CN103540778B - The chemical conversion film forming method of a kind of magnesium alloy fused mass - Google Patents
The chemical conversion film forming method of a kind of magnesium alloy fused mass Download PDFInfo
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- CN103540778B CN103540778B CN201310511730.3A CN201310511730A CN103540778B CN 103540778 B CN103540778 B CN 103540778B CN 201310511730 A CN201310511730 A CN 201310511730A CN 103540778 B CN103540778 B CN 103540778B
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- alloy
- conversion film
- magnesium alloy
- magnesium
- chemical conversion
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- 229910000861 Mg alloy Inorganic materials 0.000 title claims abstract description 34
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 20
- 238000000034 method Methods 0.000 title claims abstract description 14
- 239000000126 substance Substances 0.000 title claims abstract description 12
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 32
- 239000000956 alloy Substances 0.000 claims abstract description 32
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 20
- 239000011777 magnesium Substances 0.000 claims abstract description 20
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000007788 liquid Substances 0.000 claims abstract description 10
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 5
- 229910003120 Zn-Ce Inorganic materials 0.000 claims abstract description 4
- 238000000265 homogenisation Methods 0.000 claims abstract description 4
- 238000010309 melting process Methods 0.000 claims abstract description 4
- 229910052751 metal Inorganic materials 0.000 claims abstract description 4
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 4
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 4
- 239000002994 raw material Substances 0.000 claims abstract description 4
- 239000002184 metal Substances 0.000 claims 1
- 238000002156 mixing Methods 0.000 claims 1
- 238000005260 corrosion Methods 0.000 abstract description 4
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 abstract description 3
- 230000007797 corrosion Effects 0.000 abstract description 3
- 239000003063 flame retardant Substances 0.000 abstract description 3
- 239000000203 mixture Substances 0.000 abstract description 3
- 230000001629 suppression Effects 0.000 abstract description 3
- 238000005516 engineering process Methods 0.000 description 11
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 8
- 238000002844 melting Methods 0.000 description 8
- 230000008018 melting Effects 0.000 description 8
- 229910018575 Al—Ti Inorganic materials 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 238000010792 warming Methods 0.000 description 6
- 238000003723 Smelting Methods 0.000 description 5
- 239000004411 aluminium Substances 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 238000005266 casting Methods 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 3
- 238000005275 alloying Methods 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000009413 insulation Methods 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 230000001681 protective effect Effects 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- -1 after Mg-RE Inorganic materials 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000013021 overheating Methods 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 229910018137 Al-Zn Inorganic materials 0.000 description 1
- 229910018573 Al—Zn Inorganic materials 0.000 description 1
- 229910000691 Re alloy Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 238000007499 fusion processing Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003856 thermoforming Methods 0.000 description 1
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- Manufacture And Refinement Of Metals (AREA)
Abstract
The chemical conversion film forming method of a kind of magnesium alloy fused mass provided by the invention: (1) alloy (Mg-Al-Zn-Ce/Sc) and raw material magnesium ingot add simultaneously in advance; (2) alloy (Mg-Al-Zn-Nd/Y-Y/Ce) hot stage adds in advance; In low temperature melting process (650-760 DEG C), (3) in stove, mixed atmosphere and alloy liquid surface form low temperature conversion film; (4) formed containing rare earth pyrolytic conversion film at high-temperature homogenization and metamorphic process (760-840 DEG C), with the volatilization of the high-vapor-pressure metal elements such as Mg, Zn in this effectively suppression alloy. Chemical conversion film forming method through magnesium alloy of the present invention has effectively ensured the accurate degree of designed composition, the magnesium alloy obtained is made to have high strength (> 350MPa), high tenacity (unit elongation > 20%), low density, and the excellent comprehensive performance of excellent corrosion stability, flame retardant resistance etc.
Description
Technical field
The present invention relates to a kind of class of metal materials and field of metallurgy, in particular to the chemical conversion film forming method of a kind of melt magnesium alloy.
Background technology
Magnesium alloy has a wide range of applications in aerospace, military project, electronics, machinery, automobile and other industry, mainly owing to it possesses the features such as density is low, shock resistance, capability of electromagnetic shielding are excellent, specific tenacity specific rigidity height, machinability are good. China develops magnesium alloy industry energetically, not only has powerful resources advantage, also has the huge market requirement.
But, the material such as magnesium alloy substitution of Al alloy in recent years, the application development in every profession and trade is relatively slower, and major cause is that current magnesium alloy also also exists following obvious deficiency:
(1) intensity is low: the commercial equal < 280MPa of magnesium alloy tensile strength at present, especially mechanical behavior under high temperature is poor, when the temperature increases, its intensity and creep-resistant property significantly decline, and limit its application in the field such as structure, load-bearing;
(2) plasticity is poor: the commercial general < 10% of magnesium alloy unit elongation at present, limits its machine-shaping property. To improve intensity, then unit elongation will decline greatly, ZK61 magnesium alloy as the highest in intensity, although its intensity can reach 275-305MPa, but its unit elongation is only 4-7%;
(3) chemically reactive height, be easy to oxidizing fire, it is difficult to thermo forming;
(4) erosion resistance is poor: matrix is oxidizable in atmosphere, very easily corrodes in humid atmosphere. (5) heat resistance is poor: the magnesium alloy processed by solid gas coupling, owing to gathering of timeliness precipitated phase grows up so that it is impossible life-time service is higher than in the environment of 120 DEG C.
(5) due to highly volatile during the vapour pressure height melting of magnesium, not only environment can be polluted, and add the danger of production.What generally adopt at present is use F6S+N2(Ar) protect, although this method can obtain good effect, but F6Poisonous degradation production F can be produced after S pyrolytic decomposition2S, production environment not only can be caused severe contamination by this degradation production, and the prior healthy generation infringement to being producers, has abroad prohibited and used F6S is as protection gas medium.
Therefore, development is beneficial to the magnesium alloy smelting technology of environment protection, and develops the novel magnesium alloy technology with excellent comprehensive performance (lightweight, high-strength, Gao Ren, heat-resisting, anti-corrosion), has extremely important construction value undoubtedly.
Summary of the invention
The present invention is the chemical conversion protective membrane technology of magnesium alloy fused mass. The volatilization of alloying element when this technology can effectively suppress magnesium alloy smelting, to the pollution of environment when alleviating prior art melting, danger when reducing production, ensured the accurate degree of magnesium alloy of the present invention design composition simultaneously, make the magnesium alloy obtained compared with magnesium alloy of the prior art, there is high strength (> 350MPa), high tenacity (unit elongation > 20%), low density, and the excellent comprehensive performance of excellent corrosion stability, flame retardant resistance etc.
The technical scheme that the present invention takes is:
(1) alloy (Mg-Al-Zn-Ce/Sc) and raw material magnesium ingot add simultaneously in advance;
(2) alloy (Mg-Al-Zn-Nd/Y-Y/Ce) hot stage adds in advance;
In low temperature melting process (650-760 DEG C), (3) CO in stove2/ Ar mixed atmosphere and alloy liquid surface form low temperature conversion film;
(4) formed containing rare earth pyrolytic conversion film at high-temperature homogenization and metamorphic process (760-840 DEG C), with the volatilization of the high-vapor-pressure metal elements such as Mg, Zn in this effectively suppression alloy.
Useful effect: the volatilization of alloying element when inhibiting magnesium alloy smelting with forming technology effective by the chemical conversion film of melt magnesium alloy of the present invention, to the pollution of environment when alleviating prior art melting, danger when reducing production, ensured the accurate degree of magnesium alloy of the present invention design composition simultaneously, make the magnesium alloy obtained compared with magnesium alloy of the prior art, there is high strength (> 350MPa), high tenacity (unit elongation > 20%), low density, and the excellent comprehensive performance of excellent corrosion stability, flame retardant resistance etc.
Embodiment
Essential core technology of the present invention: the chemical conversion protective membrane smelting technique of magnesium alloy fused mass
Magnesium alloy fused mass chemical conversion protective membrane smelting technique in the melting of 1.Mg-Al-Zn compound RE alloy
Pure magnesium, aluminium, zinc, master alloy Mg-Al-RE are first preheated to 100-180 DEG C, then pure magnesium, aluminium ingot, zinc ingot are placed in CO2The melt in furnace mixed gas protected with Ar; It is incubated 25-45 minute at 650-760 DEG C after fusing, then it is warming up to 760-840 DEG C and adds Mg-Al-RE master alloy, after master alloy melts, magnesium liquid is warming up to 840-860 DEG C of insulation 30-50 minute; Being cooled to 650-700 DEG C again, leave standstill and cast after 10-20 minute, casting steel die is heated to 150-300 DEG C in advance, the high-performance magnesium-alloy of obtained Mg-Al-Zn-compound RE of the present invention.
What the alloying of the fusion process of this technology adopted is alloy technology in advance, alloy liquid protection adopts chemical conversion film to suppress volatilization technology. That is, mixed atmosphere CO in (650-760 DEG C) stove in low temperature melting process2/ Ar and alloy liquid surperficial formation low temperature conversion film, formed containing rare earth pyrolytic conversion film at high-temperature homogenization and metamorphic process (760-840 DEG C), with the volatilization of the high-vapor-pressure metal elements such as Mg, Zn in this effectively suppression alloy.
The substantive distinguishing features that the present invention has is:
(1) adopting the master alloy of alloyage process melting in advance, alloy (Mg-Al-Zn-Ce/Sc) and raw material magnesium ingot add simultaneously in advance, and alloy (Mg-Al-Zn-Nd/Y-Y/Ce) hot stage adds in advance.
(2) CO is adopted2Carry out gas melting protection with Ar mixed gas 1: 20 volume ratio, according to the differing temps stage of liquid melt, form basic, normal, high temperature chemical conversion film protection technology, decrease volatilization and the folder slag of melt liquid, ensured the pure of ingot casting and quality.
Specific embodiment:
Embodiment 1
Melting 1kg magnesium alloy, takes pure magnesium ingot (purity 99.95%) 960g, zinc ingot (purity 99.99%) 18g, master alloy (Al-20Ti) 10g, (Mg-50Nd) 3.6g, (Mg-50Y) 7.2g, (Mg-50Ce) 1.2g.
By mentioned component alloyage, its founding is: pure magnesium ingot, zinc ingot, master alloy Mg-RE and Al-Ti are first preheated to 120-140 DEG C, then pure magnesium, zinc ingot is placed in CO2The melt in furnace mixed gas protected with Ar; It is incubated 25-35 minute at 720-760 DEG C after fusing, it is warming up to 760-800 DEG C and adds Mg-RE, Al-Ti master alloy, after Mg-RE, Al-Ti master alloy melts, magnesium liquid is warming up to 770-785 DEG C of insulation and after 30 minutes, is cooled to 650-720 DEG C, leave standstill and cast after 10-20 minute, casting steel die is heated to 150-200 DEG C in advance, obtains Mg-Al-Zn-Ti-RE high strength of the present invention, big plasticity magnesium alloy.
The present embodiment gained alloy, after Overheating Treatment, room temperature tensile intensity is 295MPa, and unit elongation is 23.5%.
Embodiment 2
Melting 1kg magnesium alloy, takes pure magnesium ingot (purity 99.99%) 884g, aluminium ingot (purity 99.7%) 5g, zinc ingot (purity 99.99%) 20g, master alloy (Al-20Ti) 75g, (Mg-50Nd) 6.4g, (Mg-50Y) 6.4g, (Mg-50Ce) 3.2g.
By mentioned component alloyage, its founding is: pure magnesium ingot, zinc ingot, master alloy Mg-RE and Al-Ti are first preheated to 120-140 DEG C, then pure magnesium ingot, aluminium ingot, zinc ingot is placed in CO2The melt in furnace mixed gas protected with Ar; It is incubated 25-35 minute at 740-760 DEG C after fusing, it is warming up to 780-800 DEG C and adds Mg-RE, Al-Ti master alloy, after Mg-RE, Al-Ti master alloy melts, magnesium liquid is warming up to 770-785 DEG C of insulation and after 30 minutes, is cooled to 720-750 DEG C, leave standstill and cast after 10-20 minute, casting steel die is heated to 200-300 DEG C in advance, obtains Mg-Al-Zn-Ti-RE high strength of the present invention, big plasticity magnesium alloy.
The present embodiment gained alloy, after Overheating Treatment, room temperature tensile intensity is 360MPa, and unit elongation is 19%.
Claims (1)
1. the chemical conversion film forming method of a magnesium alloy fused mass, it is characterised in that:
(1) alloy Mg-Al-Zn-Ce/Sc and raw material magnesium ingot add simultaneously in advance;
(2) alloy Mg-Al-Zn-Nd/Y-Y/Ce adds at 760-840 DEG C of hot stage in advance;
(3) in 650-760 DEG C of low temperature melting process, in stove, CO2/Ar gas forms low temperature conversion film with the volume ratio mixing of 1:20 with alloy liquid surface;
(4) formed containing rare earth pyrolytic conversion film at 760-840 DEG C of high-temperature homogenization and metamorphic process, effectively suppress the volatilization of Mg, Zn high-vapor-pressure metal element in alloy with this.
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| CN201310511730.3A CN103540778B (en) | 2013-10-25 | 2013-10-25 | The chemical conversion film forming method of a kind of magnesium alloy fused mass |
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| CN201310511730.3A CN103540778B (en) | 2013-10-25 | 2013-10-25 | The chemical conversion film forming method of a kind of magnesium alloy fused mass |
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| CN103540778A CN103540778A (en) | 2014-01-29 |
| CN103540778B true CN103540778B (en) | 2016-06-08 |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1523127A (en) * | 2003-09-11 | 2004-08-25 | 上海交通大学 | Lost Foam Casting Magnesium Alloy and Its Melting Method |
| CN102534329A (en) * | 2012-03-29 | 2012-07-04 | 成都青元泛镁科技有限公司 | Preparation method for magnesium alloy with high strength and large plasticity |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003055728A (en) * | 2001-08-09 | 2003-02-26 | Toyota Central Res & Dev Lab Inc | Heat resistant magnesium alloy |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1523127A (en) * | 2003-09-11 | 2004-08-25 | 上海交通大学 | Lost Foam Casting Magnesium Alloy and Its Melting Method |
| CN102534329A (en) * | 2012-03-29 | 2012-07-04 | 成都青元泛镁科技有限公司 | Preparation method for magnesium alloy with high strength and large plasticity |
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| CN103540778A (en) | 2014-01-29 |
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Granted publication date: 20160608 Termination date: 20191025 |