CN101774013A - Composite grain finer for Mg-Al alloy and preparation method thereof - Google Patents
Composite grain finer for Mg-Al alloy and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a composite grain finer for Mg-Al alloy and a preparation method thereof. The composite finer comprises the following components: 50-60 percent of Al, 1-5 percent of C, 5-10.5 percent of Ca or 5-10.5 percent of Sr, and the balance of Mg. The preparation method comprises the following steps of: melting pure Al under 700-800 DEG C, adding Mg-CA or Mg-Sr intermediate alloy according to the formula, and compensating the insufficient Mg with pure Mg to obtain Al-Mg-Ca or Al-Mg-Sr intermediate alloy melt, cooling the melt to 600-650 DEG C, uniformly dispersing graphite powder into the melt by using a semi-solid stirring method, and casting to obtain the composite grain finer. The finer has the advantages of simple preparation method, easy batch production, easy control of the addition amount, no discharge of pollutant and particularly remarkable fining effect for the Mg-Al alloy with low Al content.
Description
Technical field
The present invention relates to composite grain finer of a kind of Mg-Al of being used for alloy and preparation method thereof, be specifically related to be used for the graphitiferous of Mg-Al alloy and efficient composite refining agent of alkaline-earth metal (Ca or Sr) and preparation method thereof.
Background technology
Magnesium alloy is the lightest structural metallic materials, and it is good to have a light specific gravity, specific strength height, vibration damping, and electromagnetic wave shielding is strong, is easy to advantages such as recovery, is considered to " green " material of the richest development and application potentiality of 21st century.But with respect to ferrous materials, the mechanical property of magnesium alloy materials is still lower, and it is extremely important for promoting the use of magnesium alloy further to improve its intensity, plasticity and toughness.As everyone knows, grain refinement is the important channel of improving the metal material obdurability, and for magnesium alloy, grain size is more more remarkable than the alloy of other crystal structures to the influence of its strong plasticity, also can significantly improve dense structure's property of magnesium alloy simultaneously through grain refinement.Therefore, extremely important by grain refinement technology refinement magnesium alloy for producing the high-performance magnesium-alloy goods.
Traditional crystal fining method, as solid-state processing, semi-solid-state shaping and casting crystal grain fining technology etc., refinement magnesium alloys to some extent all.Comparatively speaking, with microalloying method and carbonaceous inovulant method advantages such as to be that the casting crystal grain fining technology of representative has simple to operate, technology is easy to control, with low cost.Wherein Zr is the effective elements of Mg grain refinement, but forms compd A l because of Zr and Al very easily react
3Zr makes the Mg-Al series cast magnesium alloy that Zr is most widely used in can not effectively refinement industrial production.At the micro-alloying of Mg-Al series cast magnesium alloy refinement, alkaline-earth metal is the most effective refinement element, and its basic principle is to utilize alkaline-earth metal (Ca and Sr) in magnesium melt solidifying process segregation to take place and suppress grain growth.But along with the increase of alloy element content, the degree of refinement of Mg crystal grain reaches capacity very soon, and will generate new alloy phase, causes percentage elongation to reduce, and plasticity descends.And carbonaceous inovulant method mainly is to utilize to contain the C material to decompose the C atom that produces in magnesium melt suitable with α-Mg phase structure with the generation of Al chemical combination, the Al that lattice paprmeter is close
4C
3Particle is as due to the forming core core.
By solidifying basic theories as can be known, the final crystallite dimension of cast product is controlled by following two aspect factors mainly: the one, and the nucleation ability of nucleus and the quantity of effective nucleation thereof; The 2nd, solute element segregation and to the inhibition ability of grain growth.The nucleus nucleation ability is strong more, the dynamics degree of supercooling (T that its crystal growth is required
n) more little; The segregation ability of solute element is high more, and its ability that suppresses grain growth is strong more.
In the publication about the refinement of magnesium alloy carbonaceous, publication number is that the patent application of the Chinese patent of CN1410566 and CN1583327A relates to and utilizes the technology of carbon dust (graphite powder) as carbon source and refinement magnesium alloy separately.Based on above-mentioned composite refining thinking, publication number is the Chinese patent of CN101135013 composite refining agent of disclosing carbon containing and Rare-Earth Ce and preparation method thereof.Document [Metall.Mater.Trans., 2005:p2669] has provided Ca, Sr and three kinds of elements of Ce the inhibiting factor of Mg grain growth has been respectively 11.84,3.51 and 2.74, compares with Sr with Ca, and Ce is relatively low to the growth inhibitory action of Mg crystal grain.In above-mentioned three publications, its preparation process all comprises the links such as mixing, oven dry, compacting and sintering thereof of aluminium powder, graphite powder and magnesium powder, the subject matter that exists is that aluminium powder and magnesium powder are easy to oxidation in preparation process, is difficult to accurately control the fining agent composition.And publication number is the refining effect that the Chinese patent of CN1410566 and patent application that publication number is CN1583327 all only utilize carbon dust, compares with composite refining, and its refining effect is relatively limited.
Summary of the invention
The objective of the invention is to overcome the defective of prior art, composite grain finer of a kind of Mg-Al of being used for alloy and preparation method thereof is provided, the present invention utilizes that carbon and alkaline-earth metal (Ca or Sr) are compound to have prepared a kind of grain refiner efficiently.The inventive method is an alloy at Mg-Al, with carbon containing inovulant method and melt microalloying method Application of composite, utilizes Al
4C
3The high nucleation ability of particle and alloy element effectively suppress the double action of grain growth, obtained a kind of new efficient thinning method, composite grain finer of the present invention has thinning effect preferably, and is especially especially remarkable for the thinning effect of wrought magnesium alloy of low Al content that with AZ31 is representative.
Purpose of the present invention realizes by following technical solution.
Pollution-free, easily dispersion in preparation process that selected carbon source requires.Alloying element then requires it to have higher Mg grain growth inhibition ability, and is not easy to react with carbon source.
Selected carbon source is the graphite powder of granularity at 8～15 μ m;
Selected alloying element is alkaline-earth metal Ca and Sr, adds in the mode of intermediate alloy.
A kind of composite grain finer that is used for the Mg-Al alloy contains following composition: Al, C, Mg and Ca or Sr; The percentage by weight of each composition is: 50～60%Al, 1～5%C, 5～10.5%Ca or 5～10.5%Sr, surplus is Mg.
Prepare the method that is used for the composite grain finer of Mg-Al alloy of the present invention, specifically may further comprise the steps into:
(1) melt pure Al down at 700～800 ℃, add Mg-Ca or Mg-Sr intermediate alloy by prescription, not enough Mg adds with pure Mg form, acquisition Al-Mg-Ca or Al-Mg-Sr intermediate alloy melt;
(2) Al-Mg-Ca or Al-Mg-Sr intermediate alloy melt are cooled to 600～650 ℃, in the time of stirring, slowly add graphite powder, stirred again 2～4 minutes, obtain semi-solid melt by prescription;
(3) with the semi-solid melt cast, promptly get composite grain finer of the present invention.
The granularity of described graphite powder is at 8～15 μ m.
The speed of the described stirring of step (2) is 200～500r/min.
Described prescription is the percentage by weight of each composition in the composite grain finer of the present invention: 50～60%Al, 1～5%C, 5～10.5%Ca or 5～10.5%Sr, surplus is Mg.
Described graphite powder adds above stirring the whirlpool center.
The method that composite refining agent of the present invention uses is:
(1) fusing Mg-Al alloy is incubated after stirring melt treatment and removing slag.For guaranteeing thinning effect, the melt holding temperature needs between 740～760 ℃.
(2) add above-mentioned fining agent block in the Mg-Al alloy melt, its addition melt quality 1.0～1.2% between.The basic principle of addition control is residual for no graphite on the basis that guarantees thinning effect, and does not have the intermetallic compound growth that significantly contains Ca or Sr.
(3) fining agent is incubated the moving worker's stirring of 8～10min defensive position after adding melt, guarantees that graphite powder evenly disperses to impel C and Al to generate Al in the Mg-Al melt
4C
3Phase.Stir the back melt and still need continue to be incubated 10～12min, guarantee enough Al
4C
3Particle generates and as the forming core core of Mg crystal grain.
The present invention compares with prior art, has following advantage and beneficial effect:
(1) the present invention has thinning effect preferably to the magnesium alloy that contains Al, and is especially remarkable for its thinning effect of Mg-Al alloy of low Al content (≤6%) especially.As the AZ31 alloy that is most widely used in the industrial production for low-aluminum-content, with the AZ31 alloy phase ratio without thinning processing, degree of refinement can reach 4～5 times behind composite refining, and its intensity and percentage elongation can improve 20% and 40% respectively after thinning processing.
(2) preparation method of this fining agent is simple, can prepare the homodisperse Mg-Al alloy of graphite powder fining agent, and the grain refiner composition is easy to control, is easy to realize industrialized mass production.
(3) from the use that is prepared into of grain refiner, all contamination-free is discharged, and belongs to Environmentally-sound technology.
(4) after thinning processing, do not have obvious cenotype and generate, do not exist cenotype to generate the problem that causes plasticity to reduce.
Description of drawings
Fig. 1 is the XRD analysis result of Al-Mg-Ca-C composite crystal grain fining agent;
Fig. 2 is the XRD analysis result of Al-Mg-Sr-C composite crystal grain fining agent;
Fig. 3 is the XRD figure spectrum of Al-Mg-C grain refiner;
Fig. 4 is the metallographic structure that the Mg-3Al alloy is handled without fining agent;
Fig. 5 is the metallographic structure that the Mg-3Al alloy is handled through the Al-Mg-C grain refiner;
Fig. 6 is the metallographic structure of Mg-3Al alloy through the 0.2%Ca thinning processing;
Fig. 7 is the metallographic structure of Mg-3Al alloy through the 0.2%Sr thinning processing;
Fig. 8 is the metallographic structure that the Mg-3Al alloy is handled through the Al-Mg-Ca-C grain refiner;
Fig. 9 is the metallographic structure that the Mg-3Al alloy is handled through the Al-Mg-Sr-C grain refiner;
Figure 10 is the metallographic structure that the AZ31 magnesium alloy is handled without fining agent;
Figure 11 is the metallographic structure that the AZ31 magnesium alloy is handled through the Al-Mg-C grain refiner;
Figure 12 is the metallographic structure of AZ31 alloy through the 0.2%Ca thinning processing;
Figure 13 is the metallographic structure of AZ31 alloy through the 0.2%Sr thinning processing;
Figure 14 is the metallographic structure that the AZ31 magnesium alloy is handled through the Al-Mg-Ca-C grain refiner;
Figure 15 is the metallographic structure that the AZ31 magnesium alloy is handled through the Al-Mg-Sr-C grain refiner;
Figure 16 is the XRD figure spectrum of AZ31 magnesium alloy alloy after different fining agents are handled;
Figure 17 is the AZ31 magnesium alloy tensile stress-strain curve of handling through different fining agents;
Figure 18 is hot strength and the percentage elongation through the AZ31 magnesium alloy alloy of different fining agents processing;
Figure 19 is the metallographic structure that the AZ61 magnesium alloy is handled without fining agent;
Figure 20 is the metallographic structure that the AZ61 magnesium alloy is handled through the Al-Mg-C grain refiner;
Figure 21 is the metallographic structure that the AZ61 magnesium alloy is handled through the Al-Mg-Ca-C grain refiner;
Figure 22 is the metallographic structure that the AZ61 magnesium alloy is handled through the Al-Mg-Sr-C grain refiner;
Figure 23 is the XRD figure spectrum of AZ61 magnesium alloy alloy after different fining agents are handled;
Figure 24 is the metallographic structure that the AZ91 magnesium alloy is handled without fining agent;
Figure 25 is the metallographic structure that the AZ91 magnesium alloy is handled through the Al-Mg-C grain refiner;
Figure 26 is the metallographic structure that the AZ91 magnesium alloy is handled through the Al-Mg-Ca-C grain refiner;
Figure 27 is the metallographic structure that the AZ91 magnesium alloy is handled through the Al-Mg-Sr-C grain refiner;
Figure 28 is the XRD figure spectrum of AZ91 magnesium alloy alloy after different fining agents are handled.
The specific embodiment
In order to understand technical characterstic of the present invention better, the present invention is further illustrated below in conjunction with embodiment, need to prove, embodiment is not a limiting the scope of the invention.
The preparation of embodiment 1 Al-Mg-Ca-C composite grain finer
It is raw material that present embodiment adopts pure Al, pure Mg, Mg-30%Ca intermediate alloy and graphite powder, has prepared the Al-Mg-Ca-C composite grain finer.Wherein the preparation method of Mg-30%Ca intermediate alloy is: pure magnesium and pure Ca are put into the mild steel crucible by mass ratio at 7: 3, put into vacuum then and add stove, vacuumize and be heated to 750 ℃, after fusing, crucible is taken out and agitation as appropriate, be molded into mould and promptly get the Mg-30%Ca intermediate alloy.
Al-Mg-Ca-C composite grain finer preparation method is: melt the pure Al of 55g down at 750 ℃, according to the prescription (Ca8.1%, Al 55%, 3%C, all the other are Mg) add Mg-30%Ca intermediate alloy and the pure Mg of 15g of 27g, obtain Al-Mg-Ca intermediate alloy melt; Al-Mg-Ca intermediate alloy melt is cooled to 630 ℃, and it is stirred, mixing speed is 400r/min, stir and utilize a proboscis funnel slowly to add the graphite powder that granularity is 8～15 μ m simultaneously toward stirring the whirlpool center, addition is 3g, stirs 3 minutes again, obtains semi-solid melt.This semi-solid melt of casting promptly gets composite grain finer Al-Mg-Ca-C of the present invention.
The preparation of embodiment 2 Al-Mg-Ca-C composite grain finers
It is raw material that present embodiment adopts pure Al, pure Mg, Mg-30%Ca intermediate alloy and graphite powder, has prepared the Al-Mg-Ca-C composite grain finer.Its preparation method is: melt the pure Al of 50g down at 700 ℃, stir, according to Mg-30%Ca and the pure Mg of 32g of prescription (Ca 5%, and Al 50%, and C 1%, and all the other are Mg) adding 17g, obtain Al-Mg-Ca intermediate alloy melt; Al-Mg-Ca intermediate alloy melt is cooled to 600 ℃, and it is stirred, mixing speed is 200r/min, stir and utilize a proboscis funnel slowly to add the graphite powder that granularity is 8～15 μ m simultaneously toward stirring the whirlpool center, addition is 1g, stirs 3 minutes again, obtains semi-solid melt.This semi-solid melt of casting promptly gets composite grain finer Al-Mg-Ca-C of the present invention.
The preparation of embodiment 3 Al-Mg-Ca-C composite grain finers
It is raw material that present embodiment adopts pure Al, Mg-30%Ca intermediate alloy and graphite powder, has prepared the Al-Mg-Ca-C composite grain finer.Its preparation method is: at 800 ℃ of following pure Al of fusing 60g, stir, add the Mg-30%Ca acquisition Al-Mg-Ca intermediate alloy melt of 35g according to prescription (10.5%Ca, Al 60%, C 5%, all the other be Mg); Al-Mg-Ca intermediate alloy melt is cooled to 650 ℃, and it is stirred, mixing speed is 500r/min, stir and utilize a proboscis funnel slowly to add the graphite powder that granularity is 8～15 μ m simultaneously toward stirring the whirlpool center, addition is 5g, stirs 3 minutes again, obtains semi-solid melt.This semi-solid melt of casting promptly gets composite grain finer Al-Mg-Ca-C of the present invention.
The preparation of embodiment 4 Al-Mg-Sr-C composite grain finers
It is raw material that present embodiment adopts pure Al, pure Mg, Mg-30%Sr intermediate alloy and graphite powder, has prepared the Al-Mg-Sr-C composite grain finer.Wherein the preparation method of Mg-30%Sr intermediate alloy is: pure magnesium and pure Sr are put into the mild steel crucible by mass ratio at 7: 3, put into vacuum then and add stove, vacuumize and be heated to 750 ℃, after fusing, crucible is taken out and agitation as appropriate, be molded into mould and promptly get the Mg-30%Sr intermediate alloy.
Its preparation method is: at 750 ℃ of following pure Al of fusing 55g, add Mg-30%Sr intermediate alloy and the pure Mg of 15g of 27g, acquisition Al-Mg-Sr intermediate alloy melt according to prescription (Sr 8.1%, and Al 55%, 3%C, all the other be Mg); Al-Mg-Sr intermediate alloy melt is cooled to 630 ℃, and it is stirred, mixing speed is 400r/min, stir and utilize a proboscis funnel slowly to add the graphite powder that granularity is 8～15 μ m simultaneously toward stirring the whirlpool center, addition is 3g, stirs 3 minutes again, obtains semi-solid melt.This semi-solid melt of casting promptly gets composite grain finer Al-Mg-Sr-C of the present invention.
The preparation of embodiment 5 Al-Mg-Sr-C composite grain finers
It is raw material that present embodiment adopts pure Al, pure Mg, Mg-30%Sr intermediate alloy and graphite powder, has prepared the Al-Mg-Sr-C composite grain finer.Its preparation method is: at 700 ℃ of following pure Al of fusing 50g, stir, add Mg-30%Sr and the pure Mg of 32g of 17g, acquisition Al-Mg-Sr intermediate alloy melt according to prescription (Sr5%, Al 50%, C 1%, all the other be Mg); Al-Mg-Sr intermediate alloy melt is cooled to 600 ℃, and it is stirred, mixing speed is 200r/min, stir and utilize a proboscis funnel slowly to add the graphite powder that granularity is 8～15 μ m simultaneously toward stirring the whirlpool center, addition is 1g, stirs 3 minutes again, obtains semi-solid melt.This semi-solid melt of casting promptly gets composite grain finer Al-Mg-Sr-C of the present invention.
The preparation of embodiment 6 Al-Mg-Sr-C composite grain finers
It is raw material that present embodiment adopts pure Al, Mg-30%Sr intermediate alloy and graphite powder, has prepared the Al-Mg-Sr-C composite grain finer.Its preparation method is: at 800 ℃ of following pure Al of fusing 60g, stir, add the Mg-30%Sr acquisition Al-Mg-Sr intermediate alloy melt of 35g according to prescription (10.5%Sr, Al 60%, C 5%, all the other be Mg); Al-Mg-Sr intermediate alloy melt is cooled to 650 ℃, and it is stirred, mixing speed is 500r/min, stir and utilize a proboscis funnel slowly to add the graphite powder that granularity is 8～15 μ m simultaneously toward stirring the whirlpool center, addition is 5g, stirs 3 minutes again, obtains semi-solid melt.This semi-solid melt of casting promptly gets composite grain finer Al-Mg-Sr-C of the present invention.
The preparation of embodiment 7 Al-Mg-C composite grain finers
Be the thinning effect of comparative illustration composite refining agent, it is raw material that present embodiment adopts pure Al, pure Mg and graphite powder, has prepared the Al-Mg-C grain refiner that only contains C.Its preparation method is: at 750 ℃ of following pure Al of fusing 55g, add the pure Mg of 42g, acquisition Al-Mg intermediate alloy melt according to prescription (Al 55%, 3%C, all the other be Mg); Al-Mg intermediate alloy melt is cooled to 630 ℃, and it is stirred, mixing speed is 400r/min, stir and utilize a proboscis funnel slowly to add the graphite powder that granularity is 8～15 μ m simultaneously toward stirring the whirlpool center, addition is 3g, stirs 3 minutes again, obtains semi-solid melt.This semi-solid melt of casting promptly gets the Al-Mg-C grain refiner Al-Mg-C that only contains C.
Be the Al-Mg-Ca-C prepared among check the present invention and the thinning effect and the range of application thereof of Al-Mg-Sr-C composite refining agent, the Al-Mg-C fining agent that following embodiment 8,9,10 and 11 uses Al-Mg-Ca-C, Al-Mg-Sr-C composite refining agent to Mg-3Al, AZ31, AZ61 and AZ91 alloy respectively and only contains C carries out thinning processing, and checks its thinning effect.
The grain refinement of embodiment 8:Mg-3Al alloy is handled
The present invention selected graphite powder as carbon source to guarantee Al
4C
3Nucleus generates, and selects alkaline-earth metal to suppress element as the Mg grain growth simultaneously, and Fig. 1, Fig. 2 have provided the Al-Mg-Ca-C that embodiment 1 and embodiment 4 prepare and the XRD analysis result of two kinds of composite crystal grain fining agents of Al-Mg-Sr-C.For two kinds of intermediate alloys, all generated Al therein
4C
3Phase also exists simple substance C, i.e. graphite simultaneously.And, all generated Al with the Al reaction in preparation process for alloying element Ca or Sr
4Ca, AlSr, Al
4Intermetallic compounds such as Sr.
For the remarkable result of comparative illustration Al-Mg-Ca-C of the present invention and two kinds of composite crystal grain fining agents of Al-Mg-Sr-C, the embodiment of the invention 7 has prepared the only Al-Mg-C grain refiner of carbon containing, and Fig. 3 is the XRD figure spectrum of Al-Mg-C fining agent.In this alloy, there is Al equally
4C
3Phase also exists simple substance C, i.e. graphite simultaneously.
The Mg-3Al alloy of at first selecting only to contain 3%Al utilizes above-mentioned three kinds of grain refiners to handle, and the Mg-3Al alloy is the basic ingredient of wrought magnesium alloy AZ31 the most frequently used in the industrial production.
At first take by weighing the pure Mg of 50g and, add pure Al and fusing formation Mg-Al melt subsequently respectively 750 ℃ of fusings.Need it should be noted that, owing to all contain Al in the used grain refiner, so the Al constituent content in the fining agent that when melting proportioning, need consider to be added.Add fining agent after stirring removes slag to the Mg-Al melt, addition is 1.0～1.2% of a Mg-Al melt quality.The fining agent that adds in the present embodiment is respectively embodiment 1, example 4 and example 7 preparations and gets.The basic principle of addition control is residual for no graphite on the basis that guarantees thinning effect, and does not have the intermetallic compound growth that significantly contains Ca or Sr.The moving worker of insulation 10min defensive position stirred after fining agent added melt, guaranteed that graphite powder evenly disperses to impel C and Al to generate Al in the Mg-Al melt
4C
3Phase.Stir the back melt and still need continue to be incubated 10min, guarantee enough Al
4C
3Particle generates and as the forming core core of Mg crystal grain.
For the Al-Mg-C fining agent, after adding the Mg-Al melt, following reaction will take place with the Al in the Mg-Al melt in simple substance C:
4Al+3C＝Al
4C
3 (1)
Al
4C
3The fusing point of phase (＞2000 ℃) is very high, has very high stability in the Mg-Al melt, therefore for the Al that exists among the Al-Mg-C
4C
3Mutually will be in company with Al newly-generated in the melt
4C
3The phase disperse enters in the Mg-Al melt, and as the forming core core of Mg crystal grain, numerous Al
4C
3The existence of particle will promote the refinement of Mg crystal grain.
And for Al-Mg-Ca-C and Al-Mg-Sr-C composite refining agent, can have the reaction shown in 1 formula equally and generate Al
4C
3Phase, the intrinsic Al that exists in fining agent simultaneously
4C
3Phase, the final refinement that all disperse is evenly distributed in the Mg-Al melt and promotes Mg crystal grain; On the other hand, for the Al that exists in two kinds of fining agents
4Ca, AlSr, Al
4Phases such as Sr contrast Al-Ca and Mg-Ca phasor, Al-Sr and Mg-Sr phasor as can be known, and in 740～760 ℃ temperature range, these intermetallic compounds all following decomposition reaction can take place:
Al
4Ca＝4Al+Ca (2)
AlSr＝Al+Sr (3)
Al
4Sr＝4Al+Sr (4)
And the form with simple substance Ca or Sr exists in melt.The concentration of Ca and Sr depends on holding temperature and temperature retention time and addition thereof after the adding in the melt after decomposing.The basic principle of Ca or Sr addition control is for guaranteeing not have the intermetallic compound that significantly contains Ca or Sr and generate giving full play under the prerequisite of thinning effect.
Contain the C fining agent thinning effect of (comprising Al-Mg-C, Al-Mg-Sr-C and Al-Mg-Ca-C) for further contrasting, also utilize Mg-30%Ca and Mg-30%Sr alloy that the Mg-3Al alloy is carried out thinning processing in this enforcement, wherein the addition of Ca and Sr is suitable in the addition of Ca and Sr and the composite refining agent.
Fig. 4,5,6,7,8 and 9 has provided the not Mg-3Al of refinement respectively, and the Mg-3Al alloy metallographic structure photo after Al-Mg-C fining agent, Mg-30%Ca and Mg-30%Sr intermediate alloy and Al-Mg-Ca-C and Al-Mg-Sr-C composite refining agent are handled respectively.Relatively crystallite dimension as can be seen, after the fining agent through only containing C was handled, its degree of refinement was 3 times (among the present invention not after the crystallite dimension of thinning processing alloy and the refinement ratio of crystallite dimension be defined as degree of refinement).And for the Mg-3Al alloy that only adds Ca and Sr, its thinning effect is than slightly poor through the Mg-3Al of C refinement alloy.And for after the composite refining agent processing through containing C and alkaline-earth metal (Ca and Sr), its degree of refinement further improves, and degree of refinement can reach 5 times.As seen, carbonaceous breeds effectively refinement Mg-3Al alloy, and can obtain excellent more thinning effect under the compound action of carbon and alkaline-earth metal.
The grain refinement of embodiment 9:AZ31 magnesium alloy is handled
The AZ31 magnesium alloy is the wrought magnesium alloy that is most widely used, and its composition is 2.8～3.2%Al, 0.6～0.9%Zn, 0.2～0.3%Mn, and all the other are Mg.This alloy is compound more a spot of Zn and Mn on the basis of Mg-3Al alloy, and the purpose that adds Zn is to improve its intensity, and Mn mainly is in order to eliminate the adverse effect of Fe in the magnesium alloy.
Utilize three kinds of fining agents of Al-Mg-C, Al-Mg-Ca-C and Al-Mg-Sr-C respectively the AZ31 magnesium alloy to be carried out thinning processing.Processing procedure before the thinning processing is substantially the same manner as Example 8, and slightly different part is to need to add pure Zn before thinning processing and the Mg-Mn intermediate alloy carries out Zn and Mn Alloying Treatment.Thinning processing technology is identical with embodiment 8.Fundamental reaction after the thinning processing in melt and refinement mechanism are substantially the same manner as Example 8.
Figure 10,11,12,13,14 and 15 has provided the not AZ31 alloy of refinement respectively, and the AZ31 alloy metallographic structure photo after Al-Mg-C fining agent, Mg-30%Ca and Mg-30%Sr intermediate alloy and Al-Mg-Ca-C and Al-Mg-Sr-C composite refining agent are handled respectively.Relatively crystallite dimension as can be seen, with the AZ31 alloy phase ratio of not refinement, only contain the thinning processing of C after, the obvious refinement of AZ31 alloy grain, its degree of refinement is 3 times.And for the AZ31 alloy that only adds Ca and Sr, its thinning effect is than slightly poor through the AZ31 of C refinement alloy.And for the AZ31 alloy through Al-Mg-Ca-C and Al-Mg-Ca-C composite refining agent thinning processing, the further refinement of its crystallite dimension, its degree of refinement is further brought up to 4 times.As seen, for the AZ31 magnesium alloy, carbonaceous breeds also significantly its crystallite dimension of refinement, and can obtain excellent more thinning effect after the composite refining of carbon and alkaline-earth metal is handled.
Figure 16 has provided the not AZ31 of refinement, and the AZ31 alloy XRD figure spectrum after Al-Mg-C fining agent, Al-Mg-Ca-C and Al-Mg-Sr-C composite refining agent are handled respectively.For the AZ31 alloy, its phase composition is mainly Mg and Mg
17Al
12, after fining agent was handled, its phase composition did not have significant change, still mainly by Mg and Mg
17Al
12Form.As seen, for the AZ31 magnesium alloy, marked change can not take place in its phase composition after above-mentioned three kinds of fining agents are handled.
In the present embodiment, the not AZ31 alloy of refinement that utilized stretching test machine determination, and the strength character of the AZ31 magnesium alloy handled through Al-Mg-C fining agent, Mg-30%Ca and Mg-30%Sr intermediate alloy and Al-Mg-Ca-C and Al-Mg-Sr-C composite refining agent respectively of AZ31 alloy, shown in figure answers among Figure 17 and Figure 18.A among Figure 17 and Figure 18, b, c, d, e and f respectively corresponding not refinement the AZ31 alloy and respectively through the AZ31 alloy of Al-Mg-C, Mg-30%Ca and Mg-30%Sr intermediate alloy and Al-Mg-Ca-C and Al-Mg-Sr-C thinning processing.Wherein Figure 17 is a tensile stress strain curve, and Figure 18 is average tensile strength and percentage elongation.The result shows, compare with untreated samples, the warp AZ31 magnesium alloy strength and the percentage elongation of carbon modifying-refining separately all increases, and after carbon and the processing of alkaline-earth metal composite refining, its intensity and percentage elongation all further improve, and increase rate is about 20% and 40% respectively.
The grain refinement of embodiment 10:AZ61 magnesium alloy is handled
The AZ61 magnesium alloy is the another kind of common wrought magnesium alloy of AZ series magnesium alloy kind, compares with AZ31, and its Al content is higher.Its basis is 5.8～6.2%Al, 0.6～0.9%Zn, 0.2～0.3%Mn, and all the other are Mg.
Utilize Al-Mg-C, Al-Mg-Ca-C and three kinds of fining agents of Al-Mg-Sr-C of embodiment 7, embodiment 1 and embodiment 4 preparations that the AZ61 magnesium alloy is carried out thinning processing respectively.Technical process before and after the melt thinning processing is identical with embodiment 9 with embodiment 8, and fundamental reaction after the thinning processing in melt and refinement mechanism are substantially the same manner as Example 8.
Figure 19,20,21 and 22 has provided the not AZ61 of refinement, and the metallographic structure photo of AZ61 alloy after the Al-Mg-C fining agent through only containing C and Al-Mg-Ca-C and two kinds of composite refining agents of Al-Mg-Sr-C are handled respectively.Relatively crystallite dimension is compared the AZ61 magnesium alloy after thinning processing, the obvious refinement of its crystallite dimension as can be seen with untreated AZ61.But do not have obvious difference through its crystallite dimension of AZ61 magnesium alloy that three kinds of fining agents are handled, compare with the AZ61 magnesium alloy that is untreated, its degree of refinement is about 3 times.As seen, for the AZ61 magnesium alloy, carbonaceous breeds also significantly its crystallite dimension of refinement, but alkaline-earth metal and carbon composite refining can not further be improved its thinning effect.
Figure 23 has provided the not AZ61 of refinement, and the XRD figure spectrum of AZ61 alloy after the Al-Mg-C fining agent through only containing C and Al-Mg-Ca-C and two kinds of composite refining agents of Al-Mg-Sr-C are handled respectively.For the AZ61 alloy, its phase composition is mainly Mg and Mg
17Al
12, after fining agent was handled, its phase composition did not have significant change, still mainly by Mg and Mg
17Al
12Form.As seen, for the AZ61 magnesium alloy, marked change can not take place in its phase composition after above-mentioned three kinds of fining agents are handled.
The grain refinement of embodiment 11:AZ91 magnesium alloy is handled
The AZ91 magnesium alloy is to use cast magnesium alloy very widely in the AZ series magnesium alloy, and its composition is: 8.8～9.2%Al, 0.6～0.9%Zn, 0.2～0.3%Mn, all the other are Mg.The main feature of this alloy is an Al content height, near eutectic composition, has good casting property, the intensity advantages of higher.
Utilize Al-Mg-C, Al-Mg-Ca-C and three kinds of fining agents of Al-Mg-Sr-C of embodiment 7, embodiment 1 and embodiment 4 preparations that the AZ91 magnesium alloy is carried out thinning processing in the present embodiment respectively.Technical process before and after the melt thinning processing is identical with embodiment 8 and 9, and fundamental reaction after the thinning processing in melt and refinement mechanism are substantially the same manner as Example 8.
Figure 24,25,26 and 27 has provided the not AZ91 of refinement respectively, and the metallographic structure photo of AZ91 alloy after the Al-Mg-C fining agent through only containing C and Al-Mg-Ca-C and two kinds of composite refining agents of Al-Mg-Sr-C are handled respectively.For the AZ91 magnesium alloy, because of higher Al content, its crystallite dimension is less.Compare with untreated AZ91 magnesium alloy, its crystal particle scale of AZ91 magnesium alloy of handling through fining agent only has a little refinement, and its degree of refinement is about 1.2 times.As seen, for the AZ91 magnesium alloy, the grain size of itself is tiny, and it is all less to the influence of its crystallite dimension that independent carbonaceous breeds refinement or alkaline-earth metal and carbon composite refining, and thinning effect is not remarkable.
Figure 28 has provided the not AZ91 of refinement, and the XRD figure spectrum of AZ91 alloy after the Al-Mg-C fining agent through only containing C and Al-Mg-Ca-C and two kinds of composite refining agents of Al-Mg-Sr-C are handled respectively.For the AZ91 alloy, its phase composition is mainly Mg and Mg
17Al
12, after fining agent was handled, its phase composition did not have significant change, still mainly by Mg and Mg
17Al
12Form.As seen, for the AZ91 magnesium alloy, marked change can not take place in its phase composition after above-mentioned three kinds of fining agents are handled.
Claims (6)
1. a composite grain finer that is used for the Mg-Al alloy is characterized in that, the percentage by weight that contains following composition is:
Al 50～60％；
C 1～5％；
Ca or Sr 5～10.5%;
Surplus is Mg.
2. the described method that is used for the composite grain finer of Mg-Al alloy of preparation claim 1 is characterized in that, specifically may further comprise the steps:
(1) melt pure Al down at 700～800 ℃, add Mg-Ca or Mg-Sr intermediate alloy by prescription, not enough Mg adds with pure Mg form, acquisition Al-Mg-Ca or Al-Mg-Sr intermediate alloy melt;
(2) Al-Mg-Ca or Al-Mg-Sr intermediate alloy melt are cooled to 600～650 ℃, in the time of stirring, slowly add graphite powder, stirred again 2～4 minutes, obtain semi-solid melt by prescription;
(3) with the semi-solid melt cast, promptly get composite grain finer of the present invention.
3. method according to claim 2 is characterized in that, the granularity of described graphite powder is at 8～15 μ m.
4. method according to claim 2 is characterized in that, the speed of the described stirring of step (2) is 200～500r/min.
5. method according to claim 2 is characterized in that, described prescription is the percentage by weight of each composition:
Al 50～60％；
C 1～5％；
Ca or Sr 5～10.5%;
Surplus is Mg.
6. method according to claim 2 is characterized in that, described graphite powder adds above stirring the whirlpool center.
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Cited By (7)
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| CN102534311A (en) * | 2011-12-20 | 2012-07-04 | 暨南大学 | Aluminium calcium carbon grain refiner for Mg-Al series magnesium alloy and preparation method and application thereof |
| EP2481822A1 (en) * | 2011-02-01 | 2012-08-01 | Helmholtz-Zentrum Geesthacht Zentrum für Material- und Küstenforschung GmbH | Magnesium-aluminum based alloy with grain refiner |
| CN103502494A (en) * | 2011-03-30 | 2014-01-08 | 韩国生产技术研究院 | Mg-al-ca-based master alloy for mg alloys, and a production method therefor |
| CN107245593A (en) * | 2017-06-26 | 2017-10-13 | 重庆文理学院 | Magnesium intermediate alloy grain refiner and its preparation method and application |
| 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 |
| CN110170629A (en) * | 2019-07-05 | 2019-08-27 | 安徽楚江高新电材有限公司 | A method of reducing shaft furnace copper bar twist irregularity |
| CN115433862A (en) * | 2022-08-05 | 2022-12-06 | 太原理工大学 | Preparation method of Ni-free degradable magnesium-based material |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2481822A1 (en) * | 2011-02-01 | 2012-08-01 | Helmholtz-Zentrum Geesthacht Zentrum für Material- und Küstenforschung GmbH | Magnesium-aluminum based alloy with grain refiner |
| CN103502494A (en) * | 2011-03-30 | 2014-01-08 | 韩国生产技术研究院 | Mg-al-ca-based master alloy for mg alloys, and a production method therefor |
| CN102534311A (en) * | 2011-12-20 | 2012-07-04 | 暨南大学 | Aluminium calcium carbon grain refiner for Mg-Al series magnesium alloy and preparation method and application thereof |
| CN107245593A (en) * | 2017-06-26 | 2017-10-13 | 重庆文理学院 | Magnesium intermediate alloy grain refiner and its preparation method and application |
| 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 |
| CN110170629A (en) * | 2019-07-05 | 2019-08-27 | 安徽楚江高新电材有限公司 | A method of reducing shaft furnace copper bar twist irregularity |
| CN115433862A (en) * | 2022-08-05 | 2022-12-06 | 太原理工大学 | Preparation method of Ni-free degradable magnesium-based material |
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