CN102703786A - Heat-resisting anti-corrosion magnesium alloy for automobile engine cylinder - Google Patents

Heat-resisting anti-corrosion magnesium alloy for automobile engine cylinder Download PDF

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CN102703786A
CN102703786A CN2012102194727A CN201210219472A CN102703786A CN 102703786 A CN102703786 A CN 102703786A CN 2012102194727 A CN2012102194727 A CN 2012102194727A CN 201210219472 A CN201210219472 A CN 201210219472A CN 102703786 A CN102703786 A CN 102703786A
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alloy
magnesium
heat
corrosion
engine cylinder
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CN102703786B (en
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刘子利
李健
朱晓春
李娟�
刘希琴
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Jiangsu Favour Automotive New Stuff Sci-Tech Co Ltd
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Jiangsu Favour Automotive New Stuff Sci-Tech Co Ltd
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Abstract

The invention discloses a heat-resisting anti-corrosion magnesium alloy for an automobile engine cylinder. The heat-resisting anti-corrosion magnesium alloy comprises the components in percentage by weight: 3.5-5.5% Al, 1.5-2.5% Sr, 0.2-0.4% Sb, 0.2-0.8% Cd, 0.04-0.08% Ti and the balance of Mg. According to the heat-resisting anti-corrosion magnesium alloy, the anti-corrosion property of the alloy can be greatly improved by alloying of Sb, Cd and Ti on the basis of improving the mechanical and heat-resisting property of the Mg-Al-Sr alloy.

Description

Automobile engine cylinder-body is used the heat-proof corrosion-resistant magnesiumalloy
Technical field
The present invention relates to a kind of magnesiumalloy, particularly a kind of automobile engine cylinder-body is used the heat-proof corrosion-resistant magnesiumalloy, belongs to the light metal material technical field.
Background technology
Magnesium alloy materials has characteristics such as specific tenacity, specific rigidity height and damping shock absorption, has become the important raw and processed materials of automobile industry, and automotive industry is energy-conservation to provide bigger development space with environmental protection requirement in order to satisfy.Mg-Al is that alloy is that application is the widest in the cast magnesium alloys, and wherein AZ system and AM series magnesium alloy have obtained the wide range of commercial application in automotive industry, and these alloys not only have good castibility and also show good normal temperature mechanical property.
But since they hot strength and creep-resistant property is not good, corrosion resistance nature is relatively poor; All be as some nonessential automobile component all the time; Like bearing circle, steering post parts, test board; Seat and wheel casing etc., their application in automobile major impetus system (wheel box and motor body) have received very big restriction.
In Mg-Al base alloy, add alkaline earth element Ca or Sr, can separate out the very high A1-Ca of fusing point in mutually mutually or the A1-Sr phase at matrix.These at high temperature can not decompose mutually, can play good pinning effect to crystal boundary, thereby can improve the mechanical behavior under high temperature, particularly creep-resistant property of magnesiumalloy effectively.
It is at least a and strontium that adds in the matrix alloy in grain-refining agent antimony and the calcium at AZ91 that patent CN 1637160A (magnesium for die casting use and magnesium die casting product) discloses a kind of, improves the magnesiumalloy tissue, improves the case of alloy high-temp creep property; Its composition quality per distribution ratio is: 6.0 ~ 11.0% aluminium (Al), 0.1 ~ 2.5% zinc (Zn), 0.1 ~ 0.5% manganese (Mn); 0.1 ~ 1.5% antimony (Sb); 0.05 ~ 3.5% calcium (Ca), 0.1 ~ 2.5% strontium (Sr), surplus is a magnesium.
And for example patent CN 101643872A (a kind of HS, high plastic magnesium alloy and preparation method thereof) discloses a kind of in alloying element silicon, antimony, yttrium and the strontium one or more of in the Mg-Sn matrix alloy, adding, and improves the intensity of magnesiumalloy and the case of plasticity, and its composition quality per distribution ratio is: 6.1 ~ 9.5% aluminium (Al); 1.0 ~ 5.0% tin (Sn); 0 ~ 3.0% silicon (Si), 0 ~ 2.0% antimony (Sb), 0 ~ 3.0% yttrium (Y); 0 ~ 2.0% strontium (Sr), surplus are magnesium.
Research in recent years shows; The alloying of Sb and Cd can be improved mechanical property and corrosion resisting property in the Mg-Al-RE alloy, is that disclosed a kind of high tough heat-proof corrosion-resistant magnesium-rare earth of CN102134673A and publication No. are that the tough heat-proof corrosion-resistant magnesium-rare earth of the disclosed height of CN102127669A all is to improve alloy mechanical property through Sb and Cd like publication No..
Use material as automobile engine cylinder-body, also need have excellent corrosion resisting performance when need have good normal temperature mechanical property and resistance toheat concurrently.Though all these alloys have higher intensity, too much alloy alloying element causes second mutually more and reduced the plasticity and the corrosion resisting property of alloy in the alloy, has limited their application in automobile engine cylinder-body.
It is alloy that patent WO 01/44529 Al discloses a kind of Mg-Al-Sr, and its composition quality per distribution ratio is: 2.0 ~ 9.0% aluminium (Al), and 0.5 ~ 7.0% strontium (Sr), surplus is a magnesium.This cost of alloy is relatively low, has higher tensile yield strength (> 100MPa at the high temperature more than 150 ℃) and creep resistance (≤0.03%), and lower corrosion resistance nature (≤0.3251mm/year).Wherein, AJ62 alloy (Mg-6Al-2.4Sr) successfully has been applied to BMW six cylinder engine cylinder body.With AJ62 alloy phase ratio; AJ52 alloy (Mg-5Al-2Sr) possesses higher resistance toheat is arranged; But its normal temperature mechanical property and corrosion resistance nature are lower than AJ62 alloy (Eric Baril; Pierre Labelle, and Mihriban O. Pekguleryuz. Elevated Temperature Mg-Al-Sr:Creep Resistance, Mechanical Properties; And Microstructure. Jom-Journal of the Minerals Metals & Materials Society. 2003,55 (11): A34-A39.).
Summary of the invention
Technical problem to be solved by this invention provides a kind of automobile engine cylinder-body and uses the heat-proof corrosion-resistant magnesiumalloy, and this magnesiumalloy has excellent hot strength, plasticity, creep-resistant property and erosion resistance.
In order to solve above-mentioned technical problem, technical scheme of the present invention is: a kind of automobile engine cylinder-body is used the heat-proof corrosion-resistant magnesiumalloy, it is characterized in that the weight percent proportioning of its composition is: aluminium 3.5 ~ 5.5%; Strontium 1.5 ~ 2.5%, antimony 0.2 ~ 0.4%, cadmium 0.2 ~ 0.8%; Titanium 0.04 ~ 0.08%, all the other are magnesium.
As preferably, the weight percent proportioning of said composition is: aluminium 5.0 ~ 5.5%, and strontium 2.0 ~ 2.5%, antimony 0.2 ~ 0.25%, cadmium 0.2 ~ 0.25%, titanium 0.04 ~ 0.06%, all the other are magnesium.
Process step of the present invention is following:
Under flux and gas shield melting condition, pure magnesium and commercial-purity aluminium are put into crucible, temperature rises to 680 ~ 730 ℃ in stove; Insulation for some time, treat that magnesium ingot etc. fully after the fusing, is pressed into magnesium alloy fused mass with bell jar with Mg-Sr master alloy, star antimony and pure cadmium; Wait its fusion back to take out bell jar; Mix and continue to be warming up to 740 ~ 760 ℃, add refining agent refined magnesium alloy liquation and adds the Al-Ti master alloy after 5 ~ 10 minutes, leave standstill after 10 ~ 20 minutes and pour into a mould.This technology can be used for the manufacturing of alloy-steel casting or stock.
The present invention is improving on the Mg-Al-Sr alloy mechanical property basis of (as improving the chamber drawing by high temperature ys of alloy) through the alloying of Sb, Cd and Ti; Improve corrosion resistance of alloy (reducing the corrosion-resistant speed of alloy) significantly, its substantive distinguishing features and effect are:
(1) interpolation of employing lower melting point and the Sr of Mg-Sr master alloy realization cheaply, Sr can improve the fusing point of magnesium sosoloid, and it has lower density and in magnesiumalloy, spreads slowly; Sr has the effect of refined crystalline strengthening, can refinement magnesiumalloy crystal grain; Al in Sr and the alloy combines can generate dystectic Al4Sr mutually, reduces Mg17Al12 and separates out at crystal boundary, the hot strength and the creep-resistant property of raising alloy;
(2) surface active element Sb can improve form, quantity and the distribution of Al4Sr phase in the alloy.Sb will replace part A l and preferentially combine to form HMP diffusing particle SbSr2 mutually with Sr; This can be used as the core crystal grain thinning of the heterogeneous body forming core of α-Mg matrix in the alloy melt process of setting; In alloy substrate, can also hinder the motion of dislocation, improve the intensity of alloy.The formation of SbSr2 phase also can cause the formation of Al4Sr phase in the alloy to be restricted, and the Al constituent content of solid solution in alloy substrate increased, and has improved the effect that alloy solid solution is strengthened, and makes the tensile strength of alloy and ys be able to promote.
(3) Cd be a kind of can be in magnesium the alloying element of unlimited solid solution, the existence of Cd can be carried the base electrode current potential, and corrosion resistance of alloy is improved.
(4) Ti plays crystal grain thinning and improves crystal boundary second effect mutually, improves the mechanical property of alloy.
(5) Al of certain content can improve the castability and the corrosion resistance nature of magnesiumalloy; Guarantee the solution strengthening and the ageing strengthening effect of alloy; But reduced the high-temperature behavior and the toughness of alloy when Al content is higher again, so the mass percent of aluminium should remain on 3.5% ~ 5.5%.
Embodiment
Embodiment 1
Alloying constituent (weight percent): 3.5%Al, 1.5%Sr, 0.2%Sb, 0.2%Cd, 0.06%Ti, all the other are Mg, control impurity element Si≤0.02%, Fe≤0.005%, Cu≤0.015%, Ni≤0.002%.Under flux and gas shield melting condition, pure magnesium and commercial-purity aluminium are put into crucible, temperature rises to 700 ℃ in stove; Insulation for some time, treat that magnesium ingot etc. fully after the fusing, is pressed into magnesium alloy fused mass with bell jar with Mg-Sr master alloy, star antimony and pure cadmium; Wait its fusion back to take out bell jar; Mix and continue to be warming up to 750 ℃, add refining agent refined magnesium alloy liquation and adds the Al-Ti master alloy after 10 minutes, leave standstill after 20 minutes and pour into a mould.
Embodiment 2
Alloying constituent (weight percent): 5.0%Al, 2.0%Sr, 0.25%Sb, 0.25%Cd, 0.04%Ti, all the other are Mg, control impurity element Si≤0.02%, Fe≤0.005%, Cu≤0.015%, Ni≤0.002%.Under flux and gas shield melting condition, pure magnesium and commercial-purity aluminium are put into crucible, temperature rises to 680 ℃ in stove; Insulation for some time, treat that magnesium ingot etc. fully after the fusing, is pressed into magnesium alloy fused mass with bell jar with Mg-Sr master alloy, star antimony and pure cadmium; Wait its fusion back to take out bell jar; Mix and continue to be warming up to 760 ℃, add refining agent refined magnesium alloy liquation and adds the Al-Ti master alloy after 5 minutes, leave standstill after 20 minutes and pour into a mould.
Embodiment 3
Alloying constituent (weight percent): 5.5%Al, 2.0%Sr, 0.3%Sb, 0.6%Cd, 0.06%Ti, all the other are Mg, control impurity element Si≤0.02%, Fe≤0.005%, Cu≤0.015%, Ni≤0.002%.Under flux and gas shield melting condition, pure magnesium and commercial-purity aluminium are put into crucible, temperature rises to 730 ℃ in stove; Insulation for some time, treat that magnesium ingot etc. fully after the fusing, is pressed into magnesium alloy fused mass with bell jar with Mg-Sr master alloy, star antimony and pure cadmium; Wait its fusion back to take out bell jar; Mix and continue to be warming up to 740 ℃, add refining agent refined magnesium alloy liquation and adds the Al-Ti master alloy after 7 minutes, leave standstill after 15 minutes and pour into a mould.
Embodiment 4
Alloying constituent (weight percent): 5.0%Al, 2.5%Sr, 0.4%Sb, 0.8%Cd, 0.08%Ti, all the other are Mg, control impurity element Si≤0.02%, Fe≤0.005%, Cu≤0.015%, Ni≤0.002%.Under flux and gas shield melting condition, pure magnesium and commercial-purity aluminium are put into crucible, temperature rises to 710 ℃ in stove; Insulation for some time, treat that magnesium ingot etc. fully after the fusing, is pressed into magnesium alloy fused mass with bell jar with Mg-Sr master alloy, star antimony and pure cadmium; Wait its fusion back to take out bell jar; Mix and continue to be warming up to 750 ℃, add refining agent refined magnesium alloy liquation and adds the Al-Ti master alloy after 10 minutes, leave standstill after 10 minutes and pour into a mould.
The alloy mechanical property that obtains among above-mentioned each embodiment is as shown in table 1.
Table 1
Figure BDA0000182437911
Corrosion resistant test method of the present invention is:
According to GB10124-1988 metallic substance testing laboratory uniform corrosion total immersion test method; Sample is tiltedly stood up in 3.5%NaCl solution; Take out the corrosion product of removing specimen surface with CrO3+AgNO3+Ba (NO3) 2+ zero(ppm) water after 100 hours; And then, survey erosion rate (mm/a) with acetone and raw spirit cleaning.
The alloy corrosion speed that obtains among above-mentioned each embodiment is as shown in table 2.
Table 2
Numbering Erosion rate (mm/a)
Embodiment 1 0.3935
Embodiment 2 0.2342
Embodiment 3 0.1769
Embodiment 4 0.2418
Can find out intuitively that by table 1,2 alloying of the present invention through Sb, Cd and Ti improves corrosion resistance of alloy significantly on the basis of improving Mg-Al-Sr alloy mechanics and resistance toheat.
The foregoing description does not limit the present invention in any way, and every employing is equal to the technical scheme that replacement or the mode of equivalent transformation obtain and all drops in protection scope of the present invention.

Claims (2)

1. an automobile engine cylinder-body is used the heat-proof corrosion-resistant magnesiumalloy, it is characterized in that the weight percent proportioning of its composition is: aluminium 3.5 ~ 5.5%, and strontium 1.5 ~ 2.5%, antimony 0.2 ~ 0.4%, cadmium 0.2 ~ 0.8%, titanium 0.04 ~ 0.08%, all the other are magnesium.
2. automobile engine cylinder-body according to claim 1 is used the heat-proof corrosion-resistant magnesiumalloy, it is characterized in that the weight percent proportioning of its composition is: aluminium 5.0 ~ 5.5%, and strontium 2.0 ~ 2.5%, antimony 0.2 ~ 0.25%, cadmium 0.2 ~ 0.25%, titanium 0.04 ~ 0.06%, all the other are magnesium.
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110195181A (en) * 2018-02-26 2019-09-03 中国宝武钢铁集团有限公司 A kind of diecast magnesium alloy and its manufacturing method with high-temperature heat-resistance performance
CN111593244A (en) * 2020-06-11 2020-08-28 哈尔滨理工大学 Novel multi-element corrosion-resistant magnesium alloy and preparation method thereof

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CN102127669A (en) * 2011-02-24 2011-07-20 江苏中翼汽车新材料科技有限公司 Heatproof and anticorrosion rare earth magnesium alloy with high obdurability and preparation method thereof
CN102134673A (en) * 2011-04-13 2011-07-27 江苏中翼汽车新材料科技有限公司 High-toughness heat-resistant corrosion-resistant rare earth magnesium alloy and preparation method thereof

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CN102127669A (en) * 2011-02-24 2011-07-20 江苏中翼汽车新材料科技有限公司 Heatproof and anticorrosion rare earth magnesium alloy with high obdurability and preparation method thereof
CN102134673A (en) * 2011-04-13 2011-07-27 江苏中翼汽车新材料科技有限公司 High-toughness heat-resistant corrosion-resistant rare earth magnesium alloy and preparation method thereof

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110195181A (en) * 2018-02-26 2019-09-03 中国宝武钢铁集团有限公司 A kind of diecast magnesium alloy and its manufacturing method with high-temperature heat-resistance performance
CN110195181B (en) * 2018-02-26 2021-10-22 中国宝武钢铁集团有限公司 Die-casting magnesium alloy with high-temperature heat resistance and manufacturing method thereof
CN111593244A (en) * 2020-06-11 2020-08-28 哈尔滨理工大学 Novel multi-element corrosion-resistant magnesium alloy and preparation method thereof

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