CN114214549A - Rare earth-free low-cost high-plasticity magnesium alloy and preparation method thereof - Google Patents
Rare earth-free low-cost high-plasticity magnesium alloy and preparation method thereof Download PDFInfo
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- CN114214549A CN114214549A CN202111554071.2A CN202111554071A CN114214549A CN 114214549 A CN114214549 A CN 114214549A CN 202111554071 A CN202111554071 A CN 202111554071A CN 114214549 A CN114214549 A CN 114214549A
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C23/00—Alloys based on magnesium
- C22C23/04—Alloys based on magnesium with zinc or cadmium as the next major constituent
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21C—MANUFACTURE OF METAL SHEETS, WIRE, RODS, TUBES OR PROFILES, OTHERWISE THAN BY ROLLING; AUXILIARY OPERATIONS USED IN CONNECTION WITH METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL
- B21C23/00—Extruding metal; Impact extrusion
- B21C23/002—Extruding materials of special alloys so far as the composition of the alloy requires or permits special extruding methods of sequences
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
- C22C1/03—Making non-ferrous alloys by melting using master alloys
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/06—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of magnesium or alloys based thereon
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Abstract
The invention discloses a rare earth-free low-cost high-plasticity magnesium alloy and a preparation method thereof, wherein the magnesium alloy comprises the following components in percentage by mass: 1-2% of Zn, 0-0.5% of Ca, and the balance of Mg and inevitable impurities, wherein the content of Ca is not 0. Through the scientific and reasonable formula design of the Zn and Ca alloy elements, the content of the Zn and Ca alloy elements is low, the Zn and Ca alloy elements exist in a solid solution form, no second phase is formed, and the Co-segregation occurs in the crystal boundary, thereby being beneficial to the coordination deformation of the crystal boundary. The elongation after fracture of the alloy can reach 43 percent, the room temperature plasticity is high, the alloy does not contain rare earth elements, the cost of the alloy is low, the process is simple, the industrial large-scale production is easy to realize, the room temperature plasticity of the magnesium alloy is greatly improved at lower cost, and the application prospect is good.
Description
Technical Field
The invention relates to the technical field of metal materials, in particular to a rare earth-free low-cost high-plasticity magnesium alloy and a preparation method thereof.
Background
The magnesium alloy is used as the lightest metal structure material, has the advantages of high specific strength and specific stiffness, good damping performance, environmental protection and the like, and has great application potential in the fields of electronic communication, automobile industry and the like. However, the close-packed hexagonal structure of the magnesium alloy makes it difficult to start more slip system coordinated deformation in the plastic deformation process, the slip system is less at room temperature, the strength is low, and the plasticity is poor, so that the plastic processing forming capability at room temperature and low temperature is insufficient, therefore, the plastic forming can be performed at high temperature or medium temperature usually, the production and application cost of the magnesium alloy deformation material is high, and the industrial application is not facilitated.
Research shows that the rare earth element has the effect of weakening magnesium alloy texture and can obviously improve the room temperature plasticity and room temperature forming performance of deformation materials such as magnesium alloy plates, extrusion materials and the like. For example, Chinese patent publication No. CN103667842 discloses a high-plasticity magnesium alloy sheet containing rare earth and a hot rolling process thereof. However, the current rare earth has higher market price, and the alloy cost is still higher even if the content of the rare earth is reduced, so that the large-scale application of the rare earth magnesium alloy deformation material is limited. Therefore, the development of the low-cost and high-plasticity magnesium alloy deformation material without rare earth elements has important significance for expanding the application scale of magnesium alloy deformation materials, such as plates, bars, pipes, sections and wires.
Disclosure of Invention
Aiming at the defects of the prior art, the technical problems to be solved by the invention are as follows: the invention aims to provide a rare earth-free low-cost high-plasticity magnesium alloy and a preparation method thereof, which solve the problems that the magnesium alloy has poor processability, so that the production and application costs of a magnesium alloy deformed material are high, and the magnesium alloy deformed material is not beneficial to industrial application.
In order to solve the technical problems, the invention adopts the following technical scheme: a rare earth-free low-cost high-plasticity magnesium alloy comprises the following components in percentage by mass: 1-2% of Zn, 0-0.5% of Ca, and the balance of Mg and inevitable impurities, wherein the content of Ca is not 0.
Preferably, the magnesium alloy consists of the following components in percentage by mass: 1-2% of Zn, 0.1-0.5% of Ca, and the balance of Mg and inevitable impurities.
Preferably, the magnesium alloy consists of the following components in percentage by mass: 1% of Zn, 0.1% of Ca, and the balance of Mg and inevitable impurities.
Preferably, the composition comprises the following components in percentage by mass: zn 2%, Ca 0.5%, and Mg and inevitable impurities as the rest.
The invention also aims to provide a preparation method of the rare earth-free low-cost high-plasticity magnesium alloy, which comprises the following steps:
1) smelting: heating a pure magnesium ingot to 720-730 ℃ in a protective atmosphere, preserving heat for 10-15 min, then adding pure Zn and Mg-30Ca intermediate alloy, fully stirring and smelting, and fishing dross on the surface of a melt after the alloy is completely melted;
2) pouring: when the temperature of the melt is reduced to 710-720 ℃, pouring the melt into a mold to be cast into an ingot, taking out the ingot from the mold after the ingot is solidified, and putting the ingot into cold water to be cooled to obtain a sample;
3) and carrying out homogenization treatment and hot extrusion treatment on the sample to obtain the high-plasticity magnesium alloy.
Preferably, the protective atmosphere is CO2And SF6According to the volume ratio of 99: 1, and (2) forming a mixed gas.
Preferably, the homogenization treatment is carried out at 470-490 ℃ for 17-19 h.
Preferably, the temperature during hot extrusion is 360-380 ℃.
Preferably, the speed during hot extrusion is 1-2 mm/min, and the extrusion ratio is 28-30: 1.
compared with the prior art, the invention has the following beneficial effects:
1. according to the invention, through scientific and reasonable formula design of Zn and Ca alloy elements, the alloy elements with low Zn and Ca contents exist in a solid solution form, and no second phase is formed basically, so that the room-temperature plasticity of the second phase is prevented from being degraded. Furthermore, the co-segregation of Zn and Ca added in the crystal boundary enhances the solid solution dragging effect, inhibits the dynamic recrystallization in the hot extrusion process, hinders the grain growth and achieves the effect of grain refinement; in addition, in the process of tensile deformation of the alloy, as the atomic radius of Zn is smaller than that of Mg and the atomic radius of Ca is larger than that of Mg, the Zn and the Ca coordinate grain boundary strain together, so that the grain boundary plastic deformation capacity is improved, and the magnesium alloy has high plasticity.
2. The magnesium alloy obtained by the invention has room temperature mechanical property test, the elongation after fracture can reach 43 percent, and the room temperature plasticity is high. The alloy does not contain rare earth elements, the cost of the alloy is low, the process is simple, the adopted equipment such as a smelting furnace, a hot extrusion machine and the like are conventional general equipment, the industrial large-scale production is easy, and the invention realizes the low cost and greatly improves the room temperature plasticity of the magnesium alloy. In addition, the higher plasticity is beneficial to further large deformation and cold processing, and the invention has good application prospect.
Drawings
FIG. 1 is a microstructure diagram of a magnesium alloy prepared in example 1.
FIG. 2 is a diagram showing the segregation of the alloying elements in the grain boundaries of the magnesium alloy prepared in example 1.
FIG. 3 is a graph of room temperature tensile stress strain at ED, 45 ℃ and TD directions for the magnesium alloy sheet prepared in example 1.
Detailed Description
The present invention will be described in further detail with reference to examples.
Preparation method of rare earth-free low-cost high-plasticity magnesium alloy
Example 1
(1) Preparing materials: the magnesium alloy comprises the following components in percentage by mass: 1% of Zn, 0.1% of Ca, and the balance of Mg and inevitable impurities, wherein the raw materials comprise Mg with the purity of 99.99 wt.%, Zn with the purity of 99.9 wt.%, and Mg-30 wt.% Ca master alloy.
(2) Smelting: polishing a raw material steel brush, removing surface oxide skin, drying at 150-200 ℃, and performing SF (sulfur hexafluoride) treatment at a volume ratio of 1:1006And CO2Melting a pure magnesium ingot under the protective atmosphere, then preserving the temperature of molten magnesium at 720-730 ℃ for 10-15 min, sequentially adding pure Zn and Mg-30Ca intermediate alloy, and stirring and fishing slag after the alloy is completely melted.
(3) Pouring: and when the temperature of the melt is reduced to 710-720 ℃, pouring the melt into a mold to be cast into an ingot, taking out the ingot from the mold after the ingot is solidified, and putting the ingot into cold water for cooling to obtain a sample.
(4) And (3) heat treatment: the samples were subjected to a homogenization heat treatment at 480 ℃ for 18 h.
(5) Extruding: carrying out hot extrusion on the homogenized sample at 370 ℃, wherein the extrusion speed is 2mm/min, and the extrusion ratio is 30: 1, obtaining the high-plasticity magnesium alloy.
The experimental procedures of the following examples and comparative examples were the same as those of example 1 except that the alloy composition was different, as shown in Table 1.
TABLE 1
| Zn(wt％) | Ca(wt％) | |
| Example 1 | 1 | 0.1 |
| Example 2 | 2 | 0.5 |
| Comparative example 1 | 1 | 0 |
| Comparative example 2 | 2 | 0 |
| Comparative example 3 | 0 | 0.1 |
| Comparative example 4 | 0 | 0.5 |
| Comparative example 5 | 3 | 0.5 |
| Comparative example 6 | 0.3 | 0.1 |
Second, performance detection
1. The magnesium alloy prepared in example 1 was subjected to scanning electron microscopic structure observation, and the result is shown in fig. 1.
As can be seen from fig. 1, Zn and Ca elements exist in the matrix in the form of solid solution, and no micron-sized second phase is substantially formed.
2. The magnesium alloy prepared in example 1 was subjected to transmission electron microscopic structure observation, and the result is shown in fig. 2.
As can be seen from FIG. 2, Zn and Ca elements exist in the matrix in a solid solution form, and are co-segregated at grain boundaries, which facilitates the coordinated deformation of the grain boundaries.
3. The magnesium alloy sheet prepared in example 1 was tested for tensile stress at room temperature in the ED (extrusion outflow direction), 45 ℃ and TD (longitudinal direction of extrusion) directions, and the results are shown in FIG. 3.
As can be seen from figure 3, the alloy shows better plasticity when being stretched along ED, 45 degrees and TD three directions, the average elongation after fracture reaches 43 percent, and meanwhile, the yield strength is kept about 150MPa, and the alloy has better comprehensive mechanical properties.
4. The magnesium alloys obtained in examples 1 to 2 and comparative examples 1 to 6 were subjected to mechanical property tests, and the results of the tests on yield strength (YS, MPa), tensile strength (UTS, MPa) and elongation (EL,%) are shown in table 2.
TABLE 2
| YS | UTS | EL | |
| Example 1 | 149.9 | 235 | 43.4 |
| Example 2 | 145.5 | 241.6 | 38.8 |
| Comparative example 1 | 112.2 | 209.9 | 19.1 |
| Comparative example 2 | 109.4 | 217.9 | 29.5 |
| Comparative example 3 | 106.8 | 207.3 | 21.6 |
| Comparative example 4 | 166 | 254.8 | 23.1 |
| Comparative example 5 | 156.3 | 255.2 | 30.2 |
| Comparative example 6 | 95.4 | 105.6 | 32.1 |
As can be seen from Table 2, the elongation of the alloy of the present invention is greatly improved without affecting the yield strength and tensile strength as compared with the comparative example. This is because Zn and Ca exist in the form of solid solution at this time, no second phase is formed, plasticity deterioration caused by stress concentration in the vicinity of the second phase in the plastic deformation process is reduced, and a solid solution strengthening effect is exerted; on the other hand, the method promotes the co-segregation of Zn and Ca elements in the grain boundary, and is beneficial to the coordinated deformation of the grain boundary so as to improve the plasticity. While too high Zn and Ca elements will form more second phases, which are not good for deformation, while too low Zn and Ca elements will weaken the effect of solid solution strengthening and can not maintain better strength. Therefore, the alloy has higher plasticity, can ensure higher strength and is beneficial to further large deformation and cold working.
The above description is only exemplary of the present invention and should not be taken as limiting, and any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (9)
1. The rare earth-free low-cost high-plasticity magnesium alloy is characterized by comprising the following components in percentage by mass: 1-2% of Zn, 0-0.5% of Ca, and the balance of Mg and inevitable impurities, wherein the content of Ca is not 0.
2. The rare earth-free low-cost high-plasticity magnesium alloy according to claim 1, which is prepared from the following components in percentage by mass: 1-2% of Zn, 0.1-0.5% of Ca, and the balance of Mg and inevitable impurities.
3. The rare earth-free low-cost high-plasticity magnesium alloy according to claim 1, which is prepared from the following components in percentage by mass: 1% of Zn, 0.1% of Ca, and the balance of Mg and inevitable impurities.
4. The rare earth-free low-cost high-plasticity magnesium alloy according to claim 1, which is prepared from the following components in percentage by mass: zn 2%, Ca 0.5%, and Mg and inevitable impurities as the rest.
5. A method for preparing a rare earth-free low-cost high-plasticity magnesium alloy according to any one of claims 1 to 4, which is characterized by comprising the following steps:
1) smelting: heating a pure magnesium ingot to 720-730 ℃ in a protective atmosphere, preserving heat for 10-15 min, then adding pure Zn and Mg-30Ca intermediate alloy, fully stirring and smelting, and fishing dross on the surface of a melt after the alloy is completely melted;
2) pouring: when the temperature of the melt is reduced to 710-720 ℃, pouring the melt into a mold to be cast into an ingot, taking out the ingot from the mold after the ingot is solidified, and putting the ingot into cold water to be cooled to obtain a sample;
3) and (3) carrying out homogenization treatment and hot extrusion treatment on the sample in sequence to obtain the high-plasticity magnesium alloy.
6. The method of claim 5, wherein the protective atmosphere is CO2And SF6According to the volume ratio of 99: 1, and (2) forming a mixed gas.
7. The method for preparing the rare earth-free low-cost high-plasticity magnesium alloy according to claim 5, wherein the homogenization treatment is carried out at 470-490 ℃ for 17-19 h.
8. The method for preparing the rare earth-free low-cost high-plasticity magnesium alloy according to claim 5, wherein the temperature during hot extrusion is 360-380 ℃.
9. The method for preparing the rare earth-free low-cost high-plasticity magnesium alloy according to claim 5, wherein the hot extrusion speed is 1-2 mm/min, and the extrusion ratio is 28-30: 1.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2298944A1 (en) * | 2009-09-21 | 2011-03-23 | Korean Institute of Industrial Technology | Magnesium master alloy, manufacturing method thereof, metal alloy using the same, and method of manufacturing the metal alloy |
| CN103243251A (en) * | 2013-05-21 | 2013-08-14 | 上海交通大学医学院附属上海儿童医学中心 | Magnesium alloy and smelting and heat treatment processes thereof |
| CN106676357A (en) * | 2017-01-19 | 2017-05-17 | 重庆大学 | High-plasticity magnesium alloy and preparation method thereof |
| CN109161704A (en) * | 2018-09-18 | 2019-01-08 | 东北大学 | A kind of molten method of completing the square of Mg-Zn-Ca alloy |
-
2021
- 2021-12-17 CN CN202111554071.2A patent/CN114214549A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2298944A1 (en) * | 2009-09-21 | 2011-03-23 | Korean Institute of Industrial Technology | Magnesium master alloy, manufacturing method thereof, metal alloy using the same, and method of manufacturing the metal alloy |
| CN103243251A (en) * | 2013-05-21 | 2013-08-14 | 上海交通大学医学院附属上海儿童医学中心 | Magnesium alloy and smelting and heat treatment processes thereof |
| CN106676357A (en) * | 2017-01-19 | 2017-05-17 | 重庆大学 | High-plasticity magnesium alloy and preparation method thereof |
| CN109161704A (en) * | 2018-09-18 | 2019-01-08 | 东北大学 | A kind of molten method of completing the square of Mg-Zn-Ca alloy |
Non-Patent Citations (2)
| Title |
|---|
| BAOPING ZHANG ET AL: ""Effects of calcium on texture and mechanical properties of hot-extruded Mg–Zn–Ca alloys"", 《MATERIALS SCIENCE AND ENGINEERING A》 * |
| 千野靖正等: ""Mg-Zn-Ca合金圧延材の室温張出し成形性に及ぼす亜鉛濃度の影響"", 《日本金属学会誌》 * |
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