CN100516262C - Method for preparing magnesium and magnesium alloy composite grain refiner - Google Patents
Method for preparing magnesium and magnesium alloy composite grain refiner Download PDFInfo
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- CN100516262C CN100516262C CNB2007100535302A CN200710053530A CN100516262C CN 100516262 C CN100516262 C CN 100516262C CN B2007100535302 A CNB2007100535302 A CN B2007100535302A CN 200710053530 A CN200710053530 A CN 200710053530A CN 100516262 C CN100516262 C CN 100516262C
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Abstract
The present invention provides one kind of grain refiner for magnesium and magnesium alloy and its preparation process. The grain refiner has the chemical composition including Al 15-37.5 wt%, C 5-12.5 wt%, Ce 5-20 wt% and Mg for the rest. Its preparation process includes the following steps: mixing aluminum powder, carbon powder and magnesium powder; pressing into block and stoving, setting inside corundum crucible and covering with refractory powder, isothermal treatment inside a box-type resistance furnace at 700-900 deg.c for 30-120 min to prepare Mg-Al4C3, and remelting together with magnesium ingot and intermediate Mg-25 %Ce alloy to prepare Mg-Al4C3-Ce as composite grain refiner finally. The present invention has convenient operation and easy use in industrial production, and the prepared composite grain refiner can fine grains of magnesium and magnesium alloy obviously.
Description
Technical field
The present invention relates to metallic substance, particularly relate to a kind of magnesium and magnesium alloy composite grain refiner and preparation method thereof, the composite crystal grain fining agent of utilization preparation is refinement magnesium and magnesium alloy alloy grain effectively.
Background technology
The industrial application of magnesium alloy starts from the thirties in 20th century, at present, magnesium alloy has been widely used in fields such as traffic transport industry and 3C electronic product, and the consumption of global magnesium increases fast with annual 20% speed, this is unprecedented in the modern project metallic substance is used, therefore, magnesium alloy is described as the green engineering material that 21 century has the development and application potentiality most.Yet magnesium alloy is the close-packed hexagonal crystalline structure, and slip system is few, causes its viscous deformation difficulty.In addition, the unsound oxide film of the perishable formation of Mg alloy surface (MgO), its corrosion resistance nature is relatively poor.Therefore, add the fining agent crystal grain thinning putting forward heavy alloyed mechanical property, to improve corrosive nature and plastic deformation ability, thereby further promote the application of magnesium alloy.
Magnesium alloy by whether containing the Zr element, can being divided into contains the Zr magnesium alloy and does not contain the Zr magnesium alloy.There are some researches show that Zr can effectively suppress the grain growing of magnesium alloy, thereby crystal grain thinning be to be extensive use of in the Mg-RE system at pure Mg, Mg-Zn, but the solubleness of Zr in pure magnesium and alloy thereof is limited.Precipitate owing to Zr and Al, Mn form stable compound, can not play the effect of crystal grain thinning, therefore, can not add Zr in Mg-Al system and Mg-Mn in the alloy.The crystal fining method of magnesium and magnesium alloy mainly contains overheated method, anhydrous chlorides of rase iron processes, carbonaceous and breeds method, adds solute element (such as rare earth element ce, La, Nd, Y, or mishmetal MM etc.; Alkaline earth element Ca, Sr, Ba etc.), add particle (such as Al
4C
3, AlN, SiC, B
4C, TiC etc.).Wherein, carbonaceous breeds that the method raw material sources are extensive, and service temperature is lower, has become the topmost grain refinement technology of Mg-Al series magnesium alloy.This method is to realize grain refinement by add carbon compound in the magnesium melt.Carbon compound (such as carbon dioxide, acetylene, natural gas, calcium carbonate, magnesium carbonate, solid paraffin, graphite granule, dim, carbon trichloride, hexachloro-benzene etc.) at high temperature decomposites the Al that Al chemical combination in nascent state C atom and the alloy forms a large amount of disperses
4C
3Particle becomes the heterogeneous nucleus of α-Mg, thus the refinement alloy grain.
Al
4C
3Be the high-melting-point ceramic phase, fusing point is about 2100 ℃, therefore, has good heat endurance in magnesium alloy fused mass.Al
4C
3Be the Patterns for Close-Packed Hexagonal Crystal structure, and lattice paprmeter is close with α-Mg, it and Mg are 4.05% at the upper face mismatch along three low index crystal orientation of basal plane (0001), are the good heterogeneous nucleus of α-Mg.Magnesium is difficult for forming stable carbide, and therefore, carbide particle is stable in pure magnesium.Hence one can see that, Al
4C
3Can be used as the heterogeneous nucleus of α-Mg crystallization, improve nucleation rate, be applicable to pure magnesium and various magnesium alloy series, having potentiality aspect the refinement of the crystal grain side of magnesium and magnesium alloy.
At present, Al
4C
3The preparation method mainly contain: melt contact reaction method, mechanical alloying, controlled atmosphere isothermal processes, self propagating high temperature are synthetic and generate by interfacial reaction.
The melt contact reaction method: reactant is directly joined in the metal bath with powder or pressed compact form, by between the heat initiation reaction thing of melt inside or the exothermic reaction between the alloying element in reactant and the melt, thus the synthetic Al of original position
4C
3Utilize the melt contact reaction method to prepare Al
4C
3Mainly contain the three aspects: difficulty: the density contrast of C powder and aluminium liquid is bigger, and is difficult with in the C powder immersion aluminium liquid; The wetability of C and Al liquid is poor; The solubility of C in Al liquid is very low.
Mechanical alloying: will carry out high-energy ball milling after the powder of simple substance element or compound, to bring out the various reactions of consolidating, synthetic novel compound or composite.There are some researches show and only rely on simple mechanical alloying ball milling Al powder and C powder to be difficult to obtain Al
4C
3Compound needs the Ball-milling Time grown very much could combination without repetition (such as 220 hours) in other words, and this is unfavorable for industrial production.If will react more complete, need follow-up isothermal thermal treatment after the mechanical alloying usually.
Controlled atmosphere isothermal processes: in the protective atmosphere of vacuum or inert gas, be pressed into prefabricated section after a certain proportion of reactant powders mixed and put into heat-treatment furnace, and being incubated a period of time under the fixed temperature, contain Al with preparation
4C
3Fining agent.
Self propagating high temperature is synthetic: reactant powder art is mixed and be compacted into base, under vacuum or inert atmosphere conditions, with the base substrate heating, produce the combustion wave of height heat release, spontaneous the spreading of reaction carried out, until reaction is all finished.Al
4C
3The adiabatic temperature of self propagating high temperature reaction be 1200K, Al
4C
3syntheticly have sufficient thermodynamic condition, but this reaction belongs to weak heat release system, reaction can not spread down.Serve as detonator if in reactant, add suitable strong heat release system mixture, make reaction continue to carry out, but will be to bringing impurity in the synthetic, therefore, self propagating high temperature synthesizes Al
4C
3In experiment with industrially all be not applied.
Al
4C
3Preparation except above-mentioned synthesis technique, in the preparation of the composite of aluminium alloy, as utilize SiC particle, B
4C particle, carbon fiber etc. strengthen aluminium alloy, and generation Al is easy to react at the interface of carbide or graphite granule and aluminium liquid
4C
3Compound utilizes the method to prepare and contains a certain amount of Al
4C
3Intermediate alloy.
The Al that commercially produces
4C
3(utilize reaction 2Al
2O
3+ 9C=Al
4C
3+ 6CO) purity can be up to 99%, if but be used for magnesium alloy grains, its cost is too high.Melt contact reaction method, mechanical alloying and self propagating high temperature are synthetic all can to obtain a certain amount of Al
4C
3, but these technological operations are wayward, and can not quantitative analysis Al
4C
3Content.Controlled atmosphere Isothermal Hot facture is synthesized Al
4C
3Particle has some superiority, but higher to equipment requirement.
Rare earth element has the effect of its uniqueness in metallurgy, Material Field, it can purify alloy molten solution, improves Alloy At Room Temperature and mechanical behavior under high temperature, improves the alloy corrosion resistance energy.Rare earth also is familiar with gradually to the effect of magnesium alloy, and cerium (Ce) except above-mentioned effect is arranged, also has obvious Grain Refinement Effect to magnesium alloy.
Summary of the invention
Technical problem to be solved by this invention is: provide that a kind of do not need special atmosphere or vacuum protection environment and prepare at a lower temperature can be quantitatively and magnesium and magnesium alloy composite grain refiner with good interface; this is for improving magnesium alloy mechanical property, improving corrosion resistance nature and plastic deformation ability, widens magnesium and the Application of Magnesium scope is significant.
The present invention solves its technical problem and adopts following technical scheme:
Magnesium provided by the invention and magnesium alloy composite grain refiner contain Al, C, Mg and cerium, and the weight percent of each chemical ingredients is: 15～37.5% aluminium, and 5～12.5% carbon, 5～20% ceriums, surplus is a magnesium.
The preparation method of above-mentioned magnesium provided by the invention and magnesium alloy composite grain refiner is: utilization is done and is mixed, briquetting is that 30～60% aluminium powders, 10～20% carbon dusts and magnesium powder surplus are made prefabricated section with percentage by weight, put into corundum crucible after the oven dry and use refractory powder art landfill, put into chamber type electric resistance furnace in 700～900 ℃ of isothermal processes 30～120min, obtain Mg-(50～80%) Al
4C
3, process by remelting with magnesium ingot and Mg-25%Ce intermediate alloy again, make Mg-Al
4C
3-Ce composite crystal grain fining agent.
The present invention utilizes powder art in-situ synthesis can prepare the Mg-Al with good interface in common firing equipment (such as the common chamber type electric resistance furnace of no vacuum and protective atmosphere condition)
4C
3Intermediate alloy, and by effectively controlling percentage and reaction temperature and the temperature retention time of reactant, can obtain Al
4C
3Mg-Al with definite percentage composition and size
4C
3Intermediate alloy.
The present invention compared with prior art also has following major advantage:
(1) adopt common heating installation, utilize briquetting, aluminium foil parcel and fire-resistant powder landfill can effectively stop the oxidizing fire of reactant, preparation technology is easy, and is with low cost, is easy to realize industrialized mass production.
(2) by content and reaction temperature and the reaction time of control synthetic, can effectively control Al
4C
3Percentage composition and size.Because Al
4C
3Synthesize, grow up at the magnesium matrix situ, each has good interface and thermodynamic stability mutually in the fining agent.
(3) Al
4C
3In air, be easy to moisture absorption efflorescence and lost efficacy, therefore process by follow-up remelting and can effectively preserve Al
4C
3
(4) after magnesium and magnesium alloy are handled through composite refining agent, the alloy at room temperature mechanical property be can effectively improve, alloy corrosion resistance energy and plastic deformation ability obviously improved.
(5) magnesium and the magnesium alloy composite refining agent of present method preparation have good grain refining effect and the anti-ageing ability of moving back.The addition of this composite refining agent should guarantee Al in the alloy
4C
3Be respectively 0.1～1.0% and 0.05～0.3% with the content of Ce.
That present method can realize is with low cost, easy and simple to handle, the magnesium of effect stability and the preparation of magnesium alloy composite grain refiner.
Description of drawings
Fig. 1 is that 800 ℃ of insulation 100min prepare Mg-50%Al
4C
3The intermediate alloy X-ray diffractogram.
Fig. 2 is that 800 ℃ of insulation 100min prepare Mg-50%Al
4C
3Intermediate alloy powder sample ESEM microscopic structure.
Fig. 3 for the composite crystal grain fining agent that adds different content after magnesium alloy scanning electron microscope microstructure.
Among Fig. 3: (a) be AZ91; (b) be AZ91+0.5% (Mg-25%Al
4C
3-12%Ce).
Embodiment
The present invention is to provide a kind of magnesium and magnesium alloy composite grain refiner, contain Al, C, Mg and cerium, the weight percent of each chemical ingredients is: 15～37.5% aluminium, and 5～12.5% carbon, 5～20% ceriums, surplus is a magnesium.
The preparation method of above-mentioned magnesium provided by the invention and magnesium alloy composite grain refiner is: utilization is done and is mixed, briquetting is that 30～60% aluminium powders, 10～20% carbon dusts and magnesium powder (surplus) are made prefabricated section with percentage by weight, put into corundum crucible after the oven dry and use refractory powder art landfill, put into chamber type electric resistance furnace in 700～900 ℃ of isothermal processes 30～120min, obtain Mg-(50～80%) Al
4C
3, process by remelting with magnesium ingot and Mg-25%Ce intermediate alloy again, make Mg-Al
4C
3-Ce composite crystal grain fining agent.
Employed Al powder purity 〉=99%, granularity≤100 μ m, C powder purity 〉=99.85%, granularity≤30 μ m, Mg powder purity 〉=99%, granularity≤100 μ m, magnesium ingot purity 〉=99.97%.
The present invention adopts common chamber type electric resistance furnace to carry out isothermal processes, and the powder original position is synthesized Mg-(50～80%) Al
4C
3Intermediate alloy, and prepare above-mentioned magnesium and magnesium alloy composite grain refiner by remelting processing, concrete steps are:
(1) is that the weight proportion of magnesium powder takes by weighing starting material by 30～60%Al, 10～20%C, surplus, mixed 6～12 hours in that mixer is thousands of;
(2) to be cold-pressed into relative density be 45～55% reaction prefabricated block to the powder after will mixing under 25～35MPa pressure, and wrap up prefabricated section with aluminium foil, in 100～150 ℃ of oven dry;
(3) prefabricated section after will drying is put into corundum crucible and with fire-resistant powder landfill;
(4) will be embedded with common chamber type electric resistance furnace that the corundum crucible of prefabricated section puts into no controlled atmosphere in 700～900 ℃ of isothermal processes, temperature retention time is 30～120min, realizes Al
4C
3Original position synthetic;
(5) question response is finished and is cooled off rear taking-up prefabricated section, makes Mg-(50～80%) Al
4C
3Intermediate alloy;
(6) with percentage by weight be 25～75% Mg-(50～80%) Al
4C
3Intermediate alloy and 20～80% Mg-25%Ce intermediate alloy join remelting in the magnesium melt, finally prepare Mg-(20～50%) Al
4C
3-(5～20%) Ce composite crystal grain fining agent.
In the AZ91 magnesium alloy fused mass, add 0.3～2% Mg-(20～50%) Al
4C
3Behind the Ce of-(5～20%), make the crystallite dimension of alloy be down to 50～60 μ m by 96 μ m.
The invention will be further described below in conjunction with specific examples, but do not limit the present invention.
Example 1:Mg-20%Al
4C
3The preparation of-15%Ce composite crystal grain fining agent
(1) is that 60% aluminium powder, 20% carbon dust and 20% magnesium powder were done mixed 12 hours at batch mixer with percentage by weight, is cold-pressed into subsequently relative density and is 45% prefabricated section, process and imbed in the corundum crucible with aluminium foil parcel post-drying;
(2) use chamber type electric resistance furnace at 900 ℃ of isothermal processes 120min;
(3) take out prefabricated section, make Mg-80%Al
4C
3Intermediate alloy;
(4) with percentage by weight be 15% Mg ingot, 25% Mg-80%Al
4C
3Intermediate alloy and 60% Mg-25%Ce intermediate alloy carry out remelting to be processed, and makes Mg-20%Al
4C
3-15%Ce composite crystal grain fining agent.
(5) in the AZ91 magnesium alloy, behind this composite crystal grain fining agent of adding 1.5%, can make the grain-size of alloy reduce to 53 μ m by 96 μ m.
Example 2:Mg-25%Al
4C
3The preparation of-12%Ce composite crystal grain fining agent
(1) is that 37.5% aluminium powder, 12.5% carbon dust and 50% magnesium powder were done mixed 6 hours at batch mixer with percentage by weight, is cold-pressed into subsequently relative density and is 50% prefabricated section, process and imbed in the corundum crucible with aluminium foil parcel post-drying;
(2) adopt chamber type electric resistance furnace to carry out isothermal processes, at 700 ℃ of insulation 30min;
(3) take out prefabricated section, make Mg-50%Al
4C
3Intermediate alloy;
(4) with percentage by weight be 2% Mg ingot, 50% Mg-50%Al
4C
3Intermediate alloy and 48% Mg-25%Ce intermediate alloy carry out remelting to be processed, and makes Mg-25%Al
4C
3-12%Ce composite crystal grain fining agent.
In the AZ91 magnesium alloy, behind this composite crystal grain fining agent of adding 0.5%, can make the grain-size of alloy reduce to 58 μ m by 96 μ m.
Example 3:Mg-40%Al
4C
3The preparation of-7%Ce composite crystal grain fining agent
(1) be the magnesium powder of 48% aluminium powder, 16% carbon dust and 36% is cold-pressed into relative density 48% after batch mixer is done mixed 8 hours prefabricated section with percentage by weight, with the post-drying processing of aluminium foil parcel and imbed in the corundum crucible;
(2) in chamber type electric resistance furnace at 780 ℃ of isothermal processes 60min;
(3) take out prefabricated section, make Mg-64%Al
4C
3Intermediate alloy;
(4) with percentage by weight be 9.5% Mg ingot, 62.5% Mg-64%Al
4C
3Intermediate alloy and 28% Mg-25%Ce intermediate alloy carry out remelting to be processed, and makes Mg-40%Al
4C
3-7%Ce composite crystal grain fining agent.
In the AZ91 magnesium alloy, behind this composite crystal grain fining agent of adding 1.0%, can make the grain-size of alloy reduce to 56 μ m by 96 μ m.
Claims (4)
1. the preparation method of a magnesium and magnesium alloy composite grain refiner, it is characterized in that utilize doing mixed, briquetting is that 30～60% aluminium powders, 10～20% carbon dusts and magnesium powder surplus are made prefabricated section with percentage by weight, put into corundum crucible after the oven dry also with fire-resistant powder landfill, put into chamber type electric resistance furnace in 700～900 ℃ of isothermal processes 30～120min, obtain Mg-(50～80%) Al
4C
3, process by remelting with magnesium ingot and Mg-25%Ce intermediate alloy again, make Mg-Al
4C
3-Ce composite crystal grain fining agent; The percentage by weight of the chemical composition of described composite crystal grain fining agent is 15～37.5% aluminium, 5～12.5% carbon, and 5～20% ceriums, surplus is magnesium.
2. the preparation method of magnesium according to claim 1 and magnesium alloy composite grain refiner is characterized in that adopting the method for following steps:
(1) is that the weight proportion of magnesium powder takes by weighing starting material by 30～60%Al, 10～20%C, surplus, on mixer, does and mixed 6～12 hours;
(2) to be cold-pressed into relative density be 45～55% reaction prefabricated block to the powder after will mixing under 25～35MPa pressure, and wrap up prefabricated section with aluminium foil, in 100～150 ℃ of temperature oven dry;
(3) prefabricated section after will drying is put into corundum crucible and with fire-resistant powder landfill;
(4) corundum crucible that will be embedded with prefabricated section is inserted in the chamber type electric resistance furnace in 700～900 ℃ of isothermal processes 30～120min;
(5) question response is finished and is cooled off rear taking-up prefabricated section, makes Mg-(50～80%) Al
4C
3Intermediate alloy;
(6) with percentage by weight be 25～75% Mg-(50～80%) Al
4C
3Intermediate alloy and 20～80% Mg-25%Ce intermediate alloy join remelting in the magnesium melt, make Mg-(20～50%) Al
4C
3-(5～20%) Ce composite crystal grain fining agent.
3. the preparation method of the composite crystal grain fining agent of magnesium according to claim 2 and magnesium alloy, it is characterized in that Al powder purity 〉=99%, granularity≤100 μ m, C powder purity 〉=99.85%, granularity≤30 μ m, Mg powder purity 〉=99%, granularity≤100 μ m, magnesium ingot purity 〉=99.97%.
4. the preparation method of the composite crystal grain fining agent of magnesium according to claim 2 and magnesium alloy is characterized in that adding 0.3～2% Mg-(20～50%) Al in the AZ91 magnesium alloy fused mass
4C
3-(5～20%) Ce makes alloy grain be down to 50～60 μ m by 96 μ m.
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|---|---|---|---|
| CNB2007100535302A CN100516262C (en) | 2007-10-11 | 2007-10-11 | Method for preparing magnesium and magnesium alloy composite grain refiner |
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| CN100516262C true CN100516262C (en) | 2009-07-22 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| TWI565924B (en) * | 2014-12-30 | 2017-01-11 | 基準精密工業（惠州）有限公司 | Crucible |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101608269B (en) * | 2009-07-06 | 2011-06-29 | 武汉理工大学 | Mg-Al-C-Ce refiner for magnesium and magnesium alloy and preparation method thereof |
| 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 |
| ES2424005T3 (en) * | 2011-02-01 | 2013-09-26 | Helmholtz-Zentrum Geesthacht Zentrum für Material- und Küstenforschung GmbH | Magnesium-aluminum based alloy with grain refiner |
| CN102251129A (en) * | 2011-07-15 | 2011-11-23 | 燕山大学 | Refiner for magnesium-aluminum-based alloy and preparation method thereof |
| CN102489692A (en) * | 2011-12-05 | 2012-06-13 | 大连理工大学 | Method for preparing Al-Ti-C-Gd grain refiner of magnesium alloys by utilizing ultrasonic waves |
| CN112404374B (en) * | 2020-11-30 | 2022-05-31 | 中国科学院金属研究所 | Preparation method and application of refiner |
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Non-Patent Citations (2)
| Title |
|---|
| 铈对镁合金AZ31晶粒大小及铸态力学性能的影响. 张世军，黎文献，余琨.铸造，第51卷第12期. 2002 |
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| TWI565924B (en) * | 2014-12-30 | 2017-01-11 | 基準精密工業（惠州）有限公司 | Crucible |
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