CN101792878B - Heat-conducting and corrosion-resistant magnesium alloy and preparation method thereof - Google Patents
Heat-conducting and corrosion-resistant magnesium alloy and preparation method thereof Download PDFInfo
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- CN101792878B CN101792878B CN 200910077615 CN200910077615A CN101792878B CN 101792878 B CN101792878 B CN 101792878B CN 200910077615 CN200910077615 CN 200910077615 CN 200910077615 A CN200910077615 A CN 200910077615A CN 101792878 B CN101792878 B CN 101792878B
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Abstract
The invention discloses a heat-conducting and corrosion-resistant magnesium alloy comprising the following components: 0.5-3.5 percent by weight of Mn, 0.05-1 percent by weight of Zn, 0.05-1 percent by weight of Ca and the balance of Mg. The preparation method comprises the following steps of: preparing a cast by taking a pure magnesium ingot, a pure Zn ingot, MnCl2 or a magnesium-melting refining agent containing MnCl2, a pure Ca block or a Mg-Ca intermediate alloy as raw materials, melting a pure magnesium ingot, adding an alloy element of Mn and alloying Zn and Ca, or preparing billet ingots; carrying out uniform thermal treatment; deforming the billet ingots into plates, tubes, sections, bars, wires or various casts by adopting a rolling, pressing, pulling or forging process; and carrying out prestretching treatment. Under the condition of 20DEG C, the heat-conducting rate of the magnesium alloy is 132W.(m.K)<-1>, the corrosion speed rate of a standard salt mist is not more than 0.13g/cm<2>.24 hours, the tensile strength is more than 320Mpa and the yield strength is more than 300Mpa. The invention can be used as a structural material of a heat-radiating system in a power source and an electronic device used in the aerospace.
Description
Technical field
The present invention relates to good and corrosion resistant magnesiumalloy of a kind of thermal conductivity and preparation method thereof, belong to metal material field.
Background technology
The heat-removal system structured material of the power supply in the aerospace, electron device had both required good heat conductivility, must have also simultaneously that density is little, intensity is high.Therefore, HS, high heat conductive magnesium alloy have important application background.
The thermal conductivity of pure magnesium is 1.55W. (m.K)
-1, intensity is approximately about 10MPa; After the alloying, intensity increases substantially, and thermal conductivity significantly reduces.For example according to U.S.'s magnesium and alloy handbook (ASMSpecialty Handbook:Magnesium and magnesium Alloys), contain the magnesiumalloy AZ81 of aluminium, zinc, its tensile strength is 275Mpa, the thermal conductivity 20 ℃ the time is 51.1W. (m.K)
-1Magnesium-rare earth WE43, its intensity is 250Mpa, the thermal conductivity 20 ℃ the time is 51.3W. (m.K)
-1The magnesiumalloy ZE41 that contains zinc, rare earth, its tensile strength is 205Mpa, the thermal conductivity 20 ℃ the time is 123.1W. (m.K)
-1The magnesiumalloy ZC63 that contains zinc, copper, its tensile strength is 210Mpa, the thermal conductivity 20 ℃ the time is 122W. (m.K)
-1The magnesiumalloy QE22 of argentiferous, rare earth, its tensile strength is 260Mpa, the thermal conductivity 20 ℃ the time is 113W. (m.K)
-1
Present existing magnesiumalloy, thermal conductivity high such as ZE41, QE22, its intensity is all less than 265Mpa; And intensity higher such as AZ81, WE43, its thermal conductivity is all less than 55W. (m.K)
-1
Summary of the invention
The purpose of this invention is to provide a kind of thermal conductivity and intensity all than higher and corrosion resistant magnesiumalloy, this magnesium alloy materials is under 20 ℃ of conditions, and thermal conductivity is greater than 132W. (m.K)
-1, at the erosion rate≤0.13g/cm of standard salt-fog test
2.24 hour, tensile strength greater than 320Mpa, ys greater than 300Mpa.Can be as the power supply in the aerospace, the heat-removal system structured material of electron device.
Another object of the present invention provides a kind of thermal conductivity and intensity all than the preparation method of higher and corrosion resistant magnesiumalloy.
For realizing above-mentioned purpose, the present invention takes following technical scheme:
A kind of heat-conducting and corrosion-resistant magnesium alloy, the component content of this magnesiumalloy is: the content of Mn is 0.5～3.5wt%, and the content of Zn is 0.05～1wt%, and the content of Ca is 0.05～1wt%, and all the other are Mg.
In heat-conducting and corrosion-resistant magnesium alloy of the present invention, the content of described Mn is preferably 1.0～2.0wt%.
In heat-conducting and corrosion-resistant magnesium alloy of the present invention, the content of described Zn is preferably 0.3～0.6wt%.
In heat-conducting and corrosion-resistant magnesium alloy of the present invention, the content of described Ca is preferably 0.1～0.5wt%.
A kind of method for preparing heat-conducting and corrosion-resistant magnesium alloy of the present invention, this method comprises the steps:
(1), with the raw material of pure magnesium ingot, with the raw material of pure Zn ingot, with MnCl as the zinc element in the magnesiumalloy as the magnesium elements in the magnesiumalloy
2Perhaps contain MnCl
2Refining magnesium refining agent as the raw material of the manganese element in the magnesiumalloy, with pure Ca piece or Mg-Ca master alloy raw material, take by weighing corresponding raw material by the weight percent of the composition of above-mentioned magnesiumalloy as the calcium constituent in the magnesiumalloy;
Wherein, In with pure Ca piece or the raw material of Mg-Ca master alloy as the calcium constituent in the magnesiumalloy; The content of Ca in magnesiumalloy is under the situation of 0.05～0.5wt% (not containing 0.5wt%) (being that Ca content is less than 0.5wt%), and raw material adopts the Mg-Ca master alloy; The content of Ca in magnesiumalloy is that raw material adopts pure Ca piece under the situation of 0.5 (containing 0.5wt%)～1wt% (being that Ca content is more than or equal to 0.5wt%).
With MnCl
2Perhaps contain MnCl
2The raw material of refining magnesium refining agent as the manganese element in the magnesiumalloy in, the content of the Mn in magnesiumalloy is under 0.5～1wt% situation of (containing 1wt%), raw material adopts and to contain MnCl
2Refining magnesium refining agent; The content of Mn in magnesiumalloy is under the situation of 1 (not containing 1wt%)～3.5wt%, and raw material adopts MnCl
2
Wherein, MnCl
2The content of middle Mn is 44wt%; Contain MnCl
2Refining magnesium refining agent in MnCl
2Content be 5wt%～95wt%, all the other 95wt%～5wt% are refining magnesium refining agents, wherein refine the 30wt%～65wt%MgCl that consists of of magnesium refining agent
2+ 30wt%～60wt%KCl+5wt%～15wt%CaF; So MnCl
2Perhaps contain MnCl
2Add-on and the alloy of refining magnesium refining agent in the cubage formula of Mn be:
Formula I (MnCl
2Add-on)=(content of Mn in this magnesiumalloy) * (this magnesiumalloy total amount) ÷ 44wt%;
Formula II (contains MnCl
2The add-on of refining magnesium refining agent)={ (content of Mn in this magnesiumalloy) * (this magnesiumalloy total amount) } ÷ { 44wt% * (MnCl in the refining magnesium refining agent
2Content).
(2), with whole pure magnesium ingots with as far as possible closely mode pile up in the fusion crucible in smelting furnace; Fusing fully under the protection of shielding gas; The magnesium melt temperature is controlled at 680～780 ℃; The scum silica frost of molten surface is cleaned out, evenly sprinkled No. 2 flux or refine the magnesium insulating covering agent, prevent the magnesium burning to molten surface;
(3), according to the content of Mn in the alloy, utilize formula I (to use MnCl
2) or formula II (use contains MnCl
2Refining magnesium refining agent) calculate the MnCl that need to add
2Perhaps contain MnCl
2The amount of refining magnesium refining agent, with load weighted MnCl
2Perhaps contain MnCl
2Refining magnesium refining agent join in the magnesium melt in batches, stir while add, make MnCl
2Perhaps contain MnCl
2Refining magnesium refining agent and magnesium replacement(metathesis)reaction fully takes place; Just, work as MnCl
2Perhaps contain MnCl
2Refining magnesium refining agent join magnesium melt after, following replacement(metathesis)reaction: Mg+MnCl will take place
2=MgCl
2+ Mn, the simple substance Mn that is displaced has just become the alloying element in the magnesium melt, and 1 kilogram of simple substance Mn of every generation will approximately consume 0.44 kilogram of Mg; Reaction product MgCl
2To and separate with the refining magnesium refining agent reaction formation reaction slag that adds in the operation of the refinery practice that carries out subsequently with magnesium melt; Until MnCl
2Perhaps contain MnCl
2Refining magnesium refining agent all join in the magnesium melt and reaction thoroughly after; The scum silica frost of molten surface is cleaned out; Afterwards, cast spectrum sample carries out on-the-spot sample analysis; Composition and content according to sample determine whether reinforced the adjustment, reach the composition and the content of magnesiumalloy of the present invention until the magnesiumalloy liquation; Evenly sprinkle No. 2 flux or refine the magnesium insulating covering agent to molten surface, prevent the magnesium burning;
(4), preheating oven is warmed up to 160～380 ℃; Under with the raw material condition of Mg-Ca master alloy as the calcium constituent in the magnesiumalloy; Pure Zn ingot and Mg-Ca master alloy are preheating to 100～380 ℃ in preheating oven; Respectively the pure Zn ingot after the preheating and Mg-Ca master alloy are submerged in the magnesium melt then, be convenient to the dissolving and the diffusion of pure Zn ingot and Mg-Ca master alloy; Under with the raw material condition of pure Ca piece as the calcium constituent in the magnesiumalloy; Because pure Ca piece is to be that the unit encapsulation is in the container of protection of inert gas with 1 kilogram; Need not preheating; Only need pure Zn ingot is preheating to 100～380 ℃ in preheating oven, respectively with the pure Zn ingot after the preheating with there is not the pure Ca piece of preheating to submerge in the magnesium melt, be convenient to the dissolving and the diffusion of pure Zn ingot and pure Ca piece then.
(5), the magnesium melt temperature is controlled at 670～780 ℃, treat pure Zn ingot, and dissolve fully and be evenly distributed in the magnesium melt as the pure Ca piece of the raw material of the calcium constituent in the magnesiumalloy or Mg-Ca master alloy; After 685～750 ℃ of insulations 15～60 minutes, cast spectrum sample carries out on-the-spot sample analysis with magnesium melt, according to the composition of sample and content decision reinforced adjustment the whether, reaches the composition and the content of magnesiumalloy of the present invention until the magnesiumalloy liquation;
(6), qualified magnesiumalloy liquation is poured in permanent mold casting mould or the sand mold casting mould of abundant preheating is frozen into foundry goods; Perhaps the magnesiumalloy liquation is poured in extrusion casting machine or the pressure die-casting machine in batches extrusion casting or be cast into foundry goods according to casting weight; Perhaps adopt low-pressure casting process that the magnesiumalloy liquation is cast as foundry goods;
The method for preparing heat conductive magnesium alloy of the present invention includes fusion process and last handling process; Wherein, last handling process can be divided into two kinds: a kind of is that the foundry goods after the cast is carried out aftertreatment, another kind is that the billet after the cast is carried out aftertreatment, therefore; Because of different last handling processes; The method for preparing heat conductive magnesium alloy of the present invention also is divided into two kinds, and the method for aforesaid preparation heat conductive magnesium alloy of the present invention is wherein a kind of, is the method for first kind of heat conductive magnesium alloy of the present invention.Second kind of method for preparing heat conductive magnesium alloy of the present invention is:
A kind of method for preparing heat conductive magnesium alloy of the present invention, wherein, step (1)-(5) of the fusion process and the method for first kind of heat conductive magnesium alloy of the present invention are identical, the Therefore, omited, its step (6)-(8) are:
(6), qualified magnesiumalloy liquation is poured in permanent mold casting mould or the sand mold casting mould of abundant preheating is frozen into the billet that supplies follow-up deformation processing to use; Perhaps the magnesiumalloy liquation is transported in the mold; Carry out continuous or semicontinuous casting, be prepared into the billet that supplies follow-up deformation processing to use;
(7), the billet with the above-mentioned steps preparation carries out homogenising heat treatment; Its homogenising heat treatment process is that billet is heated to 350～400 ℃, is incubated 3～30 hours; Concrete temperature retention time confirms that based on the size of billet volume the big more temperature retention time of billet volume is long more; Directly adopt rolling, extruding, drawing or Forging Technology deformation processing to become sheet material, tubing, section bar, bar, wire rod or various forging then; Promptly adopt extruding or drawing process that the billet deformation processing is become bar or wire rod; Or billet is processed into sheet material with rolling deformation; Or adopt crimp that billet is processed into tubing or section bar, or adopt forging press that billet is forged into forging;
(8), adopt drawing machine that sheet material, tubing, section bar, bar or the wire rod of above-mentioned steps preparation carried out the room temperature preliminary draft to handle, to ys and unit elongation requirement, the deflection of preliminary draft is 0.5～10% according to application background; The ys that requires is high more, unit elongation is low more, and the deflection of preliminary draft is big more, and vice versa.
In the method for preparation heat conductive magnesium alloy of the present invention, in described step (2), during pure magnesium ingot melts under the protection of shielding gas; Be evenly to sprinkle SULPHUR POWDER in crucible bottom and pure magnesium ingot surface; The amount of SULPHUR POWDER can all change into sulfurous gas with the oxygen in the crucible after with oxidizing fire and be as the criterion, and is with crucible cover that crucible is airtight, heat temperature raising; Make the fusing fully under the remaining protection of nitrogen gas of sulfurous gas and burning back of whole pure magnesium ingots, open crucible cover again.Wherein the consumption of SULPHUR POWDER can roughly be estimated as follows: the oxidizing fire reaction of sulphur is S+O
2=SO
2, the nucleidic mass of S and O
2Molecular weight all be 32, promptly material equates with the oxygen level in the external space in the consumption of SULPHUR POWDER and the crucible; Oxygen accounts for 1/5 greatly in air, and density of air is approximately 1 grams per liter; For example the space beyond the material is 200 liters in the crucible, and wherein oxygen is 40 liters, i.e. 40 grams, so the consumption of SULPHUR POWDER are 40 grams.In addition, the oxygen of small amount of residual or sulphur can be ignored the influence of magnesium alloy smelting.In actually operating,, calculate the space beyond the material in the crucible, and, calculate oxygen weight and SULPHUR POWDER weight according to the space beyond the material in the crucible according to the volume of crucible and the TV of pure magnesium ingot.
In the method for preparation heat conductive magnesium alloy of the present invention, in described step (2), No. 2 flux that spread to molten surface are 30～65wt%MgCl
2With 35～70wt%KCl; Refining magnesium insulating covering agent is 30～63wt%MgCl
2With 35～68wt%KCl and 1～5wt%S.
Advantage of the present invention is: magnesiumalloy of the present invention is under 20 ℃ of conditions, and thermal conductivity is greater than 132W. (m.K)
-1, at the erosion rate≤0.13g/cm of standard salt-fog test
2.24 hour, tensile strength greater than 320Mpa, maximum yield strength greater than 300Mpa.Can be as the power supply in the aerospace, the heat-removal system structured material of electron device.
Embodiment
Embodiment 1:1000 kilogram Mg-0.5Mn-1Zn-0.05Ca heat-conducting and corrosion-resistant magnesium alloy (promptly the component content of this magnesiumalloy is: 0.5wt%Mn, 1wt%Zn and 0.05wt%Ca, surplus is Mg) and the plate rolling preparation method.
1, gets the raw materials ready and with pure Zn ingot and the preheating of Mg-10%Ca master alloy (component content of Mg-10%Ca master alloy is: 10wt%Ca, surplus is Mg)
Pure magnesium ingot, the pure Zn ingot that at first needs, contain MnCl according to the component content calculating of this magnesiumalloy
2The amount of all raw materials such as refining magnesium refining agent, Mg-Ca master alloy, that is: 10 kilograms of pure Zn ingots, 5 kilograms of Mg-10%Ca master alloys, 57 kilograms contain 20%MnCl
2Refining magnesium refining agent.
Adopt preheating oven that 10 kilograms of pure Zn ingots, 5 kilograms of Mg-10%Ca master alloys are preheating to 350～380 ℃.
2, pure magnesium ingot fusing
With whole 983 kilograms of pure magnesium ingots with as far as possible closely mode pile up in fusion crucible, evenly sprinkle some SULPHUR POWDERs in crucible bottom and pure magnesium ingot surface, the amount of SULPHUR POWDER can all change into sulfurous gas with the oxygen in the crucible after with oxidizing fire and be as the criterion.With crucible cover that crucible is airtight; Heat temperature raising makes the fusing fully under the remaining protection of nitrogen gas of sulfurous gas and burning back of whole pure magnesium ingots, and the magnesium melt temperature is controlled at 685～720 ℃; Open crucible cover; The scum silica frost of molten surface is cleaned out, evenly sprinkled No. 2 flux or refine the magnesium insulating covering agent, prevent the magnesium burning to molten surface;
3, add alloying element Mn
Alloying element Mn contains 20%MnCl through adding
2Refining magnesium refining agent, utilize MnCl
2With magnesium generation replacement(metathesis)reaction: Mg+MnCl
2=MgCl
2The simple substance Mn of+Mn, generation has just become the alloying element in the magnesium melt; Contain 20%MnCl with load weighted 57 kilograms
2Refining magnesium refining agent join in the magnesium melt in batches, stir while add, make to contain MnCl
2Refining magnesium refining agent and magnesium replacement(metathesis)reaction fully takes place, until 57 kilograms contain 20%MnCl
2Refining magnesium refining agent all join in the magnesium melt and reaction thoroughly after, the scum silica frost of molten surface is cleaned out, afterwards; Cast spectrum sample; Carry out on-the-spot sample analysis, according to whether reinforced adjustment of the composition of sample and content decision, Mn reaches 0.5wt% in the magnesiumalloy liquation; Evenly sprinkle No. 2 flux or refine the magnesium insulating covering agent to molten surface, prevent the magnesium burning;
4, add alloy element Zn, Ca
10 kilograms after the preheating pure Zn ingots, 5 kilograms of Mg-10%Ca master alloys are submerged respectively in the above-mentioned magnesium melt; The magnesium melt temperature is controlled at 680～700 ℃; After treating that pure Zn ingot, Mg-10%Ca master alloy dissolve fully; 685～715 ℃ of insulations 15～30 minutes, all alloying elements are evenly distributed in the magnesium melt again; Afterwards, cast spectrum sample carries out on-the-spot sample analysis, if composition and content are defective, the adjustment of can feeding in raw material is until qualified;
5, billet casting
With the melt transfer pump magnesiumalloy liquation is transported in the mold, carries out semicontinuous casting, be prepared into the billet of plate rolling processing usefulness.
6, homogenizing thermal treatment, plate rolling deformation processing and ageing treatment
The billet of above-mentioned steps preparation is carried out homogenizing thermal treatment, exactly billet is heated to 385～400 ℃, is incubated 26～30 hours, the billet rolling deformation after the back of coming out of the stove directly adopts plate mill with homogenizing thermal treatment is processed into sheet material.
7, the sheet material preliminary draft is handled
It is that 1～3% room temperature preliminary draft is handled that the sheet material that adopts drawing machine that above-mentioned steps is prepared carries out deflection.
Mg-0.5Mn-1Zn-0.05Ca magnesiumalloy of the present invention has following performance after handling through homogenizing thermal treatment, plate rolling distortion and 0.5～3% room temperature preliminary draft: under 20 ℃ of conditions, thermal conductivity is approximately 132W. (m.K)
-1, at the erosion rate≤0.13g/cm of standard salt-fog test
2.24 hour, tensile strength is that 325～335Mpa, ys are 300～310Mpa, can be as the power supply in the aerospace, the heat-removal system structured material of electron device.
Embodiment 2:1000 kilogram Mg-0.5Mn-0.8Zn-0.1Ca heat-conducting and corrosion-resistant magnesium alloy (promptly the component content of this magnesiumalloy is: 0.5wt%Mn, 0.8wt%Zn and 0.1wt%Ca, surplus is Mg) and the diecast parts preparation method.
1, gets the raw materials ready and with pure Zn ingot and the preheating of Mg-10%Ca master alloy (component content of Mg-10%Ca master alloy is: 10wt%Ca, surplus is Mg)
Pure magnesium ingot, the pure Zn ingot that at first needs, contain MnCl according to the component content calculating of this magnesiumalloy
2The amount of all raw materials such as refining magnesium refining agent, Mg-Ca master alloy, that is: 8 kilograms of pure Zn ingots, 10 kilograms of Mg-10%Ca master alloys, 57 kilograms contain 20%MnCl
2Refining magnesium refining agent.
Adopt preheating oven that 8 kilograms of pure Zn ingots, 10 kilograms of Mg-10%Ca master alloys are preheating to 350～380 ℃.
2, pure magnesium ingot fusing
With whole 980 kilograms of pure magnesium ingots with as far as possible closely mode pile up in fusion crucible, evenly sprinkle some SULPHUR POWDERs in crucible bottom and pure magnesium ingot surface, the amount of SULPHUR POWDER can all change into sulfurous gas with the oxygen in the crucible after with oxidizing fire and be as the criterion.With crucible cover that crucible is airtight; Heat temperature raising makes the fusing fully under the remaining protection of nitrogen gas of sulfurous gas and burning back of whole pure magnesium ingots, and the magnesium melt temperature is controlled at 685～720 ℃; Open crucible cover; The scum silica frost of molten surface is cleaned out, evenly sprinkled No. 2 flux or refine the magnesium insulating covering agent, prevent the magnesium burning to molten surface;
3, add alloying element Mn
Alloying element Mn contains 20%MnCl through adding
2Refining magnesium refining agent, utilize MnCl
2With magnesium generation replacement(metathesis)reaction: Mg+MnCl
2=MgCl
2The simple substance Mn of+Mn, generation has just become the alloying element in the magnesium melt; Contain 20%MnCl with load weighted 57 kilograms
2Refining magnesium refining agent join in the magnesium melt in batches, stir while add, make to contain MnCl
2Refining magnesium refining agent and magnesium replacement(metathesis)reaction fully takes place, until 57 kilograms contain 20%MnCl
2Refining magnesium refining agent all join in the magnesium melt and reaction thoroughly after, the scum silica frost of molten surface is cleaned out, afterwards; Cast spectrum sample; Carry out on-the-spot sample analysis, according to whether reinforced adjustment of the composition of sample and content decision, Mn reaches 0.5wt% in the magnesiumalloy liquation; Evenly sprinkle No. 2 flux or refine the magnesium insulating covering agent to molten surface, prevent the magnesium burning;
4, add alloy element Zn, Ca
8 kilograms after the preheating pure Zn ingots, 10 kilograms of Mg-10%Ca master alloys are submerged respectively in the above-mentioned magnesium melt; The magnesium melt temperature is controlled at 700～720 ℃; After treating that pure Zn ingot, Mg-10%Ca master alloy dissolve fully; 700～720 ℃ of insulations 15～30 minutes, all alloying elements are evenly distributed in the magnesium melt again; Afterwards, cast spectrum sample carries out on-the-spot sample analysis, if composition and content are defective, the adjustment of can feeding in raw material is until qualified;
5, casting forming
Above-mentioned magnesiumalloy melt temperature is controlled at 680～700 ℃, and is incubated; According to casting weight, with the melt quantitative shifting pump magnesiumalloy liquation is poured in the pressure chamber of cold-chamber die casting machine in batches, be cast into foundry goods.
Mg-0.5Mn-0.8Zn-0.1Ca heat-conducting and corrosion-resistant magnesium alloy of the present invention has following performance through behind the die cast: under 20 ℃ of conditions, thermal conductivity is approximately 133W. (m.K)
-1, at the erosion rate≤0.13g/cm of standard salt-fog test
2.24 hour, tensile strength is that 225～255Mpa, ys are 200～210Mpa, can be as the power supply in the aerospace, the heat-removal system structured material of electron device.
Embodiment 3:1000 kilogram Mg-3.5Mn-0.05Zn-1Ca heat-conducting and corrosion-resistant magnesium alloy (promptly the component content of this magnesiumalloy is: 3.5wt%Mn, 0.05wt%Zn and 1wt%Ca, surplus is Mg) and bar, tubing, section bar or wire rod extruding production.
1, gets the raw materials ready and with the preheating of pure Zn ingot
The pure magnesium ingot, pure Zn ingot, the MnCl that at first need according to the component content calculating of this magnesiumalloy
2, all raw materials such as pure Ca piece amount, that is: 0.5 kilogram of pure Zn ingot, 10 kilograms of pure Ca pieces, 80 kilograms of MnCl
2
Adopt preheating oven that 0.5 kilogram of pure Zn ingot is preheating to 350～380 ℃, pure Ca piece with 1 kilogram be the unit encapsulation in the container of protection of inert gas, need not preheating.
2, pure magnesium ingot fusing
With whole 970 kilograms of pure magnesium ingots with as far as possible closely mode pile up in fusion crucible, evenly sprinkle some SULPHUR POWDERs in crucible bottom and pure magnesium ingot surface, the amount of SULPHUR POWDER can all change into sulfurous gas with the oxygen in the crucible after with oxidizing fire and be as the criterion.With crucible cover that crucible is airtight; Heat temperature raising makes the fusing fully under the remaining protection of nitrogen gas of sulfurous gas and burning back of whole pure magnesium ingots, and the magnesium melt temperature is controlled at 685～720 ℃; Open crucible cover; The scum silica frost of molten surface is cleaned out, evenly sprinkled No. 2 flux or refine the magnesium insulating covering agent, prevent the magnesium burning to molten surface;
3, add alloying element Mn
Alloying element Mn is through adding MnCl
2, utilize MnCl
2With magnesium generation replacement(metathesis)reaction: Mg+MnCl
2=MgCl
2The simple substance Mn of+Mn, generation has just become the alloying element in the magnesium melt; With load weighted 80 kilograms of MnCl
2Join in the magnesium melt in batches, stir, make MnCl while add
2With magnesium replacement(metathesis)reaction takes place fully, until 80 kilograms of MnCl
2All join in the magnesium melt and reaction thoroughly after, the scum silica frost of molten surface is cleaned out, afterwards, cast spectrum sample carries out on-the-spot sample analysis, according to the composition of sample and content decision reinforced adjustment the whether, Mn reaches 3.5wt% in the magnesiumalloy liquation; Evenly sprinkle No. 2 flux or refine the magnesium insulating covering agent to molten surface, prevent the magnesium burning;
4, add alloy element Zn, Ca
0.5 kilogram after the preheating pure Zn ingot, 10 kilograms of pure Ca pieces are submerged respectively in the above-mentioned magnesium melt; The magnesium melt temperature is controlled at 760～780 ℃; After treating that pure Zn ingot, pure Ca piece dissolve fully, 730～750 ℃ of insulations 35～60 minutes, all alloying elements are evenly distributed in the magnesium melt again; Afterwards, cast spectrum sample carries out on-the-spot sample analysis, if composition and content are defective, the adjustment of can feeding in raw material is until qualified;
5, billet casting
With the melt transfer pump magnesiumalloy liquation is poured into and is frozen into the billet that supplies follow-up crimp processing usefulness in the permanent mold casting mould of abundant preheating.
6, the homogenizing thermal treatment of billet, the crimp processing of bar, tubing, section bar or wire rod
The billet of above-mentioned steps preparation is carried out homogenizing thermal treatment; Exactly billet is heated to 350～360 ℃, is incubated 3～5 hours, bar, tubing, section bar or wire rod are processed in the billet crimp after the back of coming out of the stove directly adopts extrusion machine with homogenizing thermal treatment.
7, bar, tubing, section bar or wire rod preliminary draft are handled
It is that 6～10% room temperature preliminary drafts are handled that bar, tubing, section bar or the wire rod that adopts drawing machine that above-mentioned steps is prepared carries out deflection.
Mg-3.5Mn-0.05Zn-1Ca heat-conducting and corrosion-resistant magnesium alloy of the present invention is through homogenizing thermal treatment, and bar, tubing, section bar or wire rod crimp processing and preliminary draft have following performance after handling: under 20 ℃ of conditions, thermal conductivity is approximately 137W. (m.K)
-1, at the erosion rate≤0.13g/cm of standard salt-fog test
2.24 hour, tensile strength is that 330～350Mpa, ys are 315～325Mpa, can be as the power supply in the aerospace, the heat-removal system structured material of electron device.
Embodiment 4:1000 kilogram Mg-2Mn-0.3Zn-0.5Ca heat-conducting and corrosion-resistant magnesium alloy (promptly the component content of this magnesiumalloy is: 2wt%Mn, 0.3wt%Zn and 0.5wt%Ca, surplus is Mg) and part forging preparation method.
1, gets the raw materials ready and the preheating of pure Zn ingot
The pure magnesium ingot, pure Zn ingot, the MnCl that at first need according to the component content calculating of this magnesiumalloy
2, all raw materials such as pure Ca piece amount, that is: 3 kilograms of pure Zn ingots, 5 kilograms of pure Ca pieces, 45 kilograms of MnCl
2
Adopt preheating oven that 3 kilograms of pure Zn ingots are preheating to 350～380 ℃, pure Ca piece with 1 kilogram be the unit encapsulation in the container of protection of inert gas, need not preheating.
2, pure magnesium ingot fusing
With whole 981 kilograms of pure magnesium ingots with as far as possible closely mode pile up in fusion crucible, evenly sprinkle some SULPHUR POWDERs in crucible bottom and pure magnesium ingot surface, the amount of SULPHUR POWDER can all change into sulfurous gas with the oxygen in the crucible after with oxidizing fire and be as the criterion.With crucible cover that crucible is airtight; Heat temperature raising makes the fusing fully under the remaining protection of nitrogen gas of sulfurous gas and burning back of whole pure magnesium ingots, and the magnesium melt temperature is controlled at 685～720 ℃; Open crucible cover; The scum silica frost of molten surface is cleaned out, evenly sprinkled No. 2 flux or refine the magnesium insulating covering agent, prevent the magnesium burning to molten surface;
3, add alloying element Mn
Alloying element Mn is through adding MnCl
2, utilize MnCl
2With magnesium generation replacement(metathesis)reaction: Mg+MnCl
2=MgCl
2The simple substance Mn of+Mn, generation has just become the alloying element in the magnesium melt; With load weighted 45 kilograms of MnCl
2Join in the magnesium melt in batches, stir, make MnCl while add
2With magnesium replacement(metathesis)reaction takes place fully, until 45 kilograms of MnCl
2All join in the magnesium melt and reaction thoroughly after, the scum silica frost of molten surface is cleaned out, afterwards, cast spectrum sample carries out on-the-spot sample analysis, according to the composition of sample and content decision reinforced adjustment the whether, Mn reaches 2wt% in the magnesiumalloy liquation; Evenly sprinkle No. 2 flux or refine the magnesium insulating covering agent to molten surface, prevent the magnesium burning;
4, add alloy element Zn, Ca
3 kilograms after the preheating pure Zn ingots, 5 kilograms of pure Ca pieces are submerged respectively in the above-mentioned magnesium melt; The magnesium melt temperature is controlled at 700～720 ℃; After treating that pure Zn ingot, pure Ca piece dissolve fully, 700～720 ℃ of insulations 35～60 minutes, all alloying elements are evenly distributed in the magnesium melt again; Afterwards, cast spectrum sample carries out on-the-spot sample analysis, if composition and content are defective, the adjustment of can feeding in raw material is until qualified;
5, billet casting
The magnesiumalloy liquation is poured into the billet that is frozen into the follow-up forging deformation processing of confession usefulness in the sand mold casting mould with the melt transfer pump.
6, homogenizing thermal treatment, the processing of part forging deformation and ageing treatment
The billet of above-mentioned steps preparation is carried out homogenizing thermal treatment, exactly billet is heated to 365～375 ℃, is incubated 15～17 hours, the billet forging deformation after the back of coming out of the stove directly adopts forging press with homogenizing thermal treatment is processed into part.
Mg-2Mn-0.3Zn-0.5Ca heat-conducting and corrosion-resistant magnesium alloy of the present invention has following performance through homogenizing thermal treatment, part forging deformation after processing: under 20 ℃ of conditions, thermal conductivity is approximately 136W. (m.K)
-1, at the erosion rate≤0.13g/cm of standard salt-fog test
2.24 hour, tensile strength is that 315～325Mpa, ys are 285～295Mpa, can be as the power supply in the aerospace, the heat-removal system structured material of electron device
Embodiment 5:1000 kilogram Mg-1Mn-0.6Zn-0.2Ca heat-conducting and corrosion-resistant magnesium alloy (promptly the component content of this magnesiumalloy is: 1wt%Mn, 0.6wt%Zn and 0.2wt%Ca, surplus is Mg) and tubing, bar or wire rod extruding and drawing preparation method.
1, gets the raw materials ready and with pure Zn ingot and the preheating of Mg-10%Ca master alloy (component content of Mg-10%Ca master alloy is: 10wt%Ca, surplus is Mg)
Pure magnesium ingot, the pure Zn ingot that at first needs, contain MnCl according to the component content calculating of this magnesiumalloy
2The amount of all raw materials such as refining magnesium refining agent, Mg-Ca master alloy, that is: 6 kilograms of pure Zn ingots, 20 kilograms of Mg-10%Ca master alloys, 28 kilograms contain 80%MnCl
2Refining magnesium refining agent.
Adopt preheating oven that 6 kilograms of pure Zn ingots, 20 kilograms of Mg-10%Ca master alloys are preheating to 355～380 ℃.
2, pure magnesium ingot fusing
With whole 970 kilograms of pure magnesium ingots with as far as possible closely mode pile up in fusion crucible, evenly sprinkle some SULPHUR POWDERs in crucible bottom and pure magnesium ingot surface, the amount of SULPHUR POWDER can all change into sulfurous gas with the oxygen in the crucible after with oxidizing fire and be as the criterion.With crucible cover that crucible is airtight; Heat temperature raising makes the fusing fully under the remaining protection of nitrogen gas of sulfurous gas and burning back of whole pure magnesium ingots, and the magnesium melt temperature is controlled at 685～720 ℃; Open crucible cover; The scum silica frost of molten surface is cleaned out, evenly sprinkled No. 2 flux or refine the magnesium insulating covering agent, prevent the magnesium burning to molten surface;
3, add alloying element Mn
Alloying element Mn contains 80%MnCl through adding
2Refining magnesium refining agent, utilize MnCl
2With magnesium generation replacement(metathesis)reaction: Mg+MnCl
2=MgCl
2The simple substance Mn of+Mn, generation has just become the alloying element in the magnesium melt; Contain 80%MnCl with load weighted 28 kilograms
2Refining magnesium refining agent join in the magnesium melt in batches, stir while add, make to contain MnCl
2Refining magnesium refining agent and magnesium replacement(metathesis)reaction fully takes place, until 28 kilograms contain 80%MnCl
2Refining magnesium refining agent all join in the magnesium melt and reaction thoroughly after, the scum silica frost of molten surface is cleaned out, afterwards; Cast spectrum sample; Carry out on-the-spot sample analysis, according to whether reinforced adjustment of the composition of sample and content decision, Mn reaches 1wt% in the magnesiumalloy liquation; Evenly sprinkle No. 2 flux or refine the magnesium insulating covering agent to molten surface, prevent the magnesium burning;
4, add alloy element Zn, Ca
6 kilograms after the preheating pure Zn ingots, 20 kilograms of Mg-10%Ca master alloys are submerged respectively in the above-mentioned magnesium melt; The magnesium melt temperature is controlled at 690～720 ℃; After treating that pure Zn ingot, Mg-10%Ca master alloy dissolve fully; 700～720 ℃ of insulations 15～30 minutes, all alloying elements are evenly distributed in the magnesium melt again; Afterwards, cast spectrum sample carries out on-the-spot sample analysis, if composition and content are defective, the adjustment of can feeding in raw material is until qualified;
5, billet casting
With the melt transfer pump magnesiumalloy liquation is poured into and is frozen into the billet that supplies follow-up crimp processing usefulness in the permanent mold casting mould of abundant preheating.
6, homogenizing thermal treatment, tubing, bar or wire rod extruding and drawing deformation processing
The billet of above-mentioned steps preparation is carried out homogenizing thermal treatment; Exactly billet is heated to 375～385 ℃, is incubated 18～21 hours; Tubing, bar or wire rod are processed in the billet crimp of back after directly adopting extrusion machine with homogenizing thermal treatment of coming out of the stove, and then adopt cold drawing bench that this tubing, bar or wire rod are carried out drawing deformation to be processed into the littler tubing of diameter, bar or wire rod.
7, tubing, bar or wire rod preliminary draft are handled
It is that 0.5～2% room temperature preliminary draft is handled that bar, tubing, section bar or the wire rod that adopts drawing machine that above-mentioned steps is prepared carries out deflection.
Mg-1Mn-0.6Zn-0.2Ca heat-conducting and corrosion-resistant magnesium alloy of the present invention is through homogenizing thermal treatment; Have following performance after tubing, bar or wire rod crimp processing and drawing deformation processing and preliminary draft are handled: under 20 ℃ of conditions, thermal conductivity is approximately 134W. (m.K)
-1, at the erosion rate≤0.13g/cm of standard salt-fog test
2.24 hour, tensile strength is that 335～355Mpa, ys are 325～335Mpa, can be as the power supply in the aerospace, the heat-removal system structured material of electron device.
Embodiment 6:1000 kilogram Mg-0.7Mn-0.6Zn-0.3Ca heat-conducting and corrosion-resistant magnesium alloy (promptly the component content of this magnesiumalloy is: 0.7wt%Mn, 0.6wt%Zn and 0.3wt%Ca, surplus is Mg) and extrusion casting part preparation method.
1, gets the raw materials ready and with pure Zn ingot and the preheating of Mg-10%Ca master alloy (component content of Mg-10%Ca master alloy is: 10wt%Ca, surplus is Mg)
Pure magnesium ingot, the pure Zn ingot that at first needs, contain MnCl according to the component content calculating of this magnesiumalloy
2The amount of all raw materials such as refining magnesium refining agent, Mg-Ca master alloy, that is: 6 kilograms of pure Zn ingots, 30 kilograms of Mg-10%Ca master alloys, 40 kilograms contain 40%MnCl
2Refining magnesium refining agent.
Adopt preheating oven that 6 kilograms of pure Zn ingots, 30 kilograms of Mg-10%Ca master alloys are preheating to 365～380 ℃.
2, pure magnesium ingot fusing
With whole 960 kilograms of pure magnesium ingots with as far as possible closely mode pile up in fusion crucible, evenly sprinkle some SULPHUR POWDERs in crucible bottom and pure magnesium ingot surface, the amount of SULPHUR POWDER can all change into sulfurous gas with the oxygen in the crucible after with oxidizing fire and be as the criterion.With crucible cover that crucible is airtight; Heat temperature raising makes the fusing fully under the remaining protection of nitrogen gas of sulfurous gas and burning back of whole pure magnesium ingots, and the magnesium melt temperature is controlled at 685～720 ℃; Open crucible cover; The scum silica frost of molten surface is cleaned out, evenly sprinkled No. 2 flux or refine the magnesium insulating covering agent, prevent the magnesium burning to molten surface;
3, add alloying element Mn
Alloying element Mn contains 40%MnCl through adding
2Refining magnesium refining agent, utilize MnCl
2With magnesium generation replacement(metathesis)reaction: Mg+MnCl
2=MgCl
2The simple substance Mn of+Mn, generation has just become the alloying element in the magnesium melt; Contain 40%MnCl with load weighted 40 kilograms
2Refining magnesium refining agent join in the magnesium melt in batches, stir while add, make to contain MnCl
2Refining magnesium refining agent and magnesium replacement(metathesis)reaction fully takes place, until 40 kilograms contain 40%MnCl
2Refining magnesium refining agent all join in the magnesium melt and reaction thoroughly after, the scum silica frost of molten surface is cleaned out, afterwards; Cast spectrum sample; Carry out on-the-spot sample analysis, according to whether reinforced adjustment of the composition of sample and content decision, Mn reaches 0.7wt% in the magnesiumalloy liquation; Evenly sprinkle No. 2 flux or refine the magnesium insulating covering agent to molten surface, prevent the magnesium burning;
4, add alloy element Zn, Ca
6 kilograms after the preheating pure Zn ingots, 30 kilograms of Mg-10%Ca master alloys are submerged respectively in the above-mentioned magnesium melt; The magnesium melt temperature is controlled at 725～755 ℃; After treating that pure Zn ingot, Mg-10%Ca master alloy dissolve fully; 725～735 ℃ of insulations 35～50 minutes, all alloying elements are evenly distributed in the magnesium melt again; Afterwards, cast spectrum sample carries out on-the-spot sample analysis, if composition and content are defective, the adjustment of can feeding in raw material is until qualified;
5, extrusion casting is shaped
Above-mentioned magnesiumalloy melt temperature is controlled at 695～715 ℃, and is incubated; According to casting weight, with the melt quantitative shifting pump magnesiumalloy liquation is poured in the pressure chamber of extrusion casting machine in batches, extrusion casting becomes foundry goods.
Have following performance after the Mg-0.7Mn-0.6Zn-0.3Ca heat-conducting and corrosion-resistant magnesium alloy process extrusion casting moulding of the present invention: under 20 ℃ of conditions, thermal conductivity is approximately 134W. (m.K)
-1, at the erosion rate≤0.13g/cm of standard salt-fog test
2.24 hour, tensile strength is that 235～265Mpa, ys are 205～215Mpa, can be as the power supply in the aerospace, the heat-removal system structured material of electron device.
Embodiment 7:1000 kilogram Mg-0.8Mn-0.6Zn-0.4Ca heat-conducting and corrosion-resistant magnesium alloy (promptly the component content of this magnesiumalloy is: 0.8wt%Mn, 0.6wt%Zn and 0.4wt%Ca, surplus is Mg) and low-pressure casting part preparation method.
1, gets the raw materials ready and with pure Zn ingot and the preheating of Mg-10%Ca master alloy (component content of Mg-10%Ca master alloy is: 10wt%Ca, surplus is Mg)
Pure magnesium ingot, the pure Zn ingot that at first needs, contain MnCl according to the component content calculating of this magnesiumalloy
2The amount of all raw materials such as refining magnesium refining agent, Mg-Ca master alloy, that is: 6 kilograms of pure Zn ingots, 40 kilograms of Mg-10%Ca master alloys, 30 kilograms contain 60%MnCl
2Refining magnesium refining agent.
Adopt preheating oven that 6 kilograms of pure Zn ingots, 40 kilograms of Mg-10%Ca master alloys are preheating to 360～380 ℃.
2, pure magnesium ingot fusing
With whole 953 kilograms of pure magnesium ingots with as far as possible closely mode pile up in fusion crucible, evenly sprinkle some SULPHUR POWDERs in crucible bottom and pure magnesium ingot surface, the amount of SULPHUR POWDER can all change into sulfurous gas with the oxygen in the crucible after with oxidizing fire and be as the criterion.With crucible cover that crucible is airtight; Heat temperature raising makes the fusing fully under the remaining protection of nitrogen gas of sulfurous gas and burning back of whole pure magnesium ingots, and the magnesium melt temperature is controlled at 695～725 ℃; Open crucible cover; The scum silica frost of molten surface is cleaned out, evenly sprinkled No. 2 flux or refine the magnesium insulating covering agent, prevent the magnesium burning to molten surface;
3, add alloying element Mn
Alloying element Mn contains 60%MnCl through adding
2Refining magnesium refining agent, utilize MnCl
2With magnesium generation replacement(metathesis)reaction: Mg+MnCl
2=MgCl
2The simple substance Mn of+Mn, generation has just become the alloying element in the magnesium melt; Contain 60%MnCl with load weighted 30 kilograms
2Refining magnesium refining agent join in the magnesium melt in batches, stir while add, make to contain MnCl
2Refining magnesium refining agent and magnesium replacement(metathesis)reaction fully takes place, until 30 kilograms contain 60%MnCl
2Refining magnesium refining agent all join in the magnesium melt and reaction thoroughly after, the scum silica frost of molten surface is cleaned out, afterwards; Cast spectrum sample; Carry out on-the-spot sample analysis, according to whether reinforced adjustment of the composition of sample and content decision, Mn reaches 0.8wt% in the magnesiumalloy liquation; Evenly sprinkle No. 2 flux or refine the magnesium insulating covering agent to molten surface, prevent the magnesium burning;
4, add alloy element Zn, Ca
6 kilograms after the preheating pure Zn ingots, 40 kilograms of Mg-10%Ca master alloys are submerged respectively in the above-mentioned magnesium melt; The magnesium melt temperature is controlled at 735～760 ℃; After treating that pure Zn ingot, Mg-10%Ca master alloy dissolve fully; 735～750 ℃ of insulations 35～50 minutes, all alloying elements are evenly distributed in the magnesium melt again; Afterwards, cast spectrum sample carries out on-the-spot sample analysis, if composition and content are defective, the adjustment of can feeding in raw material is until qualified;
5, low-pressure casting is shaped
With the melt transfer pump magnesiumalloy liquation of above-mentioned steps melting is transferred in the crucible of air injection machine holding furnace, the magnesiumalloy melt temperature is controlled at 705～725 ℃, and is incubated, low-pressure casting becomes foundry goods.
Mg-0.8Mn-0.6Zn-0.4Ca heat-conducting and corrosion-resistant magnesium alloy of the present invention has following performance through behind the die cast: under 20 ℃ of conditions, thermal conductivity is approximately 133W. (m.K)
-1, at the erosion rate≤0.13g/cm of standard salt-fog test
2.24 hour, tensile strength is that 225～255Mpa, ys are 200～210Mpa, can be as the power supply in the aerospace, the heat-removal system structured material of electron device.
Claims (6)
1. heat-conducting and corrosion-resistant magnesium alloy, the component content of this magnesiumalloy is: the content of Mn is 0.5～3.5wt%, and the content of Zn is 0.3～1wt%, and the content of Ca is 0.2～0.5wt%, and all the other are Mg; The process of in Mg, adding alloying element Mn, Zn, Ca is following:
With the raw material of pure magnesium ingot, with the raw material of pure Zn ingot, with MnCl as the zinc element in the magnesiumalloy as the magnesium elements in the magnesiumalloy
2Perhaps contain MnCl
2Refining magnesium refining agent as the raw material of the manganese element in the magnesiumalloy, with pure Ca piece or Mg-Ca master alloy raw material, take by weighing corresponding raw material by the weight percent of the composition of above-mentioned magnesiumalloy as the calcium constituent in the magnesiumalloy;
Wherein, in pure Ca piece or the raw material of Mg-Ca master alloy as the calcium constituent in the magnesiumalloy, the content of the Ca in magnesiumalloy is 0.2～0.5wt%, and does not contain under the situation of 0.5wt%, and raw material adopts the Mg-Ca master alloy; The content of Ca in magnesiumalloy is under the situation of 0.5wt%, and raw material adopts pure Ca piece;
With MnCl
2Perhaps contain MnCl
2The raw material of refining magnesium refining agent as the manganese element in the magnesiumalloy in, the content of the Mn in magnesiumalloy is 0.5～1wt%, raw material adopts and to contain MnCl
2Refining magnesium refining agent; The content of Mn in magnesiumalloy is 1wt%～3.5wt% and does not contain under the situation of 1wt% that raw material adopts MnCl
2
According to the content of Mn in the alloy, calculate the MnCl that needs adding
2Perhaps contain MnCl
2The amount of refining magnesium refining agent, with load weighted MnCl
2Perhaps contain MnCl
2Refining magnesium refining agent join in the magnesium melt in batches, stir while add, make MnCl
2Perhaps contain MnCl
2Refining magnesium refining agent and magnesium replacement(metathesis)reaction fully takes place; Until MnCl
2Perhaps contain MnCl
2Refining magnesium refining agent all join in the magnesium melt and reaction thoroughly after; The scum silica frost of molten surface is cleaned out; Afterwards, cast spectrum sample carries out on-the-spot sample analysis; According to whether reinforced adjustment of the composition of sample and content decision, reach the Mn component content in the above-mentioned magnesiumalloy until the magnesiumalloy liquation;
Preheating oven is warmed up to 160～380 ℃; Under with the raw material condition of Mg-Ca master alloy as the calcium constituent in the magnesiumalloy; Pure Zn ingot and Mg-Ca master alloy are preheating to 100～380 ℃ in preheating oven; Respectively the pure Zn ingot after the preheating and Mg-Ca master alloy are submerged in the magnesium melt then, be convenient to the dissolving and the diffusion of pure Zn ingot and Mg-Ca master alloy; Under with the raw material condition of pure Ca piece as the calcium constituent in the magnesiumalloy; Because pure Ca piece is to be that the unit encapsulation is in the container of protection of inert gas with 1 kilogram; Need not preheating; Only need pure Zn ingot is preheating to 100～380 ℃ in preheating oven, respectively with the pure Zn ingot after the preheating with there is not the pure Ca piece of preheating to submerge in the magnesium melt, be convenient to the dissolving and the diffusion of pure Zn ingot and pure Ca piece then.
2. heat-conducting and corrosion-resistant magnesium alloy according to claim 1 is characterized in that: the content of described Mn is 1.0～2.0wt%.
3. heat-conducting and corrosion-resistant magnesium alloy according to claim 1 and 2 is characterized in that: the content of described Zn is 0.3～0.6wt%.
4. a method for preparing the described heat-conducting and corrosion-resistant magnesium alloy of claim 1 is characterized in that, this method comprises the steps:
(1), with the raw material of pure magnesium ingot, with the raw material of pure Zn ingot, with MnCl as the zinc element in the magnesiumalloy as the magnesium elements in the magnesiumalloy
2Perhaps contain MnCl
2Refining magnesium refining agent as the raw material of the manganese element in the magnesiumalloy, with pure Ca piece or Mg-Ca master alloy raw material, take by weighing corresponding raw material by the weight percent of the composition of the described magnesiumalloy of claim 1 as the calcium constituent in the magnesiumalloy;
Wherein, in pure Ca piece or the raw material of Mg-Ca master alloy as the calcium constituent in the magnesiumalloy, the content of the Ca in magnesiumalloy is 0.2～0.5wt%, and does not contain under the situation of 0.5wt%, and raw material adopts the Mg-Ca master alloy; The content of Ca in magnesiumalloy is under the situation of 0.5wt%, and raw material adopts pure Ca piece;
With MnCl
2Perhaps contain MnCl
2The raw material of refining magnesium refining agent as the manganese element in the magnesiumalloy in, the content of the Mn in magnesiumalloy is 0.5～1wt%, raw material adopts and to contain MnCl
2Refining magnesium refining agent; The content of Mn in magnesiumalloy is 1wt%～3.5wt% and does not contain under the situation of 1wt% that raw material adopts MnCl
2
(2), whole pure magnesium ingots are piled up in the fusion crucible in smelting furnace with mode closely; Fusing fully is controlled at 680～780 ℃ with the magnesium melt temperature under the protection of shielding gas, and the scum silica frost of molten surface is cleaned out; Evenly sprinkle refining magnesium insulating covering agent to molten surface, prevent the magnesium burning;
(3), with load weighted MnCl
2Perhaps contain MnCl
2Refining magnesium refining agent join in the magnesium melt in batches, stir while add, make MnCl
2Perhaps contain MnCl
2Refining magnesium refining agent and magnesium replacement(metathesis)reaction fully takes place; Until MnCl
2Perhaps contain MnCl
2Refining magnesium refining agent all join in the magnesium melt and reaction thoroughly after; The scum silica frost of molten surface is cleaned out; Afterwards, cast spectrum sample carries out on-the-spot sample analysis; According to whether reinforced adjustment of the composition of sample and content decision, until the magnesiumalloy liquation reach the described magnesiumalloy of claim 1 in Mn composition and content; Evenly sprinkle refining magnesium insulating covering agent to molten surface, prevent the magnesium burning;
(4), preheating oven is warmed up to 160～380 ℃; Under with the raw material condition of Mg-Ca master alloy as the calcium constituent in the magnesiumalloy; Pure Zn ingot and Mg-Ca master alloy are preheating to 100～380 ℃ in preheating oven, respectively the pure Zn ingot after the preheating and Mg-Ca master alloy are submerged in the magnesium melt then; Under with the raw material condition of pure Ca piece, only need pure Zn ingot is preheating to 100～380 ℃ in preheating oven, then respectively with the pure Zn ingot after the preheating with there is not the pure Ca piece of preheating to submerge in the magnesium melt as the calcium constituent in the magnesiumalloy;
(5), the magnesium melt temperature is controlled at 670～780 ℃, treat pure Zn ingot, and dissolve fully and be evenly distributed in the magnesium melt as the pure Ca piece of the raw material of the calcium constituent in the magnesiumalloy or Mg-Ca master alloy; After 685～750 ℃ of insulations 15～60 minutes, cast spectrum sample carries out on-the-spot sample analysis with magnesium melt, according to the composition of sample and content decision reinforced adjustment the whether, reaches the composition and the content of the described magnesiumalloy of claim 1 until the magnesiumalloy liquation;
(6), qualified magnesiumalloy liquation is poured in permanent mold casting mould or the sand mold casting mould of abundant preheating is frozen into foundry goods; Perhaps the magnesiumalloy liquation is poured in extrusion casting machine or the pressure die-casting machine in batches extrusion casting or be cast into foundry goods according to casting weight; Perhaps adopt low-pressure casting process that the magnesiumalloy liquation is cast as foundry goods.
5. a method for preparing the described heat-conducting and corrosion-resistant magnesium alloy of claim 1 is characterized in that, this method comprises the steps:
(1), with the raw material of pure magnesium ingot, with the raw material of pure Zn ingot, with MnCl as the zinc element in the magnesiumalloy as the magnesium elements in the magnesiumalloy
2Perhaps contain MnCl
2Refining magnesium refining agent as the raw material of the manganese element in the magnesiumalloy, with pure Ca piece or Mg-Ca master alloy raw material, take by weighing corresponding raw material by the weight percent of the composition of the described magnesiumalloy of claim 1 as the calcium constituent in the magnesiumalloy;
Wherein, in pure Ca piece or the raw material of Mg-Ca master alloy as the calcium constituent in the magnesiumalloy, the content of the Ca in magnesiumalloy is 0.2～0.5wt%, and does not contain under the situation of 0.5wt%, and raw material adopts the Mg-Ca master alloy; The content of Ca in magnesiumalloy is under the situation of 0.5wt%, and raw material adopts pure Ca piece;
With MnCl
2Perhaps contain MnCl
2The raw material of refining magnesium refining agent as the manganese element in the magnesiumalloy in, the content of the Mn in magnesiumalloy is 0.5～1wt%, raw material adopts and to contain MnCl
2Refining magnesium refining agent; The content of Mn in magnesiumalloy is that raw material adopts MnCl under 1wt%～3.5wt% and the situation that does not contain 1wt%
2
(2), whole pure magnesium ingots are piled up in the fusion crucible in smelting furnace with mode closely; Fusing fully is controlled at 680～780 ℃ with the magnesium melt temperature under the protection of shielding gas, and the scum silica frost of molten surface is cleaned out; Evenly sprinkle refining magnesium insulating covering agent to molten surface, prevent the magnesium burning;
(3), with load weighted MnCl
2Perhaps contain MnCl
2Refining magnesium refining agent join in the magnesium melt in batches, stir while add, make MnCl
2Perhaps contain MnCl
2Refining magnesium refining agent and magnesium replacement(metathesis)reaction fully takes place; Until MnCl
2Perhaps contain MnCl
2Refining magnesium refining agent all join in the magnesium melt and reaction thoroughly after; The scum silica frost of molten surface is cleaned out; Afterwards, cast spectrum sample carries out on-the-spot sample analysis; Composition and content according to sample determine whether reinforced the adjustment, reach Mn composition and content in the described magnesiumalloy of claim 1 until the magnesiumalloy liquation; Evenly sprinkle refining magnesium insulating covering agent to molten surface, prevent the magnesium burning;
(4), preheating oven is warmed up to 160～380 ℃; Under with the raw material condition of Mg-Ca master alloy as the calcium constituent in the magnesiumalloy; Pure Zn ingot and Mg-Ca master alloy are preheating to 100～380 ℃ in preheating oven, respectively the pure Zn ingot after the preheating and Mg-Ca master alloy are submerged in the magnesium melt then; Under with the raw material condition of pure Ca piece, only need pure Zn ingot and in preheating oven, be preheating to 100～380 ℃, then respectively with the pure Zn ingot after the preheating with there is not the pure Ca piece of preheating to submerge in the magnesium melt as the calcium constituent in the magnesiumalloy;
(5), the magnesium melt temperature is controlled at 670～780 ℃, treat pure Zn ingot, and dissolve fully and be evenly distributed in the magnesium melt as the pure Ca piece of the raw material of the calcium constituent in the magnesiumalloy or Mg-Ca master alloy; After 685～750 ℃ of insulations 15～60 minutes, cast spectrum sample carries out on-the-spot sample analysis with magnesium melt, according to the composition of sample and content decision reinforced adjustment the whether, reaches the composition and the content of the described magnesiumalloy of claim 1 until the magnesiumalloy liquation;
(6), qualified magnesiumalloy liquation is poured in permanent mold casting mould or the sand mold casting mould of preheating is frozen into the billet that supplies follow-up deformation processing to use; Perhaps the magnesiumalloy liquation is transported in the mold; Carry out continuous or semicontinuous casting, be prepared into the billet that supplies follow-up deformation processing to use;
(7), the billet of above-mentioned steps (6) preparation is carried out homogenizing thermal treatment, its homogenizing heat treatment process is that billet was heated to 350～400 ℃, insulation 3～30 hours; Directly adopt rolling, extruding, drawing or forging process deformation processing to become sheet material, tubing, section bar, bar, wire rod or various forging then; Promptly adopt extruding or drawing process that the billet deformation processing is become bar or wire rod; Or billet is processed into sheet material with rolling deformation; Or adopt crimp that billet is processed into tubing or section bar, or adopt forging press that billet is forged into forging;
(8), adopt drawing machine that sheet material, tubing, section bar, bar or the wire rod of above-mentioned steps (7) preparation carried out the room temperature preliminary draft to handle, the deflection of preliminary draft is 0.5～10%.
6. according to claim 4 or the 5 described methods that prepare heat-conducting and corrosion-resistant magnesium alloy; It is characterized in that: whole pure magnesium ingots are piled up in the fusion crucible in smelting furnace with mode closely in described step (2); The process of fusing is fully under the protection of shielding gas: piled up before fusion crucible at pure magnesium ingot, evenly sprinkle SULPHUR POWDER in the fusion crucible bottom earlier, pile up after fusion crucible at pure magnesium ingot; Evenly sprinkle SULPHUR POWDER on the surface at pure magnesium ingot again; The amount of SULPHUR POWDER can all change into sulfurous gas with the oxygen in the fusion crucible after with oxidizing fire and be as the criterion, and is with crucible cover that fusion crucible is airtight, heat temperature raising; Make the fusing fully under the remaining protection of nitrogen gas of sulfurous gas and burning back of whole pure magnesium ingots, open crucible cover again.
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| CN106148784B (en) * | 2015-04-20 | 2019-03-19 | 中国科学院金属研究所 | A kind of low cost room temperature high-ductility wrought magnesium alloy material and its preparation process |
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| CN106756365B (en) * | 2015-11-24 | 2019-02-15 | 中国科学院金属研究所 | A kind of low cost high-speed extrusion magnesium alloy materials and its preparation process |
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| CN108060317B (en) * | 2017-12-14 | 2019-09-17 | 宁夏太阳镁业有限公司 | A kind of magnesium metal and magnesium alloy refining method |
| WO2023080056A1 (en) * | 2021-11-05 | 2023-05-11 | 国立研究開発法人物質・材料研究機構 | Magnesium-based alloy extension material |
| CN114540653B (en) * | 2022-02-24 | 2022-11-25 | 惠州云海镁业有限公司 | High-corrosion-resistance magnesium alloy processing technology |
| CN114574743A (en) * | 2022-03-02 | 2022-06-03 | 东北大学 | Medium-strength high-plasticity Mg-Ce-Sm series plate and pre-stretching strengthening method thereof |
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| CN101113502A (en) * | 2007-09-06 | 2008-01-30 | 北京有色金属研究总院 | Heat conductive magnesium alloy and method for preparing same |
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| CN101113502A (en) * | 2007-09-06 | 2008-01-30 | 北京有色金属研究总院 | Heat conductive magnesium alloy and method for preparing same |
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