CN101440438B - Method for thinning CaMgSn phase in Mg-Sn-Ca magnesium alloy by adding Ce - Google Patents
Method for thinning CaMgSn phase in Mg-Sn-Ca magnesium alloy by adding Ce Download PDFInfo
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- CN101440438B CN101440438B CN2008102372145A CN200810237214A CN101440438B CN 101440438 B CN101440438 B CN 101440438B CN 2008102372145 A CN2008102372145 A CN 2008102372145A CN 200810237214 A CN200810237214 A CN 200810237214A CN 101440438 B CN101440438 B CN 101440438B
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Abstract
The invention relates to a method for thinning a CaMgSn phase in Mg-Sn-Ca series magnesium alloy by adding Ce, which is achieved through adding the rare-earth element Ce. The method comprises the following steps: under protection of fusing agent or gas, blending and melting the Mg-Sn-Ca magnesium alloy according to corresponding component proportion; and heating the magnesium alloy to between 720and 740 DEG C, and then adding Mg-Ce middle alloy into the magnesium alloy, wherein the adding amount of Mg is 29 weight percent, and the adding amount of Ce is 0.5 to 1.5 weight percent of total weight of the furnace materials. The method can thin the crude CaMgSn phase in the Mg-Sn-Ca series magnesium alloy, and improves performance of the Mg-Sn-Ca series magnesium alloy, so as to accelerate industrialized application process of the series magnesium alloy.
Description
Technical field:
What the present invention relates to is the method and the process for refining of CaMgSn phase in a kind of Ce of adding refinement Mg-Sn-Ca series magnesium alloy, belongs to class of metal materials and field of metallurgy.
Background technology:
Magnesium alloy is as the commercial metal engineering structured material of light-weight, falls because of it has light specific gravity, specific tenacity specific rigidity height, damping vibration attenuation that dry ability is strong, liquid condition shaping superior performance and be easy to advantage such as recycling, is described as 21 century " green structured material ".But at present because the high-temperature creep resistance of existing magnesium alloy is poor, the long term operation temperature can not surpass 120 ℃, makes it can't be used for making to the demanding vehicle transmission parts of high temperature creep property, has therefore greatly hindered the further application of magnesium alloy.Also just because of like this, both at home and abroad given great attention with the research and development of heat resistance magnesium alloy, and serial heat resistance magnesium alloy such as Mg-Al-Si, Mg-Al-RE, Mg-Al-Ca, Mg-Al-Ca-RE, Mg-Al-Sr, Mg-Al-Sn, Mg-Zn-Al, Mg-Zn-RE, Mg-Zn-Si, Mg-Zn-Sn and Mg-Sn-Ca has been studied in trial-production successively for automobile with high-temperature creep resistance.Obtained manufacturing experimently in the heat resistance magnesium alloy of research at these, the Mg-Sn-Ca series magnesium alloy since have high-temperature behavior better, the advantage of aspect such as cost is lower and corrosion resistance is good, be considered to a kind of rising high temperature and creep resistance magnesium alloy of new generation.Compare with other heat resistance magnesium alloys, the heat-resisting strengthening mechanism of Mg-Sn-Ca series magnesium alloy mainly is to realize mutually at crystal boundary and intracrystalline formation CaMgSn with Ca by introducing low-cost alloying element Sn.Because CaMgSn is at quite stable below 300 ℃, thereby make the Mg-Sn-Ca series magnesium alloy have higher high-temperature creep resistance.Also see the advantage that the Mg-Sn-Ca series magnesium alloy is had just, thus recent years people be that the research and development of heat resistance magnesium alloy has given to pay close attention to widely and the attention of height to Mg-Sn-Ca, and this has been carried out positive research.Find by inquiry that as Huang etc. Mg-5Sn-2Ca and Mg-3Sn-2Ca ternary magnesium alloy can reach 82.5h and 358.4h respectively in the creep life under 135 ℃ and the 85MPa condition, its corresponding secondary creep speed is respectively 3.5 * 10
-8s
-1With 4.5 * 10
-9s
-1, demonstrated very high high-temperature creep resistance [Yuanding Huang, NorbertHort, Tarek Abu Leil1, Karl Ulrich Kainer and Yilin Liu, Key Engineering Materials, 2007,345-346:561-564].Although carried out certain research for the Mg-Sn-Ca series magnesium alloy both at home and abroad at present, its apply still because of the comprehensive mechanical property of alloy relatively poor etc. former thereby be subjected to a certain degree restriction.As mentioned above, the heat-resisting strengthening mechanism of Mg-Sn-Ca series magnesium alloy mainly is to realize mutually at crystal boundary and intracrystalline formation CaMgSn with Ca by introducing low-cost alloying element Sn, but it is thick to be compared by the CaMgSn that forms, and thick CaMgSn meets and becomes formation of crack and cause the creep-resistant property of alloy to descend.Therefore, refinement CaMgSn is considered to one of key factor of improving Mg-Sn-Ca series magnesium alloy creep-resistant property mutually.As everyone knows, alloying and/or microalloying are one of effective ways of second phase in refinement and/or the rotten engineering alloy.But up to now, the research about thick CaMgSn phase in alloying and/or the microalloying refinement Mg-Sn-Ca series magnesium alloy yet there are no bibliographical information.
Summary of the invention:
The objective of the invention is to influences this deficiency of alloy property at existing Mg-Sn-Ca series magnesium alloy mutually because of there being thick CaMgSn, propose to adopt the method for alloying and microalloying, comprise its process for refining, to reach thick CaMgSn phase this purpose in the refinement Mg-Sn-Ca series magnesium alloy, thereby improve the performance of Mg-Sn-Ca series magnesium alloy, accelerate the industrial applications process of this series magnesium alloy.
To achieve these goals, the present invention proposes the method for thick CaMgSn phase in a kind of Ce of adding refinement Mg-Sn-Ca series magnesium alloy, in the Mg-Sn-Ca series magnesium alloy, pass through to add the method for Mg-29wt.%Ce master alloy, come the thick CaMgSn phase in the refinement Mg-Sn-Ca series magnesium alloy, the adding of Ce simultaneously also has the effect of reinforced alloys concurrently except that above-mentioned refining effect is arranged.
The method that the present invention proposes is as follows: under flux or gas shield; the Mg-Sn-Ca magnesium alloy is warmed up to 720-740 ℃ after by the fusing of corresponding composition proportion; add the Mg-29%Ce master alloy then; the per-cent that the Ce add-on accounts for the furnace charge gross weight is 0.5-1.5wt.%; adding method: the Mg-29wt.%Ce master alloy was toasted 15-30 minute at 100-150 ℃; with pressing wooden dipper to be pressed into the alloy liquid level rapidly following about 2-6 minute, be warmed up to 720-760 ℃ after the stirring then, use C then
2Cl
6Refining agent refining treatment 5-10 minute, the refining back that finishes is stirred alloy melt and was left standstill 10-15 minute at 740 ℃, leaves standstill to drag for the alloy melt surface scum after finishing, and casts then.
Adopt the mechanism of present method refinement CaMgSn phase to be that the Ce element has the atomic radius (Ce:0.183nm bigger than the Sn element; Sn:0.141nm).When add Ce in the Mg-Sn-Ca magnesium alloy after because the solid solubility of Ce element in magnesium matrix is lower, can be in process of setting in the solid-liquid interface enrichment, thereby hinder the Sn atomic diffusion, and finally cause the refinement of CaMgSn phase.In addition, if the Ce content that adds higher (as 〉=1.0wt%), also can in alloy, form Mg
12The Ce phase is because Mg
12Ce phase thermostability is higher, and it can hinder the growth of CaMgSn phase in process of setting, thereby makes CaMgSn obtain further refinement mutually.
Description of drawings:
Figure 1A and Figure 1B are respectively the microstructure pictures of Mg-3Sn-2Ca and Mg-3Sn-2Ca-0.5Ce;
Fig. 2 A and Fig. 2 B are respectively the microstructure pictures of Mg-4Sn-1.5Ca and Mg-4Sn-1.5Ca-1.5Ce;
Fig. 3 A and Fig. 3 B are respectively the micro-metallographic structure pictures of Mg-5Sn-2.5Ca and Mg-5Sn-2.5Ca-1.0Ce.
Embodiment:
Below by three concrete embodiment technical scheme of the present invention and effect are further elaborated.
Embodiment 1: 2
#Under the flux protection, the Mg-3Sn-2Ca magnesium alloy is pressed 94.5wt.%Mg, be warmed up to 740 ℃ after the composition proportion fusing of 3wt.%Sn and 2wt.%Ca, add the Mg-29wt.%Ce master alloy.The add-on of Ce is the 0.5wt.% of furnace charge gross weight.Adding method: at 150 ℃ the Mg-29wt.%Ce master alloy was toasted 20 minutes, with pressing wooden dipper to be pressed into the alloy liquid level rapidly following about 3 minutes, be warmed up to 740 ℃ after the stirring then, use C then
2Cl
6Refining agent refining treatment 5 minutes, the refining back that finishes is stirred alloy melt and was left standstill 10 minutes at 740 ℃, leaves standstill to drag for the alloy melt surface scum after finishing, and casts into then in the metal mold that is preheating to 100-150 ℃.
Embodiment 2: 2
#Under the flux protection, the Mg-4Sn-1.5Ca-0.25Mn magnesium alloy is pressed 92.75wt.%Mg, 4wt.%Sn is warmed up to 740 ℃ after the composition proportion fusing of 1.5wt.%Ca and 0.25wt.%Mn, adds the Mg-29wt.%Ce master alloy.The Ce add-on is the 1.5wt.% of furnace charge gross weight, the adding method: at 150 ℃ the Mg-29wt.%Ce master alloy was toasted 20 minutes, with pressing wooden dipper to be pressed into the alloy liquid level rapidly following about 3 minutes, be warmed up to 740 ℃ after the stirring then, use C then
2Cl
6Refining agent refining treatment 5 minutes, the refining back that finishes is stirred alloy melt and was left standstill 10 minutes at 740 ℃, leaves standstill to drag for the alloy melt surface scum after finishing, and casts into then in the metal mold that is preheating to 100-150 ℃.
Embodiment 3: at CO
2Under the gas shield, the Mg-5Sn-2.5Ca magnesium alloy is pressed 91.5wt.%Mg, be warmed up to 740 ℃ after the composition proportion fusing of 5wt.%Sn and 2.5wt.%Ca, add the Mg-29wt.%Ce master alloy.The Ce add-on is the 1.0wt.% of furnace charge gross weight, the adding method: at 120 ℃ the Mg-29wt.%Ce master alloy was toasted 30 minutes, with pressing wooden dipper to be pressed into the alloy liquid level rapidly following about 3 minutes, be warmed up to 740 ℃ after the stirring then, use C then
2Cl
6Refining agent refining treatment 5 minutes, the refining back that finishes is stirred alloy melt and was left standstill 10 minutes at 740 ℃, leaves standstill to drag for the alloy melt surface scum after finishing, and casts into then in the metal mold that is preheating to 100-150 ℃.
With above three embodiment and do not add the composition of Mg-Sn-Ca magnesium alloy of Ce and fabric analysis and The performance test results as shown in table 1.Comparative analysis result from table 1 can see that behind a certain amount of Ce of adding, the mean sizes of CaMgSn phase obviously reduces in the alloy structure in the Mg-Sn-Ca series magnesium alloy.Simultaneously, the tensile property of alloy and creep property are improved.
Claims (2)
1. method that adds CaMgSn phase in the Ce refinement Mg-Sn-Ca series magnesium alloy, described method are to realize that by adding rare earth element ce the add-on of Ce accounts for the 0.5-1.5wt.% of furnace charge gross weight;
Described method is under flux or gas shield; the Mg-Sn-Ca magnesium alloy is warmed up to 720-740 ℃ after by the fusing of corresponding composition proportion; add the Mg-29wt.%Ce master alloy then; the Ce add-on accounts for the 0.5-1.5wt.% of furnace charge gross weight; adding method: the Mg-29wt.%Ce master alloy was toasted 15-30 minute at 100-150 ℃; with pressing wooden dipper to be pressed into the following 2-6 of alloy liquid level minute rapidly, be warmed up to 720-760 ℃ after the stirring then, use C then
2Cl
6Refining agent refining treatment 5-10 minute, the refining back that finishes is stirred alloy melt and was left standstill 10-15 minute at 740 ℃, leaves standstill to drag for the alloy melt surface scum after finishing, and casts then.
2. the method that adds CaMgSn phase in the Ce refinement Mg-Sn-Ca series magnesium alloy according to claim 1; it is characterized in that: described method is under flux or gas shield; the Mg-Sn-Ca magnesium alloy is warmed up to 740 ℃ after by the fusing of corresponding composition proportion; add the Mg-29wt.%Ce master alloy; the Ce add-on accounts for the 0.5-1.5wt.% of furnace charge gross weight; adding method: the Mg-29wt.%Ce master alloy was toasted 20 minutes at 150 ℃; then with pressing wooden dipper to be pressed into the alloy liquid level rapidly following 3 minutes; be warmed up to 740 ℃ after the stirring, use C then
2Cl
6Refining agent refining treatment 5 minutes, the refining back that finishes is stirred alloy melt and was left standstill 10 minutes at 740 ℃, leaves standstill to drag for the alloy melt surface scum after finishing, and casts then.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008102372145A CN101440438B (en) | 2008-12-23 | 2008-12-23 | Method for thinning CaMgSn phase in Mg-Sn-Ca magnesium alloy by adding Ce |
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| CN2008102372145A CN101440438B (en) | 2008-12-23 | 2008-12-23 | Method for thinning CaMgSn phase in Mg-Sn-Ca magnesium alloy by adding Ce |
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| CN101440438B true CN101440438B (en) | 2010-10-20 |
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| CN103233138B (en) * | 2013-04-28 | 2015-10-14 | 重庆大学 | Mg-Al series magnesium alloy grain-refining agent and preparation method thereof |
| CN103421998B (en) * | 2013-07-11 | 2015-09-02 | 孝义市东义镁业有限公司 | A kind of production technique of magnesium-rare earth |
| CN105420573B (en) * | 2015-12-31 | 2017-10-20 | 重庆大学 | High-damping Mg Sn Ce alloys |
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