CN111254334B - Flame-resistant magnesium alloy and preparation method thereof - Google Patents
Flame-resistant magnesium alloy and preparation method thereof Download PDFInfo
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- CN111254334B CN111254334B CN202010162678.5A CN202010162678A CN111254334B CN 111254334 B CN111254334 B CN 111254334B CN 202010162678 A CN202010162678 A CN 202010162678A CN 111254334 B CN111254334 B CN 111254334B
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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
- C22C23/02—Alloys based on magnesium with aluminium as the next major constituent
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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
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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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Abstract
The invention discloses a flame-retardant magnesium alloy, belonging to the field of magnesium-based alloy and alloying. The flame-retardant magnesium alloy is prepared by adding certain amounts of calcium and yttrium elements by a smelting metallurgy method on the basis of die-casting magnesium alloy. The application also provides a preparation method of the flame-retardant magnesium alloy, which comprises the steps of material preparation, preheating, feeding, smelting, refining and deslagging, slag removal and casting. The invention can obviously improve the ignition point of the die-casting magnesium alloy and improve the high-temperature oxidation resistance of the magnesium alloy while keeping the excellent die-casting manufacturability and low cost of the die-casting magnesium alloy, thereby improving the flame resistance and further expanding the application range of the magnesium alloy.
Description
Technical Field
The invention relates to the field of magnesium-based alloy and alloying, in particular to a flame-resistant magnesium alloy and a preparation method thereof.
Background
Magnesium alloy is regarded as the lightest engineering metal material, is known as the green engineering material of the 21 st century, and compared with the traditional material, the magnesium alloy has the performance advantages of being mainly reflected in light weight, high damping, electromagnetic interference resistance, easiness in recycling and the like, and is widely applied to the fields of aerospace, electronic communication, rail transit and the like.
However, the problem of poor high temperature oxidation resistance of magnesium alloys severely limits their wider range of applications. To solve this problem, a series of studies have been conducted by domestic and foreign scholars.
Tan et al added a trace amount (60ppm) of Be to AZ91 alloy, and the oxidation resistance thereof was remarkably improved. But Be has a larger problem of toxicity in addition to the problem of possibly causing grain coarsening of the as-cast structure of the magnesium alloy: beryllium compounds (such as beryllium oxide, beryllium fluoride, beryllium chloride, beryllium nitrate and the like) have high toxicity, particularly soluble beryllium compounds can cause pathological changes of organs or tissues to cause carcinogenesis, beryllium is listed as a carcinogen in a carcinogen list published by the world health organization, and therefore the industrial application prospect of Be is not good.
You et al investigated the surface concentration distribution of Mg-3Ca alloys using Auger electron spectroscopy. Mg and O form uniform MgO after being oxidized on pure magnesium at 440 ℃ and 500 ℃, Ca exists in the surface oxide of the Mg-3Ca alloy after being heated, and the surface layer consists of Mg oxide and Ca-containing oxide. Sakamoto et al, by forming a thin dense oxide film composed of Mg and Ca complex oxide on the surface of magnesium alloy melt, increased the ignition temperature of pure magnesium by 250 c, and the above examples show that Ca element is effective in improving the high temperature oxidation resistance of magnesium.
CN101512027A discloses a high strength flame retardant magnesium alloy, which is prepared by adding at least one substance selected from carbon, aluminum, niobium, silicon, tungsten, aluminum oxide, magnesium silicide and silicon carbide, and 0.5% calcium into a platelet-shaped magnesium alloy, and molding, sintering and plastic processing the mixture. When the solder is applied to solder, the solder has high weldability. But the process is complex, the processing flow is more, and the production cost is obviously improved.
CN106435316A discloses a flame-retardant magnesium-neodymium magnesium alloy and a casting method of a sand casting thereof, wherein the magnesium alloy comprises the following components in percentage by weight: 0.2-0.7% of Zn, 0.4-1.0% of Zr, 2.0-2.8% of Nd, 0-3.0% of Ce, 0-3.0% of La and the balance of Mg.
At present, about 90% of civil magnesium alloy parts are die-cast parts. The commonly used die-cast magnesium alloy is an Mg-Al system, has good casting process performance, low cost and excellent comprehensive mechanical property, but has poor oxidation resistance at high temperature, the ignition point of the alloy in the air is about 400-450 ℃, and the alloy is difficult to adapt to the requirement of products such as new energy automobile battery pack shells on high ignition point. Therefore, the development of a novel die-cast flame-resistant magnesium alloy is urgently needed.
However, most of the flame-resistant magnesium alloys reported in the prior literature are not die-casting alloys, are not suitable for die-casting production, and are a problem to be solved urgently.
Disclosure of Invention
The invention aims to provide a flame-retardant magnesium alloy which not only has better flame-retardant property, but also has good die-casting process property and is suitable for die-casting production.
The invention also aims to provide a preparation method of the flame-retardant magnesium alloy.
In order to realize the technical scheme, the invention provides the flame-resistant magnesium alloy, and a certain amount of calcium and yttrium elements are added by a smelting and metallurgy method on the basis of die-casting magnesium alloy.
Compared with the prior art, the flame-retardant magnesium alloy has the advantages that calcium and yttrium elements are introduced, the ignition point of the magnesium alloy can be obviously improved, the high-temperature oxidation resistance of the magnesium alloy is improved, and the flame-retardant magnesium alloy has better flame-retardant performance. And the flame resistance of the flame-resistant magnesium alloy is effectively improved through the synergistic effect of the calcium element and the yttrium element. In addition, the flame-retardant magnesium alloy has excellent die-casting manufacturability and low cost due to the die-casting magnesium alloy, and the application range of the magnesium alloy is further expanded. The flame-retardant magnesium alloy has advantages in products such as new energy automobile battery pack shells and the like.
Preferably, the contents of the calcium element and the yttrium element are respectively as follows: 0.8 to 1.2 weight percent of calcium and 0.5 to 1.5 weight percent of yttrium.
Preferably, the calcium element is added in the form of one or a mixture of two of simple substance metal calcium and magnesium-calcium intermediate alloy.
Preferably, the yttrium element is added in the form of one or a mixture of two of elementary yttrium metal and magnesium-yttrium master alloy.
Preferably, the die-cast magnesium alloy may be, but is not limited to, AM60 magnesium alloy, AM50 magnesium alloy.
Correspondingly, the application also provides a preparation method of the flame-retardant magnesium alloy, which comprises the following preparation steps:
(1) providing a die-casting magnesium alloy, a calcium element-containing substance and an yttrium element-containing substance;
(2) preheating;
(3) feeding;
(4) smelting;
(5) refining and deslagging;
(6) removing slag; and
(7) and (5) casting.
Preferably, the calcium content is 0.8-1.2 wt% and the yttrium content is 0.5-1.5 wt%.
Preferably, in the preheating step, the preheating temperature of the smelting resistance furnace is 300 ℃, and the preheating temperature of the furnace charge is 150 ℃.
Preferably, the smelting temperature is 700-.
Preferably, the refining deslagging adopts blowing refining and filtering, and a fusing agent is not used, so that the fusing agent is prevented from reacting with yttrium element.
Preferably, the calcium-containing substance is one or a mixture of two of simple substance metal calcium and magnesium-calcium intermediate alloy.
Preferably, the yttrium-containing substance is one or a mixture of two of elementary yttrium metal and magnesium-yttrium master alloy.
Has the advantages that:
the invention can obviously improve the ignition point of the die-casting magnesium alloy and improve the high-temperature oxidation resistance of the magnesium alloy while keeping the excellent die-casting manufacturability and low cost of the die-casting magnesium alloy, thereby improving the flame resistance and further expanding the application range of the magnesium alloy.
Detailed Description
The present invention will be described in further detail with reference to specific examples. The embodiments are only intended to illustrate the technical solution of the present invention and not to limit the technical solution, and after reading the present invention, a person skilled in the art should understand that the technical solution of the present invention is modified or substituted with equivalents without departing from the spirit and scope of the technical solution, and the present invention should be covered in the claims of the present invention.
Example 1
The preparation method of the flame-retardant magnesium alloy comprises the following steps:
(1) providing 1000g of AM60 magnesium alloy, 8g of elemental metal calcium and 5g of elemental metal yttrium;
(2) preheating, wherein the preheating temperature of a smelting resistance furnace is 300 ℃, and the preheating temperature of furnace burden is 150 ℃;
(3) feeding after preheating is finished;
(4) melting;
(5) refining and deslagging are carried out, wherein the method comprises air blowing refining and filtering, the smelting temperature is 700 ℃, and stirring is carried out in the smelting process so that calcium and yttrium are fully melted and uniformly distributed in magnesium liquid;
(6) removing slag;
(7) casting to prepare the flame-retardant magnesium alloy of the embodiment;
(8) sampling and inspecting, and testing, the ignition point of the alloy is 718 ℃.
Examples 2 to 6
The preparation methods of the flame-retardant magnesium alloys of examples 2 to 6 are substantially the same as those of example 1, except that the components and contents in the examples are different, and the specific differences are shown in Table 1.
Comparative example 1
The preparation method of the flame-retardant magnesium alloy in the comparative example is basically the same as that of the example 1, except that: in comparative example 1, the elemental metal calcium and the elemental metal yttrium are not contained, and specific reference is made to table 1.
Comparative example 2
The preparation method of the flame-retardant magnesium alloy in the comparative example is basically the same as that of the example 1, except that: in comparative example 2, no elemental yttrium metal is contained, and see table 1 for details.
Comparative example 3
The preparation method of the flame-retardant magnesium alloy in the comparative example is basically the same as that of the example 1, except that: in comparative example 3, no elemental yttrium metal is contained, and see table 1 for details.
The ignition point test was performed on the flame-resistant magnesium alloys prepared in examples 1 to 6 and comparative examples 1 to 3, and the test results are shown in table 1.
TABLE 1 ignition point test results of the flame-resistant magnesium alloys prepared in examples 1 to 6 and comparative examples 1 to 3
As can be seen from the data in table 1, the flame-retardant magnesium alloy of examples 1-6 of the present application has better flame-retardant performance than that of comparative examples 1-3, mainly because the flame-retardant magnesium alloy of the present application introduces calcium and yttrium elements, and the flame-retardant performance of the flame-retardant magnesium alloy is effectively improved by the synergistic effect of the calcium element and the yttrium element. In addition, the flame-retardant magnesium alloy has excellent die-casting manufacturability and low cost due to the die-casting magnesium alloy, and further expands the application range of the magnesium alloy. The flame-retardant magnesium alloy has advantages in products such as new energy automobile battery pack shells and the like.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles disclosed herein.
Claims (4)
1. The preparation method of the flame-retardant magnesium alloy is characterized by comprising the following preparation steps:
(1) providing raw materials: die casting an AM60 magnesium alloy, a calcium element-containing substance and an yttrium element-containing substance;
(2) preheating;
(3) feeding;
(4) smelting;
(5) refining and deslagging;
(6) removing slag; and
(7) the mixture is cast, and then the mixture is cast,
the calcium element is added in a form of magnesium-calcium intermediate alloy, the magnesium-calcium intermediate alloy is Mg-20Ca, the yttrium element is added in a form of magnesium-yttrium intermediate alloy, and the magnesium-yttrium intermediate alloy is Mg-20Y.
2. The method for preparing the flame-retardant magnesium alloy according to claim 1, wherein in the preheating step, the preheating temperature of the smelting resistance furnace is 300 ℃ and the preheating temperature of the furnace charge is 150 ℃.
3. The method for preparing the flame-resistant magnesium alloy as claimed in claim 1, wherein the melting temperature is 700 ℃ and 720 ℃, and stirring is performed during the melting process.
4. The method of claim 1, wherein the refining and deslagging are performed by blowing refining and filtering.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202010162678.5A CN111254334B (en) | 2020-03-10 | 2020-03-10 | Flame-resistant magnesium alloy and preparation method thereof |
| PCT/CN2021/074274 WO2021179835A1 (en) | 2020-03-10 | 2021-01-29 | Flame-resistant magnesium alloy and preparation method therefor |
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| CN202010162678.5A CN111254334B (en) | 2020-03-10 | 2020-03-10 | Flame-resistant magnesium alloy and preparation method thereof |
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| CN111254334B (en) * | 2020-03-10 | 2022-03-29 | 东莞宜安科技股份有限公司 | Flame-resistant magnesium alloy and preparation method thereof |
| CN113373398B (en) * | 2021-06-24 | 2023-04-28 | 重庆大学 | Flame-retardant magnesium alloy part |
| CN115572873A (en) * | 2022-11-07 | 2023-01-06 | 厦门大学 | Corrosion-resistant AM 60-based modified magnesium alloy and preparation method thereof |
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| CN100467647C (en) * | 2007-04-19 | 2009-03-11 | 沈阳工业大学 | High-strength heat-proof compression casting magnesium alloy and preparation method thereof |
| JP5252629B2 (en) * | 2008-08-06 | 2013-07-31 | 独立行政法人産業技術総合研究所 | Flame retardant magnesium alloy filler |
| KR101066536B1 (en) * | 2010-10-05 | 2011-09-21 | 한국기계연구원 | Ignition-proof magnesium alloy with excellent mechanical properties and method for manufacturing the ignition-proof magnesium alloy |
| KR101080164B1 (en) * | 2011-01-11 | 2011-11-07 | 한국기계연구원 | Ignition-proof magnesium alloy with excellent mechanical properties and method for manufacturing the ignition-proof magnesium alloy |
| CN102061415B (en) * | 2011-01-19 | 2012-05-09 | 创金美科技（深圳）有限公司 | Die cast magnesium alloy with heat cracking resistance and high fluidity |
| CN102899545A (en) * | 2012-10-17 | 2013-01-30 | 创金美科技（深圳）有限公司 | Rare earth magnesium alloy and preparation method thereof |
| CN103468987B (en) * | 2013-09-10 | 2015-04-01 | 河北工业大学 | Preparation method of flame-retardant magnesium alloy |
| CN103526092B (en) * | 2013-09-16 | 2016-05-04 | 上海交通大学 | Fire-retardant wrought magnesium alloy and preparation method thereof |
| CN108660348A (en) * | 2017-04-01 | 2018-10-16 | 比亚迪股份有限公司 | A kind of fire-retardant wrought magnesium alloy of high strength and low cost |
| CN109536798A (en) * | 2017-09-22 | 2019-03-29 | 比亚迪股份有限公司 | A kind of antiflaming magnesium alloy and its preparation method and application |
| CN108048720A (en) * | 2017-12-05 | 2018-05-18 | 上海航天精密机械研究所 | A kind of antiflaming magnesium alloy for adding yttrium, calcium and preparation method thereof |
| CN108315621A (en) * | 2018-01-08 | 2018-07-24 | 上海交通大学 | A kind of antiflaming magnesium alloy semi-solid rheological casting forming method |
| CN108385006A (en) * | 2018-03-19 | 2018-08-10 | 山西瑞格金属新材料有限公司 | High-strength anti-flaming diecast magnesium alloy and preparation method thereof |
| CN109881063B (en) * | 2019-04-17 | 2021-03-19 | 上海交通大学 | High-strength, high-toughness and high-modulus die-casting magnesium alloy and preparation method thereof |
| CN111254334B (en) * | 2020-03-10 | 2022-03-29 | 东莞宜安科技股份有限公司 | Flame-resistant magnesium alloy and preparation method thereof |
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