CN106756180A - A kind of calcium/magnesia grain refiner and its preparation method and application - Google Patents
A kind of calcium/magnesia grain refiner and its preparation method and application Download PDFInfo
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- CN106756180A CN106756180A CN201611111273.9A CN201611111273A CN106756180A CN 106756180 A CN106756180 A CN 106756180A CN 201611111273 A CN201611111273 A CN 201611111273A CN 106756180 A CN106756180 A CN 106756180A
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- magnesium
- grain refiner
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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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- 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
- C22C1/03—Making non-ferrous alloys by melting using master alloys
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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
Abstract
The invention discloses a kind of calcium/magnesia grain refiner and preparation method and application, belong to non-ferrous metal technical field.Grain refiner of the present invention has obvious core-shell structure, and wherein calcium constituent is distributed in the periphery of magnesium oxide particle；Particle size distribution is concentrated mainly on 200nm or so.Specifically preparation method is：Under sulfur hexafluoride and nitrogen mixed gas protection, pure magnesium is heated to half solidification state；Lime powder is added, stirring makes it be uniformly blended into the magnesium liquid of half solidification state；Raise furnace temperature to magnesium liquid to be completely melt, target product is obtained after cast iron casting molding is poured into after quiescence in high temperature.Grain refiner of the invention is obvious to magnesium and magnesium alloy grains effect；And the grain refining effect for having kept is remained in the case where different solidification cooling conditions or high temperature stand do not stir for a long time；The grain refiner preparation cost is relatively low, and adding technology is simple, is suitable to industrialized production.
Description
Technical field
The invention belongs to non-ferrous metal technical field, and in particular to a kind of calcium/magnesia grain refiner and its preparation side
The application of method and the fining agent in magnesium and magnesium alloy.
Background technology
The equiax crystal of fine uniform is magnesium and the optimal as-cast structure of magnesium alloy materials, to obtain this tissue, it is necessary to logical
Cross the miniaturization treatment of different means crystal grain thinnings, i.e. crystalline structure.Its means includes adding various intermediate alloys during liquid
Fining agent or by extraneous energy, such as mechanical oscillation, electromagnetic agitation, high speed shear, ultrasonication refine α-Mg matrixes,
So as to significantly improve the mechanical property and process industrial art performance of magnesium material.Crystal grain refinement can simultaneously improve intensity and the modeling of material
Property, it is to obtain high-quality magnesium ingot, improve the important channel of magnesium material amount.Current 90% magnesium alloy is mainly used under as cast condition, because
The crystal grain refinement of this magnesium alloy cast tissue is particularly important.Special equipment and technique is needed by extraneous energy, in actual work
It is relatively difficult to achieve in industry production, and also limited by working condition etc., its effect is limited, and process is difficult to control.In industrial production
Under the conditions of, it is most simple and effective method only to add fining agent, is also the important component of Serum Magnesium treatment technology.Mesh
The crystal grain refinement means of preceding industrial magnesium and its alloy press two kinds of situations of alloy species point：The first situation is containing almag
Crystal grain refinement.Generally using the addition of overheat, carbon or carbon compound.The stability of such fining agent grain refining effect limits it
Large-scale application industrially.Second situation is free from the crystal grain refinement of almag.Common use is added in the middle of magnesium zirconium
Alloy approach realizes crystal grain refinement.But in actual applications, the fining agent there is also noble metal zirconium consumption greatly, and zr element is chemically
Matter is active, the problems such as easily failure with other element reactions.
The content of the invention
The present invention is for existing magnesium and its alloy grain refinement deficiency and defect, it is proposed that a kind of calcium/magnesia crystal grain is thin
Agent, to having the stable performance simultaneously of stronger grain refining effect to magnesium and its alloy, being easy to industrialization.
In order to solve the above technical problems, what the present invention was achieved by the following technical programs.
The invention provides a kind of grain refiner, its forming core particle is that typical core-shell structure, i.e. calcium constituent are distributed in
The periphery of magnesium oxide particle, particle diameter distribution is uniform, and average grain diameter is 200nm.
Invention also provides the preparation method of above-mentioned grain refiner, comprise the following steps that：Crucible toward after cleaning
It is interior to add pure magnesium, under sulfur hexafluoride and nitrogen mixed gas protection, it is heated to half solidification state；It is a small amount of repeatedly to add calcium oxide powder
End, its average particle size range is 0.1~1 μm；Lime powder addition CaO by weight ratio:Mg=1~5:100；Add every time
Enter that calcium oxide powder is last, be sufficiently stirred for ensureing that the lime powder for adding is uniformly blended into the magnesium liquid of half solidification state；Continue to rise
Furnace temperature high stands insulation and is completely melt to magnesium liquid to 680~720 DEG C, is stirred well to added lime powder more uniform distribution
In Serum Magnesium；Then melt is poured into the cast iron casting mould of cylinder, casting cycle leads to protective gas, it is ensured that liquation is in the casting stage
It is missing of ignition, target product is obtained after air natural cooling：Calcium/magnesia grain refiner.
Above-mentioned grain refiner can be used for the crystal grain refinement of magnesium or magnesium alloy.In this application, the grain refiner is accounted for
The mass percent of magnesium or magnesium alloy is 0.1~1%.
The principles of science of the present invention：
Additional lime powder is unstable in pure magnesium melt, easily generates magnesia and calcium, wherein calcium by pure magnesium-reduced
Element absorption in situ forms typical core-shell structure in the mgo surface of reduction.The calcium constituent adsorbed in mgo surface leads to
Cross to form transition intermediate compound form raising magnesia to magnesium and its nucleation ability of alloy, play and effectively refine magnesium crystal grain
Effect.
Compared with prior art, the present invention has following technique effect：
1st, the preparation method of fining agent of the present invention is simple and easy to control, cheap, it is easy to accomplish industrialized production.
2nd, grain refiner particle diameter distribution prepared by the present invention is uniform, and addition manner is simple.
3rd, the grain refiner that prepared by the present invention is obvious to the grain refining effect of magnesium and its alloy.
4th, grain refiner prepared by the present invention stands what is do not stirred for a long time in different solidification cooling conditions or high temperature
In the case of remain to the grain refining effect that has kept.
Brief description of the drawings
Fig. 1 is calcium/magnesia grain refiner particulate scan transmission electron microscope picture prepared by the embodiment of the present invention 1；
Wherein：A () is calcium/magnesia grain refiner particle micro-organization chart；B () is calcium constituent distribution map, can by figure
Know, calcium constituent is distributed in the periphery of magnesium oxide particle.
Fig. 2 be after adding pure Serum Magnesium before and after grain refiner to be cast through TP1 macrostructure's comparison diagram of sample (crystal grain is thin
Agent is prepared by the embodiment of the present invention 1, similarly hereinafter)；
Wherein：A () is the macrostructure of sample after pure Serum Magnesium is cast through TP1；B () is 0.1% to add mass fraction
Grain refiner pure Serum Magnesium through TP1 cast after sample macrostructure.
Fig. 3 is the microstructure comparison diagram of Mg-3Al alloy melts sample after TP1 casting before and after addition grain refiner；
Wherein：A () is the microstructure of sample after Mg-3Al alloy melts are cast through TP1；B () is to add mass fraction
The microstructure of the Mg-3Al alloy melts of 0.1% grain refiner sample after TP1 casting.
Fig. 4 is macrostructure's comparison diagram of pure Serum Magnesium sample after wedge-shaped die casting before and after addition grain refiner；
Wherein：A () is the macrostructure of sample after pure Serum Magnesium is cast through wedge-shaped die；B () is to add mass fraction
The macrostructure of the pure Serum Magnesium of 0.1% grain refiner sample after wedge-shaped die casting.
Fig. 5 is that the pure Serum Magnesium quiescence in high temperature different time sampling of the grain refiner for adding mass fraction to be 0.1% (divides
Dui Ying 0.5h (a), 1.5h (b), 2.5h (c), 6.5h (d)) cast through TP1 after sample macrostructure's comparison diagram.
Specific embodiment
Below in conjunction with specific embodiments and the drawings in detail the present invention is described in detail, but the present invention is not limited to following embodiments.
First, the preparation of grain refiner
Embodiment 1
Pure magnesium is added in toward the crucible after cleaning, under sulfur hexafluoride and nitrogen mixed gas protection, half solidification is heated to
State；A small amount of repeatedly to add lime powder, its average grain diameter is 0.1 μm；Lime powder addition CaO by weight ratio:Mg
=1:100；Add calcium oxide powder last every time, be sufficiently stirred for ensureing that the lime powder for adding is uniformly blended into half solidification state
In magnesium liquid；Continue raise furnace temperature to 680 DEG C, stand insulation be completely melt to magnesium liquid, be stirred well to added lime powder compared with
It is evenly distributed in Serum Magnesium；30min is incubated at 680 DEG C, melt pours into the cast iron casting mould (a diameter of 10mm) of cylinder；Cast
Journey leads to protective gas, it is ensured that liquation is missing of ignition in the casting stage, and air natural cooling obtains grain refiner of the invention.
Embodiment 2
Pure magnesium is added in toward the crucible after cleaning, under sulfur hexafluoride and nitrogen mixed gas protection, half solidification is heated to
State；A small amount of repeatedly to add lime powder, its average grain diameter is 1 μm；Lime powder addition CaO by weight ratio:Mg=
1:100；Add calcium oxide powder last every time, be sufficiently stirred for ensureing that the lime powder for adding is uniformly blended into the magnesium of half solidification state
In liquid；Continue to raise furnace temperature to 680 DEG C, stand insulation and be completely melt to magnesium liquid, be stirred well to added lime powder more equal
It is even to be distributed in Serum Magnesium；30min is incubated at 680 DEG C, melt pours into the cast iron casting mould (a diameter of 10mm) of cylinder；Casting cycle
Logical protective gas, it is ensured that liquation is missing of ignition in the casting stage, and air natural cooling obtains grain refiner of the invention.
Embodiment 3
Pure magnesium is added in toward the crucible after cleaning, under sulfur hexafluoride and nitrogen mixed gas protection, half solidification is heated to
State；A small amount of repeatedly to add lime powder, its average particle size range is 0.1 μm；Lime powder addition is by weight ratio
CaO:Mg=5:100；Add calcium oxide powder last every time, be sufficiently stirred for ensureing that it is solidifying that the lime powder for adding is uniformly blended into half
In the magnesium liquid of solid-state；Continue to raise furnace temperature to 680 DEG C, stand insulation and be completely melt to magnesium liquid, be stirred well to added calcium oxide
Powder more uniform distribution is in Serum Magnesium；30min is incubated at 680 DEG C, melt pours into the cast iron casting mould (a diameter of 10mm) of cylinder；
Casting cycle leads to protective gas, it is ensured that liquation is missing of ignition in the casting stage, and air natural cooling obtains grain refiner of the invention.
Embodiment 4
Pure magnesium is added in toward the crucible after cleaning, under sulfur hexafluoride and nitrogen mixed gas protection, half solidification is heated to
State；A small amount of repeatedly to add lime powder, its average particle size range is 0.1 μm；Lime powder addition is by weight ratio
CaO:Mg=5:100；Add calcium oxide powder last every time, be sufficiently stirred for ensureing that it is solidifying that the lime powder for adding is uniformly blended into half
In the magnesium liquid of solid-state；Continue to raise furnace temperature to 720 DEG C, stand insulation and be completely melt to magnesium liquid, be stirred well to added calcium oxide
Powder more uniform distribution is in Serum Magnesium；30min is incubated at 680 DEG C, melt pours into the cast iron casting mould (a diameter of 10mm) of cylinder；
Casting cycle leads to protective gas, it is ensured that liquation is missing of ignition in the casting stage, and air natural cooling obtains grain refiner of the invention.
Embodiment 5
Pure magnesium is added in toward the crucible after cleaning, under sulfur hexafluoride and nitrogen mixed gas protection, half solidification is heated to
State；A small amount of repeatedly to add lime powder, its average particle size range is 0.1 μm；Lime powder addition is by weight ratio
CaO:Mg=5:100；Add calcium oxide powder last every time, be sufficiently stirred for ensureing that it is solidifying that the lime powder for adding is uniformly blended into half
In the magnesium liquid of solid-state；Continue to raise furnace temperature to 680 DEG C, stand insulation and be completely melt to magnesium liquid, be stirred well to added calcium oxide
Powder more uniform distribution is in Serum Magnesium；30min is incubated at 720 DEG C, melt pours into the cast iron casting mould (a diameter of 10mm) of cylinder；
Casting cycle leads to protective gas, it is ensured that liquation is missing of ignition in the casting stage, and air natural cooling obtains grain refiner of the invention.
2nd, the comparative test of grain refiner performance
Embodiment I：The pure magnesium of business level is added into low-carbon (LC) steel crucible, the melting in electrical crucible, be passed through sulfur hexafluoride and
Nitrogen mixed gas are protected, and smelting temperature is 680 DEG C；After after the fusing of pure magnesium, 680 DEG C stand isothermal holding 30min；Deslagging degasification
Afterwards, TP-1 ingot castings are cast into 680 DEG C；After cooling and demolding, the pure magnesium ingot casting of gained is cut open along longitudinal section, corrodes and observe macroscopical group
Knit.
Comparative example I：This example production stage is substantially the same manner as Example 1, be a difference in that treat pure magnesium melt completely, stand and
After deslagging degasification, the grain refiner prepared by the method for embodiment 1 disclosed by the invention is added, in an amount of from pure magnesium mass fraction
0.1%, it is sufficiently stirred for, 680 DEG C are cast into TP-1 ingot castings；After cooling and demolding, gained magnesium alloy ingot is cut open along longitudinal section, corrosion
And observe metallurgical microstructrue.
Embodiment II：Mg-3Al magnesium alloys are added into low-carbon (LC) steel crucible, the melting in electrical crucible is passed through sulfur hexafluoride
With nitrogen mixed gas protection, smelting temperature is 680 DEG C；After after magnesium alloy fusing, 680 DEG C stand isothermal holding 30min；Deslagging
After degasification, 680 DEG C are cast into TP-1 ingot castings；After cooling and demolding, gained magnesium alloy ingot is cut open along cross section, corrodes and observes and be grand
See tissue.
Comparative example II：This example production stage is substantially the same manner as Example 2, is a difference in that and treats that Mg-3Al magnesium alloys melt completely
After solution, standing and deslagging degasification, the grain refiner prepared by the method for embodiment 1 disclosed by the invention is added, closed in an amount of from magnesium
The 0.1% of golden mass fraction, is sufficiently stirred for, and 680 DEG C are cast into TP-1 ingot castings；After cooling and demolding, gained magnesium alloy ingot is along horizontal
Section, corrodes and observes metallurgical microstructrue.
Embodiment III：The pure magnesium of business level is added into low-carbon (LC) steel crucible, the melting in electrical crucible, be passed through sulfur hexafluoride and
Nitrogen mixed gas are protected, and smelting temperature is 680 DEG C；After after the fusing of pure magnesium, 680 DEG C stand isothermal holding 30min；Deslagging degasification
Afterwards, 680 DEG C pour into casting wedge shape mould；After cooling and demolding, the pure magnesium ingot casting of gained is cut open along longitudinal section, corrodes and observe macroscopical group
Knit.
Comparative example III：This example production stage is substantially the same manner as Example 3, is a difference in that and treats that pure magnesium melts, stands completely
And after deslagging degasification, the grain refiner prepared by the method for embodiment 1 disclosed by the invention is added, in an amount of from pure magnesium mass fraction
0.1%, be sufficiently stirred for, 680 DEG C pour into casting wedge shape mould；After cooling and demolding, the pure magnesium ingot casting of gained is cut open along longitudinal section, corrosion
And observe metallurgical microstructrue.
Embodiment IV：The pure magnesium of business level is added into low-carbon (LC) steel crucible, the melting in electrical crucible, by SF6/N2Mixing
Gas shield, smelting temperature is 680 DEG C；Melt completely after pure magnesium, stand and deslagging degasification after, add disclosed by the invention by reality
The grain refiner of the method for example 1 preparation is applied, in an amount of from the 0.1% of pure magnesium mass fraction, rear quiescence in high temperature is sufficiently stirred for, selected respectively
Take 0.5h, 1.5h, 2.5h and 6.5h are not cast into TP-1 ingot castings under stirring state；After cooling and demolding.Gained magnesium ingot casting cuts along vertical
Face is cut open, corrodes and observe metallurgical microstructrue.
Result shows there is obvious core-shell structure, wherein calcium constituent using calcium of the invention/magnesia grain refiner
It is distributed in the periphery of magnesium oxide particle；Grain diameter is concentrated mainly on 200nm or so (referring to Fig. 1)；The grain refiner is pure
Preferably, grainiess is changed into equiax crystal to thinning effect by typical column crystal in magnesium (referring to Fig. 2)；The grain refiner exists
Preferably, average grain size is reduced to 100 μm (referring to Fig. 3) thinning effect by 400 μm in Mg-3Al magnesium alloys；The crystal grain refinement
The crystal grain that agent remains to keep in the case where solidification cooling different condition (referring to Fig. 4) or high temperature stand do not stir for a long time is thin
Change effect (referring to Fig. 5).
Claims (3)
1. a kind of calcium/magnesia grain refiner, it is characterised in that：The fining agent has core-shell structure, and calcium constituent is distributed in oxygen
Change the periphery of magnesium granules, particle diameter distribution is uniform, and average grain diameter is 200nm.
2. the preparation method of calcium as claimed in claim 1/magnesia grain refiner, it is characterised in that comprise the following steps：
(1) toward the pure magnesium of addition in the crucible after cleaning, under sulfur hexafluoride and nitrogen mixed gas protection, it is heated to half solidification
State；
(2) a small amount of repeatedly toward addition lime powder in crucible, its average particle size range is 0.1~1 μm；Lime powder is added
Amount CaO by weight ratio:Mg=1~5:100；Add calcium oxide powder last every time, be sufficiently stirred for the calcium oxide to ensure to add
Powder is uniformly blended into the magnesium liquid of half solidification state；
(3) continue to raise furnace temperature to 680~720 DEG C, stand insulation and be completely melt to magnesium liquid, be stirred well to added calcium oxide powder
End is evenly distributed in Serum Magnesium；Then melt is poured into the cast iron casting mould of cylinder, casting cycle leads to protective gas, it is ensured that liquation
Missing of ignition in the casting stage, natural cooling obtains calcium/magnesia grain refiner under air.
3. calcium as claimed in claim 1/application of the magnesia grain refiner in magnesium or magnesium alloy, it is characterised in that：Institute
It is 0.1~1% to state grain refiner and account for magnesium or the mass percent of magnesium alloy.
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| CN201611111273.9A CN106756180B (en) | 2016-12-01 | 2016-12-01 | A kind of calcium/magnesia grain refiner and its preparation method and application |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107988500A (en) * | 2017-12-11 | 2018-05-04 | 安徽工业大学 | Application of the barium monoxide as grain refiner in magnesium or magnesium alloy |
| CN109022861A (en) * | 2018-09-30 | 2018-12-18 | 华南理工大学 | A kind of crystal fining method of Mg-Al system alloy |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100507040C (en) * | 2007-10-11 | 2009-07-01 | 武汉理工大学 | Mg-Al series alloy composite grain refiner and method for making same |
| KR101367894B1 (en) * | 2011-01-06 | 2014-02-26 | 한국생산기술연구원 | Magnesium alloy for normal temperature |
| CN101812607B (en) * | 2010-04-22 | 2011-12-28 | 东北轻合金有限责任公司 | Magnesium alloy refiner and preparation method thereof |
-
2016
- 2016-12-01 CN CN201611111273.9A patent/CN106756180B/en active Active
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107988500A (en) * | 2017-12-11 | 2018-05-04 | 安徽工业大学 | Application of the barium monoxide as grain refiner in magnesium or magnesium alloy |
| CN109022861A (en) * | 2018-09-30 | 2018-12-18 | 华南理工大学 | A kind of crystal fining method of Mg-Al system alloy |
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