CN109182858A - One kind heat resistance magnesium alloy containing Ho and preparation method thereof - Google Patents

One kind heat resistance magnesium alloy containing Ho and preparation method thereof Download PDF

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Publication number
CN109182858A
CN109182858A CN201811354331.XA CN201811354331A CN109182858A CN 109182858 A CN109182858 A CN 109182858A CN 201811354331 A CN201811354331 A CN 201811354331A CN 109182858 A CN109182858 A CN 109182858A
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magnesium alloy
heat resistance
preparation
resistance magnesium
alloy
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CN109182858B (en
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张中武
崔烨
范明雨
陈俊明
张洋
孙利昕
陈丹
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Harbin Engineering 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
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C1/00Making non-ferrous alloys
    • C22C1/02Making non-ferrous alloys by melting
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22FCHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/002Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working by rapid cooling or quenching; cooling agents used therefor
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22FCHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/06Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of magnesium or alloys based thereon

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  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
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  • Crystallography & Structural Chemistry (AREA)
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Abstract

The present invention provides one kind heat resistance magnesium alloy containing Ho and preparation method thereof, contains according to mass percentage content: Ho:1.0-12.0%, Y:1.0-5.0%, Zn:1.0-4.0%, remaining is Mg and impurity;A kind of preparation method of the heat resistance magnesium alloy containing Ho, melting;Homogenization;Deformation;Ageing treatment.The present invention is on the basis of long period ordered structure enhances MgYZn system magnesium alloy mechanical property, rare earth element Ho is added, pass through design element content and preparation process, realize the combination of dynamic strain aging and long period ordered structure reinforced phase, and content, long period ordered structure enhancing facies type, pattern and distribution of the Ho in matrix phase are controlled by homogenization, deformation, ageing treatment, to realize the control for alloy heterogeneous microstructure, achieve the purpose that while improving the elevated temperature strength and moulding of magnesium alloy.

Description

One kind heat resistance magnesium alloy containing Ho and preparation method thereof
Technical field
The present invention relates to a kind of magnesium alloys and preparation method thereof, more particularly to a kind of heat resistance magnesium alloy containing Ho and its preparation side Method belongs to magnesium alloy and its manufacturing field.
Background technique
Magnesium alloy is one of 21st century most potential metal material as novel ultra-lightweight structural material. It has high specific strength, specific stiffness, good heat conductivity and damping property, while its machining property is good, production Part size is stablized, therefore the background that has a wide range of applications in the modern industries such as aerospace, automobile.Especially aerospace And some components on automobile, such as: gear box, engine case lid, operating temperature is higher, and there is also lightweights Demand.Although magnesium and magnesium alloy have more excellent performance, but the heat-resisting quantity of magnesium alloy is poor, intensity is low, seriously limits The application of the above-mentioned industry of magnesium alloy, the magnesium alloy with excellent heat resistance energy are the essential industry materials being badly in need of.
There are rare earth resources abundant in China, how reasonably to develop and use rare earth resources to national national defense industry, boat The fields such as empty space flight, communications and transportation are of great significance.The size radius of most of rare earth elements and magnesium atom is not much different, because This has biggish solid solubility in magnesium, adds suitable rare earth element in the magnesium alloy, can play good solution strengthening and make With;The addition of rare earth can also be effectively improved alloy structure and its microstructure, improve the room temperature and mechanical behavior under high temperature of alloy, Enhance the corrosion resistance of magnesium alloy;Rare earth element is added can also be precipitated stable disperse phase particle in the magnesium alloy simultaneously, There is good precipitation enhancement.2001, scientist prepared in laboratory with long period stacking structure phase (long- Period stackingordered, LPSO) MgYZn alloy, which shows high room-temperature mechanical property, and table Reveal excellent heat resistance, becomes the important directions for developing high performance heat resistant magnesium alloy.
Currently, it is mainly focused on rare-earth element cerium, neodymium, yttrium etc. about the research that rare earth influences Properties of Magnesium Alloy, and it is right It is still few in the research that rare earth element Ho is applied in the magnesium alloy.It is adjusted simultaneously using the matrix phase constituent in Ho element regulation magnesium alloy Control LPSO phase structure is even more to have not been reported.Such as patent 201110267052.1,201210399131.2 has studied exists including Ho Influence of the interior rare earth element for magnesium alloy mechanical property, but without reference to Ho for magnesium alloy substrate phase constituent and LPSO The regulation of phase, also the influence not to Ho element to the heat resistance of magnesium alloy is furtherd investigate.In depth research rare earth member Influence of the plain Ho for magnesium alloy is conducive to develop novel high-strength, high-ductility, heat resisting magnesium-rare earth alloy, can extend magnesium conjunction The alloy system of gold promotes the extensive use of magnesium alloy in the industrial production.
Summary of the invention
The purpose of the invention is to provide a kind of containing for the high-intensitive and high moulding under lightweight, room temperature and hot environment Ho heat resistance magnesium alloy and preparation method thereof.
The object of the present invention is achieved like this:
A kind of heat resistance magnesium alloy containing Ho, contains according to mass percentage content: Ho:1.0-12.0%, Y:1.0-5.0%, Zn:1.0-4.0%, remaining is Mg and impurity.
A kind of preparation method of the heat resistance magnesium alloy containing Ho, according to mass percent Ho:1.0-12.0%, Y:1.0-5.0%, Zn:1.0-4.0%, remaining prepares raw material for Mg, carries out melting under the conditions of vacuum or protective atmosphere later, then cast alloys Ingot or casting.
The invention also includes features some in this way:
1. further including Homogenization Treatments;
2. further including deformation;
3. further including rolling rear ageing treatment;
4. the Homogenization Treatments temperature is 300-550 DEG C, the Homogenization Treatments time is 0.5-10h;
5. the deformation temperature is 250 DEG C -400 DEG C, total deformation rate 20-90%, 300-520 is heated to after the completion of deformation DEG C, 5-20min is kept the temperature, quenching is quickly cooled down;
6. the temperature that rear ageing treatment is rolled described in is 150 DEG C -300 DEG C, aging time 0.1-200h.
Compared with prior art, the beneficial effects of the present invention are:
Compared with existing MgYZn system alloy, rare earth element Ho is added in the present invention on the basis of MgYZn system alloy, makes alloy Mechanical behavior under high temperature be significantly improved, reason includes the following.It is answered firstly, the addition of Ho atom can cause dynamic Become timeliness, i.e., Ho atom dispiration is nearby spread under the high temperature conditions, reduces dislocation energy, this plays the work for hindering dislocation movement by slip With raising alloy high-temp performance.Secondly, the content of the adjustable long period ordered structure phase of Ho element is added and its in magnesium alloy In distribution, this precipitated phase can prevent crystal boundary sliding under the high temperature conditions and basal plane dislocation sliding, improve alloy High-temperature stability and intensity.Again, Ho and magnesium have similar atomic radius, and Ho is added in Mg matrix can play well admittedly Molten strengthening effect.In addition, the addition of Ho also can effectively adjust graininess such as Mg in alloy3Y(Ho)2Zn3Phase and Mg24Y(Ho)5 The content and its distribution of phase, these second phases all have the effect for hindering dislocation movement by slip, therefore the addition of Ho being capable of Effective Regulation Alloy mechanical property.As stated above, Ho element is added and Mg- can be further increased by corresponding heat treatment/deformation technique The mechanical property of rare earth-Zn system alloy, especially its mechanical behavior under high temperature are to develop LPSO to strengthen heat resistance magnesium alloy research, obtain Obtain the important directions of high-performance magnesium-alloy.
Detailed description of the invention
Fig. 1 is casting state magnesium-rare earth mechanical behavior under high temperature prepared by embodiment 1;
Fig. 2 is magnesium-rare earth rolled plate microscopic structure prepared by embodiment 2;
Fig. 3 is magnesium-rare earth rolled plate microscopic structure prepared by embodiment 3;
Fig. 4 is magnesium-rare earth rolled plate microscopic structure prepared by embodiment 4.
Specific embodiment
Present invention is further described in detail with specific embodiment with reference to the accompanying drawing.
The present invention proposes that part Y element in magnesium alloy substitution MgYZn system alloy, Effective Regulation alloy-based for Ho element is added It is dissolved atom content in body phase, while adjusting LPSO phase composition, plays the role of regulating and controlling magnesium alloy mechanical property.
Ho is added in MgYZn system magnesium alloy in the present invention, by optimizing composition proportion, homogenization process, rolling mill practice Selection, realization control effectively to content out of phase in alloy, size and distribution, and by control magnesium alloy substrate The precipitation of alloying component and intermetallic compound in the alloy regulates and controls the intensity and moulding of alloy, meets different physical conditions Using.Heat resistance magnesium alloy containing Ho of the invention has both the characteristics such as the high-intensitive and high moulding under lightweight, room temperature and hot environment, It can satisfy the heat-resisting position component performance requirement of the industries such as aerospace, automobile, electronics.
The present invention provides a kind of heat resistance magnesium alloy containing Ho with excellent in strength, plasticity.Its chemical component is (quality percentage Than): Ho 1.0-12.0%, Y 1.0-5.0%, Zn 1.0-4.0%, remaining is Mg and inevitable impurity.
The preparation method of the above-mentioned heat resistance magnesium alloy containing Ho includes the following steps: a. melting, b. Homogenization Treatments, and c. is deformed, D. rear ageing treatment is rolled.Wherein step b, c and d are optional step.
A. melting: according to mass percentage composition are as follows: Ho 1.0-12.0%, Y 1.0-5.0%, Zn 1.0-4.0%, Remaining is Mg and inevitable impurity, and melting is carried out under the conditions of vacuum or protective atmosphere, then cast alloys ingot or is directly poured Cast casting.
B. homogenize: by above-mentioned alloy cast ingot at 300-550 DEG C homogenizing annealing 0.5-10h.
C. deform: deformation temperature range is 250 DEG C -400 DEG C, and total deformation rate 20-90% can be deformed repeatedly, complete At being heated to 300-520 DEG C after last a time, 5-20min is kept the temperature, quenching is quickly cooled down.
D. ageing treatment: temperature range is 150 DEG C -300 DEG C, and aging time range is 0.1-200h.
Embodiment 1
Magnesium-rare earth chemical component in the present embodiment, by mass percentage are as follows: 3.2%Ho, 2.6%Y, 2.2%Zn, Remaining is Mg and inevitable impurity.Pure magnesium ingot, pure Zn and Mg-Ho, Mg-Y intermediate alloy are sequentially placed into crucible, with Smelting furnace is evacuated to 10 afterwards-1Pa, and being passed through argon gas makes air pressure in furnace reach 0.05MPa;When melting, step up warm in furnace Degree is warming up to 770 DEG C to alloy melt, keeps the temperature 15min, be cast into alloy cast ingot at 730 DEG C.Its mechanical behavior under high temperature is through surveying Examination: 200 DEG C of tensile strength are 176MPa, yield strength 80MPa, elongation percentage 20%.
Embodiment 2
Magnesium-rare earth chemical component in the present embodiment, by mass percentage are as follows: 1.3%Ho, 2.8%Y, 1.3%Zn, Remaining is Mg and inevitable impurity.Pure magnesium ingot, pure Zn and Mg-Ho, Mg-Y intermediate alloy are sequentially placed into crucible, with Smelting furnace is evacuated to 10 afterwards-1Pa, and being passed through argon gas makes air pressure in furnace reach 0.05MPa;When melting, step up warm in furnace Degree is warming up to 770 DEG C to alloy melt, keeps the temperature 15min, be cast into alloy cast ingot at 730 DEG C.Then by above-mentioned alloy cast ingot The homogenizing annealing 30min at 500 DEG C, to prevent from aoxidizing, heat treatment process sample aluminium foil package is put into the earthenware for filling MgO powder It is carried out in crucible;Multi- pass rolling is then carried out, rolling temperature is 500 DEG C, and the first passage deformation amount controlling is 5%, per pass later Secondary deflection is 10-12%, and the heat preservation of melting down for carrying out 5min is needed between rolling pass, and final deformation amount is 30% and is rolling finally It is put into 25 DEG C of water and is quickly cooled down after a time.Magnesium-rare earth in the present embodiment, after tested, room-temperature mechanical property are anti- Tensile strength is 242.3MPa, yield strength 148.4MPa, elongation percentage 24.7%.200 DEG C of tensile strength are 173.5MPa, are bent Taking intensity is 91.2MPa, elongation percentage 13.6%.
Embodiment 3
Magnesium-rare earth chemical component in the present embodiment, by mass percentage are as follows: 3.2%Ho, 2.6%Y, 2.2%Zn, Remaining is Mg and inevitable impurity.Pure magnesium ingot, pure Zn and Mg-Ho, Mg-Y intermediate alloy are sequentially placed into crucible, with Smelting furnace is evacuated to 10 afterwards-1Pa, and being passed through argon gas makes air pressure in furnace reach 0.05MPa;When melting, step up warm in furnace Degree is warming up to 770 DEG C to alloy melt, keeps the temperature 15min, be cast into alloy cast ingot at 730 DEG C.Then by above-mentioned alloy cast ingot The homogenizing annealing 30min at 500 DEG C, to prevent from aoxidizing, heat treatment process sample aluminium foil package is put into the earthenware for filling MgO powder It is carried out in crucible;Multi- pass rolling is then carried out, rolling temperature is 500 DEG C, and the first passage deformation amount controlling is 5%, per pass later Secondary deflection is 10~15%, needs progress 5min's to melt down heat preservation, final deformation amount 30% between rolling pass.And it is rolling most It is put into 25 DEG C of water and is quickly cooled down after a time afterwards.Magnesium-rare earth in the present embodiment, room-temperature mechanical property after tested: it is anti- Tensile strength is 260.8MPa, yield strength 160.3MPa, elongation percentage 22.4%.200 DEG C of tensile strength are 195.8MPa, are bent Taking intensity is 126.1MPa, elongation percentage 17.5%
Embodiment 4
Magnesium-rare earth chemical component in the present embodiment, by mass percentage are as follows: 5.7%Ho, 3.2%Y, 1.8%Zn, Remaining is Mg and inevitable impurity.According to the physics of raw material, chemical property, by pure magnesium ingot, pure Zn and Mg-Ho, Mg- Y intermediate alloy is sequentially placed into setting in crucible difference position, and smelting furnace is then evacuated to 10-1Pa, and be passed through argon gas and make in furnace Air pressure reaches 0.05MPa;When melting, in-furnace temperature is stepped up, 770 DEG C is warming up to alloy melt, 15min is kept the temperature, at 730 DEG C Under be cast into alloy cast ingot.Then by above-mentioned alloy cast ingot, homogenizing annealing 30min is heat-treated at 500 DEG C to prevent from aoxidizing Process sample is wrapped up being put into the crucible for filling MgO powder and be carried out with aluminium foil;Then carry out multi- pass rolling, rolling temperature 500 DEG C, the first passage deformation amount controlling is 5%, and deflection is 10~15% per pass later, needs to carry out 5min's between rolling pass Heat preservation, final deformation amount 30% are melted down, and is put into 25 DEG C of water and is quickly cooled down after rolling last a time.In the present embodiment Magnesium-rare earth, after tested, it is 230.1MPa, yield strength 132.3MPa that room-temperature mechanical property, which is tensile strength, is extended Rate is 21.2%.200 DEG C of tensile strength are 225.4MPa, yield strength 134.1MPa, elongation percentage 16.1%.
Embodiment 5
Magnesium-rare earth chemical component in the present embodiment, by mass percentage are as follows: 3.16%Ho, 3.41%Y, 2.51% Zn, remaining is Mg and inevitable impurity.Pure magnesium ingot, pure Zn and Mg-Ho, Mg-Y intermediate alloy are sequentially placed into crucible In, it is passed through the protective gas that SF6:CO2 volume ratio is 1:200;When melting, in-furnace temperature is stepped up, is heated up to alloy melt To 750 DEG C, 15-20min is kept the temperature, is cast into alloy cast ingot at 730 DEG C.Then alloy cast ingot will be appealed at 510 DEG C, solid solution Processing 8 hours, then hot water is cooling, and to prevent from aoxidizing, heat treatment process sample aluminium foil package is put into the crucible for filling MgO powder Middle progress;Multi- pass rolling is then carried out, rolling temperature is 400 DEG C, and the first passage deformation amount controlling is 5%, later per pass Deflection is 10-12%, and the heat preservation of melting down for carrying out 5min is needed between rolling pass, and final deformation amount is 50% and is rolling last Water cooling after passage.After rolling, ageing treatment is carried out under the conditions of 200 DEG C, sky is cooled to room temperature.
In summary: the invention discloses a kind of heat resistance magnesium alloys containing Ho and preparation method thereof.Ingredient is (quality percentage Than) Ho:1.0-12.0%, Y:1.0-5.0%, Zn:1.0-4.0%, remaining is Mg and inevitable impurity.Preparation method Include the following steps: melting;Homogenization;Deformation;Ageing treatment.Preparation method is to design ingredient composition according to alloying element Afterwards, melting is carried out under the conditions of vacuum or protective atmosphere, then casting alloy ingot or direct pouring are at casting, then according to reality Demand selectively homogenized, deformed, ageing treatment.The present invention enhances MgYZn system magnesium alloy power in long period ordered structure On the basis of learning performance, rare earth element Ho is added, can be drawn in MgYZnHo alloy substrate using Ho atom under the high temperature conditions The characteristics of sending out dynamic strain aging, by design element content and preparation process, realizing dynamic strain aging and long period has The combination of sequence structure reinforced phase.And content of the Ho in matrix phase is controlled by homogenization, deformation, ageing treatment, long period has Sequence structure enhances facies type, pattern and distribution, to realize the control for alloy heterogeneous microstructure, reaches while improving magnesium The elevated temperature strength of alloy and the purpose of moulding.

Claims (8)

1. a kind of heat resistance magnesium alloy containing Ho, characterized in that contain according to mass percentage content: Ho:1.0-12.0%, Y:1.0- 5.0%, Zn:1.0-4.0%, remaining is Mg and impurity.
2. the preparation method of the heat resistance magnesium alloy according to claim 1 containing Ho, characterized in that according to mass percent Ho: 1.0-12.0%, Y:1.0-5.0%, Zn:1.0-4.0%, remaining prepares raw material for Mg, later in vacuum or protective atmosphere condition Lower carry out melting, then cast alloys ingot or casting.
3. the preparation method of the heat resistance magnesium alloy according to claim 2 containing Ho, characterized in that further include Homogenization Treatments.
4. the preparation method of the heat resistance magnesium alloy according to claim 2 containing Ho, characterized in that further include deformation.
5. the preparation method of the heat resistance magnesium alloy according to claim 2 containing Ho, characterized in that further include rolling at rear timeliness Reason.
6. the preparation method of the heat resistance magnesium alloy according to claim 3 containing Ho, characterized in that the Homogenization Treatments temperature It is 300-550 DEG C, the Homogenization Treatments time is 0.5-10h.
7. the preparation method of the heat resistance magnesium alloy according to claim 4 containing Ho, characterized in that the deformation temperature is 250 DEG C -400 DEG C, total deformation rate 20-90%, it is heated to 300-520 DEG C after the completion of deformation, keeps the temperature 5-20min, quenching is quickly cooled down.
8. the preparation method of the heat resistance magnesium alloy according to claim 5 containing Ho, characterized in that described to roll rear ageing treatment Temperature is 150 DEG C -300 DEG C, aging time 0.1-200h.
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CN113667872A (en) * 2021-08-25 2021-11-19 哈尔滨工程大学 Ho reinforced magnesium-lithium alloy and preparation method thereof

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CN110616356B (en) * 2019-10-15 2022-01-14 哈尔滨工程大学 Er-containing magnesium alloy and preparation method thereof
CN113667872A (en) * 2021-08-25 2021-11-19 哈尔滨工程大学 Ho reinforced magnesium-lithium alloy and preparation method thereof

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