CN109082572A - A kind of novel flame-retardant and magnesium alloy and its processing technology with high damping properties - Google Patents

A kind of novel flame-retardant and magnesium alloy and its processing technology with high damping properties Download PDF

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Publication number
CN109082572A
CN109082572A CN201811216699.XA CN201811216699A CN109082572A CN 109082572 A CN109082572 A CN 109082572A CN 201811216699 A CN201811216699 A CN 201811216699A CN 109082572 A CN109082572 A CN 109082572A
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magnesium alloy
alloy
retardant
magnesium
degree
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CN201811216699.XA
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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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    • 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
    • C22F1/06Changing 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 novel flame-retardant and with the magnesium alloy and its processing technology of high damping properties.According to weight percent, the ingredient of the alloy are as follows: B:0.1-0.2wt.%, Li:0.8-1.2wt.%, In:2.0-2.5wt.%, Bi:0.4-0.8wt.%, Cu:3.0-4.0wt.%, Hf:0.8-1.2wt.%, Mn:4.0-5.0wt.%, Al:3.5-3.8wt.%, surplus are magnesium.The material provides the fire-retardant scheme for causing magnesium alloy to burn due to friction or outer fire heating.It is contemplated that the implementation and industrialization of the alloy can push significantly China in light-weighted field to the business demand of antiflaming magnesium alloy.

Description

A kind of novel flame-retardant and magnesium alloy and its processing technology with high damping properties
Technical field
The present invention relates to technical field of alloy, specifically, being related to a kind of magnesium alloy.
Background technique
With the continuous development of modern science and technology, the consumption of metal material is growing day by day, and metallic mineral resources gradually tend to be withered It exhausts.Magnesium is one of the most abundant element of reserves on the earth, is 2.3% in the resource content of veneer of crust metallic ore, occupies common gold The 4th belonged to.Magnesium alloy density is about 2/3rds of aluminium alloy, and less than the half of titanium alloy, lightweight is with the obvious advantage.It should The feature of alloy maximum is that intensity height, impact resistance, good heat dissipation, dimensionally stable and elasticity modulus are big, absorbs impact load-carrying ability ratio Aluminium alloy is strong.These characteristics keep magnesium alloy application field very extensive, such as communications and transportation, electronics industry, military project field.
By feat of speed is fast, low energy consumption, the design feature of amenity, high-speed rail is in modern transportation means in occupation of extremely Important position.In order to guarantee the optimization of these aspect characteristics, train lightweight is very important technology, thus magnesium alloy exists There is critically important purposes in high-speed rail field.Currently, the high-speed rail of multiple countries such as France, Japan, China, is largely being closed using magnesium Gold production components, become the light-weighted critical material of bullet train.
However, magnesium alloy be used as rotary part when, be easy to happen magnesium kindling, such case mainly by rotating vane with start Wall friction leads to vane tip local heating and causes in box body.Because the characteristics of magnesium first is that the oxidation generated at high temperature Magnesium can not form one layer of fine and close protective film in Mg alloy surface.So magnesium and aluminium are different, cannot be protected with oxidation film Oneself, is extremely easy burning at high temperature.Magnesium alloy fire hazards are huge, will cause extremely heavy loss.Magnesium fire is once Occur, develop in the air-flow environment of high temperature, high pressure and high speed in fission formula, the components sustained combustion time is no more than 20s, difficult To take effective fire suppression measures, part scaling loss or burn-through are caused, or even burns entire mechanical device.Therefore, it thoroughly eradicates Magnesium fire has become the major issue of whole world concern, and scholars have actively developed the research of magnesium alloy flame-proof technology in recent years.
Traditionally, the combustion problem that solve magnesium alloy needs to start in terms of three :(a) alloying is carried out, so that in magnesium The oxide that the forward position of alloy melting forms covering effect carrys out the contact of starvation.In general, being currently by being closed in magnesium Add what Ca member was usually realized in gold.CaO the and MgO covering formed in oxidation process can play fire-retardant effect.(b) it improves The heating conduction of magnesium alloy, when so that magnesium alloy is on fire not yet by friction, heat can be distributed quickly, from And a possibility that reducing magnesium alloy kindling.It can only be risen for the very big element of this mentality of designing activity this for magnesium alloy To the effect of auxiliary.(c) lower the generation heat of magnesium alloy oxide by the method for alloying, that is, reduce magnesium alloy oxygen The heat released when change.In view of the activity of magnesium alloy, this design concept can only also play certain booster action, without Magnesium fire can be completely eliminated.
With the Magnesium Alloy Industry stable development of China, the application of magnesium material expands year by year.Not in particular with every profession and trade technology Disconnected to update, equipment develops to enlargement, automation, serialization and lightweight direction, and the application range of magnesium material increases year by year with quantity Add.Simultaneously with the increase of the operating power of every field machinery, it is desirable that magnesium alloy has the demand of more excellent fire-retardancy Also more more and more urgent.In view of the application field and usage amount of magnesium alloy, it may be said that the development and application of novel magnesium alloy material, Represent a national scientific and technological level to a certain extent.The magnesium alloy resource in China has been developed and utilized with particularly significant Realistic meaning.Predictably magnesium alloy can show more extensive application prospect in industrial circle and national defence.
Summary of the invention
The purpose of the present invention is to overcome the deficiency in the prior art, provides a kind of novel flame-retardant and the magnesium with high damping properties Alloy and its processing technology.
To achieve the goals above, the present invention adopts the following technical scheme:
A kind of novel flame-retardant and magnesium alloy and its processing technology with high damping properties.By weight percentage, the group of alloy As B:0.1-0.2wt.%, Li:0.8-1.2wt.%, In:2.0-2.5wt.%, Bi:0.4-0.8wt.%, Cu:3.0- 4.0wt.%, Hf:0.8-1.2wt.%, Mn:4.0-5.0wt.%, Al:3.5-3.8wt.%, surplus are magnesium.
A kind of above-mentioned novel flame-retardant and with high damping properties magnesium alloy and its processing technology, include the following steps: by As above the raw material matched is added in the electric induction furnace of argon gas protection, and uses silicon carbide crucible.Induction heating is formed to 760 degree Alloy melt, and be sufficiently stirred 12 minutes or so using electromagnetic agitation effect.Alloy melt is stood 12 minutes in 760 degree of heat preservations After be cast in waterglass or graphite jig and carry out casting and forming.Ingot casting is subjected to deformation process at room temperature, per pass Rolling lower amount is 3-4%.Every 3 passes need to carry out an intermediate heat-treatment to eliminate processing hardening, technique are as follows: 300 degree of heat preservations 1.2 hours.Final Heat Treatment Process after rolling are as follows: vacuum solid solution handles 320 degree and keeps the temperature 4 hours;Vacuum aging processing 180 Degree heat preservation 1.5 hours.
Compared with prior art, the invention has the following beneficial effects:
(1) under harsh working environment, magnesium alloy will first be fired by the situation of external friction sharply or outer fire It burns, forms magnesium fire.For flame-retardant alloy design, raising alloy thermal conductivity and the generation heat for reducing the alloyed oxide are all Fire-retardant supplementary means can not be inherently eliminated the burning of magnesium alloy.And influence magnesium alloy flame-proof performance most important factor The effective protection film that oxygen and magnesium alloy can be stopped to contact exactly is formed in alloy surface.Traditionally, antiflaming magnesium alloy is set Meter is to form the composite oxide layer of CaO and MgO in oxidation by the way that Ca element is added to stop the diffusion of oxygen.But The protective layer that CaO and MgO are formed substantially is still that solid oxide particle is dispersed in Serum Magnesium surface and causes diffusion barrier Layer, is substantially still loose immanent structure.As increasingly harshness, all trades and professions of magnesium alloy operating condition have increasing need for one The highly efficient magnesium alloy flame-proof design method of kind.The antiflaming magnesium alloy of present patent application protection uses a kind of substantially complete Different fire-retardant mode, by low melting point oxide layer the connecing come abundant starvation for generating one layer of liquid in Mg alloy surface Touching is a kind of innovation substantially compared with traditional CaO and MgO loose solid-oxide protective layer constituted.
(2) basic ideas of this patent be after solid Magnesium Alloy temperature is increased to certain temperature, it is some in magnesium alloy It is present in Grain-Boundary Phase or element occurs to melt and be oxidized the oxide melt for generating low melting point.The oxide of these low melting points Melt is sprawled due to having extremely excellent surface tension in Mg alloy surface, and the separation layer of liquid is formd, by oxygen and Magnesium alloy substrate isolation is opened.These low melting point liquid oxygen compounds can subtract due to acting as the effect of lubricant in Mg alloy surface Small frictional heat generation, simultaneously because shielding the inhibit magnesium alloy burning with contacting with effect of oxygen and magnesium alloy.Because The dry friction of Mg alloy surface becomes the friction of liquid phase lubrication under higher temperatures, so drastically reducing frictional work and frictional heat generation Amount.This design method can not only substantially reduce alloying element usage amount, while obtaining extraordinary mechanical property also Extraordinary flame retardant effect can be obtained.
(3) during solidification, the alloying element with higher melt will form first analyses the magnesium alloy of this patent design It is mutually precipitated from melt, is then precipitated between dendrite or between high-melting-point phase interface along with the solid phase of low melting point out.? After cold working or hot-working after magnesium alloy cast, these low melting points are met forms the structure of network in magnesium alloy substrate, And in the matrix of magnesium alloy.In the then magnesium alloy temperature-rise period as caused by friction or outer fire, these low melting points It meets and oxidation at first occurs, and form low melting point oxide melt.The low melting point oxide melt is by Li2O, B2O3And In2O3 It forms, wherein Li2O and In2O3It is basic anhydride, B2O3Belong to acidic oxide.These alkalinity and acidic oxide can also structures At compound complex compound, thus there can be extremely low fusing point.The fusing point of the magnesium alloy is 520-580 degree, and shape after surface oxidation At low melting point oxide melting range be 250-320 degree.Fusing point due to the temperature well below magnesium alloy, thus it is a small amount of These low melting point products can reach necessary flame retardant effect.
(4) alloy has wider solid liquid phase solidification temperature range, is enable to oxidation and fire-retardant alloy member Element can be adequately gathered in crystal boundary network-like structure, to establish structure basis for the fire-retardant of magnesium alloy.In addition, the conjunction Fitting has the advantages that excellent mobility, filling capacity is good, and shrinkage cavity tendency is small.Hot cracking tendency is small in casting process, and heat adds The technical characterstic of high yield rate after work and cold working.The material other than with excellent flame retardant property also there is traditional magnesium to close The mechanical property of gold: elasticity modulus 52-68GPa, yield strength 95-128MPa, tensile strength 150-170MPa extend Rate is 8-12%.And the high damping properties that there is traditional magnesium alloy not have: SDC=48-52%, traditional material are SDC=30% left It is right.Since processing smelting process is simple, the requirement to equipment is reduced, thus production cost is low.
Specific embodiment
Embodiment 1
A kind of novel flame-retardant and magnesium alloy and its processing technology with high damping properties.By weight percentage, the group of alloy As B:0.1wt.%, Li:0.8wt.%, In:2.0wt.%, Bi:0.4wt.%, Cu:3.0wt.%, Hf:0.8wt.%, Mn: 4.0wt.%, Al:3.5wt.%, surplus are magnesium.A kind of above-mentioned novel flame-retardant and magnesium alloy and its processing with high damping properties Technique 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 earthenware Crucible.Induction heating forms alloy melt to 760 degree, and is sufficiently stirred 12 minutes or so using electromagnetic agitation effect.Alloy is melted Body is cast in waterglass or graphite jig after 760 degree of heat preservations stand 12 minutes and carries out casting and forming.By ingot casting in room temperature Lower carry out deformation process, amount is 3-4% under rolling per pass.Every 3 passes need to carry out an intermediate heat-treatment to eliminate and add Work hardening, technique are as follows: 300 degree of 1.2 hours of heat preservation.Final Heat Treatment Process after rolling are as follows: vacuum solid solution handles 320 degree of guarantors Temperature 4 hours;Vacuum aging handles 180 degree and keeps the temperature 1.5 hours.
The alloy after cold working or hot-working, meet and form the structure of network in magnesium alloy substrate by low melting point, and In the matrix of magnesium alloy.In the then magnesium alloy temperature-rise period as caused by friction or outer fire, these low melting point phases Oxidation at first can occur, and form low melting point oxide melt.The fusing point of the magnesium alloy is 525-562 degree, and surface oxidation The melting range of the low melting point oxide formed afterwards is 258-273 degree.Fusing point due to the temperature well below magnesium alloy, thus These a small amount of low melting point products can reach necessary flame retardant effect.The alloy has wider solid liquid phase setting temperature model It encloses, is enable to oxidation and fire-retardant alloying element can be adequately gathered in crystal boundary network-like structure, to be magnesium The fire-retardant of alloy has established structure basis.In addition, the alloy has excellent mobility, and filling capacity is good, and shrinkage cavity tendency is small etc. Advantage.Hot cracking tendency is small in casting process, and after hot-working and cold working high yield rate technical characterstic.The material is in addition to tool Have outside excellent flame retardant property, also have the mechanical property of traditional magnesium alloy: elasticity modulus 58GPa, yield strength are 105MPa, tensile strength 162MPa, elongation percentage 10%.And the high damping properties that there is traditional magnesium alloy not have: SDC= 49%, traditional material is SDC=30% or so.
Embodiment 2
A kind of novel flame-retardant and magnesium alloy and its processing technology with high damping properties.By weight percentage, the group of alloy As B:0.2wt.%, Li:1.2wt.%, In:2.5wt.%, Bi:0.8wt.%, Cu:4.0wt.%, Hf:1.2wt.%, Mn: 5.0wt.%, Al:3.8wt.%, surplus are magnesium.A kind of above-mentioned novel flame-retardant and magnesium alloy and its processing with high damping properties Technique 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 earthenware Crucible.Induction heating forms alloy melt to 760 degree, and is sufficiently stirred 12 minutes or so using electromagnetic agitation effect.Alloy is melted Body is cast in waterglass or graphite jig after 760 degree of heat preservations stand 12 minutes and carries out casting and forming.By ingot casting in room temperature Lower carry out deformation process, amount is 3-4% under rolling per pass.Every 3 passes need to carry out an intermediate heat-treatment to eliminate and add Work hardening, technique are as follows: 300 degree of 1.2 hours of heat preservation.Final Heat Treatment Process after rolling are as follows: vacuum solid solution handles 320 degree of guarantors Temperature 4 hours;Vacuum aging handles 180 degree and keeps the temperature 1.5 hours.
The alloy after cold working or hot-working, meet and form the structure of network in magnesium alloy substrate by low melting point, and In the matrix of magnesium alloy.In the then magnesium alloy temperature-rise period as caused by friction or outer fire, these low melting point phases Oxidation at first can occur, and form low melting point oxide melt.The fusing point of the magnesium alloy is 535-562 degree, and surface oxidation The melting range of the low melting point oxide formed afterwards is 265-294 degree.Fusing point due to the temperature well below magnesium alloy, thus These a small amount of low melting point products can reach necessary flame retardant effect.The alloy has wider solid liquid phase setting temperature model It encloses, is enable to oxidation and fire-retardant alloying element can be adequately gathered in crystal boundary network-like structure, to be magnesium The fire-retardant of alloy has established structure basis.In addition, the alloy has excellent mobility, and filling capacity is good, and shrinkage cavity tendency is small etc. Advantage.Hot cracking tendency is small in casting process, and after hot-working and cold working high yield rate technical characterstic.The material is in addition to tool Have outside excellent flame retardant property, also have the mechanical property of traditional magnesium alloy: elasticity modulus 60GPa, yield strength are 112MPa, tensile strength 165MPa, elongation percentage 11%.And the high damping properties that there is traditional magnesium alloy not have: SDC= 51%, traditional material is SDC=30% or so.
Embodiment 3
A kind of novel flame-retardant and magnesium alloy and its processing technology with high damping properties.By weight percentage, the group of alloy As B:0.1wt.%, Li:0.9wt.%, In:2.4wt.%, Bi:0.5wt.%, Cu:3.5wt.%, Hf:0.9wt.%, Mn: 4.2wt.%, Al:3.6wt.%, surplus are magnesium.A kind of above-mentioned novel flame-retardant and magnesium alloy and its processing with high damping properties Technique 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 earthenware Crucible.Induction heating forms alloy melt to 760 degree, and is sufficiently stirred 12 minutes or so using electromagnetic agitation effect.Alloy is melted Body is cast in waterglass or graphite jig after 760 degree of heat preservations stand 12 minutes and carries out casting and forming.By ingot casting in room temperature Lower carry out deformation process, amount is 3-4% under rolling per pass.Every 3 passes need to carry out an intermediate heat-treatment to eliminate and add Work hardening, technique are as follows: 300 degree of 1.2 hours of heat preservation.Final Heat Treatment Process after rolling are as follows: vacuum solid solution handles 320 degree of guarantors Temperature 4 hours;Vacuum aging handles 180 degree and keeps the temperature 1.5 hours.
The alloy after cold working or hot-working, meet and form the structure of network in magnesium alloy substrate by low melting point, and In the matrix of magnesium alloy.In the then magnesium alloy temperature-rise period as caused by friction or outer fire, these low melting point phases Oxidation at first can occur, and form low melting point oxide melt.The fusing point of the magnesium alloy is 530-560 degree, and surface oxidation The melting range of the low melting point oxide formed afterwards is 240-290 degree.Fusing point due to the temperature well below magnesium alloy, thus These a small amount of low melting point products can reach necessary flame retardant effect.The alloy has wider solid liquid phase setting temperature model It encloses, is enable to oxidation and fire-retardant alloying element can be adequately gathered in crystal boundary network-like structure, to be magnesium The fire-retardant of alloy has established structure basis.In addition, the alloy has excellent mobility, and filling capacity is good, and shrinkage cavity tendency is small etc. Advantage.Hot cracking tendency is small in casting process, and after hot-working and cold working high yield rate technical characterstic.The material is in addition to tool Have outside excellent flame retardant property, also have the mechanical property of traditional magnesium alloy: elasticity modulus 56GPa, yield strength are 108MPa, tensile strength 164MPa, elongation percentage 10%.And the high damping properties that there is traditional magnesium alloy not have: SDC= 49%, traditional material is SDC=30% or so.

Claims (3)

1. a kind of novel flame-retardant and magnesium alloy and its processing technology with high damping properties;According to weight percent, the alloy Ingredient are as follows: B:0.1-0.2wt.%, Li:0.8-1.2wt.%, In:2.0-2.5wt.%, Bi:0.4-0.8wt.%, Cu:3.0- 4.0wt.%,Hf:0.8-
1.2wt.%, Mn:4.0-5.0wt.%, Al:3.5-3.8wt.%, surplus are magnesium.
2. a kind of novel flame-retardant and magnesium alloy and its processing technology with high damping properties according to claim 1, special Sign is to include following smelting step: the raw material as above matched being added in the electric induction furnace of argon gas protection, and using carbonization Silica crucible;Induction heating forms alloy melt to 760 degree, and is sufficiently stirred 12 minutes or so using electromagnetic agitation effect;It will close Golden melt is cast in waterglass or graphite jig after 760 degree of heat preservations stand 12 minutes and carries out casting and forming.
3. a kind of novel flame-retardant and magnesium alloy and its processing technology with high damping properties according to claim 1, special Sign is comprising following procedure of processing: ingot casting being carried out deformation process at room temperature, amount is 3-4% under rolling per pass;Every 3 Secondary rolling needs to carry out an intermediate heat-treatment to eliminate processing hardening, technique are as follows: 300 degree of 1.2 hours of heat preservation;After rolling Final Heat Treatment Process are as follows: vacuum solid solution handles 320 degree and keeps the temperature 4 hours;Vacuum aging handles 180 degree and keeps the temperature 1.5 hours.
CN201811216699.XA 2018-10-18 2018-10-18 A kind of novel flame-retardant and magnesium alloy and its processing technology with high damping properties Pending CN109082572A (en)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101121979A (en) * 2007-09-20 2008-02-13 上海交通大学 Method for preparing Mg-Zn-Zr deformation magnesium alloy
CN101205583A (en) * 2006-07-26 2008-06-25 哈尔滨工业大学 High strength and ductility high-damping wrought magnesium alloy and preparation 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
CN107893171A (en) * 2017-12-02 2018-04-10 广州宇智科技有限公司 Containing the highly conductive high-damping contact material palladium magnesium alloy of magnesium
WO2018154124A1 (en) * 2017-02-24 2018-08-30 Innomaq 21, S.L. Method for the economic manufacture of light components

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101205583A (en) * 2006-07-26 2008-06-25 哈尔滨工业大学 High strength and ductility high-damping wrought magnesium alloy and preparation thereof
CN101121979A (en) * 2007-09-20 2008-02-13 上海交通大学 Method for preparing Mg-Zn-Zr deformation magnesium alloy
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
CN107893171A (en) * 2017-12-02 2018-04-10 广州宇智科技有限公司 Containing the highly conductive high-damping contact material palladium magnesium alloy of magnesium

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