CN1952196A - Mg-Al-Si-Mn-Ca alloy and method for preparing same - Google Patents
Mg-Al-Si-Mn-Ca alloy and method for preparing same Download PDFInfo
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- CN1952196A CN1952196A CN 200510048417 CN200510048417A CN1952196A CN 1952196 A CN1952196 A CN 1952196A CN 200510048417 CN200510048417 CN 200510048417 CN 200510048417 A CN200510048417 A CN 200510048417A CN 1952196 A CN1952196 A CN 1952196A
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Abstract
This invention involves a Mg-Al-Si-Mn-Ca alloy and its preparation method. The alloy consists of the following components (by wt. ratio): Al 5.0-7.0%, Mn 0.2-0.5%, Zn<=0.2%, Si 0.5-2.0%, Ca<=0.3%, magnesium as the rest. Its preparation method contains: introducing protective gas into the furnace, heating to 400-500 DEG C, adding preheated the pure aluminum ingots, pure magnesium ingots, raising the temperature to 680-720DEG C,adding preheated aluminium-mangnaese interalloy after the furnace materials melting, adding pure Zn, stirring uniformly after melting; raising the furnace temperature to 760-780DEG C, adding silicocalcium stirring uniformly, standing for 25-40 minutes, cooling down to 690-720DEG C, preheating the cast form, casting after the temperature of the magnesium alloy liquid dropping down to 690-720DEG C. In the invention Si, Ca alloy elements are added into the Al-Mg alloy, which improves the microstructure of the alloy, thereby enhances the strength, plastic hardness and toughness of the alloys.
Description
Technical field
The invention belongs to magnesium alloy and preparation method thereof, be specifically related to the Mg-Al-Si-Mn-Ca Alloy And Preparation Method.
Background technology
Magnesium alloy is the lightest so far structural metallic materials, because it has higher specific tenacity, specific rigidity and bigger damping coefficient, therefore, is widely used in industries such as automobile, space flight, communication and computer.Most widely used magnesium alloy is a Mg-Al series at present, as AZ91 and Mg-Al system.But the intensity of this class alloy, toughness and high-temperature behavior all do not reach requirement aspect a lot, thereby have limited Application of Magnesium.In order to improve the performance of magnesium alloy, to satisfy the application of each side, many researchists once attempted adding alloying element in existing alloy, improved its performance.For example people such as the Ceng Xiaoqin of Shanghai Communications University, Peng Liming have studied the influence (Cao Xing of rare earth adding Mg-Al system back to alloy structure and mechanical property, Peng Liming, Ceng Xiaoqin etc., mechanical engineering material, 27 volume the 2nd phases (2003): the 21-24 page or leaf), after adding rare earth, form acicular rare earth in the alloy and isolate matrix mutually easily, and add the cost that rare earth element has improved magnesium alloy.Shanghai Communications University and the Yuan Guang of Southeast China University silver etc. have been studied Sb, and (Yuan Guang silver Sun Yang is kind, and the China YouSe Acta Metallurgica Sinica 9 that waits is rolled up 4 phases (1999): the 779-784 page or leaf to the tissue of Mg-9Al and Mg-Al-Zn-Si and Effect on Performance; Full 38 volume 10 phases (2002) of equality Acta Metallurgica Sinica of Yuan Guang silver Liu: the 1101-1108 page or leaf), add that the mechanical property of alloy is greatly improved behind the Sb, but the density of Sb is bigger, and Sb is rare elements, improved the cost of alloy after the adding.
Adopt discontinuous cheaply particle or fibre-reinforced magnesium alloy materials in addition, have higher specific tenacity, specific rigidity, premium properties such as high temperature resistant, wear-resistant, be subject to people's attention gradually.Adopt in-situ reaction to obtain the magnesium alloy materials of spontaneous particle wild phase, because wild phase generates at the matrix internal reaction, have that size is little, clean pollution-free, the Heat stability is good in interface,, advantage such as preparation cost low good with the matrix consistency, become an important development direction in the Study for Magnesium Composites.Adopt high strength, high-modulus, low density wild phase can improve the ambient temperature mechanical properties of magnesium alloy, and significantly improve the hot strength and the high temperature creep property of magnesium alloy.As Mg
2The Si phase, its fusing point height (1085 ℃), density is low by (1.99 * 103Kg/m3), hardness height (4500GPa), thermal expansivity is low, and (CTE=7.5 * 10-6K-1) and Young's modulus height (120GPa) can improve the thermostability and the creep-resistant property of material in order to reinforced magnesium alloy.Si has studied to AZ91 magnesium alloy tissue and Effect on Performance (Huang Zhenghua, 6 phases of material engineering such as Guo Xuefeng (2004): the 28-32 page or leaf), behind the adding element silicon, formed thick Chinese character shape Mg in the alloy in Xi'an University of Technology
2The Si phase reduces alloy mechanical property significantly.Ca has studied in Southeast China University, Si is compound, and (the firm Sun Yang of Min Xue is kind, and the Southeast China University's journal 32 that waits is rolled up 3 phases (2002): the 409-414 page or leaf) to AZ91 alloy organizing and Effect on Performance, Ca has studied in neat Xinhua of Zhengzhou University etc., the Si composite alloying to Mg-Al be alloy organizing and Effect on Performance (the compound adding of .Ca, Si such as neat Xinhua is to Mg-Al series magnesium alloy tissue and Effect on Performance. light alloy processing technology .2004,32 (8): 48-51.) studies show that the thick Mg of Ca to formation
2Si has metamorphism mutually, makes to change the polygon-shaped of rule into, thereby improves the performance of alloy.But this combined microalloying need add master alloy twice, and promptly operation is more, thereby cost is higher.
Industrial silicocalcium is to smelt high-quality steel ideal composite deoxidant, desulfuration agent; Can prevent ladle mouth dross, replace aluminium to carry out the final deoxygenation of continuous casting steel molten steel; The silicocalcium pulvis has become the main pulvis that steel spraying powder is used, and can change the form of steel inclusion, thereby increases substantially the castability and the mechanical property of steel.Silicocalcium is also as nucleating agent and additive in the Cast Iron Production.Silicocalcium has become indispensable alloy material in high-quality smelting steel and the Cast Iron Production, yet there are no report in the document at home and abroad but silicocalcium is applied to the magnesium alloy field.
Summary of the invention
The purpose of this invention is to provide a kind of Mg-Al-Si-Mn-Ca alloy, by in containing aluminum magnesium alloy, adding Si, Ca alloying element, in the magnesium alloy fusion-casting process by being reflected on its matrix spontaneous particle wild phase improving the microtexture of alloy, thereby improve intensity, hardness and the plasticity and toughness of such alloy.
The present invention also aims to provide the method for preparing the Mg-Al-Si-Mn-Ca alloy.
For achieving the above object, the present invention adopts following technical scheme: the Mg-Al-Si-Mn-Ca alloy is made up of the component of following weight per-cent: Al 5.0～7.0%, Mn 0.2～0.5%, Zn≤0.2%, Si 0.5～2.0%, Ca≤0.3%, surplus are magnesium.
The process for preparing above-mentioned Mg-Al-Si-Mn-Ca alloy may further comprise the steps:
1. in smelting furnace, feed shielding gas in advance, to be heated to 400～500 ℃, add and calculate fine aluminium ingot, the pure magnesium ingot that has passed through preheating in proportion;
2. furnace temperature is risen to 680～720 ℃, the furnace charge that is housed to all after the fusing, adds the aluminium manganese master alloy of preheating, treat the master alloy fusing after, add the pure Zn of weight ratio≤0.2% at last, after the fusing alloy liquid is stirred;
3. furnace temperature being warming up to 760～780 ℃, is the silicocalcium adding alloy liquid of 0.5～2.0% (calculating with Si) with weight ratio, stirs, and removes surperficial slag;
4. after stirring, left standstill 25～40 minutes, cool to 690～720 ℃ then;
5. casting mold is preheated to 220～260 ℃, pours into a mould when the temperature for the treatment of liquid magnesium alloy is reduced to 690～720 ℃.Promptly get the Mg-Al-Si-Mn-Ca alloy that contains spontaneous particle wild phase after the ingot casting cooling.
In order to eliminate the ununiformity such as component segregation that cause in castingprocesses, cast back ingot casting will be incubated 6～20 hours down at 390～420 ℃ and carry out the homogenizing processing, carries out artificial aging at 200～210 ℃ subsequently and handles.
The shielding gas that is fed is CO
2: SF
6=6～10: 1.
In charging and melting process, find that magnesium liquid exposes and when burning, should suitably increase air flow it is blown out.
Take the slag on liquid magnesium alloy surface during cast off, cast gate near casting mold, blows to fluid surface with shielding gas in the casting process as far as possible.
The present invention is to introduce Si and Ca element in the alloy by directly join Mg-Al with silicocalcium, thereby directly producing interpolation Si makes Ca play metamorphic purpose again simultaneously, and in the silicocalcium a small amount of Al itself be exactly Mg-Al be the matrix composition of alloy, influence is little, and a spot of C also can play the effect of grain refining.The present invention is Mg by reacting the spontaneous particle wild phase that the little and disperse of direct acquisition size distributes on magnesium alloy substrate
2Si, alloy grain refinement, second-phase dispersion distribute, and performances such as tensile strength, hardness, elongation, ballistic work equal strength and plasticity and toughness have a more substantial increase, and corrosion resistance nature and castability also increase.Add silicocalcium also improved the flowability of magnesium alloy and wherein inclusion morphology etc. such as its effect in steel.Simultaneously, the present invention prepares by the mode that adds silicocalcium and contains aluminum magnesium alloy and overcome the deficiency that adds silicon, calcium in the master alloy mode, and with Al-Ca, master alloy modes such as Mg-Si or Mg-Ca generated particle and strengthen Mg in magnesium alloy with in the past
2The technology of Si phase is compared, and founding operation of the present invention reduces, and is simple to operate, thereby saved the alloy production cost.
Fig. 1 a, 1b are that Mg-Al is the as-cast microstructure photo that adds the silicocalcium front and back in the alloy, behind the adding silicocalcium, form the changeable shape Mg that disperse distributes on the matrix
2The Si phase plays certain dispersion-strengthened action to matrix.
Fig. 2 is for Mg-Al is an XRD facies analysis collection of illustrative plates after alloy adds silicocalcium, show add silicocalcium after, generated fusing point and the higher particle wild phase Mg of stability by reaction on the alloy substrate
2The Si phase.
Fig. 3 a, 3b are that Mg-Al is the microstructure after alloy adds homogenizing before and after the silicocalcium, from organizing as can be seen, add silicocalcium after, the obvious refinement of microstructure.
Fig. 4 is shown by figure that for Mg-Al is the weight-loss corrosion test that alloy adds the silicocalcium front and back Mg-Al is that its corrosion resistance nature also is greatly increased after adding silicocalcium in the alloy.
Fig. 5 is that alloy adds the electropotential test result before and after the silicocalcium for Mg-Al, from figure liquid as can be seen, the corrosion resistance nature that adds Mg-Al behind the silicocalcium and be alloy is greatly increased.
Fig. 6 is that Mg-Al is the microhardness of alloy casting state matrix, Fig. 7 is alloy casting state Mechanics Performance Testing result, show that by Fig. 6 and Fig. 7 add that Mg-Al is that the alloy casting state microhardness significantly improves behind the suitable silicocalcium, tensile strength, ballistic work, elongation etc. also are significantly improved.
Fig. 8 is the alloy flowability test result, and as seen from the figure, behind the adding silicocalcium, the flowability of alloy is greatly improved.
Description of drawings
Fig. 1 a, 1b are respectively the as-cast microstructure photos that adds the silicocalcium front and back in the Mg-Al system;
Fig. 2 is the XRD facies analysis collection of illustrative plates after Mg-Al system adds silicocalcium;
Fig. 3 a, 3b are respectively the microstructures after Mg-Al system adds homogenizing before and after the silicocalcium;
Fig. 4 is the weight-loss corrosion test that alloy adds the silicocalcium front and back for Mg-Al;
Fig. 5 is the electropotential test result that alloy adds the silicocalcium front and back for Mg-Al;
Fig. 6 is the microhardness of alloy casting state matrix for Mg-Al;
Fig. 7 is alloy casting state Mechanics Performance Testing result;
Fig. 8 is the alloy flowability test result.
Embodiment
Embodiment 1:
The Mg-Al-Si-Mn-Ca alloy, form by the component of following weight per-cent: Al 6.0%, Mn0.5%, Zn 0.2%, Si 1.0%, Ca 0.18%, surplus is a magnesium.
Its preparation method is:
1. feed in advance to smelting furnace and be CO in proportion
2: SF
6=10: 1 shielding gas, to be heated to 400 ℃, adding by burn out rate is fine aluminium ingot and the pure magnesium ingot that preheating has been passed through in 10% calculating.
2. furnace temperature is risen to 700 ℃, the furnace charge that is housed to all after the fusing, adds the Al～10Mn master alloy (also can be Al-20Mn) of preheating, treat the master alloy fusing after, add pure Zn at last, after the fusing alloy liquid is stirred.
3. furnace temperature is warming up to 780 ℃, weight ratio 1.0% (pressing Si calculates) silicocalcium is added alloy liquid, stir, and remove surperficial slag.
4. after stirring 2 minutes, left standstill 30 minutes.
5. casting mold is preheated to 250 ℃, the temperature of liquid magnesium alloy is reduced to 720 ℃ and is poured into a mould.Take the slag on liquid magnesium alloy surface off, cast gate uses the protection air-blowing to fluid surface, in order to avoid magnesium liquid is oxidized as far as possible near casting mold in the casting process.Promptly get the aluminum magnesium alloy that contains that contains spontaneous particle wild phase after the ingot casting cooling.
Thermal treatment:
Solid solution temperature is 410 ℃, soaking time 12 hours.Adopting from the beginning, water as medium carries out quench treatment.The artificial aging temperature is 205 ℃.
Embodiment 2:
The Mg-Al-Si-Mn-Ca alloy, form by the component of following weight per-cent: Al 7.0%, Mn0.2%, Zn 0.2%, Si 1.8%, Ca 0.28%, surplus is a magnesium.
Its preparation method is:
1. feed in advance to smelting furnace and be CO in proportion
2: SF
6=8: 1 shielding gas, to be heated to 450 ℃, adding by burn out rate is fine aluminium ingot and the pure magnesium ingot that preheating has been passed through in 10% calculating.
2. furnace temperature is risen to 680 ℃, the furnace charge that is housed to all after the fusing, adds the Al-10Mn master alloy of preheating, treat the master alloy fusing after, add pure Zn at last, after the fusing alloy liquid is stirred.
3. furnace temperature is warming up to 770 ℃, weight ratio 1.8% (pressing Si calculates) silicocalcium is added alloy liquid, stir, and remove surperficial slag.
4. after stirring 2 minutes, left standstill 25 minutes.
5. casting mold is preheated to 220 ℃, the temperature of liquid magnesium alloy is reduced to 690 ℃ and is poured into a mould.Take the slag on liquid magnesium alloy surface off, cast gate uses the protection air-blowing to fluid surface, in order to avoid magnesium liquid is oxidized as far as possible near casting mold in the casting process.Promptly get the aluminum magnesium alloy that contains that contains spontaneous particle wild phase after the ingot casting cooling.
Thermal treatment:
Solid solution temperature is 420 ℃, soaking time 8 hours.Adopting from the beginning, water as medium carries out quench treatment.The artificial aging temperature is 210 ℃.
Metallograph shows that regular blocky Mg is distributing on the matrix
2The Si particle is identical with embodiment 1.It is more just to add silicocalcium, and more Mg is distributing on the matrix
2Si.
Embodiment 3:
The Mg-Al-Si-Mn-Ca alloy, form by the component of following weight per-cent: Al 5.0%, Mn0.2%, Zn 0.2%, Si 0.6%, Ca 0.1%, surplus is a magnesium.
Its preparation method is:
1. feed in advance to smelting furnace and be CO in proportion
2: SF
6=6: 1 shielding gas, to be heated to 500 ℃, adding by burn out rate is fine aluminium ingot and the pure magnesium ingot that preheating has been passed through in 10% calculating.
2. furnace temperature is risen to 720 ℃, the furnace charge that is housed to all after the fusing, adds the Al～10Mn master alloy of preheating, treat the master alloy fusing after, add pure Zn at last, after the fusing alloy liquid is stirred.
3. furnace temperature is warming up to 760 ℃, weight ratio 0.6% (pressing Si calculates) silicocalcium is added alloy liquid, stir, and remove surperficial slag.
4. after stirring 2 minutes, left standstill 40 minutes.
5. casting mold is preheated to 260 ℃, the temperature of liquid magnesium alloy is reduced to 700 ℃ and is poured into a mould.Take the slag on liquid magnesium alloy surface off, cast gate uses the protection air-blowing to fluid surface, in order to avoid magnesium liquid is oxidized as far as possible near casting mold in the casting process.Promptly get the aluminum magnesium alloy that contains that contains spontaneous particle wild phase after the ingot casting cooling.
Thermal treatment:
Solid solution temperature is 390 ℃, soaking time 20 hours.Adopting from the beginning, water as medium carries out quench treatment.The artificial aging temperature is 200 ℃.
Metallograph shows that less regular blocky Mg is distributing on the matrix
2The Si particle is identical with embodiment 1.
As-cast characteristic compares:
| Numbering | σ b/MPa | δ/％ | A k/J | HV 0.1 | |
| Embodiment 1 | Before adding SiCa | 150 | 7 | 8 | 48 |
| After adding SiCa | 164 | 8.7 | 12 | 56 | |
| |
Before adding SiCa | 155 | 5.2 | 6 | 54 |
| After adding SiCa | 180 | 7 | 10 | 65 | |
| Embodiment 3 | Before adding SiCa | 144 | 8 | 10 | 50 |
| After adding SiCa | 161 | 9 | 16 | 55 |
The standard analysis such as the following table of the silicocalcium that the present invention adopts,
The composition of industrial silicon calcium alloy (percentage composition %)
| The trade mark | Ca％ | Si％ | C％ | Al％ | P％ | S％ |
| Greater than | Scope | Less than | ||||
| Ca31Si60 | 31 | 55～65 | 0.8 | 2.4 | 0.04 | 0.06 |
Claims (9)
1, a kind of Mg-Al-Si-Mn-Ca alloy is characterized in that, it is made up of the component of following weight per-cent: Al 5.0～7.0%, Mn 0.2～0.5%, Zn≤0.2%, Si 0.5～2.0%, Ca≤0.3%, surplus are magnesium.
2, alloy as claimed in claim 1 is characterized in that, it is made up of the component of following weight per-cent: Al 6.0%, Mn 0.5%, Zn 0.2%, and Si 1.0%, Ca 0.18%, surplus is a magnesium.
3, alloy as claimed in claim 1 is characterized in that, is made up of the component of following weight per-cent: Al 7.0%, Mn 0.2%, Zn 0.2%, and Si 1.8%, Ca 0.28%, surplus is a magnesium.
4, alloy as claimed in claim 1 is characterized in that, it is made up of the component of following weight per-cent: Al 5.0%, Mn 0.2%, Zn 0.2%, and Si 0.6%, Ca 0.1%, surplus is a magnesium.
5, prepare the method for claim 1,2,3 or 4 described Mg-Al-Si-Mn-Ca alloys, it is characterized in that it may further comprise the steps:
1. in smelting furnace, feed shielding gas in advance, to be heated to 400～500 ℃, add and calculate fine aluminium ingot, the pure magnesium ingot that has passed through preheating in proportion;
2. furnace temperature is risen to 680～720 ℃, the furnace charge that is housed to all after the fusing, adds the aluminium manganese master alloy of preheating, treat the master alloy fusing after, add the pure Zn of weight ratio≤0.2% at last, after the fusing alloy liquid is stirred;
3. furnace temperature is warming up to 760～780 ℃, silicocalcium is added alloy liquid, stir, and remove surperficial slag;
4. after stirring, left standstill 25～40 minutes, cool to 690～720 ℃ then;
5. casting mold is preheated to 220～260 ℃, the temperature for the treatment of liquid magnesium alloy is reduced to 690～720 ℃ and is poured into a mould.
6, preparation method as claimed in claim 5 is characterized in that, after the cast, ingot casting is incubated 6～20 hours down at 390～420 ℃ and carries out the homogenizing processing, carries out artificial aging at 200～210 ℃ and handles.
7, preparation method as claimed in claim 6 is characterized in that, used shielding gas is CO2: SF6=6～10: 1.
8, preparation method as claimed in claim 7 is characterized in that, in charging and melting process, finds that magnesium liquid exposes and when burning, should increase air flow in right amount it is blown out.
9, preparation method as claimed in claim 8 is characterized in that, takes the slag on liquid magnesium alloy surface before the cast earlier off, and cast gate uses the protection air-blowing to fluid surface, in order to avoid magnesium liquid is oxidized as far as possible near casting mold in the casting process.
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| CNB2005100484176A CN100410407C (en) | 2005-10-19 | 2005-10-19 | Mg-Al-Si-Mn-Ca alloy and method for preparing same |
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| CN100410407C CN100410407C (en) | 2008-08-13 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102230118A (en) * | 2011-07-05 | 2011-11-02 | 重庆大学 | Magnesium alloy of high intensity and high yield ratio and preparation method thereof |
| CN103031474A (en) * | 2011-09-29 | 2013-04-10 | 比亚迪股份有限公司 | Magnesium lithium alloy |
| CN103436828A (en) * | 2013-09-04 | 2013-12-11 | 中南大学 | Homogenization heat treatment process of large-size magnesium alloy ingot |
| CN112853184A (en) * | 2021-01-08 | 2021-05-28 | 南昌大学 | Process method for improving mechanical property of Mg-Al-Si series magnesium alloy |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1339888B1 (en) * | 2000-09-26 | 2011-04-13 | Kwang Seon Shin | High strength magnesium alloy |
| CN1190511C (en) * | 2003-01-28 | 2005-02-23 | 东南大学 | Heat-resistant light metals magnesium alloy |
| KR101127113B1 (en) * | 2004-01-09 | 2012-03-26 | 켄지 히가시 | Magnesium alloy for die cast and magnesium die cast products using the same |
| CN100339497C (en) * | 2004-09-29 | 2007-09-26 | 上海交通大学 | High-strength creep resistant deforming magnesium alloy containing Ca and Si |
-
2005
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102230118A (en) * | 2011-07-05 | 2011-11-02 | 重庆大学 | Magnesium alloy of high intensity and high yield ratio and preparation method thereof |
| CN102230118B (en) * | 2011-07-05 | 2012-06-27 | 重庆大学 | Magnesium alloy of high intensity and high yield ratio and preparation method thereof |
| CN103031474A (en) * | 2011-09-29 | 2013-04-10 | 比亚迪股份有限公司 | Magnesium lithium alloy |
| CN103436828A (en) * | 2013-09-04 | 2013-12-11 | 中南大学 | Homogenization heat treatment process of large-size magnesium alloy ingot |
| CN103436828B (en) * | 2013-09-04 | 2015-06-03 | 中南大学 | Homogenization heat treatment process of large-size magnesium alloy ingot |
| CN112853184A (en) * | 2021-01-08 | 2021-05-28 | 南昌大学 | Process method for improving mechanical property of Mg-Al-Si series magnesium alloy |
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