CN111485151A - Corrosion-resistant cast magnesium alloy and manufacturing method thereof - Google Patents
Corrosion-resistant cast magnesium alloy and manufacturing method thereof Download PDFInfo
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- CN111485151A CN111485151A CN202010433871.8A CN202010433871A CN111485151A CN 111485151 A CN111485151 A CN 111485151A CN 202010433871 A CN202010433871 A CN 202010433871A CN 111485151 A CN111485151 A CN 111485151A
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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
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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
Abstract
The invention provides a corrosion-resistant cast magnesium alloy which comprises the following components in percentage by weight: 5.0-8.0% of Sn, 3.0-5.0% of Si, 0.1-1.2% of Al, 0.004-0.05% of P, 0.1-2% of Fe, and the balance of magnesium and other elements; part of Si is added in the form of Si and Mg intermediate alloy, the other part of Si is added in the form of powder with the particle size of below 80um, and the weight ratio of the Si added in the form of Si and Mg intermediate alloy to the Si added in the form of powder is 1:1-3: 1. The magnesium alloy has excellent ductility and mechanical properties, has excellent corrosion resistance, and is suitable for being used in a humid environment. In addition, the formula has the advantages of cheap and easily-obtained raw materials and simple preparation process, and is suitable for large-scale industrial production.
Description
Technical Field
The invention relates to an alloy material, in particular to a corrosion-resistant casting magnesium alloy material and a manufacturing method thereof.
Background
China is rich in magnesium resources, and the domestic magnesium yield is at the top of the world. The magnesium alloy has high specific strength and rigidity, good damping performance and cutting performance, magnetic shielding performance and recyclability, so that the magnesium alloy is more and more widely applied to industry in recent years. China is rich in magnesium resources, and the domestic magnesium yield is at the top of the world. The magnesium alloy has high specific strength and rigidity, good damping performance and cutting performance, magnetic shielding performance and recyclability, so that the magnesium alloy is more and more widely applied to industry in recent years. Magnesium and its alloy are the lightest metal structure materials, and its density is 1/4 of steel only, 2/3 of aluminium, have specific strength, specific stiffness high, electromagnetic shielding performance is good, good heat dissipation, shock attenuation performance etc. many advantages. Since pure magnesium has too low strength (tensile yield strength in the as-cast state is only about 21 MPa) and is poor in castability, and alloying is the most effective method for improving mechanical properties and castability, magnesium alloy is used instead of pure magnesium in practical applications. In the existing magnesium alloy processing method, because the die casting process has the advantages of high production efficiency, low cost, high dimensional precision of prepared parts and components and the like, most of the existing magnesium alloy parts are prepared by the die casting process, and more than 90 percent of the magnesium alloy parts are die castings. The magnesium alloy is mainly applied to parts such as automobiles and 3C, and the like, and meets the requirement of industrial lightweight of automobiles and 3C. Since parts such as automobiles and 3C need to have higher strength, rigidity and plasticity, and also need to have wear resistance, corrosion resistance and good surface finish, and can be used under severe environmental conditions, the magnesium alloy as a structural material is a hot spot for research and application in industries such as automobiles and 3C. At present, the comprehensive properties of the cast magnesium alloy need to be further improved, particularly the strength, the rigidity and the corrosion resistance.
CN104278179A discloses a Si reinforced Mg-Sn cast magnesium alloy with excellent mechanical properties, but not optimized for other properties such as corrosion resistance.
Disclosure of Invention
In view of the above problems, the present invention provides a corrosion-resistant cast magnesium alloy which has excellent corrosion resistance while ensuring excellent ductility and mechanical properties, and is suitable for use in a humid environment. In addition, the formula has the advantages of cheap and easily-obtained raw materials and simple preparation process, and is suitable for large-scale industrial production.
The invention provides a corrosion-resistant cast magnesium alloy which comprises the following components in percentage by weight: 5.0-8.0% of Sn, 3.0-5.0% of Si, 0.1-1.2% of Al, 0.004-0.05% of P, 0.1-2% of Fe, and the balance of magnesium and other elements; part of Si is added in the form of Si and Mg intermediate alloy, the other part of Si is added in the form of powder with the particle size of below 80um, and the weight ratio of the Si added in the form of Si and Mg intermediate alloy to the Si added in the form of powder is 1:1-3: 1.
Preferably, the optimal alloy components are as follows: 6% Sn, 4% Si, 0.25% Al, 0.01% P, 0.5% Fe, the balance being magnesium and other elements.
Preferably, wherein P is added in the form of an Al and P master alloy.
Preferably, the other elements include oxygen, nitrogen, and other unavoidable impurities.
Preferably, Si added in powder form forms silicon dioxide and silicon nitride with oxygen and nitrogen elements at high temperature, and concentrates on the surface layer of the alloy.
Preferably, the weight ratio of the Si added therein in the form of an intermediate alloy of Si and Mg to the Si added in the form of powder is 2: 1.
The invention also provides a manufacturing method of the corrosion-resistant cast magnesium alloy, which comprises the following steps and conditions: (1) taking 5.0-8.0% of Sn, 3.0-5.0% of Si, 0.1-1.2% of Al, 0.004-0.05% of P, 0.1-2% of Fe and the balance of magnesium as raw materials according to the weight ratio, preheating an iron crucible to 120-250 ℃, putting the raw materials into the iron crucible, heating and heating to 720-770 ℃ for melting, wherein a part of Si elements are added into the alloy in the form of Mg-5% of Si intermediate alloy, P is added in the form of Al-3.5% of P intermediate alloy, and standing for 10-30 minutes after the alloy is completely melted; (2) when the temperature of the melt reaches 720-770 ℃, adding powder Si with the particle size of below 80um, uniformly stirring, after the intermediate alloy is completely melted and the alloy liquid is adjusted to 710-760 ℃, standing for 10-30 minutes, pouring into an iron mold, solidifying and forming to obtain the cast magnesium alloy, and introducing SF6 in the smelting process: n is a radical of2And carrying out anti-oxidation protection on the alloy liquid by using the mixed gas with the volume ratio of 200: 1.
Si added to the alloy in the form of an Mg-5% Si master alloy is Mg in the magnesium alloy2The Si phase exists in a thick Chinese character shape. The phase is hard, and can play a role in strengthening the phase, thereby improving the strength and the wear resistance of the material. However, this phase is brittle and has a large size, which causes embrittlement of the matrix. On the other hand, Si is added in the form of powder with the grain diameter less than 80um, Fe is used as a catalyst under the high temperature condition, and silicon dioxide or silicon nitride molecules are formed in the alloy with residual trace oxygen elements and nitrogen elements and move to the surface layer in the rolling processThe surface layer is formed with a protective layer to enhance the corrosion resistance, and impurities such as Ca, Ti and the like are easy to form eutectic with silicon, and the proper addition amount can promote sintering and improve the mechanical properties and the like of the product. The weight ratio of Si added in the form of Si and Mg master alloy to Si added in the form of powder is 1:1 to 3:1, and the addition of Si in this ratio range sufficiently achieves a balanced improvement in strength and corrosion resistance. The particle size of the added silicon powder is less than 80um, the smaller the particle size is, the better the particle size is, no limitation is caused, the small-particle silicon powder can effectively disperse Si in the alloy molten mass and tend to concentrate on the surface layer, and the corrosion resistance effect is fully improved.
On the basis of Mg-Sn-Si magnesium alloy, a certain amount of P is added through a proper process to carry out modification and refinement treatment on Si-containing phase so as to lead Mg to be modified and refined2The Si phase is changed from the original thick Chinese character shape into fine and granular phases and is distributed uniformly, thereby improving the mechanical properties and the like of the alloy.
Fe is used as an additive and can be used as a catalyst in the reaction process to promote the surface of a product to generate an SiO2 oxidation film, an iron silicon melting system is formed, nitrogen is dissolved in liquid FeSi2 to promote the generation of β -Si3N4, but the iron particles are too large or the content of the iron particles is too high, the defects such as air holes and the like can also appear in the product, and the performance is reduced, so that the Fe preferably contains 0.1-2% in consideration of comprehensive mechanical properties.
By adding a certain amount of P to the Mg-Sn-Si magnesium alloy, a part of P exists in a solid solution state, and the other part of P exists in the form of Al-P. Due to the existence of P and Al-P, the growth mode of the Chinese character-shaped Mg2Si phase is changed, and the phase of Mg2Si is promoted to be converted into particles. The volatile P component is added into the Mg-Sn-Si magnesium alloy in the form of Al-P intermediate alloy, the generated Al-P compound particles can be dispersed and distributed in the magnesium melt to form a large amount of heterogeneous cores, and the primary phase of Mg2Si grows up by taking the Al compound as a nucleation core, so that the Al-P intermediate alloy plays a role in modifying and refining the Mg2Si phase. Through the modification and refinement of P, Mg is effectively refined on the premise of not reducing the elastic modulus of the magnesium alloy2Size of Si, TiThe strength, hardness and other properties of the alloy are improved.
The invention discovers that the corrosion resistance and the mechanical property of the product can be improved with a synergistic effect by adding the two forms of Si with proper proportion and addition amount and adding the Fe and the P.
Detailed Description
The manufacturing method of the cast magnesium alloy of examples 1 to 5 and comparative examples 1 to 8 has the following steps and conditions: (1) preheating an iron crucible to 120-250 ℃ and putting the iron crucible into raw materials according to the weight ratio of the following table, heating and heating to 720-770 ℃ for melting, wherein a part of Si element is added into the alloy in the form of Mg-5% Si intermediate alloy, P is added in the form of Al-3.5% P intermediate alloy, and standing for 10-30 minutes after the alloy is completely melted; (2) when the temperature of the melt reaches 720-770 ℃, adding powder Si with the particle size of below 80um, uniformly stirring, after the intermediate alloy is completely melted and the alloy liquid is adjusted to 710-760 ℃, standing for 10-30 minutes, pouring into an iron mold, solidifying and forming to obtain the cast magnesium alloy, and introducing SF6 in the smelting process: n is a radical of2And carrying out anti-oxidation protection on the alloy liquid by using the mixed gas with the volume ratio of 200: 1.
| Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | Comparative example 5 | Comparative example 6 | Comparative example 7 | Comparative example 8 | |
| Sn | 6% | 6% | 6% | 6% | 6% | 6% | 6% | 6% | 6% | 6% | 6% | 6% | 6% |
| Added in the form of an Mg-5% Si master alloy Si | 2.67% | 2% | 3% | 2.67% | 2.67% | 4% | 2.67% | 0 | 3.33% | 2.67% | 2.67% | 0 | 2.67% |
| Powder Si | 1.37% | 2% | 1% | 1.37% | 1.37% | 0 | 1.37% | 4% | 0.67% | 1.37% | 1.37% | 0 | 1.37% |
| Ratio of two kinds of Si | 2:1 | 1:1 | 3:1 | 2:1 | 2:1 | - | 2:1 | 0 | 5:1 | 2:1 | 2:1 | - | 2:1 |
| Al | 0.25% | 0.25% | 0.25% | 0.25% | 0.25% | 0.25% | 0.25% | 0.25% | 0.25% | 0.25% | 0.25% | 0.25% | 0.25% |
| P | 0.01% | 0.01% | 0.01% | 0.01% | 0.01% | 0.01% | 0.01% | 0.01% | 0.01% | 0.01% | 0.01% | 0 | 0 |
| Fe | 0.5% | 0.5% | 0.5% | 0.1% | 2% | 0.5% | 0 | 0.5% | 0.5% | 4% | 0.05% | 0 | 0.5% |
Comparative example 9
The same procedure as in example 1 was repeated, except that the particle diameter of the Si powder was 200. mu.m.
After rolling into a sheet having a thickness of 0.1mm, a test piece of 3mm × 4mm × 40mm was prepared, and the breaking strength at each 10 points was measured by a four-point bending test in accordance with JIS R1601 (the test method was carried out in accordance with JIS R1601).
The metal tensile strength was tested according to ASTM E-8.
After 6h of testing in acid salt spray the 0.1mm thick panels produced were tested for tensile strength according to the GB T10125-1997 standard and the degree of reduction in tensile strength was calculated as a percentage in comparison with the non-corroded.
| Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | Comparative example 5 | Comparative example 6 | Comparative example 7 | Comparative example 8 | Comparative example 9 | |
| Brinell hardness/HB | 73 | 71 | 75 | 69 | 81 | 72 | 69 | 64 | 69 | 83 | 67 | 60 | 61 | 69 |
| Breaking strength/MPa | 367 | 342 | 364 | 361 | 336 | 364 | 359 | 323 | 351 | 304 | 359 | 282 | 312 | 305 |
| Tensile strength/MPa | 230 | 226 | 211 | 231 | 202 | 231 | 230 | 208 | 222 | 195 | 230 | 182 | 214 | 206 |
| Fracture strength after corrosion Reduce the content | 6% | 8% | 6% | 8% | 6% | 20% | 15% | 10% | 16% | 10% | 13% | 25% | 14% | 12% |
Comparing the above examples with comparative examples 1,3 and 4, it can be found that adding two forms of Si with appropriate proportion and addition amount can better improve the corrosion resistance and mechanical property of the product. In comparison with the comparative examples 2,5 and 6, the addition of Fe has a synergistic effect on Si, so that the mechanical property and the corrosion resistance can be effectively improved, and the balanced improvement of the properties of the Fe and the Si can be realized. The comparative examples and comparative example 8 have found that the addition of P has an excellent effect of improving corrosion resistance and performance. Compared with the comparative example 9, the grain size requirement of the powder Si is high, and the excessive grain size greatly reduces the mechanical property and obtains poor corrosion resistance. Comparing the example with the comparative example 7, it is found that the performance of the product is sharply reduced without adding P, Fe and Si, and comparing with other comparative examples, it is found that adding Si in two forms of proper proportion and addition amount and adding Fe and P together can improve the corrosion resistance and mechanical property of the product with synergistic effect.
Claims (7)
1. The corrosion-resistant cast magnesium alloy is characterized by comprising the following components in parts by weight: 5.0-8.0% of Sn, 3.0-5.0% of Si, 0.1-1.2% of Al, 0.004-0.05% of P, 0.1-2% of Fe, and the balance of magnesium and other elements; part of the Si is added in the form of Si and Mg master alloy, the other part of the Si is added in the form of powder with the grain diameter of below 80um, and the weight ratio of the Si added in the form of Si and Mg master alloy to the Si added in the form of powder is 1:1-3: 1.
2. The cast magnesium alloy of claim 1, wherein the optimum alloy composition is: 6% Sn, 4% Si, 0.25% Al, 0.01% P, 0.5% Fe, the balance being magnesium and other elements.
3. The cast magnesium alloy of claim 1, wherein P is added as an intermediate alloy of Al and P.
4. The cast magnesium alloy of claim 1, wherein the other elements include oxygen and nitrogen.
5. The cast magnesium alloy as claimed in claim 4, wherein Si added in powder form forms silicon dioxide and silicon nitride with oxygen and nitrogen elements at a high temperature and is concentrated on the surface layer of the alloy.
6. The cast magnesium alloy of claim 1, wherein the weight ratio of Si added as an intermediate alloy of Si and Mg to Si added as a powder is 2: 1.
7. A method for manufacturing corrosion-resistant cast magnesium alloy is characterized by comprising the following steps and conditions: (1) taking 5.0-8.0% of Sn, 3.0-5.0% of Si, 0.1-1.2% of Al, 0.004-0.05% of P, 0.1-2% of Fe and the balance of magnesium as raw materials according to the weight ratio, preheating an iron crucible to 120-250 ℃, putting the raw materials into the iron crucible, heating and heating to 720-770 ℃ for melting, wherein a part of Si elements are added into the alloy in the form of Mg-5% of Si intermediate alloy, P is added in the form of Al-3.5% of P intermediate alloy, and standing for 10-30 minutes after the alloy is completely melted; (2) when the temperature of the melt reaches 720-770 ℃, adding powder Si with the particle size of below 80um, uniformly stirring, after the intermediate alloy is completely melted and the alloy liquid is adjusted to 710-760 ℃, standing for 10-30 minutes, pouring into an iron mold, solidifying and forming to obtain the cast magnesium alloy, and introducing SF6 in the smelting process: n is a radical of2And carrying out anti-oxidation protection on the alloy liquid by using the mixed gas with the volume ratio of 200: 1.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104278179A (en) * | 2013-12-13 | 2015-01-14 | 济南大学 | Si-intensified Mg-Sn casting magnesium alloy material |
| CN107419149A (en) * | 2017-04-13 | 2017-12-01 | 济南大学 | A kind of Mg Sn Si Al P magnesium alloys of Al P intermediate alloys enhancing and preparation method thereof |
| CN107815574A (en) * | 2017-09-28 | 2018-03-20 | 江苏晶王新材料科技有限公司 | A kind of corrosion resistant magnesium alloy materials |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104278179A (en) * | 2013-12-13 | 2015-01-14 | 济南大学 | Si-intensified Mg-Sn casting magnesium alloy material |
| CN107419149A (en) * | 2017-04-13 | 2017-12-01 | 济南大学 | A kind of Mg Sn Si Al P magnesium alloys of Al P intermediate alloys enhancing and preparation method thereof |
| CN107815574A (en) * | 2017-09-28 | 2018-03-20 | 江苏晶王新材料科技有限公司 | A kind of corrosion resistant magnesium alloy materials |
Non-Patent Citations (1)
| Title |
|---|
| 邝生鲁: "《现代精细化工高新技术与产品合成工艺》", 31 December 1991 * |
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