CN106967913A - A kind of Mg-Zn-Al-RE-Ca heat resistance magnesium alloys - Google Patents

A kind of Mg-Zn-Al-RE-Ca heat resistance magnesium alloys Download PDF

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Publication number
CN106967913A
CN106967913A CN201610025316.5A CN201610025316A CN106967913A CN 106967913 A CN106967913 A CN 106967913A CN 201610025316 A CN201610025316 A CN 201610025316A CN 106967913 A CN106967913 A CN 106967913A
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China
Prior art keywords
rare earth
alloy
alloys
heat resistance
magnesium
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Pending
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CN201610025316.5A
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Chinese (zh)
Inventor
肖文龙
张文强
马朝利
王方
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Beihang University
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Beihang University
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making alloys
    • C22C1/02—Making alloys by melting
    • C22C1/03—Making alloys by melting using master alloys
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C23/00—Alloys based on magnesium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C23/00—Alloys based on magnesium
    • C22C23/02—Alloys based on magnesium with aluminium as the next major constituent
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C23/00—Alloys based on magnesium
    • C22C23/04—Alloys based on magnesium with zinc or cadmium as the next major constituent
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C23/00—Alloys based on magnesium
    • C22C23/06—Alloys based on magnesium with a rare earth metal as the next major constituent

Abstract

The invention provides one kind using Mg-Zn-Al alloys as bulk alloy, the Mg-Zn-Al-RE-Ca heat resistance magnesium alloys of its heat resistance and casting character are improved by the compound action of light rare earth (or mixed light rare earth) and calcium, it is mainly characterized by：(1) Zn, Al, light rare earth (or mixed light rare earth), Ca, Mg, and a small amount of or micro impurity element are contained in alloy simultaneously；(2) according to Zn, Al content and Zn/Al ratios in Mg-Zn-Al bulk alloys, suppress low melting point Mg-Al, Mg-Zn and the phases of Mg-Zn-Al second in bulk alloy by controlling light rare earth (or mixed light rare earth) and calcium to be combined addition so that second phases (RE represents rare earth element) such as Al-RE-Zn, Al-RE, Al-Ca, Al-Mg-Ca and Ca-Mg-Zn of high heat stability are formed in alloy.Invention significantly improves the room temperature of Mg-Zn-Al alloys and mechanical behavior under high temperature, while improving the casting characters such as its hot tearing, mucous membrane, mobility.

Description

A kind of Mg-Zn-Al-RE-Ca heat resistance magnesium alloys
Technical field
The present invention relates to a kind of light metal structure material, more particularly, to a kind of heat resistance magnesium alloy.
Background technology
Magnesium alloy has density small, the advantages of specific strength is high, is widely used in automobile, aviation boat The field such as it.But, cast magnesium alloy generally existing intensity is relatively low, high-temperature heat-resistance performance deficiency etc. Problem, limits its large-scale application.It is mainly using more cast magnesium alloy at present Mg-Al-Zn (Mn) system.Due to the reasons such as hot tearing, decay resistance, Mg-Al-Zn (Mn) The content of Zn elements is limited within 1% (mass percent) in system magnesium alloy.Research discovery, By selecting suitable Zn/Al ratios, high zinc content Mg-Zn-Al alloys equally have good casting Make performance and decay resistance.Also, the mechanical behavior under high temperature of this kind of alloy is better than traditional low zinc A kind of Mg-Al-Zn (Mn) alloy, it is considered to be inexpensive heat resistance magnesium alloy system.However, by It is extremely sensitive to casting technique in the casting character (such as heat crack resistance) of Mg-Zn-Al alloys, and And the formation of a large amount of thick, hard crisp phases of eutectic second causes the temperature-room type plasticity of alloy poor, therefore should System alloy does not obtain large-scale promotion application always.
The addition of micro or a small amount of alkali earth metal (Ca and Sr etc.) can improve Mg-Zn-Al The heat resistance of system alloy, but the casting problem such as sticking to mould can be carried out to alloy strip.In Mg-Zn-Al In alloy add high level light rare earth (or mixed light rare earth) can reduce or suppress low melting point, The thick phase of eutectic second, generates the Al of high thermal stability2REZn2、Al2RE and Al11RE3(RE For rare earth) etc. the second phase.Moreover, the content by controlling Zn, Al and RE, Mg-Zn-Al-RE Alloy has good casting character and room temperature and the strong plasticity of high temperature.Therefore, further reduce into This, development improves Mg-Zn-Al alloys by RE alloyed and other alloy element collective effects The alloyage process of casting character and mechanical property, with important engineering application value.
The content of the invention
According to an aspect of the invention, there is provided a kind of Mg-Zn-Al-RE-Ca heat resistance magnesium alloys, It is made up of following component (mass percent)：Zinc 2-8%, aluminium 2-8%, rare earth 0.1-4%, Calcium 0.1-4%, impurity content are less than 0.2%, and remaining is magnesium.
Beneficial effects of the present invention include：
1) zinc is main alloying elements, and the addition of zinc can improve the plasticity of alloy, and zinc is in magnesium Maximum solid solution degree (mass percent) be 6.2%, and solid solubility reduces with the reduction of temperature, has Solution strengthening and the double action of ageing strengthening, and Zn in creep process to Grain Boundary Segregation, from And limit dislocation creep.
2) aluminium is main alloy element, can improve the mobility of magnesium alloy, so as to improve casting Make performance.
3) rare earth has double action in the present invention：First, rare earth is to be used to improve in the present invention The element of heat resistance, rare earth generates Al after adding with Zn, Al2RE and Al2REZn2It is contour molten The second phase of point；And rare earth can improve Mg-Zn-Al-Ca casting character.
4) calcium is the element for being used in the present invention improve heat resistance, and calcium is generated after adding Ca2Mg6Zn3, second phase of high thermal stability such as Al-Ca and Al-Mg-Ca.Moreover, the addition of calcium can To refine arborescent structure, so as to improve room temperature and mechanical behavior under high temperature.In addition, calcium is with low cost, Available for industrial production.
Brief description of the drawings
Fig. 1 shows embodiments of the invention 1-4 room temperature tensile mechanical property.
Fig. 2 shows embodiments of the invention 1-4 drawing by high temperature mechanical property.
Fig. 3 shows the heating curves that embodiments of the invention 1-4 differential scanning calorimetry is determined.
Fig. 4 shows the surface quality of continuous castings of embodiments of the invention 1 and 3-6 sample object.
Fig. 5 shows the as-cast structure of embodiments of the invention 3.
Embodiment
The present invention provides a kind of Mg-Zn-Al-RE-Ca heat resistance magnesium alloys, and the heat resistance magnesium alloy has height Warm intensity is good, and casting character is excellent, the features such as inexpensive.
A kind of Mg-Zn-Al-RE-Ca heat resistance magnesium alloys, it is characterised in that including zinc, aluminium, rare earth, Calcium and magnesium, its match (mass percent) be：Zinc 2-8%, aluminium 2-8%, rare earth：0.1%-4%, Calcium：0.1%-4%；Rare earth and calcium used in the embodiment of the present invention is respectively with Mg-RE and Mg-Ca The form of intermediate alloy is added, and the composition (mass percent) of intermediate alloy is Mg-30RE, Mg-20Ca.In raw material magnesium (Mg), zinc (Zn), aluminium (Al) involved by present example Between alloy Mg-RE and Mg-Ca be that product are sold in market.The purity of raw material is Mg:99.9%； Al:99.9%；Zn:99.9%；Mg-30RE:99.5%；Mg-20Ca:99.5%.
Embodiment 1
Dispensing：
Dispensing is carried out by following mass percents：Zn:4%；Al:4%；RE:3%；Ca:1%, Surplus is Mg.The rare earth of this example is rich lanthanum mixed rear earth.Above-mentioned raw materials pass through mechanical grinding, remove Remove dirt, the oxide on surface.Before melting, raw material is being preheated to 175 DEG C, warp in drying box Cross 20min heating and remove moisture.
Prepare：
Using 45# steel molds, the coating of brush one on mould, 200 are preheated to by mould in advance ℃.Paint ingredient is talcum powder, boric acid, waterglass and water.Coverture is NaCl and KCl, is matched somebody with somebody Than for NaCl：KCl=3:1 (mass percent).The composition of refining agent is 85-90% (quality percentages Number) coverture+10-15%CaF2(mass percent).
The instruments such as stirring rod, slag scoop and crucible preheat 20min at 175 DEG C.
Prepare：
First, one layer of coverture is spread in advance in crucible bottom, and crucible is heated to kermesinus, throw Enter magnesium ingot, furnace temperature is risen to 780 DEG C.After after magnesium ingot all fusing, pure Zn, pure Al are sequentially added, Mg-20Ca intermediate alloys, Mg-30RE intermediate alloys, sprinkle coverture again.When raw material is whole After fusing, it is pressed into aluminium foil parcel refining agent in melt, 3min is refined with stirring rod.Use slag scoop Remove surface scum.Then, furnace temperature is down to 740 DEG C, stands 20min.Skim, cast.
Embodiment 2
Dispensing：
Dispensing is carried out by following mass percents：Zn:4%；Al:4%；RE:2.5%；Ca:1.5%, Surplus is Mg.The rare earth of this example is rich lanthanum mixed rear earth.Above-mentioned raw materials pass through mechanical grinding, remove Remove the dirt on surface, oxide.Before melting, raw material is being preheated to 175 DEG C, warp in drying box Cross 20min heating and remove moisture.
Prepare：
Using 45# steel molds, the coating of brush one on mould, 200 are preheated to by mould in advance ℃.Paint ingredient is talcum powder, boric acid, waterglass and water.Coverture is NaCl and KCl, is matched somebody with somebody Than for NaCl：KCl=3:1 (mass percent).The composition of refining agent is 85-90% (quality percentages Number) coverture+10-15%CaF2(mass percent).
The instruments such as stirring rod, slag scoop and crucible preheat 20min at 175 DEG C.
Prepare：
First, one layer of coverture is spread in advance in crucible bottom, and crucible is heated to kermesinus, throw Enter magnesium ingot, furnace temperature is risen to 780 DEG C.After after magnesium ingot all fusing, pure Zn, pure Al are added, Mg-20Ca intermediate alloys, Mg-30RE intermediate alloys, sprinkle coverture again.When raw material is whole After fusing, it is pressed into aluminium foil parcel refining agent in melt, 3min is refined with stirring rod.Use slag scoop Remove surface scum.Then, furnace temperature is down to 740 DEG C, stands 20min.Skim, cast.
Embodiment 3
Dispensing：
Dispensing is carried out by following mass percents：Zn:4%；Al:4%；RE:2%；Ca:2%, Surplus is Mg.The rare earth of this example is rich lanthanum mixed rear earth.Above-mentioned raw materials pass through mechanical grinding, remove Remove the dirt on surface, oxide.Before melting, raw material is being preheated to 175 DEG C, warp in drying box Cross 20min heating and remove moisture.
Prepare：
Using 45# steel molds, the coating of brush one on mould, 200 are preheated to by mould in advance ℃.Paint ingredient is talcum powder, boric acid, waterglass and water.Coverture is NaCl and KCl, is matched somebody with somebody Than for NaCl：KCl=3:1 (mass percent).The composition of refining agent is 85-90% (quality percentages Number) coverture+10-15%CaF2(mass percent).
The instruments such as stirring rod, slag scoop and crucible preheat 20min at 175 DEG C.
Prepare：
First, one layer of coverture is spread in advance in crucible bottom, and crucible is heated to kermesinus, put into magnesium Ingot, 780 DEG C are risen to by furnace temperature.After after magnesium ingot all fusing, pure Zn, pure Al, Mg-20Ca are added Intermediate alloy, Mg-30RE intermediate alloys, sprinkles coverture again.After raw material all melts, It is pressed into aluminium foil parcel refining agent in melt, 3min is refined with stirring rod.Surface is removed with slag scoop Scum silica frost.Then, furnace temperature is down to 740 DEG C, stands 20min.Skim, cast.
Embodiment 4
Dispensing：
Dispensing is carried out by following mass percents：Zn:4%；Al:4%；RE:1%；Ca:3%, Surplus is Mg.The rare earth of this example is rich lanthanum mixed rear earth.Above-mentioned raw materials pass through mechanical grinding, remove Remove the dirt on surface, oxide.Before melting, raw material is being preheated to 175 DEG C, warp in drying box Cross 20min heating and remove moisture.
Prepare：
Using 45# steel molds, the coating of brush one on mould, 200 are preheated to by mould in advance ℃.Paint ingredient is talcum powder, boric acid, waterglass and water.Coverture is NaCl and KCl, is matched somebody with somebody Than for NaCl：KCl=3:1 (quality amount percentage).The composition of refining agent is 85-90% (quality hundred Fraction) coverture+10-15%CaF2(mass percent).
The instruments such as stirring rod, slag scoop and crucible preheat 20min at 175 DEG C.
Prepare：
First, one layer of coverture is spread in advance in crucible bottom, and crucible is heated to kermesinus, put into magnesium Ingot, 780 DEG C are risen to by furnace temperature.After after magnesium ingot all fusing, pure Zn, pure Al, Mg-20Ca are added Intermediate alloy, Mg-30RE intermediate alloys, sprinkles coverture again.After raw material all melts, It is pressed into aluminium foil parcel refining agent in melt, 3min is refined with stirring rod.Surface is removed with slag scoop Scum silica frost.Then, furnace temperature is down to 740 DEG C, stands 20min.Skim, cast.
Embodiment 5
Dispensing：
Dispensing is carried out by following mass percents：Zn:6%；Al:2%；RE:1%；Ca:3%, Surplus is Mg.The rich cerium mixed rear earth of the rare earth of this example.Above-mentioned raw materials pass through mechanical grinding, remove The dirt on surface, oxide.Before melting, raw material is being preheated to 175 DEG C, process in drying box 20min heating removes moisture.
Prepare：
Using 45# steel molds, the coating of brush one on mould, 200 are preheated to by mould in advance ℃.Paint ingredient is talcum powder, boric acid, waterglass and water.Coverture is NaCl and KCl, is matched somebody with somebody Than for NaCl：KCl=3:1 (mass percent).The composition of refining agent is 85-90% (quality percentages Number) coverture+10-15%CaF2(mass percent).
The instruments such as stirring rod, slag scoop and crucible preheat 20min at 175 DEG C.
Prepare：
First, one layer of coverture is spread in advance in crucible bottom, and crucible is heated to kermesinus, put into magnesium Ingot, 780 DEG C are risen to by furnace temperature.After after magnesium ingot all fusing, pure Zn, pure Al, Mg-20Ca are added Intermediate alloy, Mg-30RE intermediate alloys, sprinkles coverture again.After raw material all melts, It is pressed into aluminium foil parcel refining agent in melt, 3min is refined with stirring rod.Surface is removed with slag scoop Scum silica frost.Then, furnace temperature is down to 740 DEG C, stands 20min.Skim, cast.
Embodiment 6
Dispensing：
Dispensing is carried out by following mass percents：Zn:2%；Al:6%；RE:1%；Ca:3%, Surplus is Mg.The rare earth of this example is rich cerium mixed rear earth.Above-mentioned raw materials pass through mechanical grinding, remove Remove the dirt on surface, oxide.Before melting, raw material is being preheated to 175 DEG C, warp in drying box Cross 20min heating and remove moisture.
Prepare：
Using 45# steel molds, the coating of brush one on mould, 200 are preheated to by mould in advance ℃.Paint ingredient is talcum powder, boric acid, waterglass and water.Coverture is NaCl and KCl, is matched somebody with somebody Than for NaCl：KCl=3:1 (mass percent).The composition of refining agent is 85-90% (quality percentages Number) coverture+10-15%CaF2(mass percent).
The instruments such as stirring rod, slag scoop and crucible preheat 20min at 175 DEG C.
Prepare：
First, one layer of coverture is spread in advance in crucible bottom, and crucible is heated to kermesinus, put into magnesium Ingot, 780 DEG C are risen to by furnace temperature.After after magnesium ingot all fusing, pure Zn, pure Al, Mg-20Ca (matter are added Measure percentage) intermediate alloy, Mg-30La (mass percent) intermediate alloy sprinkles coverture again. After raw material all melts, it is pressed into aluminium foil parcel refining agent in melt, 3min is refined with stirring rod. Surface scum is removed with slag scoop.Then, furnace temperature is down to 740 DEG C, stands 20min.Skim, Casting.
Fig. 1 and Fig. 2 are embodiment 1-4 room temperature and drawing by high temperature curve respectively, from Fig. 1 and Fig. 2 It can be seen that RE and Ca is added in Mg-Zn-Al systems alloy has obtained preferably mechanical property. Fig. 1 is the room temperature tensile curve of embodiment 1-4 sample, it is seen then that pass through the compound of RE and Ca The tensile strength for adding alloy is higher than 156MPa, and yield strength is higher than 72MPa, and elongation percentage is more than 2.4%.Fig. 2 is high temperature (175 DEG C) stress strain curve of embodiment 1-4 sample, can be with from figure Find out：With the rise of temperature, the tensile strength loss of alloy does not become very big.When RE with When Ca content is respectively 2% and 2% (mass percent), preferably mechanical property has been obtained.
Show that addition RE and Ca can improve Mg-Zn-Al casting character from Fig. 3 and Fig. 4. Fig. 3 is the freezing curve of the sample for the embodiment 1-6 that differential scanning calorimetry is surveyed；Fig. 3 shows, RE and Ca addition expands α-Mg freezing range, improves the mobility of melt, favorably Type is filled in alloy.Fig. 4 is the surface quality of continuous castings of alloy, can be evident that：With not adding Plus Ca is compared with RE Mg-4Zn-4Al, the surface quality of embodiment 1 and 3-6 sample Gloss, oxidation is less, and mold-filling capacity is good.
Fig. 5 is the typical as-cast structure of the sample of embodiments of the invention 3, as can be seen from the figure Addition RE and Ca inhibits the phase of the low melting points such as Mg-Al, Mg-Zn, Mg-Zn-Al second so that Al-RE-Zn, Al-RE, Al-Ca, Al-Mg-Ca and Ca-Mg-Zn of high heat stability are formed in alloy Deng the second phase.Moreover, these containing RE or Ca second mutually have high heat endurance.In deformation During can prevent the sliding of crystal boundary.

Claims (4)

1. a kind of Mg-Zn-Al-RE-Ca heat resistance magnesium alloys, are made up of the component of following mass percent： Zinc 2-8%, aluminium 2-8%, rare earth 0.1-4%, calcium 0.1-4%, impurity content are less than 0.2%, remaining is magnesium.
2. heat resistance magnesium alloy according to claim 1, it is characterised in that the rare earth be lanthanum, cerium, One or more in praseodymium, neodymium.
3. the heat resistance magnesium alloy according to claim 1 and 2, it is characterised in that control Zn and Al Content and proportioning, while adding rare earth and calcium to improve the room temperature and high-temperature mechanics of magnesium alloy Can, improve its casting character.
4. the heat resistance magnesium alloy according to claim 1-3, it is characterised in that described heat resistant magnesium is closed Gold be by magnesium, zinc, aluminium, Mg-RE and Mg-Ca intermediate alloys be the smelting casting of raw material Form.
CN201610025316.5A 2016-01-14 2016-01-14 A kind of Mg-Zn-Al-RE-Ca heat resistance magnesium alloys Pending CN106967913A (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003091465A1 (en) * 2002-04-23 2003-11-06 Ahresty Corporation Magnesium alloy for diecasting
CN104498797A (en) * 2014-12-31 2015-04-08 上海交通大学 High-strength casting magnesium alloy with low hot cracking tendency and preparation method for high-strength casting magnesium alloy
CN105039817A (en) * 2015-07-22 2015-11-11 河南科技大学 Preparation method for multi-element heat-resisting magnesium alloy and multi-element heat-resisting magnesium alloy

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003091465A1 (en) * 2002-04-23 2003-11-06 Ahresty Corporation Magnesium alloy for diecasting
CN104498797A (en) * 2014-12-31 2015-04-08 上海交通大学 High-strength casting magnesium alloy with low hot cracking tendency and preparation method for high-strength casting magnesium alloy
CN105039817A (en) * 2015-07-22 2015-11-11 河南科技大学 Preparation method for multi-element heat-resisting magnesium alloy and multi-element heat-resisting magnesium alloy

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Application publication date: 20170721