CN102618765B - Magnesium alloy with hot cracking resistance and low linear shrinkage - Google Patents

Magnesium alloy with hot cracking resistance and low linear shrinkage Download PDF

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CN102618765B
CN102618765B CN201210107744.4A CN201210107744A CN102618765B CN 102618765 B CN102618765 B CN 102618765B CN 201210107744 A CN201210107744 A CN 201210107744A CN 102618765 B CN102618765 B CN 102618765B
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magnesium alloy
alloy
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magnesium
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CN102618765A (en
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冯俊
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Jiaxing Jiasi Beite New Material Co Ltd
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Jianghan University
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Abstract

The invention discloses a magnesium alloy with hot cracking resistance and low linear shrinkage, and belongs to the magnesium alloy field. The magnesium alloy is composed of elements of Mg, Zn, rare earths, Nb, Al and Li, and comprises, by weight, 0.2 to 9 percents of Zn, 0.0002 to 2 percents of Zr, 0.0002 to 16 percents of rare earths, 0.0002 to 4 percents of Nb, 0.001 to 1.49 percents of Al, 0.0002 to 9 percents of Li, and the balance Mg. According to the magnesium alloy, the structure of Beta phase is changed by adding rare earth elements and the Nb element into the magnesium alloy; grains are refined by adding the Li and Zr elements; and the crystallization latent heat is changed when the magnesium alloy is solidified by the combined action of the elements, so that the heat resistant magnesium alloy which has good mold-filling capacities, low shrinkage rate, good mechanical properties, machinability, mobility and die-casting properties and is suitable for casting is obtained.

Description

The low linear shrinkage ratio cast magnesium alloys of a kind of thermal crack resistant
Technical field
The present invention relates to a kind of magnesium alloy, particularly a kind of thermal crack resistant high performance cast magnesium alloy of applicable cast form.
Background technology
Along with scientific and technological development, the vehicles that the automobile of take is representative need to, by alleviating the weight of vehicle body, further be researched and developed the product innovation that fuel availability is higher.In automobile industry, magnesium alloy, as a kind of novel lightweight metal material, is used for substituting traditional cast iron by automaker, to realize the object that alleviates tare.
At present, the domestic cast magnesium alloys trade mark has ZM2, ZM3, ZM4, ZM6 etc., and wherein, above-mentioned ZM series magnesium alloy contains cerium mishmetal or La mixed rare earth, zinc, zirconium.The alloy of these trades mark has: mechanical property, castability be good feature all.
In realizing process of the present invention, contriver finds that prior art at least exists following problem: magnesium alloy is when casting, molten metal is in being frozen into the process of solid, be subject to the impact of volumetric shrinkage, internal stress is very large, easily cause cast(ing) surface cracking, the phenomenon that foundry goods die sinking ruptures even occurs.The impact that this decrepitation is serious the application of cast magnesium alloys, have influence on the qualification rate of magnesium alloy member.Above-mentioned diecast magnesium alloy linear shrinkage ratio is 1.5-2%, has obvious decrepitation, has limited its use range.
Summary of the invention
In order to solve above-mentioned problems of the prior art, the embodiment of the present invention provides a kind of thermal crack resistant low linear shrinkage ratio cast magnesium alloys.Described technical scheme is as follows:
The low linear shrinkage ratio cast magnesium alloys of a kind of thermal crack resistant, described magnesium alloy is comprised of Mg, Zn, Zr, rare earth, Nb, Al and Li, its weight percent consists of Zn 0.2-9%, Zr 0.0002-2%, rare earth 0.0002-16%, Nb 0.0002-4%, Al0.001-1.49%, Li 0.0002-9%, and all the other are Mg.
Wherein, described rare earth is at least one in Gd, Y, Sc, Sm, Nd, Pr, Yb, La, Ce, Tb, Dy, Ho and Er.
Preferably, described rare earth is at least one in Gd or Gd and Y, Sc, Sm, Nd, Pr, Yb, La, Ce, Tb, Dy, Ho and Er.
Preferably, its weight percent consists of Zn 0.2-0.7%, Zr 0.4-1%, Gd 0.1-4%, Nb 0.05-1%, Al 0.03-0.6%, Li 0.001-1%, and all the other are Mg.
Preferably, its weight percent consists of Zn 3.5-5.5%, Zr 0.4-1%, Gd 0.1-4%, Nb 0.05-1%, Al 0.03-0.6%, Li 0.05-6%, and all the other are Mg.
Preferably, its weight percent consists of Zn 7.5-9%, Zr 0.5-1%, Gd 0.1-2.5%, Nb 0.05-1%, Al 0.04-0.6%, Li 0.05-4%, and all the other are Mg.
More preferably, its weight percent consists of Zn 0.6%, Zr 0.8%, Gd 2.2%, Nb 0.2%, Al 0.1%, Li 0.2%, and all the other are Mg.
Wherein, described Nb and Al add described magnesium alloy by the form of NbAl master alloy or AlNb master alloy.
The beneficial effect that the technical scheme that the embodiment of the present invention provides is brought is: in cast magnesium alloys provided by the invention, RE can form MgRE compound with Mg, Nb can form some resistant to elevated temperatures metallic compounds with other elements (as Al), and Li and Zr have strong crystal grain thinning and purify aluminium alloy effect.Combined action due to above-mentioned element, the particularly effect of Li element, while making alloy graining, latent heat changes, under the heat absorption of above-mentioned element, heat release combined action, it is diecast magnesium alloy that the time that aluminium alloy provided by the invention keeps liquid in mould is obviously longer than existing ZM, make alloy in process of setting, feeding is abundant, built-in thermal stress is little, heat crack resistance is good, simultaneously, because magnesium alloy liquid volume and solid-state volume variation that the embodiment of the present invention provides are very little, therefore there is the feature that cavity filling ability is good, shrinking percentage is low.The characteristics such as alloy of the present invention also has good mechanical property, and machinability, mobility and die casting are good.
Embodiment
For making the object, technical solutions and advantages of the present invention clearer, below embodiment of the present invention is described further in detail.
Manufacture craft, the heat treating method of the magnesium alloy that the embodiment of the present invention provides are described as follows:
1, the magnesium alloy that the embodiment of the present invention provides can be made by following three kinds of melting technologies:
Technique one: the magnesium alloy providing according to the embodiment of the present invention forms and content alloyage, adds magnesium ingot, aluminium ingot, zinc ingot metal, MgZr master alloy, NbAl master alloy or AlNb master alloy in resistance furnace.Heat up to resistance furnace used, when the above-mentioned metal adding melts soon, adopt argon shield or magnesium alloy covering agent protection.While being warmed up to 720 ℃-780 ℃, add MgRE master alloy (as MgGd, MgY, MgNd etc.), AlLi master alloy or MgLi master alloy, and stir, 720 ℃ of-780 ℃ of standing insulations 30 minutes, obtain aluminium alloy.With gained aluminium alloy, water a fritter sample, detect its Melting Quality, as: according to gas content inspection method, carry out gas content inspection, if second-rate, need carry out refining treatment; If up-to-standard, described aluminium alloy temperature adjustment to 700 ℃-740 ℃ is skimmed, then pour into a mould, obtain the foundry goods of alloy of the present invention.
In this technique, resistance furnace also can replace with other smelting furnaces; Magnesium alloy covering agent and master alloy product are market sale product, and wherein NbAl master alloy is chosen the product that Al content is low, for example NbAl 80 and NbAl 75, and their Al content is respectively 15%-20%, 20%-25%; Refining treatment method adopts the ordinary method of the industry.
Technique two: the magnesium alloy providing according to the embodiment of the present invention forms and content alloyage, adds magnesium ingot, zinc ingot metal, MgZr master alloy, NbAl master alloy or AlNb master alloy in vacuum oven.Be warming up to 820 ℃, insulation 2-8 hour, then cools to 720 ℃-780 ℃, adds RE, AlLi master alloy or MgLi master alloy.After added melting of metal, 720 ℃-780 ℃ insulations 30 minutes, obtain aluminium alloy, adopt argon shield or magnesium alloy covering agent protection to prevent aluminium alloy oxidation.With gained aluminium alloy, water a fritter sample, detect its Melting Quality, as: the inspection of gas content, if second-rate, need carry out refining treatment; If up-to-standard, described aluminium alloy temperature adjustment to 700 ℃-740 ℃ is skimmed, then pour into a mould, obtain the foundry goods of alloy of the present invention.
In this technique, vacuum oven can substitute with other smelting furnaces such as main frequency furnaces; Magnesium alloy covering agent, rare earth, master alloy are sell goods on market, and wherein NbAl master alloy is chosen the product that Al content is low, for example NbAl 80 and NbAl 75, and their Al content is respectively 15%-20%, 20%-25%; Refining treatment method adopts the ordinary method of the industry.
Technique three: the magnesium alloy providing according to the embodiment of the present invention forms and content alloyage adds cast magnesium alloys (as at least one in ZM2, ZM3, ZM4, ZM6), NbAl master alloy or the AlNb master alloy of standard brand in smelting furnace.Above-mentioned metal adopts argon shield or magnesium alloy covering agent protection while melting soon.While being warmed up to 720 ℃-780 ℃, add MgRE master alloy (as MgGd, MgY, MgNd etc.), AlLi master alloy or MgLi master alloy, and stir, 720 ℃ of-780 ℃ of standing insulations 30 minutes, obtain aluminium alloy.With gained aluminium alloy, water a fritter sample, detect its Melting Quality, as: according to gas content inspection method, carry out gas content inspection, if second-rate, need carry out refining treatment; If up-to-standard, described aluminium alloy temperature adjustment to 700 ℃-740 ℃ is skimmed, then pour into a mould, obtain the foundry goods of alloy of the present invention.
In this technique, magnesium alloy covering agent and master alloy agent are sell goods on market; Refining treatment method adopts the ordinary method of the industry.
Thermal treatment and the treatment process thereof of the magnesium alloy that 2, the embodiment of the present invention provides:
Die casting in the diecast magnesium alloy that the embodiment of the present invention provides can not heat-treated, and the cast member of other form can be heat-treated, and generally adopts T4 solution treatment.T4 solid solution treatment process is: cast member is warming up in chamber type electric resistance furnace to 400 ℃, argon shield, is incubated 15 hours, cast member come out of the stove after shrend, 40 ℃ of water temperatures.
Be subject to fusion process to select the impact of some other inevitable factor in the purity of raw material and melting, castingprocesses, the diecast magnesium alloy that the embodiment of the present invention provides may contain inevitable impurity, as Fe, Cu, Be etc., as long as described impurity does not cause obvious impact to the performance of magnesium alloy, and total impurities is controlled at the weight percent < 0.5% in described magnesium alloy finished product, in the weight percent < 0.1% of single contaminant in described magnesium alloy finished product, exist trace impurity also to allow.
Embodiment 1
By step described in above-mentioned technique one, prepare magnesium alloy, foundry goods adopts die cast, and the weight percent of described magnesium alloy consists of Zn 0.2%, Zr 0.0002%, Y 0.0002%, Nb 0.0002%, Al 0.001%, Li 0.0002%, and all the other are Mg.
Foundry goods is heat-treated.
The performance of the Mg alloy castings that the present embodiment provides is referring to table 1.
Embodiment 2
By step described in above-mentioned technique two, prepare magnesium alloy, foundry goods adopts semi-solid casting, and the weight percent of described magnesium alloy consists of Zn 9%, Zr 2%, Sc 16%, Nb4%, Al 1.49%, Li 9%, and all the other are Mg.
Foundry goods is heat-treated.
The performance of the Mg alloy castings that the present embodiment provides is referring to table 1.
Embodiment 3
By step described in above-mentioned technique two, prepare magnesium alloy, foundry goods adopts Hpdc, and the weight percent of magnesium alloy consists of Zn0.2%, Zr 0.4%, Sm 0.1%, Nb 0.05%, Al 0.03%, Li 0.01%, and all the other are Mg.
The performance of the Mg alloy castings that the present embodiment provides is referring to table 1.
Embodiment 4
By step described in above-mentioned technique one, prepare magnesium alloy, foundry goods adopts low-pressure casting, and the weight percent of described magnesium alloy consists of Zn 0.7%, Zr 1%, Nd 4%, Nb 1%, Al 0.6%, Li 1%, and all the other are Mg.
Foundry goods is heat-treated.
The performance of the Mg alloy castings that the present embodiment provides is referring to table 1.
Embodiment 5
By step described in above-mentioned technique three, prepare magnesium alloy, described standard brand diecast magnesium alloy used in preparation process is ZM2, foundry goods adopts precision casting, the weight percent of described magnesium alloy consists of Zn 3.5%, Zr 0.55%, (Ce+La) 0.9%, Nb 0.05%, Al 0.03%, Li 0.05%, and all the other are Mg.
Foundry goods is heat-treated.
The performance of the Mg alloy castings that the present embodiment provides is referring to table 1.
Embodiment 6
By step described in above-mentioned technique one, prepare magnesium alloy, foundry goods adopts sand mold casting, and the weight percent of described magnesium alloy consists of Zn 5.5%, Zr 1%, Ce 4%, Nb 1%, Al 0.6%, Li 6%, and all the other are Mg.
Foundry goods is heat-treated.
The performance of the Mg alloy castings that the present embodiment provides is referring to table 1.
Embodiment 7
By step described in above-mentioned technique two, prepare magnesium alloy, foundry goods adopts Hpdc, and the weight percent of described magnesium alloy consists of Zn 7.5%, Zr 0.5%, Tb 0.1%, Nb 0.05%, Al 0.04%, Li 0.05%, and all the other are Mg.
The performance of the Mg alloy castings that the present embodiment provides is referring to table 1.
Embodiment 8
By step described in above-mentioned technique two, prepare magnesium alloy, foundry goods adopts Hpdc, and the weight percent of described magnesium alloy consists of Zn 9%, Zr 1%, Dy 2.5%, Nb 1%, Al 0.6%, Li 4%, and all the other are Mg.
The performance of the Mg alloy castings that the present embodiment provides is referring to table 1.
Embodiment 9
By step described in above-mentioned technique two, prepare magnesium alloy, foundry goods adopts Hpdc, and the weight percent of described magnesium alloy consists of Zn 0.5%, Zr 0.6%, Gd 1%, Nb 0.5%, Al 0.4%, Li 0.5%, and all the other are Mg.
The performance of the Mg alloy castings that the present embodiment provides is referring to table 1.
Embodiment 10
By step described in above-mentioned technique two, prepare magnesium alloy, foundry goods adopts die cast, and the weight percent of described magnesium alloy consists of Zn 0.5%, Zr 0.6%, Gd 0.7%, Gd 0.3%, Nb 0.5%, Al 0.4%, Li 0.5%, and all the other are Mg.
Foundry goods is heat-treated.
The performance of the Mg alloy castings that the present embodiment provides is referring to table 1.
Embodiment 11
By step described in above-mentioned technique one, prepare magnesium alloy, foundry goods adopts sand mold casting, and the weight percent of described magnesium alloy consists of Zn 0.5%, Zr 0.6%, Er 1%, Nb 0.5%, Al 0.4%, Li 0.5%, and all the other are Mg.
Foundry goods is heat-treated.
The performance of the Mg alloy castings that the present embodiment provides is referring to table 1.
Embodiment 12
By step described in above-mentioned technique two, prepare magnesium alloy, foundry goods adopts die cast, and the weight percent of described magnesium alloy consists of Zn 6%, Zr 1.5%, Ho 8%, Nb 3%, Al 1%, Li 7%, and all the other are Mg.
Foundry goods is heat-treated.
The performance of the Mg alloy castings that the present embodiment provides is referring to table 1.
Embodiment 13
By step described in above-mentioned technique two, prepare magnesium alloy, foundry goods adopts die cast, and the weight percent of described magnesium alloy consists of Zn 2%, Zr 0.3%, Sc 0.05%, Nb 0.04%, Al 1.4%, Li 8%, and all the other are Mg.
Foundry goods is heat-treated.
The performance of the Mg alloy castings that the present embodiment provides is referring to table 1.
Embodiment 14
By step described in above-mentioned technique two, prepare magnesium alloy, foundry goods adopts die cast, and the weight percent of described magnesium alloy consists of Zn 4%, Zr 0.2%, Gd 3%, Nb 0.08%, Al 0.2%, Li 5%, and all the other are Mg.
Foundry goods is heat-treated.
The performance of the Mg alloy castings that the present embodiment provides is referring to table 1.
Embodiment 15
By step described in above-mentioned technique one, prepare magnesium alloy, foundry goods adopts Hpdc, and described magnesium alloy weight percent consists of Zn0.6%, Zr 0.8%, Gd 2.2%, Nb 0.2%, Al 0.1%, Li 0.2%, and all the other are Mg.
The performance of the Mg alloy castings that the present embodiment provides is referring to table 1.
Comparative example 1
By step described in above-mentioned technique one, prepare magnesium alloy, foundry goods adopts Hpdc, and described magnesium alloy weight percent consists of Zn0.6%, Zr 0.8%, Gd 2.2%, Al 0.1%, Li 0.2%, and all the other are Mg and inevitable impurity.
The performance of the Mg alloy castings that the present embodiment provides is referring to table 1.
Comparative example 2
By step described in above-mentioned technique one, prepare magnesium alloy, foundry goods adopts Hpdc, and described magnesium alloy weight percent consists of Zn0.6%, Zr 0.8%, Gd 2.2%, Nb 0.2%, Al 0.1%, and all the other are Mg and inevitable impurity.
The performance of the Mg alloy castings that the present embodiment provides is referring to table 1.
Comparative example 3
By step described in above-mentioned technique one, prepare magnesium alloy, foundry goods adopts Hpdc, and described magnesium alloy weight percent consists of Zn0.6%, Zr 0.8%, Gd 2.2%, Al 0.1%, and all the other are Mg and inevitable impurity.
The performance of the Mg alloy castings that the present embodiment provides is referring to table 1.
The Mg alloy castings that each embodiment provides above can contain micro-impurity, the weight percent < 0.5% of described inevitable total impurities in described magnesium alloy finished product, the weight percent < 0.1% of single contaminant in described magnesium alloy finished product.
The linear shrinkage ratio of the Mg alloy castings that various embodiments of the present invention and comparative example provide is referring to table 1.
The linear shrinkage ratio table of the Mg alloy castings that each embodiment of table 1 provides
Sample Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4 Embodiment 5 Embodiment 6
Linear shrinkage ratio/% 0.7 0.6 0.2 0.3 0.4 0.3
Sample Embodiment 7 Embodiment 8 Embodiment 9 Embodiment 10 Embodiment 11 Embodiment 12
Linear shrinkage ratio/% 0.4 0.2 0.08 0.07 0.2 0.6
Sample Embodiment 13 Embodiment 14 Embodiment 15 Comparative example 1 Comparative example 2 Comparative example 3
Linear shrinkage ratio/% 0.6 0.07 0.01 1.6 1.5 2
As shown in Table 1, the linear shrinkage ratio of the magnesium alloying part that the embodiment of the present invention provides is all less than 1%, well below existing similar Mg alloy castings, has good hot-cracking resistance; Simultaneously referring to embodiment 15 and comparative example 1-3, the Mg alloy castings that the embodiment of the present invention provides is compared with not adding Li or Nb or Mg alloy castings that both all do not add, has better hot-cracking resistance; By the contrast between embodiment 9-11, the known RE containing has the effect of Gd better; The linear shrinkage ratio of the Mg alloy castings that embodiment 15 provides is minimum, and the Mg alloy castings hot-cracking resistance that embodiment 15 provides is the strongest.
The foregoing is only preferred embodiment of the present invention, in order to limit the present invention, within the spirit and principles in the present invention not all, any modification of doing, be equal to replacement, improvement etc., within all should being included in protection scope of the present invention.

Claims (7)

1. the low linear shrinkage ratio cast magnesium alloys of thermal crack resistant, it is characterized in that, described magnesium alloy is by Mg, Zn, Zr, rare earth, Nb, Al and Li form, its weight percent consists of Zn0.2-9%, Zr0.0002-2%, rare earth 0.0002-16%, Nb0.0002-4%, Al0.001-1.49%, Li0.0002-9%, all the other are Mg, described Nb and Al add described magnesium alloy by the form of NbAl master alloy or AlNb master alloy, in described cast magnesium alloys, Nb and Al form resistant to elevated temperatures metallic compound, the smelting temperature of the described Nb master alloy adding is 720 ℃-780 ℃ or 820 ℃.
2. magnesium alloy according to claim 1, is characterized in that, described rare earth is at least one in Gd, Y, Sc, Sm, Nd, Pr, Yb, La, Ce, Tb, Dy, Ho and Er.
3. magnesium alloy according to claim 2, is characterized in that, described rare earth is at least one in Gd or Gd and Y, Sc, Sm, Nd, Pr, Yb, La, Ce, Tb, Dy, Ho and Er.
4. according to the magnesium alloy described in claim 1-3 any one, it is characterized in that, its weight percent consists of Zn0.2-0.7%, Zr0.4-1%, Gd0.1-4%, Nb0.05-1%, Al0.03-0.6%, Li0.001-1%, and all the other are Mg.
5. according to the magnesium alloy described in claim 1-3 any one, it is characterized in that, its weight percent consists of Zn3.5-5.5%, Zr0.4-1%, Gd0.1-4%, Nb0.05-1%, Al0.03-0.6%, Li0.05-6%, and all the other are Mg.
6. according to the magnesium alloy described in claim 1-3 any one, it is characterized in that, its weight percent consists of Zn7.5-9%, Zr0.5-1%, Gd0.1-2.5%, Nb0.05-1%, Al0.04-0.6%, Li0.05-4%, and all the other are Mg.
7. according to the magnesium alloy described in claim 1-3 any one, it is characterized in that, its weight percent consists of Zn0.6%, Zr0.8%, Gd2.2%, Nb0.2%, Al0.1%, Li0.2%, and all the other are Mg.
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CN104004949B (en) * 2014-05-21 2016-06-01 上海交通大学 The preparation method of a kind of high strength magnesium lithium alloy
TWI537395B (en) * 2014-12-02 2016-06-11 安立材料科技股份有限公司 Magnesium alloy
CN106498252B (en) * 2016-10-27 2018-04-13 江苏理工学院 A kind of high-strength magnesium neodymium zinc zirconium lithium alloy and preparation method thereof
CN107130158B (en) * 2017-04-20 2018-09-21 赣南师范大学 A kind of high heat conduction magnesium-rare earth and preparation method thereof
CN108456813B (en) * 2018-01-22 2020-02-21 上海交通大学 Mg-Li-Al-Zn-Y series cast magnesium-lithium alloy and heat treatment method thereof

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