CN100497697C - Pseudo-crystal reinforced high zinc magnesium alloy and method for manufacturing same - Google Patents
Pseudo-crystal reinforced high zinc magnesium alloy and method for manufacturing same Download PDFInfo
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- CN100497697C CN100497697C CNB2006101023044A CN200610102304A CN100497697C CN 100497697 C CN100497697 C CN 100497697C CN B2006101023044 A CNB2006101023044 A CN B2006101023044A CN 200610102304 A CN200610102304 A CN 200610102304A CN 100497697 C CN100497697 C CN 100497697C
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Abstract
The invention discloses a quasi-crystalline reinforced high-zinc magnesium alloy and making method, which comprises the following parts: 2.50-5.00% Al, 6.00-20.00% Zn, 40-1.00% Y0., 0.40-1.20% Mn, 0.003-0.005% Ni, 0.03-0.05% Fe, 0.03-0.05% Cu and Mg. the cast shaped tissue is alpha-Mg+Tau (Mg32(Al, Zn)49)+phi (Al2Mg5Zn2)+, which is displayed in the alpha-Mg or tao-phase and phi-phase rim constituted by MgxZnuYtMnw magnesium-based four-phased composite tissues of quasi-crystalline with relative bulk at 1.50-4.00% in the high-zinc magnesium alloy material.
Description
Technical field
The invention belongs to magnesium alloy and manufacturing field thereof, particularly relate to a kind of with brilliant enhanced high-zinc magnesium alloy material of magnesium benchmark and manufacture method thereof.
Background technology
Technology formerly, publication number be CN1488773's " a kind of rare earth high-zinc magnesium alloy and preparation method thereof that contains ", this alloy is mainly elementary composition by Mg, Zn, Al, Mn, RE, its principal character is to add the RE element in high-zinc magnesium alloy, crystal grain thinning forms cenotype, has improved the room temperature and the mechanical behavior under high temperature of high-zinc magnesium alloy, and having overcome the shortcoming that the ZAC8506 magnesium alloy adds calcium easy oxidation, preparation technology is simple.
Technology formerly, publication number is " siliceous high-zinc magnesium alloy and the preparation technology thereof " of CN1546711, its moiety mass fraction is: Zn:6～10%, Al:2～5%, Mn:0.2～0.4%, Si:0.3～1.6%, surplus is Mg.The adding of Si forms Mg
2The Si phase, on the one hand flowability significantly improves, thereby has improved castability, adds alterant AlP on the other hand in containing the Si magnesium alloy again, makes Chinese character shape Mg
2Si and alloy substrate are organized obvious refinement, thereby have significantly improved the normal temperature and high temperature (150 ℃) mechanical property of alloy.This alloy preparation technology is simple, and alterant Al-AlP master alloy is easy to add in this magnesium alloy, and is pollution-free, reactionless slag, modification effect is long-acting stable, has overcome elemental phosphorous easy firing when rotten, has produced shortcoming such as a large amount of smoke pollution of environment, has realized green rotten.
High-zinc magnesium alloy and preparation method thereof, though on magnesium alloy and preparation method thereof, done improvement, Zn, RE and Si element have been added, improved the room temperature and the mechanical behavior under high temperature of high-zinc magnesium alloy to a certain extent, but deficiency such as prepared high-zinc magnesium alloy still exists poor toughness, moulding is difficult to and mechanical property is low.The concrete grammar that is used at present improving and improve the magnesium alloy performance both at home and abroad as mentioned above, be that magnesium alloy is carried out alloying, add single element Ca, Be and rare earth element, or improve point of ignition and the oxidation-resistance and the mechanical property of magnesium alloy, but action effect is limited by polynary complex element.
For this reason, if can suitably increase the content of the 2nd or the 3rd main added elements in the magnesium alloy, not only can reduce in the magnesium alloy magnesium dividing potential drop with magnesium homeostasis, increase the standard formation reaction free energy that forms magnesium oxide, but also can reduce the necessary temperature of superheat of Foundry Production, thereby make the magnesium alloy can melting in atmospheric environment by the fusing point that reduces magnesium alloy.Simultaneously; behind the content that increases the 2nd or the 3rd main added elements, the density of its magnesium alloy can increase to some extent, therefore reduces solvent load and make solvent float over the surface of liquid magnesium alloy as much as possible when protecting with solvent; really play a protective role, and make slag liquid separate easily reach the purpose of cleaning molten.Because the raising of point of ignition also can realize utilizing the die casting production of common pressure die-casting machine,, the deep processing of magnesium alloy and cost create favorable conditions for reducing and enlarge the market range of application.
For these reasons, Zn as the 2nd main added elements in the magnesium alloy, and is used Mg
xZn
uY
tMn
wThe brilliant particle of magnesium benchmark is as obdurability and the thermotolerance of high-zinc magnesium alloy dispersion-strengthened with the raising high-zinc magnesium alloy.The high brittle disadvantageous effect that elimination is brought to magnesium alloy by the Zn height.
Summary of the invention
The present invention is in order to overcome the weak point of existing magnesium alloy, it is easy to propose a kind of technology, cost is cheap relatively, can significantly improve the brilliant enhanced high-zinc magnesium alloy of magnesium benchmark and the manufacture method thereof of point of ignition and obdurability again, existing cast magnesium alloys point of ignition is low to solve, poor toughness, moulding difficulty, mechanical property and corrosion resistance nature is low and the high deficiency of production cost.
The present invention utilizes accurate brilliant psuedo-periodicity to arrange, and crystallization nuclei is many, and crystalline growth velocity is slow, in accurate crystalline phase low characteristics of surface energy at the interface, in the high-zinc magnesium alloy fusion process, adds a certain amount of Mg of containing for preparing in advance
xZn
uY
tMn
wThe master alloy of magnesium benchmark crystalline phase is handled through melt being carried out accurate brilliant homogenizing, the insulation refining skim and leave standstill after pour in ingot mould or the casting mold, make it in process of setting, to have formed α-Mg+ τ (Mg
32(Al, Zn)
49)+φ (Al
2Mg
5Zn
2)+Mg
xZn
uY
tMn
wThe brilliant particulate four phase complex tissues of magnesium benchmark.Because α in this magnesium alloy cast matrix-Mg crystal grain is inner and τ mutually or the boundary of φ phase the Mg of a large amount of tiny even dispersion distributions appears
xZn
uY
tMn
wThe brilliant particle particle of magnesium benchmark and the pinning crystal boundary also because the appearance of a large amount of high-melting-point τ phases is improved the obdurability of this material and thermotolerance, obtains a kind of novel magnesium alloy that development and application prospect are arranged very much thus.
The brilliant enhanced high-zinc magnesium alloy of magnesium benchmark of the present invention is characterised in that this high-zinc magnesium alloy Wt% meter by mass percentage, its chemical ingredients is: Al:2.50～5.00, Zn:6.00～20.00, Mn:0.40～1.20, Y0.:40～1.00, Ni:0.003～0.005, Fe:0.03～0.05, Cu:0.03～0.05, all the other are Mg.
The feature of the brilliant enhanced high-zinc magnesium alloy of magnesium benchmark of the present invention is that also the Characteristics of As-cast Structure of this high-zinc magnesium alloy is α-Mg+ τ { Mg
32(Al, Zn)
49}+φ (Al
2Mg
5Zn
2)+disperse is uniformly distributed among α-Mg or near the Mg T phase and φ phase edge
xZn
uY
tMn
wThe heterogeneous structure that the brilliant particle four of magnesium benchmark coexists is mutually formed.Mg in its high-zinc magnesium alloy
xZn
uY
tMn
wThe volume relative content of the brilliant particle of magnesium benchmark in the high-zinc magnesium alloy material is: 1.50%～4.00%.The middle mutually x+u+t+w=100 of its quasicrystal particle is an atomic percent.Wherein: 26≤x≤40,51≤u≤62,6≤t≤10,1≤w≤3.
A kind of method that is used to make the brilliant enhanced high-zinc magnesium alloy of magnesium benchmark of the present invention, this method is undertaken by following two steps:
(1) at first gets the raw materials ready by the required brilliant master alloy composition of the magnesium benchmark requirement of high-zinc magnesium alloy design mix, in melt quality percentage ratio Wt%, 1# magnesium ingot 40.00～50.00, the pure zinc 43.00～55.00 of 1#, pure yttrium 2.00～5.00, electrolytic manganese 1.00～3.00, and carry out preheating at 180 ℃～230 ℃, pack into then in the stove, at SF
6Melting under the gas shield, and after being incubated 20～30 minutes under 720 ℃～740 ℃, refining was also left standstill 30～40 minutes, then at 720 ℃～740 ℃ casting of coming out of the stove, obtained Mg
xZn
uY
tMn
wThe master alloy ingot of magnesium benchmark crystalline phase.X+u+t+w=100 is an atomic percent in its accurate crystalline phase.Wherein: 26≤x≤40,51≤u≤62,6≤t≤10,1≤w≤3.
(2) by the requirement of design high-zinc magnesium alloy composition, weigh up required high-zinc magnesium alloy basis furnace charge, by melt quality per-cent Wt%, 1# magnesium ingot 75.50～90.40, A00 aluminium ingot 2.50～5.00,1# zinc ingot metal 6.00～20.00, electrolytic manganese 0.40～1.10, and carry out preheating at 200 ℃, shove charge is at SF then
6Gas or solvent protection melting down, and after being warming up to 680 ℃～700 ℃, be incubated 10～15 minutes, add the Mg that accounts for melt gross weight 2.00%～8.00% again
xZn
uY
tMn
wThe brilliant master alloy of magnesium benchmark, melt is carried out homogenizing to be handled, be incubated 10～15 minutes, carry out leaving standstill 0.5～1 hour after the refining, take off removing dross, obtain the brilliant enhanced high-zinc magnesium alloy of magnesium benchmark liquid, come out of the stove at 680 ℃～700 ℃ at last, directly casting solidification is shaped or is cast into foundry goods, or reduces to 650 ℃～680 ℃ and pour into alloy cast ingot.
The final state matrix of the brilliant enhanced high-zinc magnesium alloy of magnesium benchmark of the present invention is by α-Mg+ τ (Mg
32(Al, Zn)
49)+φ (Al
2Mg
5Zn
2)+disperse is uniformly distributed within α-Mg phase or near the Mg the edge of τ phase and φ phase
xZn
uY
tMn
wThe heterogeneous structure that the brilliant particle four of magnesium benchmark coexists is mutually formed.Mg
xZn
uY
tMn
wThe volume relative content of the brilliant particle of magnesium benchmark in high-zinc magnesium alloy is 1.50～4.00%.At Mg of the present invention
xZn
uY
tMn
wOwing to having interfacial energy, accurate crystalline phase hangs down and eco-friendly characteristics in the brilliant master alloy of magnesium benchmark; so in the high-zinc magnesium alloy matrix for preparing; magnesium benchmark crystalline phase particle is as wild phase disperse uniform distribution; size is significantly less than the wild phase that generates with other method; and it is spherical that shape is tending towards; effect of isolating and stress concentration degree to matrix alleviate; the obdurability of alloy is improved; high-zinc magnesium alloy kindling temperature height of the present invention, good casting property, mechanical property is superior; and technology is easy; with low cost, be suitable for large-scale industrial production, have wide market application prospect.
Description of drawings
Fig. 1 is the accurate brilliant enhanced high-zinc magnesium alloy light microscopic photo of the embodiment of the invention 1
Fig. 2 is the accurate brilliant enhanced high-zinc magnesium alloy light microscopic photo of the embodiment of the invention 2
Fig. 3 is the accurate brilliant enhanced high-zinc magnesium alloy light microscopic photo of the embodiment of the invention 3
Embodiment
Below can be described in further detail technical scheme of the present invention by specific embodiment.
Embodiment 1
The chemical ingredients (by mass percent Wt%) of the brilliant enhanced high-zinc magnesium alloy of magnesium benchmark: Al:2.50, Zn:6.00, Mn:1.20, Y0.:40, Ni:0.005, Fe:0.04, Cu:0.03, all the other are Mg.
At first get the raw materials ready (by melt quality percentage ratio Wt%) 1# magnesium ingot 40.00, the pure zinc 55.00 of 1# by the required magnesium base master alloy composition requirement of high-zinc magnesium alloy design mix, pure yttrium 2.00, electrolytic manganese 3.00 also carries out preheating at 200 ℃ and toasts, in the stove of packing into then, at SF
6Under the gas shield; in induction furnace or resistance furnace according to conventional magnesium alloy smelting method 730 ℃ of insulation refinings and leaving standstill 30 minutes after 25 minutes; melt out the accurate brilliant master alloy liquid that meets the chemical ingredients requirement, coming out of the stove at 730 ℃ pours into solidification forming in the metal mold, prepares a kind of Mg of having
26Zn
62Y
10Mn
2The master alloy ingot of magnesium benchmark crystalline phase.
Secondly get the raw materials ready (by melt quality percentage ratio Wt%) 1# magnesium ingot 90.40, A00 aluminium 2.50 by the required basic furnace charge of design high-zinc magnesium alloy, the pure zinc 6.00 of 1#, electrolytic manganese 1.10, and carry out the preheating baking, pack into then in the resistance melting furnace, routinely magnesium alloy smelting method with alloy at SF
6Gas or flux protection be fusing down, and after being warming up to 680 ℃, is incubated 10 minutes, adds the Mg for preparing in advance that accounts for melt gross weight 2.00%
26Zn
62Y
10Mn
2The brilliant intermediate alloy ingot of magnesium benchmark is carried out homogenizing to melt and is handled, and be incubated after 15 minutes, carries out refining, leaves standstill after 0.5 hour and takes off removing dross, is cooled to 690 ℃ and comes out of the stove and directly pour into a mould (or die casting) foundry goods or reduce to 650 ℃ that to pour into alloy cast ingot stand-by.And in metal mold, pour into a mould out the mechanical property sample simultaneously, the final state matrix of this high-zinc magnesium alloy is by α-Mg+ τ (Mg
32(Al, Zn)
49)+φ (Al
2Mg
5Zn
2)+disperse is uniformly distributed within α-Mg phase or near the Mg the edge of τ phase and φ phase
26Zn
62Y
10Mn
2The heterogeneous structure that the brilliant particle four of magnesium benchmark coexists is mutually formed.Mg
26Zn
62Y
10Mn
2The volume relative content of the brilliant particle of magnesium benchmark in the high-zinc magnesium alloy material is 1.50%.Microstructure picture is shown in accompanying drawing 1-1, and measured mechanical property is shown in subordinate list.
Embodiment 2
The chemical ingredients (by mass percent Wt%) of the brilliant enhanced high-zinc magnesium alloy of magnesium benchmark: Al:5.00, Zn:13.00, Mn:0.40, Y1.:00, Ni:0.003, Fe:0.03, Cu:0.05, all the other are Mg.
At first get the raw materials ready (by melt quality percentage ratio Wt%) 1# magnesium ingot 50.00, the pure zinc 46.00 of 1# by the required brilliant master alloy composition of the magnesium benchmark requirement of high-zinc magnesium alloy design mix, pure yttrium 3.00, electrolytic manganese 1.00 also carries out preheating at 200 ℃ and toasts, in the stove of packing into then, at SF
6Under the gas shield; in induction furnace or resistance melting furnace according to conventional magnesium alloy smelting method 720 ℃ of insulation refinings and leaving standstill 35 minutes after 20 minutes; melt out and meet the accurate brilliant master alloy liquid that chemical ingredients requires; coming out of the stove at 720 ℃ pours into solidification forming in the metal mold, prepares a kind of Mg of having
40Zn
51Y
8Mn
1The master alloy ingot of magnesium benchmark crystalline phase.
Secondly, by design high-zinc magnesium alloy required basic furnace charge get the raw materials ready (by melt quality per-cent Wt%), 1# magnesium ingot 82.60, A00 aluminium 5.00, the pure zinc 12.00 of 1#, electrolytic manganese 0.40, and carry out preheating at 200 ℃ and toast, pack into then in the resistance melting furnace, routinely magnesium alloy smelting method with alloy at SF
6Gas or flux protection be fusing down, and after being warming up to 700 ℃, is incubated 12 minutes, adds the Mg for preparing in advance that accounts for melt gross weight 5.00%
40Zn
51Y
8Mn
1The brilliant intermediate alloy ingot of magnesium benchmark is carried out accurate brilliant homogenizing to melt and is handled, and be incubated after 10 minutes, carries out refining, leaves standstill after 0.8 hour and takes off removing dross, is cooled to 700 ℃ and comes out of the stove and directly pour into a mould (or die casting) foundry goods or reduce to 680 ℃ that to pour into alloy cast ingot stand-by.And in metal mold, pour into a mould out the mechanical property sample simultaneously, the final state matrix of this high-zinc magnesium alloy is by α-Mg+ τ (Mg
32(Al, Zn)
49)+φ (Al
2Mg
5Zn
2)+disperse is uniformly distributed within α-Mg phase or near the Mg the edge of τ phase and φ phase
40Zn
51Y
8Mn
1The heterogeneous structure that the brilliant particle four of magnesium benchmark coexists is mutually formed.Mg
40Zn
51Y
8Mn
1The volume relative content of the brilliant particle of magnesium benchmark in the high-zinc magnesium alloy material is 2.50%.Microstructure picture is shown in accompanying drawing 1-2, and measured mechanical property is shown in subordinate list.
Embodiment 3
The chemical ingredients (by mass percent Wt%) of the brilliant enhanced high-zinc magnesium alloy of magnesium benchmark: Al:3.50, Zn:20.00, Mn:0.70, Y0.:70, Ni:0.004, Fe:0.05, Cu:0.04, all the other are Mg.
At first get the raw materials ready (by melt quality percentage ratio Wt%) 1# magnesium ingot 44.00, the pure zinc 49.00 of 1# by the required brilliant master alloy composition of the magnesium benchmark requirement of high-zinc magnesium alloy design mix, pure yttrium 5.00, electrolytic manganese 2.00 also carries out preheating at 200 ℃ and toasts, in the stove of packing into then, at SF
6Under the gas shield; in induction furnace or resistance melting furnace according to conventional magnesium alloy smelting method 740 ℃ of insulation refinings and leaving standstill 40 minutes after 30 minutes; melt out and meet the accurate brilliant master alloy liquid that chemical ingredients requires; coming out of the stove at 740 ℃ pours into solidification forming in the metal mold, prepares a kind of Mg of having
34Zn
57Y
6Mn
3The master alloy ingot of magnesium benchmark crystalline phase.
Secondly by the required basic furnace charge of design high-zinc magnesium alloy get the raw materials ready (by melt quality per-cent Wt%); 1# magnesium ingot 75.50; A00 aluminium ingot 3.80, the pure zinc 20.00 of 1#, electrolytic manganese 0.70; and carry out preheating at 200 ℃ and toast; in the melting resistance of packing into the then furnace, magnesium alloy smelting method melts alloy under SF6 gas or flux protection routinely, and is warming up to after 690 ℃; be incubated 15 minutes, add the Mg for preparing in advance that accounts for melt gross weight 8.00%
34Zn
56Y
7Mn
3The brilliant intermediate alloy ingot of magnesium benchmark is carried out accurate brilliant homogenizing to melt and is handled, and be incubated after 12 minutes, carries out refining, leaves standstill after 1 hour and takes off removing dross, is cooled to 680 ℃ and comes out of the stove and directly pour into a mould (or die casting) foundry goods or reduce to 670 ℃ that to pour into alloy cast ingot stand-by.And in metal mold, pour into a mould out the mechanical property sample simultaneously, the final state matrix of this high-zinc magnesium alloy is by α-Mg+ τ (Mg
32(Al, Zn)
49)+φ (Al
2Mg
5Zn
2)+disperse is uniformly distributed within α-Mg phase or near the Mg the edge of τ phase and ψ phase
34Zn
56Y
6Mn
3The heterogeneous structure that the brilliant particle four of magnesium benchmark coexists is mutually formed.Mg
34Zn
56Y
6Mn
3The volume relative content of the brilliant particle of magnesium benchmark in the high-zinc magnesium alloy material is 4.00%.Its microstructure picture is shown in accompanying drawing 1-3, and measured mechanical property is shown in subordinate list.
Table 1
Claims (2)
1. the brilliant enhanced high-zinc magnesium alloy of a magnesium benchmark, it is characterized in that this high-zinc magnesium alloy Wt% meter by mass percentage, its chemical ingredients is: Al:2.50～5.00, Zn:6.00～20.00, Y:0.40～1.00, Mn:0.40～1.20, Ni:0.003～0.005, Fe:0.03～0.05, Cu:0.03～0.05, surplus is Mg, and the Characteristics of As-cast Structure of described high-zinc magnesium alloy is α-Mg+ τ-Mg
32(Al, Zn)
49+ φ-Al
2Mg
5Zn
2+ disperse is uniformly distributed among α-Mg or near the Mg τ phase and φ phase edge
xZn
uY
tMn
wThe heterogeneous structure that the brilliant particle four of magnesium benchmark coexists is mutually formed; Wherein, Mg
xZn
uY
tMn
wThe volume relative content of the brilliant particle of magnesium benchmark in the high-zinc magnesium alloy material is: 1.50%～4.00%; The middle mutually x+u+t+w=100 of its quasicrystal particle is an atomic percent; Wherein: 26≤x≤40,51≤u≤62,6≤t≤10,1≤w≤3.
2. be used to make the method for the brilliant enhanced high-zinc magnesium alloy of the described standard of claim 1, it is characterized in that this method undertaken by following two steps:
(1) the magnesium base master alloy composition requirement that at first needs by the high-zinc magnesium alloy design mix is got the raw materials ready, in melt quality percentage ratio Wt%, 1# magnesium ingot 40.00～50.00, the pure zinc 43.00～55.00 of 1#, pure yttrium 2.00～5.00, electrolytic manganese 1.00～3.00, and carry out preheating at 180 ℃～230 ℃, pack into then in the stove, at SF
6Melting under the gas shield, and after being incubated 20～30 minutes under 720 ℃～740 ℃, refining was also left standstill 30～40 minutes, then at 720 ℃～740 ℃ casting of coming out of the stove, obtained Mg
xZn
uY
tMn
wThe master alloy ingot of magnesium benchmark crystalline phase;
X+u+t+w=100 is an atomic percent in its accurate crystalline phase;
Wherein: 26≤x≤40,51≤u≤62,6≤t≤10,1≤w≤3;
(2) by the requirement of design high-zinc magnesium alloy composition, weigh up required high-zinc magnesium alloy basis furnace charge, by melt quality per-cent Wt%, 1# magnesium ingot 75.50～90.40, A00 aluminium ingot 2.50～5.00,1# zinc ingot metal 6.00～20.00, electrolytic manganese 0.40～1.10, and carry out preheating at 200 ℃, shove charge is at SF then
6Melting under gas or the flux protection, and after being warming up to 680 ℃～700 ℃, be incubated 10～15 minutes, add the Mg that accounts for melt gross weight 2.00%～8.00% again
xZn
uY
tMn
wThe brilliant master alloy of magnesium benchmark, melt is carried out homogenizing to be handled, be incubated 10～15 minutes, carry out leaving standstill 0.5～1 hour after the refining, take off removing dross, obtain the brilliant enhanced high-zinc magnesium alloy of magnesium benchmark liquid, come out of the stove at 680 ℃～700 ℃ at last, directly casting solidification is shaped or is cast into foundry goods, or reduces to 650 ℃～680 ℃ and pour into alloy cast ingot.
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|---|---|---|---|
| CNB2006101023044A CN100497697C (en) | 2006-12-20 | 2006-12-20 | Pseudo-crystal reinforced high zinc magnesium alloy and method for manufacturing same |
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|---|---|---|---|
| CNB2006101023044A CN100497697C (en) | 2006-12-20 | 2006-12-20 | Pseudo-crystal reinforced high zinc magnesium alloy and method for manufacturing same |
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| CN102618766B (en) * | 2012-04-23 | 2013-07-31 | 华东交通大学 | Preparation method of quasi-crystal enhanced high-strength magnesium-zinc-yttrium (Mg-Zn-Y) alloy |
| CN108467957B (en) * | 2018-04-25 | 2019-10-15 | 中北大学 | A kind of preparation method of quasi-crystalline substance reinforced type magnesium based composites |
| CN108611505B (en) * | 2018-04-29 | 2019-11-15 | 中北大学 | A kind of preparation method of spontaneous quasi-crystalline substance enhanced magnesium alloy material |
| CN115896573B (en) * | 2022-12-23 | 2023-09-01 | 深圳市鑫申新材料科技有限公司 | High-strength high-heat-conductivity die-casting magnesium alloy and preparation method and application thereof |
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