CN105525178A - High-thermal-conductivity die-castable Mg-Y-Zr series multielement magnesium alloy and preparation method thereof - Google Patents
High-thermal-conductivity die-castable Mg-Y-Zr series multielement magnesium alloy and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a high-thermal-conductivity die-casting corrosion-resistant magnesium alloy. The magnesium alloy comprises, by weight percentage, 1.5-4% of Y, 0.001-1% of Mn, 0.001-2% of Zn, 0.001-1% of Ca, 0.4-0.8% of Zr and the balance Mg. A preparation method of the magnesium alloy comprises the steps that a Mg-Y intermediate alloy (wherein Y represents one or any combination of La, Ce, Pr, Sm and Y), a Mg-Zr intermediate alloy and pure Mg ingots are adopted as raw materials; or based on the raw materials, one or any combination of two of a Mg-Mn intermediate alloy, a Mg-Ca intermediate alloy or pure Zn ingots are added; or based on the mixture, pure ingots containing Mn, Ca and Zn or an intermediate alloy containing Mn, Ca and Zn are/is added at the same time, so that the multielement magnesium alloy is obtained. After pure magnesium ingots are molten, two or more of the Mg-Zr intermediate alloy, the Mg-Mn intermediate alloy, the Mg-Ca intermediate alloy, the pure Zn ingots and the Mg-Y intermediate alloy are added appropriately according to the compounded alloy constituents, a refining agent special for the magnesium alloy is adopted for refining, and then the magnesium alloy is made into castings or ingots. After the magnesium alloy is subjected to aging treatment at the temperature of 25 DEG C, the thermal conductivity is greater than 100 W/(m.K), the corrosion rate in a 72-hour standard neutral salt spray test is less than 1 mg/cm<2>.D; the tensile strength of the die-casting ingots ranges from 140MPa to 190MPa; the yield strength is greater than 100MPa; and the elongation is greater than 4%. The magnesium alloy can be used as a structural material for a heat dissipation system of an electronic device and applied to places where corrosion resistance and high thermal conductivity are required.
Description
Technical field
The present invention relates to a kind of thermal conductivity high corrosion resistance good, and be applicable to magnesium alloy of high-pressure casting and preparation method thereof, belong to metal material field.
Background technology
The heat sink material that aerospace, automobile and 3C Product use not only requires to have good heat conductivility, and requires that density is low, intensity is high.Under room temperature, the thermal conductivity of (20 DEG C) pure magnesium is 156W/ (mK), and after magnesium carries out alloying, its intensity increases substantially, and thermal conductivity is different with the alloying element added, and it is also slightly different, totally on a declining curve that it reduces degree.Commercial magnesium alloy Mg-Al system AZ91, AM60B, AZ80 over-all properties is well found broad application, but its room temperature (20 DEG C) thermal conductivity is less than 61W. (m.K)
-1; WE cording has excellent mechanical property, can carry out Die Casting, but its 20 DEG C of room temperature thermal conductivities of WE43, WE91, EW75 are all less than 51W. (m.K)
-1; Common Mg-Zn system, the room temperature thermal conductivity (20 DEG C) as ZK60, ZE41A, ZC63A is all greater than 100W. (m.K)
-1, show that the thermal conductivity impact of the Zn element in Mg-Zn system on pure Mg is more slow.But Mg-Zn system freezing range is large, coarse grains, and easy to crack in the course of processing, the Mg-Zn alloy for die casting does not almost have.
Containing the magnesium alloy ZE41 of zinc, rare earth, its tensile strength be 205MPa, 20 DEG C time thermal conductivity be 123.1W (m.K)
-1; In CN101709418A (a kind of heat conductive magnesium alloy and preparation method thereof) containing zinc, silicon magnesium alloy, its tensile strength be 265-380MPa, 20 DEG C time thermal conductivity be greater than 100W. (m.K)
-1; Add Y in CN101709418, its thermal conductivity is not adversely effected, and y alloy is because its outstanding cleaning molten effect and good die cast, makes Mg-Y-Zn alloy become the preferred object of high heat conduction diecast magnesium alloy research.
But Mg-Y die casting Mg alloy is compared with conventional commercial Mg alloy AZ91, and a very large problem is its poor corrosion resistance.Wherein impurity element Ni Co Fe Cu be its important influence factor.Consider to add appropriate Mn Ca element impurity element can be replaced, increase the purity of melt, thus improve the erosion resistance of Mg-Y alloy.Ca can also play the effect of refined crystalline strengthening, improves mechanical property, and it is more slow to reduce degree to Mg alloy thermal conductivity; Zn and Mg has identical hcp structure, has very strong Precipitation effect, and a small amount of Zn obviously can strengthen the tensile strength of Mg-Y; Mn can also play the effect of grain refining, thus can to attempt in Mg-Y alloy corrosion-resistantly adding with the requirement of mechanical property Mn Ca one or more in Zn.Zr element is then proved to be can remarkable refinement Mg-Y system alloy, is the excellent alterant of Mg-Y alloy.Therefore be basis with Mg-Y-Zr, according to different performance requriements choose reasonable Zn Mn one or more in Ca, prepare the die casting Mg alloy of high heat-conducting and corrosion-resistant, become possibility.
Summary of the invention
The object of this invention is to provide a kind of thermal conductivity and the high and corrosion resistant magnesium alloy of specific tenacity, this magnesium alloy materials is under 20 DEG C of conditions, and thermal conductivity is greater than 100W/ (mK), is less than 1g/cm in the erosion rate of 72 hours standard salt fog test
2, ingot casting tensile strength is greater than 140 ~ 190MPa, and yield strength is greater than 100MPa, and unit elongation is greater than 4%, can be used as the cooling system structure material of electron device, also can be used for all to corrosive nature and the high occasion of heat conductivility requirement.
Another object of the present invention is to provide a kind of thermal conductivity and all higher and preparation method of corrosion resistant magnesium alloy of intensity.
For achieving the above object, the present invention takes following technical scheme:
A kind of high heat conduction die casting corrosion-resistant magnesium alloy, the component content of this magnesium alloy is: the content of Y is 1.5 ~ 4wt.%, the content of Mn is 0.001 ~ 1wt.%, the content of Zn is 0.001 ~ 2wt.%, the content of Ca is 0.001 ~ 1wt.%, the content of Zr is 0.4 ~ 0.8wt.%, and all the other are Mg and inevitable impurity element.
At high heat conduction die casting corrosion-resistant magnesium alloy of the present invention, the content of described Y is preferably 1.5 ~ 4wt.%.
At high heat conduction die casting corrosion-resistant magnesium alloy of the present invention, the content of described Mn is preferably 0.001 ~ 1wt.%.
At high heat conduction die casting corrosion-resistant magnesium alloy of the present invention, the content of described Zn is preferably 0.001 ~ 2wt.%.
At high heat conduction die casting corrosion-resistant magnesium alloy of the present invention, the content of described Ca is preferably 0.001 ~ 1wt.%.
In high heat conduction die casting corrosion-resistant magnesium alloy of the present invention, all the other content are Mg and other inevitable impurity element.
Prepare a method for high heat conduction die casting corrosion-resistant magnesium alloy of the present invention, the method comprises the steps:
(1) raw material using pure magnesium ingot as the magnesium elements in magnesium alloy, the raw material using Mg-Y master alloy as magnesium alloy rare earth elements, with Mg-Mn master alloy or pure Mn powder or MnCl
2as the raw material of manganese element in magnesium alloy, using Mg-Ca master alloy or pure Ca as the raw material of calcium constituent in magnesium alloy, using pure Zn ingot as the raw material of zinc element in magnesium alloy, after above-mentioned magnesium alloy composition considers scaling loss by desired properties choose reasonable with Mg-Y-Zr be base add Zn Ca one or more in Mn, take corresponding raw material according to weight percent;
(2) whole pure magnesium ingot is put in well formula electrical crucible, at shielding gas SF
6and N
2under melt completely, magnesium melt temperature is controlled between 700 ~ 780 DEG C;
(3) magnesium liquid temp rises to more than 700 DEG C, by load weighted Mg-Zr master alloy separately or add in magnesium melt be preheating to optimal temperature in preheating oven together with Mg-Mn master alloy after, be incubated straight master alloy all to melt, or add Mn powder or MnCl while Mg-Zr master alloy after adding preheating
2flux;
(4) by load weighted Mg-Y master alloy separately or in preheating oven, be preheating to optimal temperature together with Mg-Ca master alloy.Magnesium liquid temp rises to more than 710 DEG C, adds in magnesium melt respectively by pure Zn ingot, Mg-Ca master alloy or the Ca powder after preheating and Mg-Y master alloy, and insulation is until each alloy raw material all melts;
(5) magnesium liquid temp rises to more than 730 DEG C, starts to add the special refining agent of magnesium alloy and carries out refining, and in refining process, refining spoon immerses 2/3 place of liquid magnesium alloy, and the fierce aluminium alloy of stirring is from top to bottom till specular gloss appears in liquid level.In stirring, constantly on alloy liquid level, spread refining flux.Refining is complete, removes the solvent on liquid level and scum silica frost, then sprinkles one deck insulating covering agent gently.Temperature is down to and is mingled with abundant floating or sinking 730 DEG C of standing making, and skims;
(6) temperature is adjusted to suitable temp, is poured in fully preheated metal casting mould by magnesium alloy liquation and is frozen into foundry goods; Or magnesium alloy liquation is poured in pressure die-casting machine carries out high-pressure casting or low-pressure casting produces die casting; Or carry out extrusion production; Or be rolled, forge.
The method preparing high heat conduction die casting corrosion-resistant magnesium alloy of the present invention includes fusion process and press casting procedure.Wherein, high-pressure casting process: adopt pressure die-casting machine to carry out high-pressure casting to melted high heat conduction die casting corrosion-resistant magnesium alloy.Low pressure casting process: adopt air injection machine to carry out low-pressure casting to the liquation after melting.[19] prepare a method for high heat conduction die casting corrosion-resistant magnesium alloy of the present invention, wherein, fusion process is identical with step (1)-(5) of the method for high heat conduction die casting corrosion-resistant magnesium alloy of the present invention, therefore omits.High-pressure casting step is (7).
(7) high heat conduction die casting corrosion-resistant magnesium alloy temperature good for refining is adjusted to optimal temperature, by die heater, the temperature of die-cast metal mould is adjusted to more than 160 degree, adjustment low speed speed is to suitable, and high speed speed is 2 ~ 10m/s, and joint face casting pressure is 60 ~ 100MPa.High heat conduction die casting corrosion-resistant magnesium alloy liquid is poured into injection mouth, determines each to water fluence according to the volume size of mould product, then carry out injection, obtain high heat conduction die casting corrosion-resistant magnesium alloy die casting.
Advantage of the present invention is: this high heat conduction die casting Corrosion resistant magnesium alloy material is under 20 DEG C of conditions, and thermal conductivity is greater than 100W/ (mK), is less than 1g/cm in the erosion rate of 72 hours standard salt fog test
2, tensile strength is greater than 190MPa, and yield strength is greater than 100MPa, and unit elongation is greater than 4%, can be used as the cooling system structure material of electron device and require high occasion for corroding.
Another one advantage of the present invention is: this high heat conduction die casting corrosion-resistant magnesium alloy is simply shaping, can Die Casting thin-wall part.
Accompanying drawing explanation
Fig. 1 is Mg-1Nd-1Y-0.5Zr;
Fig. 2 is Mg-1Nd-1Y-0.5Zr room temperature thermal capacitance Cp;
Fig. 3 is Mg-1Nd-1Y-0.5Zr room temperature thermal diffusivity.
Embodiment
It is below the embodiment of invention.The example done in embodiment, only as example, object of protection involved in the present invention, is not limited to example, comprises all by the alloying constituent configured in claims and illustrated working method.
Embodiment 1:25 kilogram of Mg-1Nd-1Y-0.5Zr height heat conduction die casting corrosion-resistant magnesium alloy (namely the component content of this magnesium alloy is: 2wt.%Y, 0.5wt.%Zr, and surplus is Mg and other inevitable impurity elements) and diecast parts preparation method thereof.
1, get the raw materials ready: consider that suitable burn out rate is got the raw materials ready according to weight percent, preheating is carried out to Mg-30wt.%Zr master alloy, Mg-wt.90%Nd master alloy and Mg-25wt.%Y master alloy.The purity of master alloy is 99.9wt.%, and except Y element and inevitable impurity, other element is pure Mg.
2, pure magnesium ingot fusing
Put whole pure magnesium ingot into well formula electrical crucible in mode closely of trying one's best, sprinkle some SULPHUR POWDER in crucible bottom and pure magnesium ingot surface uniform.With crucible cover by crucible, pass into by body SF
6and N
2the shielding gas of composition, heat temperature raising, makes whole pure magnesium ingot melt completely under sulfurous gas and shielding gas, magnesium melt temperature is controlled at 700 ~ 780 DEG C;
3, alloying element Nd, Y is added
Alloying element Nd Y by adding Mg-25wt.%Y and Mg-90wt.%Nd master alloy to realize.Magnesium liquid temp rises to more than 700 DEG C, is joined in magnesium melt by preheated Mg-Y master alloy in batches, and insulation is until master alloy all melts;
4, alloy element Zr is added
Magnesium liquid temp rises to more than 710 DEG C, adds in above-mentioned magnesium melt respectively by the Mg-30%Zr master alloy after preheating, and insulation is until an alloy all melts;
5, magnesium alloy refining
Magnesium liquid temp rises to more than 730 DEG C, starts to add the special refining agent of magnesium alloy and carries out refining.In refining process, refining spoon immerses 2/3 place of liquid magnesium alloy, and the fierce aluminium alloy of stirring is from top to bottom till specular gloss appears in liquid level.In stirring, constantly on alloy liquid level, spread refining flux.Refining is complete, removes the solvent on liquid level and scum silica frost, then sprinkles one deck insulating covering agent gently.Cooling to optimal temperature leaves standstill until be mingled with and fully float or sink, after skim;
6, magnesium alloy high-pressure casting
High heat conduction die casting corrosion-resistant magnesium alloy temperature good for refining is adjusted to suitable teeming temperature; Abundant preheating die-cast metal mould; Adjustment pressure die-casting machine parameter is to optimum: if setting low speed speed is 0.1 ~ 0.6m/s, high speed speed is 1 ~ 8m/s, and casting pressure is 60 ~ 110MPa.Die-casting technological parameter should according to the practical situation of pressure die-casting machine, to advance adjustment, until obtain qualified die casting within the scope of above-mentioned die-casting technological parameter to die-casting technological parameter.
Volume size according to mould product determines each liquid inlet volume, high heat conduction die casting corrosion-resistant magnesium alloy liquid is poured into injection mouth and carries out injection, namely obtains high heat conduction die casting corrosion-resistant magnesium alloy die casting.
Mg-1Nd-1Y-0.5Zr height heat conduction die casting Corrosion resistant magnesium alloy material tensile strength of the present invention is 164.6MPa, yield strength is greater than 100MPa, unit elongation is 9.7%, its die casting appearance component and stress strain curve and metallographic are shown in Fig. 1, die casting complete appearance, without cracking, average grain size is 15-20um.
Room temperature (25 DEG C) thermal capacitance of Mg-1Nd-1Y-0.5Zr of the present invention and thermal diffusivity are shown in Fig. 2-3, survey its density be about 1.83g/cm with Archimedes method
3, recording its room temperature thermal conductivity is 111W.m
-1k
-1.Completely to use as dissipation from electronic devices structural part.
Embodiment 2-3: respectively prepared 25 kilograms of Mg-2Nd-1Y-0.5Zr and Mg-3Y-1Nd-0.5Zr in an identical manner.Record both yield strengths and be all greater than 120MPa, tensile strength is all greater than 170MPa, and unit elongation is all greater than 6%, and 25 DEG C of thermal conductivities are all greater than 100W.m
-1k
-1.72h standard Neutral salt-fog test records erosion rate and is less than 1mg/cm
2.D, wherein, Mg-2Nd-1Y-0.5Zr erosion rate, close to commercial AZ91, has excellent over-all properties.
(namely the component content of this magnesium alloy is embodiment 4:25 kilogram of Mg-2Nd-1Y-0.1Ca-0.5Zr height heat conduction die casting corrosion-resistant magnesium alloy: 2wt.%Nd, 1wt.%Y, 0.1wt.%Ca and 0.5wt.%Zr, surplus is inevitable impurity and Mg element) and diecast parts preparation method.
1, consider that suitable burn out rate is got the raw materials ready according to weight percent, preheating is carried out to Mg-30wt.%Zr master alloy, Mg-wt.90%Nd master alloy and Mg-25wt.%Y master alloy and Mg-30wt.% master alloy.The purity of master alloy is 99.9wt.%, and except Y element and inevitable impurity, other element is pure Mg.
2, pure magnesium ingot fusing
Put whole pure magnesium ingot into well formula electrical crucible in mode closely of trying one's best, sprinkle some SULPHUR POWDER in crucible bottom and pure magnesium ingot surface uniform.With crucible cover by crucible, pass into by body SF
6and N
2the shielding gas of composition, heat temperature raising, makes whole pure magnesium ingot melt completely under sulfurous gas and shielding gas, magnesium melt temperature is controlled at 700 ~ 780 DEG C;
3, alloying element Nd, Y is added
Alloying element Nd Y Ca by adding Mg-25wt.%Y, Mg-90wt.%Nd and Mg-30wt.%Ca master alloy to realize.Magnesium liquid temp rises to more than 700 DEG C, joins in magnesium melt by preheated Mg-Y master alloy and Mg-Ca master alloy, and insulation is until master alloy all melts;
4, alloy element Zr is added
Magnesium liquid temp rises to more than 710 DEG C, adds in above-mentioned magnesium melt respectively by the Mg-30%Zr master alloy after preheating, and insulation is until an alloy all melts;
5, magnesium alloy refining
Magnesium liquid temp rises to more than 730 DEG C, starts to add the special refining agent of magnesium alloy and carries out refining, and in refining process, refining spoon immerses 2/3 place of liquid magnesium alloy, and the fierce aluminium alloy of stirring is from top to bottom till specular gloss appears in liquid level.In stirring, constantly on alloy liquid level, spread refining flux.Refining is complete, removes the solvent on liquid level and scum silica frost, then sprinkles one deck insulating covering agent gently.Temperature is down to and is mingled with abundant floating or sinking standing the making of optimal temperature, skims;
6, magnesium alloy high-pressure casting
High heat conduction die casting corrosion-resistant magnesium alloy temperature good for refining is adjusted to suitable teeming temperature; Abundant preheating die-cast metal mould; Adjustment pressure die-casting machine parameter is to optimum: if setting low speed speed is 0.1 ~ 0.6m/s, high speed speed is 1 ~ 8m/s, and casting pressure is 60 ~ 110MPa.Die-casting technological parameter should according to the practical situation of pressure die-casting machine, to advance adjustment, until obtain qualified die casting within the scope of above-mentioned die-casting technological parameter to die-casting technological parameter.
Volume size according to mould product determines each liquid inlet volume, high heat conduction die casting corrosion-resistant magnesium alloy liquid is poured into injection mouth and carries out injection, namely obtains high heat conduction die casting corrosion-resistant magnesium alloy die casting.
Mg-2Nd-1Y-0.1Ca-0.5Zr height heat conduction die casting Corrosion resistant magnesium alloy material die cast of the present invention is good, and accessory appearance is complete without cracking.Under 25 DEG C of conditions, thermal conductivity is 104.3W/ (mK), is less than 1g/cm in the erosion rate of 72 hours standard salt fog test
2, tensile strength is greater than 150MPa, and yield strength is greater than 130MPa, and unit elongation is greater than 4%, can be used as the cooling system structure material of electron device.
(namely the component content of this magnesium alloy is embodiment 5:25 kilogram of Mg-2Nd-1Y-0.5Mn-0.5Zr height heat conduction die casting corrosion-resistant magnesium alloy: 2wt.%Nd, 1wt.%Y, 0.5wt.%Mn and 0.5wt.%Zr, surplus is inevitable impurity and Mg element) and diecast parts preparation method.
The implementation case is except Addition ofelements Mn is different and except case study on implementation 1-3, other implementation step is identical, therefore omits.Compared with enforcement case row 4, the Ca of 0.1wt.% is changed to 0.5wt.%, other implementation step is identical.
Part yield strength measured by the implementation case is about 120MPa, and tensile strength is 150MPa, and unit elongation is between 4-5%.25 DEG C of room temperature thermal conductivities are about 100W.m
-1k
-1.72h standard salt fog test records erosion rate and is less than 1mg/cm
2.D.Over-all properties is good.
Claims (1)
1. a high heat conduction die casting corrosion-resistant magnesium alloy, the component content of this magnesium alloy is: the content of Y is 1.5 4wt.%; The content of the content of Mn to be the content of 0.001 1wt.%, Zn be 0.001 2wt.%, Ca is the content of 0.001 1wt.%, Zr is 0.4 0.8wt.%, and all the other are Mg;
High heat conduction die casting corrosion-resistant magnesium alloy according to claim 1, is characterized in that: the content of described Y is 1.5 4wt.%;
High heat conduction die casting corrosion-resistant magnesium alloy according to claim 1, is characterized in that: the content of described Mn is 0.001 1wt.%;
High heat conduction die casting corrosion-resistant magnesium alloy according to claim 1, is characterized in that: the content of described Zn is 0.001 2wt.%;
High heat conduction die casting corrosion-resistant magnesium alloy according to claim 1, is characterized in that: the content of described Ca is 0.001 1wt.%;
Prepare a method for high heat conduction die casting corrosion-resistant magnesium alloy according to claim 1, it is characterized in that the method comprises the steps:
(1) raw material using pure magnesium ingot as the magnesium elements in magnesium alloy, the raw material using Mg-Y master alloy as the Y element in magnesium alloy, with Mg-Mn master alloy or Mn powder, MnCl
2flux is as the raw material of the manganese element in magnesium alloy, using Mg-Ca master alloy or pure Ca as the raw material of the calcium constituent in magnesium alloy, using pure Zn ingot as the raw material of the zinc element in magnesium alloy, with due regard to after scaling loss, take corresponding raw material by the weight percent of above-mentioned magnesium alloy composition;
(2) whole pure magnesium ingot is put in well formula electrical crucible, at shielding gas SF
6and N
2under melt completely, magnesium melt temperature is controlled between 700 780 DEG C;
(3) magnesium liquid temp rises to more than 700 DEG C, if need add Mn element, then add in magnesium melt after load weighted Mg-Mn master alloy being preheating to suitable temp in preheating oven, held for some time is until Mg-Mn master alloy all melts; Or be sprinkled in magnesium melt by load weighted pure Mn powder, or add the MnCl measured
2flux;
(4) if need add Zn one in Ca or 2 kinds of elements, after then pure Zn ingot, Mg-Ca master alloy can being preheating to suitable temp with Mg-Y master alloy in preheating oven, treat that magnesium liquid temp rises to more than 710 DEG C, then add in magnesium melt by it with Mg-Y alloy, insulation is until the one of pure Zn ingot, Mg-Ca master alloy or two kinds and Mg-Y master alloy all melt;
(5) magnesium liquid temp rises to more than 730 DEG C, adds the special refining agent of magnesium alloy and carries out refining, and in refining process, refining spoon immerses 2/3 place of liquid magnesium alloy, and the fierce aluminium alloy of stirring from top to bottom, till specular gloss appears in liquid level;
In stirring, constantly on alloy liquid level, spread refining flux;
Refining is complete, removes the solvent on liquid level and scum silica frost, then sprinkles one deck insulating covering agent gently;
Temperature is down in optimal temperature static, makes to be mingled with fully to float or sink, and then skims;
(6) after being adjusted to specified temp, magnesium alloy liquation is poured in fully preheated metal casting mould and is frozen into foundry goods; Or magnesium alloy liquation is poured into cold-chamber die casting machine high-pressure casting production die casting; Or magnesium alloy liquation is carried out low-pressure casting; Maybe the magnesium alloy ingot after cast is carried out extrusion production or rolling, forging.
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| CN109234592A (en) * | 2018-11-19 | 2019-01-18 | 河北工业大学 | Tough wrought magnesium alloy of a kind of zerolling height and preparation method thereof |
| CN109454209A (en) * | 2018-11-29 | 2019-03-12 | 蒙雪锋 | A kind of modifier powder raw material strainer formula feeding device |
| CN109811224A (en) * | 2019-03-29 | 2019-05-28 | 南京航空航天大学 | High-toughness heat-resistant die casting Mg-Y-Er alloy and preparation method thereof |
| CN113337765A (en) * | 2021-05-27 | 2021-09-03 | 长春理工大学 | High-temperature and high-pressure creep-resistant die-casting magnesium alloy and preparation method thereof |
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Application publication date: 20160427 |