CN109022984A - A kind of corrosion-proof rare earth magnesium alloy of the element containing Zn and preparation method thereof - Google Patents
A kind of corrosion-proof rare earth magnesium alloy of the element containing Zn and preparation method thereof Download PDFInfo
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- CN109022984A CN109022984A CN201811112642.5A CN201811112642A CN109022984A CN 109022984 A CN109022984 A CN 109022984A CN 201811112642 A CN201811112642 A CN 201811112642A CN 109022984 A CN109022984 A CN 109022984A
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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
- C22C23/06—Alloys based on magnesium with a rare earth metal as the next major constituent
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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
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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
- C22C1/06—Making non-ferrous alloys with the use of special agents for refining or deoxidising
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C23/00—Alloys based on magnesium
- C22C23/04—Alloys based on magnesium with zinc or cadmium as the next major constituent
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/002—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working by rapid cooling or quenching; cooling agents used therefor
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/06—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of magnesium or alloys based thereon
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Abstract
The invention belongs to the scope of industrial magnesium alloy materials, corrosion-proof rare earth magnesium alloy of specifically a kind of element containing Zn and preparation method thereof.Alloy forms by weight percentage are as follows: Zn:2.0~6.0%, Y:4.5~5.5%, Nd:1.0~2.0%, Zr:0.3~0.7%, surplus is Mg, Mg-Y-Nd-Zn-Zr alloy melting, Homogenization Treatments, hot extrusion deformation, two-stage time effect are strengthened, that is, obtain the corrosion-proof rare earth magnesium alloy of the element containing Zn.The present invention forms equally distributed cathode precipitated phase by element Zn, Y, Nd and Mg matrix, cathode precipitated phase passes through scanning Kelvin probe force microscopy (SKPFM) test, microcell current potential is in -50mv or so, lower than α-Mg matrix current potential, the corrosion of α-Mg matrix will largely be inhibited, the intensity that Zn element further increases magnesium alloy is taken full advantage of simultaneously, has prepared corrosion-resistant magnesium alloy with high performance.It has wide range of applications through Mg-Y-Nd-Zn-Zr high performance corrosion-proof magnesium alloy of the invention, actual demand of the fields such as automobile, rail traffic to magnesium alloy materials can be met.
Description
Technical field
The invention belongs to the scope of industrial magnesium alloy materials, the corrosion-proof rare earth magnesium of specifically a kind of element containing Zn
Alloy and preparation method thereof.
Background technique
Magnesium alloy has many advantages, such as that specific strength and specific stiffness height, damping shock absorption are good as most light structural metallic materials,
All there is important application value and vast market prospect in fields such as automobile, rail traffics.Because the chemical property of magnesium is non-
It is often active, loose porous MgO film is capable of forming with oxygen in air, the PBR of film is only 0.8, cannot rise and protect to matrix
Shield effect；And the standard electrode potential of magnesium is -2.37V, and the corrosion potential in typical media is very low, therefore magnesium alloy corrosion resistant
Corrosion can be bad.Application of the magnesium alloy in various environment, will necessarily generate etching problem.Magnesium alloy is in various Service Environments
In, corrosion will affect its service life, increase danger coefficient, therefore etching problem is the pass for restricting magnesium alloy and applying in each field
Key.
Summary of the invention
For the problem that above-mentioned magnesium alloy overall corrosion resistance energy is poor, the present invention provides a kind of corrosion resistants of element containing Zn
Lose magnesium alloy and preparation method thereof.
To achieve the above object, The technical solution adopted by the invention is as follows:
A kind of preparation method of the corrosion-proof rare earth magnesium alloy of the element containing Zn, it is characterised in that: form by weight percentage
Are as follows: Zn:2.0~6.0%, Y:4.5~5.5%, Nd:1.0~2.0%, Zr:0.3~0.7%, surplus Mg, by Mg-Y-Nd-
Zn-Zr alloy melting, Homogenization Treatments, hot extrusion deformation, two-stage time effect are strengthened, that is, obtain the corrosion-proof rare earth magnesium of the element containing Zn
Alloy.
Specifically:
(1) it is preheated in raw material holding furnace: holding furnace being warming up to 300-350 DEG C, smelting furnace is passed through CO2And SF6Mixing protect
Gas is protected, is continuously heating to 680 DEG C, for use；
(2) pure magnesium (99.95%), yttrium alloy melting: is added after to preheating in raw material holding furnace according to the above ratio
(99.9%), neodymium (99.9%), Zr (99.9%) and zinc (99.9%), make raw material be heated to being completely melt, at the same to melt into
Row mechanical stirring and refining treatment；The magnesium alloy melt of refining is maintained the temperature between 650 DEG C -680 DEG C and is poured, is made
Magnesium alloy billet；
(3) Homogenization Treatments: by above-mentioned acquisition magnesium alloy billet in closed Muffle furnace, 515-535 DEG C is carried out uniformly
Change processing takes out the cooling in 70 DEG C of warm water after keeping the temperature 16-20h；
(4) hot extrusion deformation: by above-mentioned acquisition Mg-Y-Nd-Zn-Zr magnesium alloy after Homogenization Treatments, at 500-535 DEG C
Lower heat preservation 30-40min carries out hot extrusion, water quenching；
(5) two-stage time effect is strengthened: it is double that the Mg-Y-Nd-Zn-Zr magnesium alloy after hot extrusion deformation is put into progress in aging furnace
Grade failure heat treatment, technological parameter are as follows: preageing 4~6 hours first at 100 DEG C~120 DEG C, then at 220 DEG C~230 DEG C
Lower peak timeliness 10~14 hours.
The CO2And SF6Hybrid protection gas, volume fraction C O2For 99%, SF6It is 1%.
Step (2) refining treatment is that refining agent is added in the molten magnesium oxide, the nitride removed in magnesium
With the impurity such as alkali metal, one layer of continuous, strict protective film can be formed on magnesium melt surface；Wherein, refining agent adds
Dosage is that can form one layer of continuous, strict protective film on magnesium melt surface；Refining agent is MgCl2。
A kind of corrosion-resistant magnesium alloy of the element containing Zn is closed by the corrosion-resistant magnesium that the method prepares the element containing Zn
Gold.The heterogeneous microstructure of alloy is by α-Mg matrix and equally distributed precipitation phase composition.Meanwhile with the increasing of element Zn content
Add, magnesium alloy crystallite dimension is not much different, but crystal boundary is more clear, and the quantity and volume fraction of precipitated phase are gradually increased, and even
Continuous distribution reticulates.Equally distributed cathode precipitated phase forms corrosion barrier, largely inhibits the corruption of α-Mg matrix
Erosion, it is important that Zn element also adds the intensity of magnesium alloy.
Advantage for present invention:
Zn element, rare earth element y and Nd is added in the present invention in the magnesium alloy, is uniformly distributed by Zn, Y, Nd and Mg formation
Cathode precipitated phase inhibit the corrosion of α-Mg matrix, while taking full advantage of the intensity that Zn element further increases magnesium alloy,
Corrosion-resistant magnesium alloy with high performance is prepared.On the other hand, the addition of rare earth metal y and Nd can be improved magnesium alloy
Fining degree so that Magnesium Alloy is more uniform, can effectively improve the corrosion resistance of magnesium alloy, mechanical strength and
Toughness.Therefore, the present invention passes through the content for selecting different alloy element and allotment different component, so that the intensity of magnesium alloy
It is greatly improved with corrosion resistance；The Mg-Y-Nd-Zn-Zr magnesium alloy of preparation has good corrosion resistance.
Detailed description of the invention
Fig. 1 is the heterogeneous microstructure figure of the Mg-4.5Y-1.0Nd-2Zn-0.3Zr magnesium alloy of preparation of the embodiment of the present invention.
Fig. 2 is the heterogeneous microstructure figure of the Mg-5.0Y-1.5Nd-4Zn-0.5Zr magnesium alloy of preparation of the embodiment of the present invention.
Fig. 3 is the heterogeneous microstructure figure of the Mg-5.5Y-2.0Nd-6Zn-0.7Zr magnesium alloy of preparation of the embodiment of the present invention.
Specific embodiment
Below with reference to embodiment the present invention will be further explained explanation, all features disclosed in this specification, or
Disclosed all methods or in the process the step of, can be in any way other than mutually exclusive feature and/or step
Combination.
The weight percent of magnesium alloy of the present invention forms are as follows: and Zn:2.0~6.0%, Y:4.5~5.5%, Nd:1.0~
2.0%, Zr:0.3~0.7%, surplus Mg.The preparation step of the alloy is successively are as follows: alloy melting, homogenization, hot extrusion buckling
Shape, two-stage time effect intensive treatment.The present invention forms equally distributed cathode precipitated phase by element Zn, Y, Nd and Mg matrix, yin
Pole precipitated phase is lower than α-Mg base in -50mv or so by scanning Kelvin probe force microscopy (SKPFM) test, microcell current potential
Bulk potential will largely inhibit the corrosion of α-Mg matrix, while take full advantage of Zn element and further increase magnesium alloy
Intensity, prepared corrosion-resistant magnesium alloy with high performance.Through Mg-Y-Nd-Zn-Zr high performance corrosion-proof magnesium of the invention
Alloyapplication is in extensive range, can meet actual demand of the fields such as automobile, rail traffic to magnesium alloy materials.
Embodiment 1
The standard chemical ingredient of corrosion-resistant magnesium alloy of the invention are as follows: Zn:2.0%, Y:4.5%, Nd:1.0%, Zr:
0.3%, surplus Mg.
(1) holding furnace alloy melting: is warming up to 300 DEG C；It is 99%CO that smelting furnace, which is passed through volume fraction,2+ 1%SF6It is mixed
Protective gas is closed, is warming up to 680 DEG C；Industry is added according to the ratio of above-mentioned raw materials into the raw material holding furnace for be preheated to 300 DEG C
Pure magnesium (content 99.95wt%), yttrium (99.9wt%), neodymium (99.9wt%), Zr (99.9wt%) and zinc (99.9wt%) arrive
It is heated to being completely melt in smelting furnace, while mechanical stirring is carried out to melt, then refining agent is added in molten magnesium and removes magnesium
In the impurity such as oxide, nitride and alkali metal；The magnesium alloy melt of refining is maintained the temperature at 660 DEG C or so to pour
Note, is made magnesium alloy billet；Wherein, the additive amount of refining agent is that can form one layer of continuous, strict guarantor on magnesium melt surface
Cuticula is added according to the actual situation；The main component of refining agent is MgCl2。
(2) Homogenization Treatments: the magnesium alloy billet of above-mentioned acquisition is uniformly placed in closed Muffle furnace, 515 DEG C into
Row Homogenization Treatments take out the cooling in 70 DEG C of warm water after keeping the temperature 16h；
(3) hot extrusion deformation: by above-mentioned acquisition Mg-4.5Y-1.0Nd-2Zn-0.3Zr magnesium alloy after Homogenization Treatments,
Ingot casting is kept the temperature into 30min at 500 DEG C, guarantees the abundant heat penetration of ingot casting, then directly carries out hot extrusion, squeezes the section for using ingot casting
The ratio between product and the sectional area of magnesium alloy rod after extruding are 20:1, water quenching.
(4) two-stage time effect is strengthened: the Mg-4.5Y-1.0Nd-2Zn-0.3Zr magnesium alloy after hot extrusion deformation is put into timeliness
Twin-stage failure heat treatment is carried out in furnace, technological parameter is 100 DEG C × 4h+220 DEG C × 10h, it is air-cooled, and then obtain the corrosion resistant containing magnesium
The Mg-4.5Y-1.0Nd-2Zn-0.3Zr magnesium alloy of erosion (referring to Fig. 1).
By Mg-4.5Y-1.0Nd-2Zn-0.3Zr magnesium alloy prepared by the present invention, by national standard GB/T228.1-2010 into
Row test, average tensile strength is up to 430MPa or more, and average yield strength is up to 320MPa or more；By national standard GB/
T10125-2012 is tested, and average corrosion weight loss rate is in 0.4mgcm-2·h-1Below.
Embodiment 2
The standard chemical ingredient of corrosion-resistant magnesium alloy of the invention are as follows: Zn:4.0%, Y:5.0%, Nd:1.5%, Zr:
0.5%, surplus Mg.
(1) holding furnace alloy melting: is warming up to 300 DEG C；It is 99%CO that smelting furnace, which is passed through volume fraction,2+ 1%SF6It is mixed
Protective gas is closed, is warming up to 680 DEG C；After being preheated in raw material holding furnace, into the raw material holding furnace for be preheated to 300 DEG C according to above-mentioned
The ratio of raw material, which is added to, to be heated to being completely melt in smelting furnace, while carrying out mechanical stirring to melt, then adds refining agent
Enter the impurity such as oxide, nitride and the alkali metal removed in magnesium in molten magnesium；The magnesium alloy melt of refining is maintained the temperature at
670 DEG C or so are poured, and magnesium alloy billet is made；
(2) Homogenization Treatments: magnesium alloy billet is uniformly placed in closed Muffle furnace, 525 DEG C of progress Homogenization Treatments,
The cooling in 70 DEG C of warm water is taken out after keeping the temperature 18h；
(3) hot extrusion deformation: Mg-5.0Y-1.5Nd-4Zn-0.5Zr magnesium alloy is after Homogenization Treatments, by ingot casting 500
30min is kept the temperature at DEG C, guarantees the abundant heat penetration of ingot casting, then directly carries out hot extrusion, is squeezed with after the sectional area of ingot casting and extruding
The ratio between sectional area of magnesium alloy rod is 20:1, water quenching.
(4) two-stage time effect is strengthened: the Mg-5.0Y-1.5Nd-4Zn-0.5Zr magnesium alloy after hot extrusion deformation is put into timeliness
Twin-stage failure heat treatment is carried out in furnace, technological parameter is 110 DEG C × 5h+225 DEG C × 12h, it is air-cooled, and then obtain the corrosion resistant containing magnesium
The Mg-5.0Y-1.5Nd-4Zn-0.5Zr magnesium alloy (referring to fig. 2) of erosion.
By Mg-5.0Y-1.5Nd-4Zn-0.5Zr magnesium alloy prepared by the present invention, by national standard GB/T228.1-2010 into
Row test, average tensile strength is up to 440MPa or more, and average yield strength is up to 330MPa or more；By national standard GB/
T10125-2012 is tested, and average corrosion weight loss rate is in 0.4mgcm-2·h-1Below.
Embodiment 3
The standard chemical ingredient of corrosion-resistant magnesium alloy of the invention are as follows: Zn:6.0%, Y:5.5%, Nd:2.0%, Zr:
0.7%, surplus Mg.
(1) holding furnace alloy melting: is warming up to 300 DEG C；It is 99%CO that smelting furnace, which is passed through volume fraction,2+ 1%SF6It is mixed
Protective gas is closed, is warming up to 650 DEG C；After being preheated in raw material holding furnace, into the raw material holding furnace for be preheated to 300 DEG C according to above-mentioned
The ratio of raw material, which is added to, to be heated to being completely melt in smelting furnace, while carrying out mechanical stirring to melt, then adds refining agent
Enter the impurity such as oxide, nitride and the alkali metal removed in magnesium in molten magnesium；The magnesium alloy melt of refining is maintained the temperature at
680 DEG C are poured, and magnesium alloy billet is made；
(2) Homogenization Treatments: magnesium alloy billet is uniformly placed in closed Muffle furnace, 535 DEG C of progress Homogenization Treatments,
The cooling in 70 DEG C of warm water is taken out after keeping the temperature 20h；
(3) hot extrusion deformation: Mg-5.5Y-2.0Nd-6Zn-0.7Zr magnesium alloy is after Homogenization Treatments, by ingot casting 500
30min is kept the temperature at DEG C, guarantees the abundant heat penetration of ingot casting, then directly carries out hot extrusion, is squeezed with after the sectional area of ingot casting and extruding
The ratio between sectional area of magnesium alloy rod is 20:1, water quenching.
(4) two-stage time effect is strengthened: the Mg-5.5Y-2.0Nd-6Zn-0.7Zr magnesium alloy after hot extrusion deformation is put into timeliness
Twin-stage failure heat treatment is carried out in furnace, technological parameter is 120 DEG C × 6h+230 DEG C × 14h, it is air-cooled, and then obtain the corrosion resistant containing magnesium
The Mg-5.5Y-2.0Nd-6Zn-0.7Zr magnesium alloy of erosion (referring to Fig. 3).
By Mg-5.5Y-2.0Nd-6Zn-0.7Zr magnesium alloy prepared by the present invention, by national standard GB/T228.1-2010 into
Row test, average tensile strength is up to 450MPa or more, and average yield strength is up to 340MPa or more；By national standard GB/
T10125-2012 is tested, and average corrosion weight loss rate is in 0.4mgcm-2·h-1Below.
Claims (5)
1. a kind of preparation method of the corrosion-proof rare earth magnesium alloy of element containing Zn, it is characterised in that: form by weight percentage are as follows:
Zn:2.0~6.0%, Y:4.5~5.5%, Nd:1.0~2.0%, Zr:0.3~0.7%, surplus Mg, by Mg-Y-Nd-Zn-
Zr alloy melting, Homogenization Treatments, hot extrusion deformation, two-stage time effect are strengthened, i.e. the corrosion-proof rare earth magnesium of acquisition element containing Zn closes
Gold.
2. the preparation method of the corrosion-resistant magnesium alloy of the element according to claim 1 containing Zn, it is characterised in that:
(1) it is preheated in raw material holding furnace: holding furnace being warming up to 300-350 DEG C, smelting furnace is passed through CO2And SF6Hybrid protection gas
Body is continuously heating to 680 DEG C, for use；
(2) pure magnesium (99.95%), yttrium alloy melting: is added after to preheating in raw material holding furnace according to the above ratio
(99.9%), neodymium (99.9%), Zr (99.9%) and zinc (99.9%), make raw material be heated to being completely melt, at the same to melt into
Row mechanical stirring and refining treatment；The magnesium alloy melt of refining is maintained the temperature between 650 DEG C -680 DEG C and is poured, is made
Magnesium alloy billet；
(3) Homogenization Treatments: by above-mentioned acquisition magnesium alloy billet in closed Muffle furnace, 515~535 DEG C are carried out at homogenization
Reason takes out the cooling in 70 DEG C of warm water after keeping the temperature 16~20h；
(4) it hot extrusion deformation: by above-mentioned acquisition Mg-Y-Nd-Zn-Zr magnesium alloy after Homogenization Treatments, is protected at 500-535 DEG C
Warm 30-40min carries out hot extrusion, water quenching；
(5) two-stage time effect is strengthened: the Mg-Y-Nd-Zn-Zr magnesium alloy after hot extrusion deformation is put into progress twin-stage mistake in aging furnace
Effect heat treatment, technological parameter is (100~120) DEG C × (4~6) h+ (220~230) DEG C × (10~14) h, air-cooled.
3. the preparation method of the corrosion-resistant magnesium alloy of the element according to claim 2 containing Zn, it is characterised in that: the CO2With
SF6Hybrid protection gas, volume fraction C O2For 99%, SF6It is 1%.
4. the preparation method of the corrosion-resistant magnesium alloy of the element according to claim 2 containing Zn, it is characterised in that: the step
(2) refining treatment is that refining agent is added in the molten magnesium impurity removed in raw material, can be in magnesium melt surface shape
At one layer of continuous, strict protective film.
5. a kind of corrosion-resistant magnesium alloy of the element containing Zn prepared by claim 1, it is characterised in that: according to claim 1
Method prepares the corrosion-resistant magnesium alloy of the element containing Zn.
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| CN113388767A (en) * | 2021-08-02 | 2021-09-14 | 西安四方超轻材料有限公司 | High-performance magnesium alloy material and preparation method thereof |
| CN115449680A (en) * | 2022-08-17 | 2022-12-09 | 深圳市飞航精工科技有限公司 | Corrosion-resistant magnesium alloy material and preparation method thereof |
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| CN113388767A (en) * | 2021-08-02 | 2021-09-14 | 西安四方超轻材料有限公司 | High-performance magnesium alloy material and preparation method thereof |
| CN115449680A (en) * | 2022-08-17 | 2022-12-09 | 深圳市飞航精工科技有限公司 | Corrosion-resistant magnesium alloy material and preparation method thereof |
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