CN100540717C - The thermal treatment process of Chinese character shaped eutectic Mg2Si phase in the Mg-Si-Sn series magnesium alloy - Google Patents
The thermal treatment process of Chinese character shaped eutectic Mg2Si phase in the Mg-Si-Sn series magnesium alloy Download PDFInfo
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- CN100540717C CN100540717C CNB2007101446999A CN200710144699A CN100540717C CN 100540717 C CN100540717 C CN 100540717C CN B2007101446999 A CNB2007101446999 A CN B2007101446999A CN 200710144699 A CN200710144699 A CN 200710144699A CN 100540717 C CN100540717 C CN 100540717C
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Abstract
The present invention proposes a kind of Mg-Si-Sn series magnesium alloy and rotten wherein Chinese character shaped eutectic Mg
2The thermal treatment process of Si phase.Preferred each component of Mg-Si-Sn series magnesium alloy and weight percent thereof are: Si 1-3%, and Sn 1-3%, surplus is Mg.The Mg-Si-Sn series magnesium alloy adopts technical pure magnesium ingot, industrial crystallization silica flour and pure tin ingot to carry out melting, casting.To place the chamber type electric resistance furnace that has protective atmosphere to be incubated by the Mg-Si-Sn series magnesium alloy foundry goods of composition proportion melting, temperature range be 490 ℃～550 ℃, and soaking time is 1～4 hour, and quick then taking-up is put into water and quenched.The present invention has opened up a new way for the cheap heat resistance magnesium alloy of exploitation.The Mg-Si-Sn series magnesium alloy is considered to that one of cheap heat resistance magnesium alloy of development potentiality is arranged most, can be used to produce component such as automobile engine cylinder head, crankcase and wheel casing.
Description
Technical field
What the present invention relates to is a kind of Mg-Si-Sn series magnesium alloy and the rotten wherein thermal treatment process of Chinese character shaped eutectic Mg2Si phase.
Background technology
Magnesium alloy is as the lightest engineering metal structured material, because have the performance of many excellences such as specific tenacity and specific rigidity height, electrical and thermal conductivity is good, have good damping shock absorption and capability of electromagnetic shielding concurrently, be easy to be shaped advantage such as good regeneration and be considered to have most this century " the green engineering material " of exploitation future and application potential.But the resistance toheat that magnesium alloy is lower (heat resistance energy and thermal stability) has limited its further application.
At present, the heat resistance magnesium alloy system mainly contains magnesium-aluminium system, magnesium-zinc system and magnesium-rare earth system.For magnesium-aluminium system, there is (1) Mg-Al-Si (AS) to be again, as commercial AS41, AS21 alloy.The heat-resisting strengthening mechanism of this class alloy mainly is the thermally-stabilised phase Mg that forms small and dispersed at the crystal boundary place
2Si, this is at quite stable below 300 ℃, but the flowability of this type of alloy is poor, casting difficulty, difficult the application; (2) Mg-Al-Ca (AC) is to be " containing Ca, Si high-strength creep resistant deforming magnesium alloy ", MgAlCa33 and ACM522 alloy in 200410066789.7 patents of invention as people's application numbers such as Wang Qudong.The heat-resisting strengthening mechanism of this class alloy mainly is that Al and the Mg in Ca and the alloy forms high melting compound Al
2Ca and Mg
2Ca, but, form thick Al owing to used the Ca element of high level
2Ca, the moulding and toughness of alloy is very low, and castability is also very poor.Simultaneously, if the addition of Ca is also uneconomical economically above 0.5%; (3) Mg-Al-RE (AE) is, as commercial AE42 alloy.Because the AE alloy contains rare earth element, so the production cost height.Generally speaking, owing to exist low melting point eutectic phase Mg inevitably in magnesium-aluminum series alloy tissue
17Al
12(437 ℃) similarly, also exist a kind of low melting point eutectic phase MgZn phase (347 ℃) in magnesium-zinc system, make that the life-time service temperature of this two classes alloy can not be above 120～200 ℃.Though magnesium-rare earth-based alloy such as WE54, has significant age hardening effect, room temperature, high temperature tensile properties and creep-resistant property are all very excellent, be that thermotolerance is best in the commercialization alloy, the life-time service temperature also only is 300 ℃, its shortcoming is because content of rare earth is higher, causes the relatively poor and cost height of castability, and commercial applications is difficult to promote.Therefore, the exploitation of current heat resistance magnesium alloy should take into account and improve the performance and two aspects that reduce cost.Recently, Si, Sn etc. are widely regarded as and improve magnesium alloy strength and stable on heating beneficial element, therefore, unite and add Si, Sn and carry out alloying to improve the performance of existing heat resistance magnesium alloy and the cheap heat resistance magnesium alloy of development of new will be important developing direction from now on.
In order to satisfy the service requirements of creep-resistant property under the higher temperature, must avoid the low melting point eutectic phase in the alloy, as above-mentioned Mg as far as possible
17Al
12Mutually with MgZn formation mutually; Simultaneously, in order to give full play to the thermally-stabilised precipitated phase of high-melting-point (as above-mentioned Mg
2The Si phase) strengthening effect must improve its content.Regrettably,, contain the Si magnesium alloy under slower cooling conditions, can form the nascent Mg of thick dendroid along with the increase of Si content
2Si and Chinese character shape or fibrous eutectic Mg
2Si, such Mg
2Can there be very big stress concentration in Si on every side mutually, and isolate matrix, thereby worsened the mechanical property of alloy, particularly unit elongation significantly, and the speed of cooling thick dendroid of easy more more slowly formation and Chinese character shape or fibrous Mg
2Si makes that containing the Si magnesium alloy is only applicable to rate of cooling die casting faster, and can't be used for technologies such as traditional gravitational casting and sand mold casting.Therefore, exploration contains Mg in the Si magnesium alloy
2The metamorphic mechanism of Si phase and process optimization make Mg
2Si is distributed in magnesium alloy substrate and the crystal boundary with tiny, disperse form, for improving and improve the comprehensive mechanical property that contains the Si magnesium alloy and and then realizing that industrial applications just seems particularly important.
In recent years, Chinese scholars from alloying and or microalloying, adopt multiple alterant as adopting Sb, Na salt, KBF
4, the agent of Sr iso-metamorphism suppresses nascent Mg
2The preferential growth of Si phase makes the thick dendroid Mg that comes into being
2Si changes tiny Polygons bulk into; Adopt Ca, P, AlP and the agent of rare earth Nd iso-metamorphism to make Chinese character shape or fibrous eutectic Mg
2Si phase granulation.But also be accompanied by the generation of various problem in the time of rotten, inflammable and produce a large amount of smog as P, make add-on be difficult to control; Na salt, KBF
4Can produce in the process on the turn and splash and be mingled with; Ca easily causes hot tearing etc.Therefore, the existence of these problems makes by alloying and or the microalloying means Mg that goes bad
2Si phase pattern has been subjected to very big restriction on industrial production is used.
The isothermal heat treatment method Chinese character shaped eutectic Mg that can effectively go bad
2The Si phase, can consult people's application number such as Yang Mingbo and be 200610095200.5 " be used for rotten Mg-Al-Si series magnesium alloy Chinese character shape Mg
2The isothermal heat treatment method of Si phase " patent of invention.Because what this patent was rotten is Mg-Al-Si (AS) series magnesium alloy, wherein exists low melting point eutectic phase Mg inevitably
17Al
12(437 ℃).For avoiding producing heat treating faults such as burning, distortion, thermal treatment temp can not be too high, and usually less than 425 ℃, therefore, reach rotten preferably treatment effect just needs insulation for a long time, wants 12～24 hours usually, and production efficiency is not high as a result, and energy consumption is bigger.
Summary of the invention
The objective of the invention is to overcome the not enough of existing heat resistance magnesium alloy and break through traditional alloying and or microalloying means Mg that goes bad of passing through
2The method of Si phase pattern proposes a kind of Mg-Si-Sn series magnesium alloy and the rotten wherein thermal treatment process of Chinese character shaped eutectic Mg2Si phase.By uniting cheap elements Si and the Sn that adding typically has the precipitation strength effect, make the two and magnesium form very effective high-melting-point strengthening phase Mg
2Si and Mg
2Sn comes compound reinforced magnesium alloy, overcomes merely with Mg
2Si or Mg
2Problems such as Sn enhancing magnesium alloy thermotolerance deficiency and comprehensive mechanical property are relatively poor.Simultaneously, adopt eutectic Mg in the rotten Mg-Si-Sn series magnesium alloy of high temperature, short time isothermal thermal treatment
2The novel process of Si phase makes Chinese character shape or fibrous eutectic Mg
2The Si nodularization, tiny thus, subsphaeroidal Mg
2The disperse of Si phase is distributed in magnesium alloy substrate and crystal boundary, has both strengthened matrix, again pinning crystal boundary, thereby improved the high temperature creep property and the comprehensive mechanical property of Mg-Si-Sn series magnesium alloy.
A kind of Mg-Si-Sn of the present invention is a heat resistance magnesium alloy, and the theoretical foundation of its design is: according to Mg-Si and Mg-Sn binary phase diagram, the solid solubility of Si in magnesium is very little, is 0.003 at.% only, and most of Si and Mg reaction is with Mg in process of setting
2The Si form is separated out; Eutectic transformation temperature (561.2 ℃) in the rich Mg side of Mg-Sn binary phase diagram is located, and the saturated solid solubility of Sn in Mg is 14.85wt.%, only is 0.035 at.% under the room temperature.The saturated solid solubility of Sn in Mg descends with temperature and reduces fast, helps taking ageing treatment, promotes the tiny spherical second phase Mg
2Sn crystal boundary and-the Mg matrix in precipitation separate out, obtain the tissue of dispersion-strengthened.In addition, Sn rate of diffusion in Mg is lower, and spread coefficient only is 1.0 * 10 in the time of 400 ℃
-14m
2/ s.Intermetallic compound Mg
2Si has high-melting-point (1085 ℃), low density (1.99 * 10
3Kgm
-3), high rigidity (460HV), low thermal coefficient of expansion (7.5 * 10
-6K
-1) and high elastic coefficient (120Gpa).And Mg
2Sn fusing point (770 ℃) and hardness (119HV) are also higher, belong to the hard phase.In sum, Si and Sn are the elements that typically has the precipitation strength effect, the two and the formed intermetallic compound Mg of magnesium
2Si and Mg
2Sn is very effective strengthening phase, can improve the high temperature tensile properties and the creep property of magnesium alloy.
A kind of Mg-Si-Sn of the present invention is that preferred each component of heat resistance magnesium alloy and weight percent thereof are: Si 1-3%, and Sn 1-3%, surplus is Mg.The alloy that this preferred each component and weight percent thereof obtain has higher high temperature creep property and comprehensive mechanical property.
A kind of Mg-Si-Sn of the present invention is that heat resistance magnesium alloy obtains by following prepared: press mentioned component proportioning alloyage; under the RJ-2 flux protection; after pure magnesium melted fully; successively add industrial crystallization silicon and pure tin; after treating that alloying element all dissolves; carry out mechanical stirring so that its homogenizing is dragged for alloy liquid surface scum at last, be poured into immediately and carry out gravitational casting in metal mold or the sand mold.
Compare with existing heat resistance magnesium alloy, Mg-Si-Sn of the present invention is cheap elements Si and Sn and the formed high-melting-point strengthening phase of the magnesium Mg that the heat resistance magnesium alloy utilization typically has the precipitation strength effect
2Si and Mg
2Sn comes compound reinforced magnesium alloy matrix and crystal boundary, thereby can effectively stop crystal boundary slippage and restriction dislocation motion.Therefore, can improve the high temperature tensile properties and the creep property of magnesium alloy.Because Mg-Si-Sn of the present invention does not contain Al and Zn in the heat resistance magnesium alloy, avoided the two and magnesium to form low melting point eutectic Mg
17Al
12Mutually with MgZn mutually, overcome the insufficient problem of thermotolerance; Simultaneously, wherein also do not contain Ca and RE element, the unlikely cost of alloy that causes improves.Therefore, the Mg-Si-Sn series magnesium alloy will be that one of cheap heat resistance magnesium alloy of development potentiality is arranged most.
Rotten Chinese character shaped eutectic Mg of the present invention
2The isothermal heat treatment process of Si phase is to place the chamber type electric resistance furnace that has protective atmosphere to be incubated on the Mg-Si-Sn series magnesium alloy foundry goods by the composition proportion melting and casting; quick then taking-up is put into water and is quenched; the isothermal thermal treatment temp is 490 ℃～550 ℃, and soaking time is 1～4 hour.
Adopt the rotten Chinese character shaped eutectic Mg of the present invention
2The theoretical foundation of the isothermal heat treatment process of Si phase is: by Mg-Si and Mg-Sn binary phase diagram as can be seen, the eutectic temperature of the two is respectively 637.6 ℃ and 561.2 ℃, and is much higher than 437 ℃ of Mg-Al binary alloy eutectic temperatures.Though heat analyze (differential scanning calorimetric analysis, DSC) result shows, to make Mg-Si be that the eutectic temperature of alloy decreases in the affiliation that adds of Sn, after adding 3wt.% Sn, the eutectic temperature of Mg-Si alloy has descended 14 ℃, but still up to 623 ℃.Therefore, the Mg-Si-Sn series magnesium alloy can be taked higher aging temperature, makes rate of diffusion obviously accelerate, and has so both increased the effect of magnesium alloy ageing treatment, has improved heat treated efficient simultaneously again.
Adopt the rotten Chinese character shaped eutectic Mg of the present invention
2The mechanism of the isothermal heat treatment process of Si phase is: for Chinese character shape in the Mg-Si-Sn series magnesium alloy (in fact can be regarded as by bending fibrous) or fibrous eutectic Mg
2The Si phase, its Fibre diameter can not be uniformly absolute, can produce Rayleigh (Rayleigh) shape unstability thus, under the acting in conjunction of phase driving force and interfacial tension, the groove that Rayleigh (Rayleigh) shape unstability forms tends to further deepen so that rupture at last subsequently.Because the fusing point of second phase is relevant with its radius-of-curvature, it is big that its fusing point that radius-of-curvature is little will be lower than radius-of-curvature.Therefore, the Mg of fracture
2Si phase sharp corner dissolves owing to radius-of-curvature is less, and the Mg of place, plane
2Si grows up mutually and radius-of-curvature is reduced, and a fiber will change a succession of ball into as a result, and the diameter of ball and spacing are decided by interfacial energy and spread coefficient.The isothermal thermal treatment temp is high more, and the diffusibility of atom is strong more, and then nodularization process is more fast.Therefore, the high temperature, short time isothermal heat treatment process eutectic Mg in the Mg-Si-Sn series magnesium alloy that can effectively go bad
2The Si phase makes Chinese character shape or fibrous eutectic Mg
2Si finally develops into Mg tiny, subsphaeroidal and that disperse distributes mutually
2The Si particle.
Compared with prior art, the rotten Chinese character shaped eutectic Mg of the present invention
2The isothermal heat treatment process of Si phase has the characteristics of high temperature, short time, Chinese character shape or fibrous eutectic Mg in to the Mg-Si-Sn series magnesium alloy
2Si carries out effectively rotten the processing mutually, when enhancing productivity, avoided traditional metallurgical method as adding many drawbacks that alloying elements such as Ca, P, Sb and rare earth bring again, make the Mg-Si-Sn series magnesium alloy can be used for technologies such as traditional gravitational casting and sand mold casting, opened up a new way for developing cheap heat resistance magnesium alloy.
Description of drawings
Fig. 1 is the figure of as-cast metallographic structure without the heat treated Mg-3Si-3Sn magnesium alloy of isothermal.
Fig. 2 is without the heat treated Mg-3Si-3Sn magnesium alloy of isothermal X-ray diffraction (XRD) collection of illustrative plates.
Fig. 3 is through 490 ℃, is incubated the metallographic structure figure of 4 hours heat treated Mg-3Si-3Sn magnesium alloy of isothermal.
Fig. 4 is through 520 ℃, is incubated the metallographic structure figure of 2 hours heat treated Mg-3Si-3Sn magnesium alloy of isothermal.
Fig. 5 is through 550 ℃, is incubated the metallographic structure figure of 1 hour heat treated Mg-3Si-3Sn magnesium alloy of isothermal.
Embodiment
The present invention will be further elaborated implementing process of the present invention and effect by following four embodiment.
Embodiment 1:
Adopt technical pure magnesium ingot (purity 99.5%); industrial crystallization silica flour (purity 99.4%; particle diameter 0.5～2mm) and pure tin ingot (purity 99.9%); press Mg-3Si-3Sn alloying constituent alloyage; under the RJ-2 flux protection; earlier pure magnesium ingot is melted in resistance furnace; when temperature is raised to 780 ℃, add silica flour and be incubated 1 hour; add pure tin afterwards; be incubated 5 minutes; carry out mechanical stirring subsequently so that alloy element silicon and tin homogenizing left standstill 10～15 minutes, when treating that at last temperature is reduced to 720 ℃; drag for alloy liquid surface scum, be poured into and carry out gravitational casting in metal mold or the sand mold.The as cast condition Mg-3Si-3Sn alloy that adopts the present invention to obtain is done metallographic structure observation and X-ray diffraction (XRD) analysis, and the result respectively as depicted in figs. 1 and 2.In conjunction with Fig. 1 and Fig. 2 as can be seen, as cast condition Mg-3Si-3Sn alloy is by α-Mg matrix, granular Mg
2Sn phase, the nascent Mg of Polygons
2Si phase and Chinese character shape or fibrous eutectic Mg
2The Si phase composite.
Embodiment 2:
To pour into by the Mg-3Si-3Sn magnesium alloy of composition proportion melting and carry out gravitational casting in metal mold or the sand mold.After this foundry goods is placed the chamber type electric resistance furnace that has protective atmosphere to be incubated, quick then taking-up is put into water and is quenched, and the isothermal thermal treatment temp is 490 ℃, and soaking time is 4 hours.The alloy that adopts the present invention to obtain is done metallographic structure observe, the result as shown in Figure 3.As can be seen from the figure, and compare without the figure of the as-cast metallographic structure of the heat treated Mg-3Si-3Sn magnesium alloy of isothermal (Fig. 1), after the method that adopts the present invention to propose is handled, Chinese character shape or fibrous eutectic Mg in the alloy structure
2Si major part has mutually become granularly, illustrates that the method that adopts the present invention to propose handles the Mg-3Si-3Sn magnesium alloy, can make Chinese character shape or fibrous eutectic Mg in the alloy structure
2Si is rotten mutually.
Embodiment 3:
To pour into by the Mg-3Si-3Sn magnesium alloy of composition proportion melting and carry out gravitational casting in metal mold or the sand mold.After this foundry goods is placed the chamber type electric resistance furnace that has protective atmosphere to be incubated, quick then taking-up is put into water and is quenched, and the isothermal thermal treatment temp is 520 ℃, and soaking time is 2 hours.The alloy that adopts the present invention to obtain is made metallographic structure analysis, and the result as shown in Figure 4.As can be seen from the figure, after the method that adopts the present invention to propose is handled alloy, Chinese character shape or fibrous eutectic Mg in the alloy structure
2Si major part has mutually become granularly, illustrates that the method that adopts the present invention to propose handles the Mg-3Si-3Sn magnesium alloy, can make Chinese character shape or fibrous eutectic Mg in the alloy structure
2Si is rotten mutually.
Embodiment 4:
To pour into by the Mg-3Si-3Sn magnesium alloy of composition proportion melting and carry out gravitational casting in metal mold or the sand mold.After this foundry goods is placed the chamber type electric resistance furnace that has protective atmosphere to be incubated, quick then taking-up is put into water and is quenched, and the isothermal thermal treatment temp is 550 ℃, and soaking time is 1 hour.The alloy that adopts the present invention to obtain is made metallographic structure analysis, and the result as shown in Figure 5.As can be seen from the figure, after the method that adopts the present invention to propose is handled alloy, Chinese character shape or fibrous eutectic Mg in the alloy structure
2Si has become granular mutually basically fully, and the method processing Mg-3Si-3Sn magnesium alloy that adopts the present invention to propose is described, can make Chinese character shape or fibrous eutectic Mg in the alloy structure
2Si obtains effectively rotten mutually.
Can draw advantage of the present invention from above-mentioned test is, alloy element Si and Sn can form heat-staple Mg with Mg
2Si and Mg
2Sn complex intensifying phase.Simultaneously, the high temperature, short time thermal treatment process can make Chinese character shaped eutectic Mg in the Mg-Si-Sn series magnesium alloy
2The Si facies evolution is tiny, the subsphaeroidal Mg that disperse is distributed in magnesium alloy substrate and crystal boundary
2The Si phase had both been strengthened matrix, again pinning crystal boundary, thereby improved the resistance toheat and the comprehensive mechanical property of Mg-Si-Sn series magnesium alloy.Therefore, the present invention has opened up a new way for the cheap heat resistance magnesium alloy of exploitation.
Claims (1)
1.Mg-Si-Sn the thermal treatment process of Chinese character shaped eutectic Mg2Si phase in the series magnesium alloy; it is characterized in that: will be by weight percentage for Si 1-3%, Sn 1-3%, surplus be that the Mg-Si-Sn series magnesium alloy foundry goods of the composition proportion melting and casting of Mg places the chamber type electric resistance furnace that has protective atmosphere to be incubated; quick then taking-up is put into water and is quenched; holding temperature is 490 ℃～550 ℃, and soaking time is 1～4 hour.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007101446999A CN100540717C (en) | 2007-11-29 | 2007-11-29 | The thermal treatment process of Chinese character shaped eutectic Mg2Si phase in the Mg-Si-Sn series magnesium alloy |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007101446999A CN100540717C (en) | 2007-11-29 | 2007-11-29 | The thermal treatment process of Chinese character shaped eutectic Mg2Si phase in the Mg-Si-Sn series magnesium alloy |
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| CN101161840A CN101161840A (en) | 2008-04-16 |
| CN100540717C true CN100540717C (en) | 2009-09-16 |
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Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101982553B (en) * | 2010-09-21 | 2012-08-08 | 华南理工大学 | Heat resistant magnesium alloy without Al and preparation method thereof |
| CN102409208A (en) * | 2011-11-25 | 2012-04-11 | 沈阳工业大学 | Sr-containing heat-resisting casting magnesium alloy |
| CN102888544B (en) * | 2012-09-11 | 2015-12-02 | 西安理工大学 | Heat resistance magnesium alloy of a kind of Sn, Si complex intensifying and preparation method thereof |
| CN103700759B (en) * | 2012-09-27 | 2016-01-13 | 北京工业大学 | A kind of nano composite structure Mg 2si base thermoelectricity material and preparation method thereof |
| CN103334037B (en) * | 2013-07-04 | 2015-09-30 | 哈尔滨工程大学 | Si, Sn composite heat-resisting enhance magnesium alloy and plate rolling method |
| CN105044151B (en) * | 2015-08-26 | 2017-06-16 | 中南大学 | A kind of method for measuring aluminium alloy continuous cooling transformation (CCT) curve |
| CN109072359B (en) * | 2017-02-27 | 2020-09-08 | 韩国机械研究院 | Aging heat treatment type high-strength magnesium alloy and preparation method thereof |
| CN110195178B (en) * | 2018-02-26 | 2021-10-22 | 中国宝武钢铁集团有限公司 | High-strength high-plasticity heat-resistant flame-retardant magnesium alloy and manufacturing method thereof |
| CN108823476A (en) * | 2018-08-27 | 2018-11-16 | 重庆大学 | The controllable Mg-Zn-Sn system magnesium alloy and its preparation method and application of degradation rate |
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