CN103184378B - A kind of magnesium alloy and preparation method thereof - Google Patents
A kind of magnesium alloy and preparation method thereof Download PDFInfo
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- CN103184378B CN103184378B CN201110444150.8A CN201110444150A CN103184378B CN 103184378 B CN103184378 B CN 103184378B CN 201110444150 A CN201110444150 A CN 201110444150A CN 103184378 B CN103184378 B CN 103184378B
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Abstract
The invention provides a kind of magnesium alloy, with the total mass of magnesium alloy for benchmark, described magnesium alloy contains following component: the Ti of the Mn of the Zn of the Li of 6-8.6wt%, 0.5-1.5wt%, 0.1-0.5wt%, 0.01-0.5wt%, surplus comprise magnesium, containing or free from foreign meter.Magnesium alloy provided by the invention, by introducing Ti and Mn on Mg-Li-Zn system alloy basis, and the content of Li, Ti, Mn element is suitably selected, under guarantee has the prerequisite of lower cost, make Mg-Li-Zn series magnesium alloy provided by the invention can have higher intensity and erosion resistance simultaneously.
Description
Technical field
The invention belongs to technical field of metal, particularly relate to a kind of magnesium alloy and preparation method thereof.
Background technology
Magnesium alloy is that in all structure metallic substance, weight is the lightest, and density is 1.75-1.90g/cm
3, be only 2/3 of aluminium alloy, 1/4 of iron and steel.Compared with other structural metallic materialss, magnesium alloy has high specific strength, specific rigidity, damping property, electromagnetic wave shielding and capability of resistance to radiation are strong, the series of advantages such as Cutting free processing, easily recovery, having extremely important using value and wide application prospect at automobile, electronic apparatus, communication, aerospace and national defense and military industrial circle, is the 3rd metalloid structured material grown up after iron and steel and aluminium alloy.
At present, report various novel magnesium alloy both at home and abroad, but these material major parts have single performance excellence.Such as, CN1676646A discloses a kind of high-strength heat-resisting magnesium alloy, and its maximum intensity reaches more than 450MPa, but this alloy ductility bad, and adding due to a large amount of heavy rare earth Gds, improve the proportion of alloy, compromise the advantage of magnesium alloy lightweight.CN1482268A discloses a kind of high extension magnesium alloy, and room temperature unit elongation reaches 40%, can realize room temperature deep-draw, but the intensity of this alloy is lower, and maximum yield strength is only 160MPa, constrains the application of its industrialized scale.Therefore, engineering more need magnesium alloy materials have good over-all properties.In addition, for different magnesium alloy systems, because contained main element is different, therefore its over-all properties such as intensity, erosion resistance is difficult to meet simultaneously.
Summary of the invention
The invention solves magnesium alloy of the prior art exist be difficult to have higher intensity and the technical problem of erosion resistance concurrently.
The invention provides a kind of magnesium alloy, with the total mass of magnesium alloy for benchmark, described magnesium alloy contains following component: the Ti of the Mn of the Zn of the Li of 6-8.6wt%, 0.5-1.5wt%, 0.1-0.5wt%, 0.01-0.5wt%, surplus comprise magnesium, containing or free from foreign meter.
Present invention also offers the preparation method of described magnesium alloy, comprise the following steps: raw material magnesium alloy molten alloy is obtained magnesium lithium zinc-manganese titanium alloy melting liquid, then cast, obtain described magnesium alloy; Described raw material magnesium alloy comprises: magnesium ingot, magnesium lithium alloy, zinc ingot metal, manganese ingot, titanium silk; In described magnesium alloy, the weight percent of each component is: Li 6-8.6wt%, Zn 0.5-1.5wt%, Mn 0.1-0.5wt%, Ti 0.01-0.5wt%, and surplus comprises magnesium, contains or element free from foreign meter.
Magnesium alloy provided by the invention, for Mg-Li-Zn system alloy, by under the prerequisite of introducing Li element in magnesium alloy system, add Ti element crystal grain thinning simultaneously, improve yield strength and the breaking tenacity of described magnesium alloy, add Mn element simultaneously, improve the erosion resistance of magnesium alloy, in alloy system, the content of Li, Ti, Mn element is suitably selected simultaneously, under guarantee has the prerequisite of lower cost, make Mg-Li-Zn series magnesium alloy provided by the invention can have higher intensity and erosion resistance simultaneously.
Embodiment
The invention provides a kind of magnesium alloy, with the total mass of magnesium alloy for benchmark, described magnesium alloy contains following component: the Ti of the Mn of the Zn of the Li of 6-8.6wt%, 0.5-1.5wt%, 0.1-0.5wt%, 0.01-0.5wt%, surplus comprise magnesium, containing or free from foreign meter.
Magnesium alloy provided by the invention, for Mg-Li-Zn system alloy, by under the prerequisite of introducing Li element in magnesium alloy system, add Ti element crystal grain thinning simultaneously, improve yield strength and the breaking tenacity of described magnesium alloy, add Mn element simultaneously, improve the erosion resistance of magnesium alloy, in alloy system, the content of Li, Ti, Mn element is suitably selected simultaneously, under guarantee has the prerequisite of lower cost, make Mg-Li-Zn series magnesium alloy provided by the invention can have higher intensity and erosion resistance simultaneously.
As the common practise of those skilled in the art, intensity and the plasticity of metallic substance oppose the performance disappeared mutually often, can the plasticity of expendable material while improving intensity, and vice versa.And magnesium alloy is as Structural Engineering materials application, intensity and plasticity are absolutely necessary again, and because magnesium is hexagonal closed-packed, slip system is few, and deformability is poor, and ductility can not effectively improve always, especially room temperature ductility.Therefore, the present inventor introduces Li element in magnesium-zinc alloy system, and suitably selects the content of Li element, can change crystalline structure, improves plastic deformation ability, thus improves its ductility.
Particularly, when lithium content in alloy is more than 6wt%, have obvious body-centred structure tissue and produce, along with the raising of the addition of lithium, structure organization also increases relatively, and then the ductility of material also improves.And the content of Li more than 20wt% time, low-alloyed intensity can be fallen.
And introduce Li element in magnesium-zinc alloy after, alloy system becomes Mg-Li-Zn system.For this kind of alloy system, how to improve intensity and erosion resistance, relevant elaboration in prior art simultaneously.The present inventor is found by great many of experiments, directly in Mg-Li-Zn system alloy, add Ti element and Mn element, after adding Li and Ti, Mn, the content of other element inherently respective change in alloy system, is therefore difficult to ensure that gained magnesium alloy has higher intensity and erosion resistance simultaneously.And if reduce the addition of Li and Ti, Mn, can not ensure that again each Addition ofelements gives the respective performances of alloy system.The present inventor surprisingly finds, by suitably reducing adjustment to the content of Li element, and then adds Ti, Mn, the high ductibility basis that can retain Mg-Li-Zn system alloy is improved simultaneously erosion resistance and the mechanical property of magnesium alloy.Simultaneously, because lithium is a kind of relatively expensive metal, reduce lithium ratio in the alloy and can reduce cost of alloy, increase product competitiveness, therefore need to find lithium trim point in the alloy, the good plasticity of former alloy can either be kept, ensure that again lithium content can not be too high, the present invention verifies through test of many times, can produce a desired effect when Li content is 6-8.6wt%.
Particularly, in described magnesium alloy, the content of each component is: the Ti of the Mn of the Zn of the Li of 6-8.6wt%, 0.5-1.5wt%, 0.1-0.5wt%, 0.01-0.5wt%, surplus comprise magnesium, containing or free from foreign meter.
As a kind of preferred implementation of the present invention, in order to obtain the better magnesium alloy of over-all properties, in described magnesium alloy, the content of each component is: the Ti of the Mn of the Zn of the Li of 7-8.6wt%, 0.6-1.2wt%, 0.1-0.4wt%, 0.1-0.5wt%, and surplus is magnesium.
In the present invention, described impurity element is one or more in Fe, Cu, Ni.With the total mass of described magnesium alloy for benchmark, the content of impurity element is less than 0.015wt%.By controlling the content of impurity element to be also one of important channel of improving corrosion resistance of magnesium alloy.Therefore, under preferable case, containing Fe, Cu and Ni in described impurity element.With the total mass of described magnesium alloy for benchmark, wherein the content of Fe is no more than 0.005wt%.
Present invention also offers the preparation method of described magnesium alloy, comprise the following steps: raw material magnesium alloy molten alloy is obtained magnesium lithium zinc-manganese titanium alloy melting liquid, then cast, obtain described magnesium alloy; Described raw material magnesium alloy comprises: magnesium ingot, magnesium lithium alloy, zinc ingot metal, manganese ingot, titanium silk; In described magnesium alloy, the weight percent of each component is: Li 6-8.6wt%, Zn 0.5-1.5wt%, Mn 0.1-0.5wt%, Ti 0.01-0.5wt%, and surplus comprises magnesium, contains or element free from foreign meter.
Wherein, the step of raw material magnesium alloy molten alloy is comprised: first magnesium ingot is melted completely, then add magnesium lithium alloy, zinc ingot metal, manganese ingot and titanium silk, treat whole melting, stir, remove surface scum.
In the present invention, in magnesium alloy, Li element is introduced by adopting the mode of master alloy (i.e. magnesium lithium alloy), prevents scaling loss and causes component segregation.Need to stir in smelting process, the time of described stirring is 30-60min, promotes the abundant alloying of each element simultaneously.Described stirring is various mechanical stirring conventional in prior art.
In preparation method provided by the invention, because the fusing point of metal titanium and manganese is higher, in molten alloy process, not easily enter solution, easily cause alloying constituent segregation.Therefore, under preferable case, when proportioning raw materials, the consumption of titanium silk and manganese ingot can add 3-5wt%.Namely in the present invention, in described raw material magnesium alloy, the consumption of manganese ingot is 1.03-1.05 times of manganese element content in magnesium alloy, and the consumption of titanium silk is 1.03-1.05 times of titanium elements content in magnesium alloy.
Under preferable case, described magnesium ingot is the pure magnesium ingot containing more than Mg 99.9wt%.Described zinc ingot metal is the pure zinc ingot containing more than Zn 99.9wt%.Described titanium silk is the pure titanium silk containing Ti 99.95wt%.Described manganese ingot is for containing the pure manganese ingot of Mn 99.7wt%.More preferably, in situation, described manganese ingot adopts electrolytic manganese ingot.Described magnesium lithium alloy adopts Mg
31li
69the Mg-Li alloy of model.
In the present invention, the step of described raw material magnesium alloy molten alloy is carried out under gas or insulating covering agent protective condition.Described gas is selected from SF
6, N
2, one or more in rare gas element.Under preferable case, described gas adopts SF
6and N
2mixed gas.More preferably in situation, in described mixed gas, N
2content is 99.8 volume %, SF
6content is 0.2 volume %.Adopt this mixed gas as shielding gas, lower than employing rare gas element expense, reduce the cost of manufacture of alloy.
Described insulating covering agent is selected from various salts conventional in prior art.Under preferable case, described insulating covering agent is calcium chloride or sodium-chlor.
In the present invention, the temperature of molten alloy is 650-780 DEG C.Under preferable case, the temperature of molten alloy is 700-740 DEG C.
Magnesium alloy prepared by the present invention can be processed into circular casting rod, is squeezed into different section bars, and the material mechanical performance of acquisition is better.
In order to make technical problem solved by the invention, technical scheme and beneficial effect clearly understand, below in conjunction with embodiment, the present invention is further elaborated.Should be appreciated that specific embodiment described herein only in order to explain the present invention, be not intended to limit the present invention.In embodiment and comparative example adopt raw material to be all commercially available.
Embodiment 1
Take raw material according to following constituent content: Li:6.0wt%, Zn:0.5wt%, Mn:0.1wt%, Ti:0.2wt%, Impurity Fe, Cu, Ni total amount are 0.013wt%, and wherein the content of Fe is 0.004wt%, and surplus is magnesium.Wherein the amount of taking of titanium silk is 1.05 times of Ti constituent content, and the amount of taking of manganese ingot is 1.05 times of Mn constituent content.
Then at N
2(99.8 volume %) and SF
6(0.2 volume %) mixed gas air pressure is under the protective atmosphere of 0.4MPa, and first by magnesium ingot complete melting in crucible, then by zinc ingot metal, titanium silk, manganese ingot and magnesium lithium alloy, (model is Mg
31li
69) put into crucible, after treating that furnace charge melts completely at 720 DEG C, stir 40min, remove surface scum, obtain magnesium lithium zinc-manganese titanium alloy melting liquid, after casting, obtain magnesium alloy S1.
Embodiment 2
The step identical with embodiment 1 is adopted to prepare the magnesium alloy S2 of the present embodiment, difference is: take raw material according to following constituent content: Li:7.0wt%, Zn:0.6wt%, Mn:0.2wt%, Ti:0.2wt%, Impurity Fe, Cu, Ni total amount are 0.014wt%, wherein the content of Fe is 0.004wt%, and surplus is magnesium; And wherein the amount of taking of titanium silk is 1.05 times of Ti constituent content, the amount of taking of manganese ingot is 1.05 times of Mn constituent content.
Embodiment 3
The step identical with embodiment 1 is adopted to prepare the magnesium alloy S3 of the present embodiment, difference is: take raw material according to following constituent content: Li:8.0%, Zn:1.0%, Mn:0.3%, Ti:0.4%, Impurity Fe, Cu, Ni total amount are 0.013%, wherein the content of Fe is 0.003%, and surplus is magnesium; Wherein the amount of taking of titanium silk is 1.03 times of Ti constituent content, and the amount of taking of manganese ingot is 1.03 times of Mn constituent content.
Embodiment 4
The step identical with embodiment 1 is adopted to prepare the magnesium alloy S4 of the present embodiment, difference is: take raw material according to following constituent content: Li:8.0%, Zn:1.0%, Mn:0.5%, Ti:0.5%, Impurity Fe, Cu, Ni total amount are 0.014%, wherein the content of Fe is 0.005%, and surplus is magnesium; Wherein the amount of taking of titanium silk is 1.05 times of Ti constituent content, and the amount of taking of manganese ingot is 1.05 times of Mn constituent content.
Embodiment 5
The step identical with embodiment 1 is adopted to prepare the magnesium alloy S5 of the present embodiment, difference is: take raw material according to following constituent content: Li:8.6%, Zn:1.0%, Mn:0.5%, Ti:0.5%, Impurity Fe, Cu, Ni total amount are 0.015%, wherein the content of Fe is 0.005%, and surplus is magnesium; Wherein the amount of taking of titanium silk is 1.05 times of Ti constituent content, and the amount of taking of manganese ingot is 1.05 times of Mn constituent content.
Embodiment 6
The step identical with embodiment 1 is adopted to prepare the magnesium alloy S2 of the present embodiment, difference is: take raw material according to following constituent content: Li:8.6%, Zn:1.0%, Mn:0.5%, Ti:0.4%, Impurity Fe, Cu, Ni total amount are 0.015%, wherein the content of Fe is 0.003%, and surplus is magnesium; Wherein the amount of taking of titanium silk is 1.05 times of Ti constituent content, and the amount of taking of manganese ingot is 1.05 times of Mn constituent content.
Embodiment 7
The step identical with embodiment 1 is adopted to prepare the magnesium alloy S2 of the present embodiment, difference is: take raw material according to following constituent content: Li:8.6%, Zn:1.0%, Mn:0.5%, Ti:0.4%, Impurity Fe, Cu, Ni total amount are 0.014%, wherein the content of Fe is 0.004%, and surplus is magnesium; Wherein the amount of taking of titanium silk is 1.04 times of Ti constituent content, and the amount of taking of manganese ingot is 1.04 times of Mn constituent content.
Comparative example 1
Take raw material magnesium ingot, magnesium lithium alloy, zinc ingot metal according to following constituent content: Li:8.6wt%, Zn:0.5wt%, Impurity Fe, Cu, Ni total amount are 0.013wt%, and wherein the content of Fe is 0.004wt%, and surplus is magnesium.
Then at N
2(99.8 volume %) and SF
6(0.2 volume %) mixed gas air pressure is under the protective atmosphere of 0.4MPa, and first by magnesium ingot complete melting in crucible, then by zinc ingot metal and magnesium lithium alloy, (model is Mg
31li
69) put into crucible, 720 DEG C treat that furnace charge melts completely after, stir stir 40min, remove surface scum, obtain magnesium lithium zinc-manganese titanium alloy melting liquid, after casting, obtain magnesium alloy DS1.
Comparative example 2
Take raw material according to following constituent content: Li:10.1wt%, Zn:0.5wt%, Mn:0.5wt%, Ti:0.4wt%, Impurity Fe, Cu, Ni total amount are 0.013wt%, and wherein the content of Fe is 0.004wt%, and surplus is magnesium; Wherein the amount of taking of titanium silk is 1.05 times of Ti constituent content, and the amount of taking of manganese ingot is 1.05 times of Mn constituent content.
Then at N
2(99.8 volume %) and SF
6(0.2 volume %) mixed gas air pressure is under the protective atmosphere of 0.4MPa, and first by magnesium ingot complete melting in crucible, then by zinc ingot metal, titanium silk, manganese ingot and magnesium lithium alloy, (model is Mg
31li
69) put into crucible, 720 DEG C treat that furnace charge melts completely after, stir 40min, remove surface scum, obtain magnesium lithium zinc-manganese titanium alloy melting liquid, after casting, obtain magnesium alloy DS2.
Performance test
1, erosion rate test
From each magnesium alloy S1-S7 and DS1-DS2, cut the sample being of a size of 25mm × 35mm × 3mm, hang on by thin cord after cleaning-dry-survey size-weigh and fill in the salts solution of 5%NaCl, a beaker only hangs a sample.Test after 7 days, adopt chemical process cleaning corrosion product.Concrete solution ratio is as follows: 100g CrO3,5g AgNO3,500mL deionized water, and sample is placed in one about 5min.Cleaning post-drying, weighs, and calculates erosion rate.
2, tensile strength test
By magnesium alloy S1-S7 and DS1-DS2 of preparation by extruding, obtained 50mm × 50mm, wall thickness is the square tube of 2mm, then in square tube, intercept sample according to GB GBT 228-2002 and carry out Elongation test, testing tool choosing has conventional omnipotent mechanics machine, rate of extension is 1mm/min, tests yield strength and the breaking tenacity of each magnesium alloy.
3, grain fineness number test
Be mounted in bakelite by magnesium alloy S1-S7 and DS1-DS2 of preparation taking off 10mm × 10mm × 10mm mono-piece, then metallographic sample is prepared in polishing, and according to GB GBT 4296-2004, testing tool is conventional metaloscope.
And adopt simultaneously Mg-Al-Zn series of transformations magnesium alloy AZ31B, AZ61, AZ91D in contrast sample carry out above-mentioned test.
Concrete test result is as shown in table 1.
Table 1
。
As can be seen from the test result of table 1, magnesium alloy of the present invention is due to Mg-Li-Zn system alloy basis with the addition of Mn and Ti element, and the content of Li, Ti, Mn element is suitably selected, make magnesium alloy of the present invention have higher erosion resistance and mechanical property simultaneously, meet the service requirements of various complex working condition in engineering, range of application is wider.
Because Li constituent content is higher in DS2, both added the cost of magnesium alloy, the intensity of magnesium alloy decreases again.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any amendments done within the spirit and principles in the present invention, equivalent replacement and improvement etc., all should be included within protection scope of the present invention.
Claims (10)
1. a magnesium alloy, is characterized in that, with the total mass of magnesium alloy for benchmark, described magnesium alloy contains following component: the Ti of the Mn of the Zn of the Li of 6-8.6wt%, 0.5-1.5wt%, 0.1-0.5wt%, 0.01-0.5wt%, surplus be magnesium, containing or free from foreign meter.
2. magnesium alloy according to claim 1, is characterized in that, with the total mass of magnesium alloy for benchmark, described magnesium alloy contains following component: the Ti of the Mn of the Zn of the Li of 7-8.6wt%, 0.6-1.2wt%, 0.1-0.4wt%, 0.1-0.5wt%, and surplus is magnesium.
3. magnesium alloy according to claim 1, is characterized in that, described impurity element is one or more in Fe, Cu, Ni; With the total mass of described magnesium alloy for benchmark, the content of impurity element is less than 0.015wt%.
4. magnesium alloy according to claim 3, is characterized in that, containing Fe, Cu and Ni in described impurity element; With the total mass of described magnesium alloy for benchmark, the content of Fe is no more than 0.005wt%.
5. the preparation method of magnesium alloy according to claim 1, is characterized in that, comprises the following steps: raw material magnesium alloy molten alloy is obtained magnesium lithium zinc-manganese titanium alloy melting liquid, then cast, obtain described magnesium alloy; Described raw material magnesium alloy comprises: magnesium ingot, magnesium lithium alloy, zinc ingot metal, manganese ingot, titanium silk; In described magnesium alloy, the weight percent of each component is: Li 6-8.6wt%, Zn 0.5-1.5wt%, Mn 0.1-0.5wt%, Ti 0.01-0.5wt%, and surplus is magnesium, contains or element free from foreign meter.
6. preparation method according to claim 5, is characterized in that, the step of raw material magnesium alloy molten alloy is comprised: first melted completely by magnesium ingot, then magnesium lithium alloy, zinc ingot metal, manganese ingot and titanium silk is added, treat whole melting, stir, remove surface scum.
7. preparation method according to claim 6, is characterized in that, the time of described stirring is 30-60min.
8. the preparation method according to claim 5 or 6, is characterized in that, the temperature of molten alloy is 650-780 DEG C.
9. the preparation method according to claim 5 or 6, is characterized in that, in raw material magnesium alloy, the consumption of manganese ingot is 1.03-1.05 times of manganese element content in magnesium alloy, and the consumption of titanium silk is 1.03-1.05 times of titanium elements content in magnesium alloy.
10. preparation method according to claim 5, is characterized in that, the step of described raw material magnesium alloy molten alloy is carried out under gas or insulating covering agent protective condition; Described gas is selected from SF
6, N
2, one or more in rare gas element; Described insulating covering agent is calcium chloride or sodium-chlor.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1614062A (en) * | 2004-09-29 | 2005-05-11 | 上海交通大学 | High-strength deforming magnesium alloy containing Ti |
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| JPH06235041A (en) * | 1993-02-09 | 1994-08-23 | Nippon Steel Corp | Magnesium base alloy for casting excellent in heat resistance |
| JPH08134581A (en) * | 1994-11-14 | 1996-05-28 | Mitsui Mining & Smelting Co Ltd | Production of magnesium alloy |
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| CN1614062A (en) * | 2004-09-29 | 2005-05-11 | 上海交通大学 | High-strength deforming magnesium alloy containing Ti |
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| Title |
|---|
| The formability of a thin sheet of Mg-8.5Li-1Zn alloy;H. Takuda et al;《Journal of Materials Processing Technology》;20001231;第101卷;第281页 * |
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