting after solution treatment is put into aging oven, be warming up to 175~240 DEG C and keeps the temperature 36~84 hours, then It takes out air-cooled.
2. the preparation method of multicomponent heat-resistant corrosion-resistant magnesium alloy according to claim 1, it is characterised in that:The purity of magnesium ingot >= 99.99%, 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.
3. the preparation method of multicomponent heat-resistant corrosion-resistant magnesium alloy according to claim 2, 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.
4. the preparation method of multicomponent heat-resistant corrosion-resistant magnesium alloy according to claim 3, which is characterized in that further include that raw material is pre- Heat:Raw material are put into 90~135 DEG C of baking oven and are placed 0.5~1 hour.
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