CN109022982A - A kind of liquid metal flame retardant type magnesium alloy with excellent high temperature mechanical property - Google Patents

A kind of liquid metal flame retardant type magnesium alloy with excellent high temperature mechanical property Download PDF

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Publication number
CN109022982A
CN109022982A CN201811225286.8A CN201811225286A CN109022982A CN 109022982 A CN109022982 A CN 109022982A CN 201811225286 A CN201811225286 A CN 201811225286A CN 109022982 A CN109022982 A CN 109022982A
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magnesium alloy
alloy
degree
mechanical property
liquid metal
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CN201811225286.8A
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杨长江
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Guangzhou Xianzhi Technology Co Ltd
Guangzhou Yuzhi Technology Co Ltd
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Guangzhou Xianzhi Technology Co Ltd
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Priority to CN201811225286.8A priority Critical patent/CN109022982A/en
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    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C23/00Alloys based on magnesium
    • C22C23/04Alloys based on magnesium with zinc or cadmium as the next major constituent
    • 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
    • C22F1/02Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working in inert or controlled atmosphere or vacuum
    • 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

Abstract

The invention discloses a kind of liquid metal flame retardant type magnesium alloy with excellent high temperature mechanical property.According to weight percent, the ingredient of the alloy are as follows: In:2.0-2.5wt.%, Sn:1.0-1.8wt.%, Pb:2.0-2.5wt.%, Zn:4.0-4.5wt.%, Sc:0.2-0.4wt.%, Ni:1.0-1.5wt.%, Si:0.4-0.8wt.%, Ta:0.1-0.2wt.%, surplus are magnesium.The material is that the fire-retardant of magnesium alloy provides a kind of materialogy scheme that liquid-metal layer is formed based on surface, and the alloy is cast magnesium alloy.The implementation and industrialization of the alloy can push significantly China in high-end field to the business upgrade requirement of high-quality magnesium alloy materials.

Description

A kind of liquid metal flame retardant type magnesium alloy with excellent high temperature mechanical property
Technical field
The present invention relates to technical field of alloy, specifically, being related to a kind of magnesium alloy.
Background technique
Magnesium is one of the most abundant light metal alloy of reserves on the earth, and specific gravity is 1.74g/cm3, only aluminium 2/3, titanium 2/5, the 1/4 of steel.The storage very abundant of nature magnesium is that aluminium, iron are only second in the earth's crust, is the highest structure of third abundance Metal.The primary purposes of magnesium metal is used as alloy addition element;Followed by casting and deformed Mg of the manufacture suitable for making structural member Alloy;It is finally for steel desulfurization.
Magnesium alloy is formd after adding a series of alloying element in magnesium.According to manufacturing method, magnesium alloy is divided into casting Magnesium alloy and wrought magnesium alloy.Either cast magnesium alloy or wrought magnesium alloy all have the advantages that a series of: (1) than In terms of intensity.The specific strength of magnesium alloy is higher than aluminium alloy and iron, therefore, under the intensity for not reducing components, can reduce aluminium or The weight of the components of iron.(2) in terms of electromagnetic wave shielding.The electromagnetic wave shielding performance energy effect of magnesium alloy is good.Use magnesium alloy The electroplating work procedure of electromagnetic shielding film can be saved.(3) in terms of machining property.Cutting resistance of the magnesium alloy than other metals It is small, it can faster speed processing in machining.(4) in terms of vibration damping.Since magnesium alloy is to the absorbability of vibrational energy Can be good, using vibration can be reduced on the component for driving and being driven.
Magnesium alloy early in two prewar i.e. with its applicability on various structures (such as aircraft structure), and become it is most light High-test metal structural material.Magnesium alloy is used as structural member, and crossing, removal is outer in aerospace field application, due at basis Because not being widely applied as aluminium alloy.With the development that novel magnesium alloy designs, more and more magnesium alloys are For aerospace field, and achieve the very big market sales volume.In field of traffic, in order to solve energy consumption and environmental issue and Largely use magnesium alloy.Magnesium alloy can mitigate car weight and reduce fuel consumption, and safety and comfort aspect are better than aluminium and cast iron.? Under the promotion of auto industry, magnesium alloy was constantly expanding market within past 10 years, with average annual 15% growth rate.This right-hand side Machine shell, laptop computer, Advanced Videos equipment and digital camera shell in be widely used Magnesium Alloys Components, give full play to Magnesium alloy is light, durable, vibration damping, shields the functions such as nonmagnetic.Magnesium alloy production is constantly expanded with the field of application and purposes, greatly There is gesture in the ascendant.
The extremely active natural attribute of magnesium alloy also brings serious using problem.In certain temperature, pressure is gentle It flows under environment, magnesium alloy can lead to the burning of magnesium alloy due to friction or outer fire.The burning velocity of magnesium alloy quickly, from combustion Burn end only 20 seconds or so, it is difficult to take common fire suppression measures.Thus to the demanding occasion of material safety energy Limit further using for magnesium alloy.In order to solve the combustion problem of magnesium alloy, people are added to Ca in the magnesium alloy, thus In one layer of the Surface Creation of Serum Magnesium finer and close CaO and MgO mixture oxide layer in combustion process.Since the oxide layer hinders Gear effect, so that oxygen contact magnesium alloy fused mass is suppressed, so as to avoid the burning of magnesium alloy.Further, it is also possible to pass through Fire-retardant positive effect is played by flame retardant coating technology in Mg alloy surface, but can't fundamentally solve magnesium alloy Combustion problem.
Material is the material base that human society is depended on for existence, makes a general survey of the history of human development, every kind of important new material It was found that and using all the capability improving of mankind's nature remodeling to a new level.In the contemporary society that science and technology is with rapid changepl. never-ending changes and improvements, The breakthrough of the great science and technology of each single item also largely has relied on the development of corresponding new material.New material is modern science and technology Originally, the development of new and high technology at this stage is often to break through with new material technology for development.In view of magnesium alloy application field and Usage amount, it may be said that the development and application of novel magnesium alloy material represents a national scientific and technological level to a certain extent.
Have benefited from the transition and upgrade of Chinese industrial and being obviously improved for China's economic status, magnesium alloy industry enables market see It is good.Wherein, the lightweight of automobile industry, the development and research and development of magnesium alloy technology of environmental protection demand, especially new-energy automobile With being constantly progressive for recovery and utilization technology, sufficient social base is provided to the market demand for wideling popularize magnesium alloy.It can It is anticipated that magnesium alloy can show more extensive application prospect in industrial circle and national defence.China possesses abundant Magnesium resource, magnesium reserves occupy first place in the world, develop magnesium alloy and have broad prospects.Currently, facing international magnesium alloy high speed hair The advantageous situation of exhibition, has developed and utilized China's magnesium resource and has been of great practical significance.
Summary of the invention
The purpose of the present invention is to overcome the deficiency in the prior art, provides a kind of liquid gold with excellent high temperature mechanical property Belong to flame retardant type magnesium alloy.
To achieve the goals above, the present invention adopts the following technical scheme:
A kind of liquid metal flame retardant type magnesium alloy with excellent high temperature mechanical property.By weight percentage, the composition of alloy For In:2.0-2.5wt.%, Sn:1.0-1.8wt.%, Pb:2.0-2.5wt.%, Zn:4.0-4.5wt.%, Sc:0.2-0.4wt.%, Ni:1.0-1.5wt.%, Si:0.4-0.8wt.%, Ta:0.1-0.2wt.%, surplus are magnesium.
A kind of above-mentioned liquid metal flame retardant type magnesium alloy with excellent high temperature mechanical property, including the following steps: will such as The raw material of upper proportion is added in the electric induction furnace of argon gas protection, and uses silicon carbide crucible.Induction heating is closed to 800 degree of formation Golden melt, and be sufficiently stirred 15 minutes or so using electromagnetic agitation effect.By alloy melt after 800 degree of heat preservations stand 15 minutes It is cast in waterglass or graphite jig and carries out casting and forming.Resulting ingot casting is heated to 700 degree simultaneously under protection of argon gas Heat preservation 10 minutes;Then the melt is poured into and carries out cast molding in the mold being ready for;Disappear after cooling and demolding Except casting stress vacuum annealing, temperature is 140 degree, and the time is 0.2 hour.
Compared with prior art, the invention has the following beneficial effects:
(1) aluminium alloy is because aluminum alloy surface can form fine and close oxidation film, suppression in air there is no the danger of burning Transmitting of the oxygen to aluminum alloy surface is made.In comparison, magnesium alloy aoxidizes the magnesia to be formed since consistency problem cannot Fire-retardant effect is played to magnesium alloy.Traditionally, the design of antiflaming magnesium alloy is to be formed by the way that Ca element is added in oxidation The composite oxide layer of CaO and MgO stops the diffusion of oxygen.But the protective layer that CaO and MgO is formed substantially is still Solid oxide particle is dispersed in Serum Magnesium surface and causes diffusion barrier layer, is substantially still open structure.As magnesium closes Golden operating condition is increasingly harsh, and all trades and professions have increasing need for a kind of highly efficient magnesium alloy flame-proof design method.This patent Shen The magnesium alloy that please be protected uses a kind of protection mechanism of low melting point liquid metal.Since the low melting point liquid metal is from magnesium alloy The crystal boundary of matrix generates, and is completely covered on Mg alloy surface.It thus can be by magnesium alloy before magnesium alloy temperature reaches fusing point Surface is completely covered, and has sufficiently completely cut off contact of the oxygen with Mg alloy surface, has established structure basis to be fire-retardant.
(2) for the magnesium alloy during solidification, the alloying element with higher melt will form first precipitated phase from melt Then middle precipitation is precipitated between dendrite or between high-melting-point phase interface along with low melting point solid phase.These low melting points are met The structure of network is formed in magnesium alloy substrate, and in the matrix of magnesium alloy.Then since friction or outer fire cause Magnesium alloy temperature-rise period in, these low melting points meet generation at first fusing and in Mg alloy surface drawout.Since these are low Essential element contained by fusing point phase has than magnesium and the lower affinity of oxygen, thus can be used as effective diffusion barrier layer for oxygen It comes with Mg alloy surface barrier.In addition, these low melting point liquid metals are due to acting as lubricant in Mg alloy surface It can reduce frictional heat generation.So that the dry friction of Mg alloy surface becomes the friction of liquid phase lubrication at higher temperatures, from And drastically reduce frictional work and heating amount.This design method can not only substantially reduce alloying element usage amount, obtain Extraordinary flame retardant effect can also be obtained while conventional magnesium alloy mechanical property.
(3) magnesium alloy has wider solid liquid phase solidification temperature range, the gold element so that composition low melting point is harmonious It can adequately be gathered in network-like structure, to establish structure basis for the fire-retardant of magnesium alloy.In addition, the alloy has There is the advantages that excellent mobility, filling capacity is good, and shrinkage cavity tendency is small.Thus the tendency of hot tearing is small in casting process, casting Hole and loose few, and high yield rate after hot-working and cold working.The whole melting range of the magnesium alloy is (220-490 Degree), and wherein the fusing point of intergranular low melting point phase is (220-250 degree).Since low melting point liquid metal has very low surface Power, thus these a small amount of low melting point products can adequately spread over Mg alloy surface, arrive necessary flame retardant effect.
(4) magnesium alloy in addition to due to friction or it is outer fiery can be in Surface Creation when temperature is increased to fusing point or less Low melting point liquid metal is fire-retardant outer to carry out, moreover it is possible to reach the mechanical property of traditional magnesium alloy: elasticity modulus 75-82GPa, bend Taking intensity is 110-125MPa, tensile strength 142-158MPa, elongation percentage 10-12%.And there is traditional magnesium alloy not have Mechanical behavior under high temperature: under 100 degree, yield strength 130-150MPa, and traditional magnesium alloy is under 100 degree, yield strength For 100MPa or less.While guaranteeing that the alloy has excellent anti-flammability, but also alloy uses mechanics in higher temperature Performance has guarantee.It is not only convenient for industrialized production, it may have highly significant light weight effect.
Specific embodiment
Embodiment 1
A kind of liquid metal flame retardant type magnesium alloy with excellent high temperature mechanical property.By weight percentage, the composition of alloy For In:2.0wt.%, Sn:1.0wt.%, Pb:2.0wt.%, Zn:4.0wt.%, Sc:0.2wt.%, Ni:1.0wt.%, Si: 0.4wt.%, Ta:0.1wt.%, surplus are magnesium.A kind of above-mentioned liquid metal flame retardant type magnesium with excellent high temperature mechanical property closes Gold includes the following steps: that the raw material that will as above match is added in the electric induction furnace of argon gas protection, and uses silicon carbide crucible. Induction heating forms alloy melt to 800 degree, and is sufficiently stirred 15 minutes or so using electromagnetic agitation effect.Alloy melt is existed 800 degree of heat preservations are cast in waterglass or graphite jig after standing 15 minutes and carry out casting and forming.By resulting ingot casting in argon It is heated to 700 degree under gas shielded and keeps the temperature 10 minutes;Then the melt is poured into and carries out cast molding in the mold being ready for; It carries out eliminating casting stress vacuum annealing after cooling and demolding, temperature is 140 degree, and the time is 0.2 hour.
The whole melting range of the magnesium alloy is (220-450 degree), and wherein the fusing point of intergranular low melting point phase is (220-230 degree).Since low melting point liquid metal has very low surface tension, thus these a small amount of low melting point products can Adequately to spread over Mg alloy surface, necessary flame retardant effect is arrived.The magnesium alloy is in addition to due to friction or outer fiery in temperature It can be fire-retardant outer to carry out in Surface Creation low melting point liquid metal when being increased to fusing point or less, moreover it is possible to reach traditional magnesium alloy Mechanical property: elasticity modulus 76GPa, yield strength 118MPa, tensile strength 145MPa, elongation percentage 10%.And have The mechanical behavior under high temperature that traditional magnesium alloy does not have: under 100 degree, yield strength 132MPa, and traditional magnesium alloy is at 100 degree Under, yield strength is 100MPa or less.While guaranteeing that the alloy has excellent anti-flammability, but also alloy is in higher temperatures Degree has guarantee using mechanical property.
Embodiment 2
A kind of liquid metal flame retardant type magnesium alloy with excellent high temperature mechanical property.By weight percentage, the composition of alloy For In:2.5wt.%, Sn:1.8wt.%, Pb:2.5wt.%, Zn:4.5wt.%, Sc:0.4wt.%, Ni:1.5wt.%, Si: 0.8wt.%, Ta:0.2wt.%, surplus are magnesium.A kind of above-mentioned liquid metal flame retardant type magnesium with excellent high temperature mechanical property closes Gold includes the following steps: that the raw material that will as above match is added in the electric induction furnace of argon gas protection, and uses silicon carbide crucible. Induction heating forms alloy melt to 800 degree, and is sufficiently stirred 15 minutes or so using electromagnetic agitation effect.Alloy melt is existed 800 degree of heat preservations are cast in waterglass or graphite jig after standing 15 minutes and carry out casting and forming.By resulting ingot casting in argon It is heated to 700 degree under gas shielded and keeps the temperature 10 minutes;Then the melt is poured into and carries out cast molding in the mold being ready for; It carries out eliminating casting stress vacuum annealing after cooling and demolding, temperature is 140 degree, and the time is 0.2 hour.
The whole melting range of the magnesium alloy is (225-480 degree), and wherein the fusing point of intergranular low melting point phase is (225-240 degree).Since low melting point liquid metal has very low surface tension, thus these a small amount of low melting point products can Adequately to spread over Mg alloy surface, necessary flame retardant effect is arrived.The magnesium alloy is in addition to due to friction or outer fiery in temperature It can be fire-retardant outer to carry out in Surface Creation low melting point liquid metal when being increased to fusing point or less, moreover it is possible to reach traditional magnesium alloy Mechanical property: elasticity modulus 80GPa, yield strength 115MPa, tensile strength 145MPa, elongation percentage 11%.And have The mechanical behavior under high temperature that traditional magnesium alloy does not have: under 100 degree, yield strength 142MPa, and traditional magnesium alloy is at 100 degree Under, yield strength is 100MPa or less.While guaranteeing that the alloy has excellent anti-flammability, but also alloy is in higher temperatures Degree has guarantee using mechanical property.
Embodiment 3
A kind of liquid metal flame retardant type magnesium alloy with excellent high temperature mechanical property.By weight percentage, the composition of alloy For In:2.4wt.%, Sn:1.2wt.%, Pb:2.1wt.%, Zn:4.2wt.%, Sc:0.3wt.%, Ni:1.2wt.%, Si: 0.6wt.%, Ta:0.1wt.%, surplus are magnesium.A kind of above-mentioned liquid metal flame retardant type magnesium with excellent high temperature mechanical property closes Gold includes the following steps: that the raw material that will as above match is added in the electric induction furnace of argon gas protection, and uses silicon carbide crucible. Induction heating forms alloy melt to 800 degree, and is sufficiently stirred 15 minutes or so using electromagnetic agitation effect.Alloy melt is existed 800 degree of heat preservations are cast in waterglass or graphite jig after standing 15 minutes and carry out casting and forming.By resulting ingot casting in argon It is heated to 700 degree under gas shielded and keeps the temperature 10 minutes;Then the melt is poured into and carries out cast molding in the mold being ready for; It carries out eliminating casting stress vacuum annealing after cooling and demolding, temperature is 140 degree, and the time is 0.2 hour.
The whole melting range of the magnesium alloy is (230-450 degree), and wherein the fusing point of intergranular low melting point phase is (230-240 degree).Since low melting point liquid metal has very low surface tension, thus these a small amount of low melting point products can Adequately to spread over Mg alloy surface, necessary flame retardant effect is arrived.The magnesium alloy is in addition to due to friction or outer fiery in temperature It can be fire-retardant outer to carry out in Surface Creation low melting point liquid metal when being increased to fusing point or less, moreover it is possible to reach traditional magnesium alloy Mechanical property: elasticity modulus 81GPa, yield strength 120MPa, tensile strength 145MPa, elongation percentage 12%.And have The mechanical behavior under high temperature that traditional magnesium alloy does not have: under 100 degree, yield strength 142MPa, and traditional magnesium alloy is at 100 degree Under, yield strength is 100MPa or less.While guaranteeing that the alloy has excellent anti-flammability, but also alloy is in higher temperatures Degree has guarantee using mechanical property.

Claims (3)

1. a kind of liquid metal flame retardant type magnesium alloy with excellent high temperature mechanical property;According to weight percent, the alloy Ingredient are as follows: In:2.0-2.5wt.%, Sn:1.0-1.8wt.%, Pb:2.0-2.5wt.%, Zn:4.0-4.5wt.%, Sc:0.2- 0.4wt.%,Ni:1.0-
1.5wt.%, Si:0.4-0.8wt.%, Ta:0.1-0.2wt.%, surplus are magnesium.
2. a kind of liquid metal flame retardant type magnesium alloy with excellent high temperature mechanical property according to claim 1, feature It is to include following smelting step: the raw material as above matched is added in the electric induction furnace of argon gas protection, and uses silicon carbide Crucible;Induction heating forms alloy melt to 800 degree, and is sufficiently stirred 15 minutes or so using electromagnetic agitation effect;By alloy Melt is cast in waterglass or graphite jig after 800 degree of heat preservations stand 15 minutes and carries out casting and forming.
3. a kind of liquid metal flame retardant type magnesium alloy with excellent high temperature mechanical property according to claim 1, feature It is comprising using step as follows: resulting ingot casting is heated to 700 degree under protection of argon gas and keeps the temperature 10 minutes;Then should Melt, which pours into, carries out cast molding in the mold being ready for;It carries out eliminating casting stress vacuum annealing after cooling and demolding, Temperature is 140 degree, and the time is 0.2 hour.
CN201811225286.8A 2018-10-20 2018-10-20 A kind of liquid metal flame retardant type magnesium alloy with excellent high temperature mechanical property Pending CN109022982A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113373398A (en) * 2021-06-24 2021-09-10 重庆大学 Flame-retardant magnesium alloy part

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104233181A (en) * 2012-12-18 2014-12-24 太原理工大学 Method for mechanical infiltration of Ni in surface mechanical attrition process of pure Mg-based sheet material
CN105908035A (en) * 2016-04-26 2016-08-31 哈尔滨工程大学 High-temperature-resistant high-strength magnesium-based composite and preparation method thereof
CN107523724A (en) * 2017-09-11 2017-12-29 广州宇智科技有限公司 Magnesium lithium alloy and its processing technology with high thermal conductivity alpha+beta containing two-phase
WO2018154124A1 (en) * 2017-02-24 2018-08-30 Innomaq 21, S.L. Method for the economic manufacture of light components

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104233181A (en) * 2012-12-18 2014-12-24 太原理工大学 Method for mechanical infiltration of Ni in surface mechanical attrition process of pure Mg-based sheet material
CN105908035A (en) * 2016-04-26 2016-08-31 哈尔滨工程大学 High-temperature-resistant high-strength magnesium-based composite and preparation method thereof
WO2018154124A1 (en) * 2017-02-24 2018-08-30 Innomaq 21, S.L. Method for the economic manufacture of light components
CN107523724A (en) * 2017-09-11 2017-12-29 广州宇智科技有限公司 Magnesium lithium alloy and its processing technology with high thermal conductivity alpha+beta containing two-phase

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113373398A (en) * 2021-06-24 2021-09-10 重庆大学 Flame-retardant magnesium alloy part

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