CN102485928A - Cerium-rich mischmetal-containing high-strength heat-resisting magnesium alloy and preparation method thereof - Google Patents

Cerium-rich mischmetal-containing high-strength heat-resisting magnesium alloy and preparation method thereof Download PDF

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Publication number
CN102485928A
CN102485928A CN2010105809211A CN201010580921A CN102485928A CN 102485928 A CN102485928 A CN 102485928A CN 2010105809211 A CN2010105809211 A CN 2010105809211A CN 201010580921 A CN201010580921 A CN 201010580921A CN 102485928 A CN102485928 A CN 102485928A
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ingot
magnesium alloy
magnesium
cerium
magnesiumalloy
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张奎
李兴刚
李永军
马志新
马鸣龙
张凤岗
王强
曹忠
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Beijing General Research Institute for Non Ferrous Metals
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Beijing General Research Institute for Non Ferrous Metals
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Abstract

The invention discloses a cerium-rich mischmetal-containing high-strength heat-resisting magnesium alloy and a preparation method thereof. The cerium-rich mischmetal-containing high-strength heat-resisting magnesium alloy comprises: by weight, 6.5 to 15% of Y, 0.7 to 3.0% of cerium-rich mischmetal, 0.4 to 1.2% of Zr and the balance Mg. The preparation method comprises the following steps of 1, preparing raw materials, pre-heating a pure magnesium ingot, a pure Y ingot, a cerium-rich mischmetal ingot and a Mg-Zr intermediate alloy ingot, melting the pre-heated pure magnesium ingot, dissolving the pre-heated pure Y ingot, the pre-heated cerium-rich mischmetal ingot and the pre-heated Mg-Zr intermediate alloy ingot in the magnesium melt to obtain magnesium alloy melt, and pouring or casting the magnesium alloy melt into a magnesium alloy ingot blank, 2, carrying out uniformization heat treatment through processes of 1), heating the magnesium alloy ingot blank to a temperature of 490 to 540 DEG C and 2), carrying out heat preservation for 10 to 60 hours so that the alloy elements of Y, cerium-rich mischmetal and Zr are uniformly distributed in the base metal, 3, carrying out thermal deformation processing, 4, carrying out waste heat quenching processing, and 5, carrying out aging treatment. The cerium-rich mischmetal-containing high-strength heat-resisting magnesium alloy can satisfy requirements of high mechanical properties and high-temperature creep-resistant properties. The thermal deformation processing is directly carried out after the uniformization heat treatment and the waste heat quenching and the aging treatment are adopted, and thus the preparation method can solve the problems of poor reinforcement effects and poor stability of cerium-rich mischmetal alloy elements of Ce, La and Pr in magnesium.

Description

The high-strength heat-resisting magnesium alloy and the preparation working method thereof that contain cerium-rich mischmetal
Technical field
The present invention relates to contain the high-strength heat-resisting magnesium alloy and the preparation working method thereof of cerium-rich mischmetal; So-called cerium-rich mischmetal metal is exactly the mischmetall that consists predominantly of Ce, La, Nd, Pr, and wherein Ce is approximately 50wt%, La and is approximately that 30wt%, Nd are approximately 15wt%, Pr is approximately 5wt%.The category that belongs to industrial magnesiumalloy.
Background technology
At present; Along with energy-conserving and environment-protective and automotive performance promote improving constantly of requiring; Magnesiumalloy is because density is little, the specific tenacity specific rigidity is high, good casting property; Especially be easy to die cast, remove this and also have good damping property and be easy to advantage such as recovery, present flourish gesture in the application of automotive industry.The continuous expansion of on automobile, using along with magnesiumalloy; Like structural part and the functional part development of component from original gear box casing, panel board, car door etc. to critical positions such as engine support, piston, wheel hubs; People also satisfy the magnesiumalloy of various demands of different in exploitation, like high-strength and high ductility heat resistance magnesium alloy, high temperature and creep resistance corrosion-resistant magnesium alloy etc.
Traditional magnesiumalloy such as AZ91D, AM60B, AS41, AE42 etc. have obtained to use widely, still are several kinds of maximum magnesiumalloy of present application quantity.But these alloys all have some shortcoming, for example the intensity in temperature more than 250 ℃ very low (≤100MPa), corrosion resistance is poor, creep-resistant property low (AZ91D, AM60B), and its cutting be easy to the burning, the poor stability during mechanical workout.Restricting the application of magnesiumalloy on vitals such as mover.
On the other hand, China's rare-earth mineral is main with the light rare earths component, and wherein components such as cerium, lanthanum, yttrium account for more than 60%.Along with China's rare earth permanent-magnetic material, rare earth luminescent material, polishing powder from rare earth, rare earth enlarge in the medium Application Areas of metallurgical industry year by year; The demand of home market centering heavy rare earths also increases fast; Because rare earth resources is non-renewable; Add in recent years irrational extraction of resources to the rare earth Mineral resources; Make country all the more strict to the management and the exploitation of existing rare earth resources, cause the price of pure rare earth element to rise year by year, these all cause indirectly with the preparation cost of pure rare earth element (Y, Nd etc.) for the magnesiumalloy of main alloy element and improve constantly.
The applicant proposes " a kind of heat resistance magnesium alloy of H.T. and melting method thereof " (patent No. is 200510130470.0) on December 13rd, 2005, propose to contain 8~16wt%Y in the magnesiumalloy.
The applicant proposes " high-strength heat-resistant magnesium alloy and melting method thereof " (patent No. is 200610112627.1) on August 25th, 2006, propose to contain 7~16wt%Y in the magnesiumalloy; 2~4.5wtNd.
The applicant proposes " a kind of high-strength heat-resistant magnesium alloy and melting method thereof " (patent No. is 200610112622.9) on August 25th, 2006, propose to contain 4.5~10wt%Y, 0~8wt%Gd in the magnesiumalloy; 0~5wt%Dy, 0~5wt%Tb, 0~5wt%Ho; 0~5wt%Er; 0~5wt%Tm, 2~4.5wt%Nd, 0~3.5wt%Sm.
The applicant proposes " creep resistance Dow metal and preparation method thereof " (patent No. is 200710118287.8) on July 4th, 2007, proposes to contain 1.5~10wt%Y, 0.15~2.0wt%Zr, 0.3~2.0wt%Nd in the magnesiumalloy; 2.5~8wt%Gd, and among Sm, Dy, Tb, Ho, Er, Tm and the Eu one or more, wherein, 0~1.5wt%Sm; 0~5wt%Dy, 0~5wt%Tb, 0~5wt%Ho; 0~5wt%Er, 0~5wt%Tm, 0~5wt%Eu.
When proposing above-mentioned magnesiumalloy; Proposition contains the preparation method of the magnesiumalloy of alloy element (mainly being rare earth metal) again; This preparation method is: earlier with pure magnesium ingot, and the preheating respectively of the master alloy of alloy element (mainly being rare earth metal) and/or alloy element and magnesium; Fusing earlier accounts for the preheating pure magnesium ingot of smelting furnace weight 1/2~1/20 under the protection of shielding gas, more in batches with remaining preheating pure magnesium ingot fusing; The master alloy of the alloy element after the preheating (mainly being rare earth metal) and/or alloy element and magnesium is submerged in the magnesium melt dissolving and diffusion in magnesium melt together with the charging basket that adds that holds them; At last, the magnesiumalloy liquation is poured into ingot casting or foundry goods; Perhaps the magnesiumalloy liquation is carried out continuously or semicontinuous casting, adopt rolling, extruding, drawing or forging process deformation processing to become sheet material, tubing, section bar, bar, wire rod or various forging then; Perhaps with the extrusion casting of magnesiumalloy liquation or be cast into foundry goods; Perhaps adopt low-pressure casting process that casting of magnesium alloy is caused foundry goods.
Have H.T., thermotolerance and creep resistance though contain the magnesiumalloy of rare earth metal or other alloy element, because the price of pure rare earth element rises year by year, the magnesiumalloy preparation cost that causes containing rare earth metal improves constantly.On the other hand; In the exploitation of China's rare earth with when using, have a large amount of cerium-rich mischmetals and produce, and cerium-rich mischmetal is because associated element is many; Smelt purification difficult; Its application is restricted, and has caused a large amount of of light rare earthss such as abundant cerium, lanthanum, yttrium to overstock, cause the exploitation of China's rare earth resources and use between exist serious imbalance.The solid solubility of alloying element in MAGNESIUM METAL 99 such as the Ce that contains in the cerium-rich mischmetal, La, Pr are all lower; Be difficult to obtain bigger degree of supersaturation in the homogenizing process; The effect of solution strengthening and timeliness precipitation strength is less, and is general not with the main alloy element of REEs such as Ce, La, Pr as magnesiumalloy.
Summary of the invention
The purpose of this invention is to provide the high-strength heat-resisting magnesium alloy that contains cerium-rich mischmetal.It can satisfy the requirement of higher mechanical property and high-temperature creep resistance, and its cutting be not easy the burning, the security during mechanical workout is more much higher than existing magnesiumalloy.Solve the problem of the comprehensive utilization of rare earth resources on the other hand again.
Another object of the present invention provides the preparation working method of the high-strength heat-resisting magnesium alloy that contains the cerium-rich mischmetal metal.
For realizing above-mentioned purpose, the present invention takes following technical scheme:
The high-strength heat-resisting magnesium alloy that contains the cerium-rich mischmetal metal, the component content of this magnesiumalloy is: Y6.5~15wt%, cerium-rich mischmetal 0.7~3.0wt%, Zr0.4~1.2wt%, all the other are Mg; Wherein, the component content of cerium-rich mischmetal is: Ce:50 ± 5wt%; La:30 ± 3wt%; Nd:15 ± 2wt%; Pr:5 ± 1wt%.
In the high-strength heat-resisting magnesium alloy that contains the cerium-rich mischmetal metal of the present invention, the optimum content of described Y is 7.5~9.5wt%.
In the high-strength heat-resisting magnesium alloy that contains the cerium-rich mischmetal metal of the present invention, the optimum content of described cerium-rich mischmetal metal is 1~2wt%.
In the high-strength heat-resisting magnesium alloy that contains the cerium-rich mischmetal metal of the present invention, the optimum content of described Zr is 0.5~0.7%.
The high-strength heat-resisting magnesium alloy that contains the cerium-rich mischmetal metal of the present invention is magnesium alloy workpiece or material.
The workpiece of the high-strength heat-resisting magnesium alloy that contains the cerium-rich mischmetal metal of the present invention or material be be equipped with according to the weight percent of magnesiumalloy composition of the present invention raw material process the magnesiumalloy liquation; The magnesiumalloy liquation is poured into magnesium alloy ingot blank; Perhaps the magnesiumalloy liquation is carried out continuously or semicontinuous casting becomes magnesium alloy ingot blank; Again magnesium alloy ingot blank is carried out homogenizing thermal treatment; Be about to magnesium alloy ingot blank and be heated to 490~540 ℃ of insulations 10~60 hours, alloying element Y, rich norium and Zr are evenly distributed in the matrix metal, process through thermal distortion then; Immediate quenching processing and ageing treatment are made.
Contain the preparation working method of the high-strength heat-resisting magnesium alloy of cerium-rich mischmetal metal, this method comprises the steps:
(1), gets the raw materials ready by the weight percent of the composition of above-mentioned magnesiumalloy of the present invention; And preheating pure magnesium ingot and the pure Y ingot of preheating, rich norium ingot and Mg-Zr master alloy; Melting preheated pure magnesium ingot is a magnesium melt; Pure Y ingot after the preheating, rich norium ingot and Mg-Zr intermediate alloy ingot are dissolved in magnesium melt, process the magnesiumalloy liquation; The magnesiumalloy liquation is poured into magnesium alloy ingot blank; Perhaps the magnesiumalloy liquation is carried out continuously or semicontinuous casting becomes magnesium alloy ingot blank;
(2), magnesium alloy ingot blank is carried out homogenizing thermal treatment, be about to magnesium alloy ingot blank and be heated to 490~540 ℃ of insulations 10~60 hours, alloying element Y, rich norium and Zr are evenly distributed in the matrix metal;
(3), the magnesiumalloy billet after the homogenizing thermal treatment is carried out magnesium alloy workpiece or the material that various sizes is processed in thermal distortion; Thermal distortion processing comprises conventional crimp, forging and pressing distortion, rolling deformation and their combination or other deformation processing; The beginning texturing temperature is 490~540 ℃, and the distortion end temp is 430~530 ℃;
(4), to magnesium alloy workpiece or material that thermal distortion is processed into, carry out immediate quenching immediately and handle, after immediate quenching is handled and is exactly the thermal distortion process finishing, make the temperature of workpiece or material drop to room temperature rapidly with water coolant or blowing immediately;
(5), magnesium alloy workpiece or material after immediate quenching handled carry out ageing treatment, is about to magnesium alloy workpiece or material and is heated to 190~250 ℃ of insulations 1~30 hour, promptly obtains magnesium alloy workpiece of the present invention or material.
Step in the method for the invention (1): get the raw materials ready by the weight percent of the composition of above-mentioned magnesiumalloy of the present invention (1); And preheating pure magnesium ingot and the pure Y ingot of preheating, rich norium ingot and Mg-Zr master alloy; The melting pure magnesium ingot is a magnesium melt; Pure Y ingot after the preheating, rich norium ingot and Mg-Zr intermediate alloy ingot are dissolved in magnesium melt, process the magnesiumalloy liquation; The magnesiumalloy liquation is poured into magnesium alloy ingot blank; Perhaps the magnesiumalloy liquation is carried out continuously or semicontinuous casting becomes magnesium alloy ingot blank.It is basic identical that the technology of this step (1) and disclosed contains preparing method's the technology of magnesiumalloy of alloy element (mainly being rare earth metal), and this step (1) particularly comprises following content:
(1) ', gets the raw materials ready by the weight percent of magnesiumalloy composition of the present invention;
(2) ', preheating oven is warmed up to 160~660 ℃, and smelting furnace is warmed up to 500~800 ℃, and feeds shielding gas to smelting furnace;
(3) ', in preheating oven, pure magnesium ingot is preheating to 100~600 ℃, simultaneously pure Y ingot, rich norium ingot and Mg-Zr intermediate alloy ingot are preheating to 100~500 ℃;
(4) ', in the smelting furnace of preheating, carry out the melting of pure magnesium ingot; The preheating pure magnesium ingot that at first will account for the fusing weight 1/2~1/20 of 1 smelting furnace adds in the smelting furnace; Make its fusing fully under the protection of shielding gas, then remaining preheating pure magnesium ingot is joined in the smelting furnace, after a collection of preheating pure magnesium ingot melts before treating in batches; Add the next batch preheated magnesium ingot again, every batch of add-on is submerged in the magnesium melt fully with pure magnesium ingot and is as the criterion; So repeat, reach preset value, after the fusing, the scum silica frost of molten surface is cleaned out fully, temperature is controlled at 680~860 ℃ until the pure magnesium ingot add-on;
(5) ', the pure Y ingot after the preheating, rich norium ingot and Mg-Zr intermediate alloy ingot are submerged in the magnesium melt together with the charging basket that adds that holds them; Adding charging basket is that soft steel or high chromium steel are processed; Be thick with a large amount of apertures on it, be convenient to treat the dissolving and the diffusion of Y, rich norium and Mg-Zr master alloy;
(6) ', the magnesium melt temperature is controlled at 720~860 ℃; After treating that Y, rich norium and Mg-Zr master alloy dissolve fully; 750~860 ℃ of insulations 10~60 minutes, alloying element Y, rich norium and Zr are evenly distributed in the magnesium melt again;
(7) ', above-mentioned magnesiumalloy liquation is poured in the permanent mold casting mould of abundant preheating is frozen into ingot blank; Perhaps above-mentioned magnesiumalloy liquation is transported in the mold, carries out continuously or semicontinuous casting becomes ingot bad.
Different with prior art is: preparation working method of the present invention is that magnesium alloy ingot blank is carried out homogenizing thermal treatment, and alloying element Y, rich norium and Zr are evenly distributed in the matrix metal; Because the solid solubility of alloying element in MAGNESIUM METAL 99 problems low, that strengthening effect is not high such as the Ce in the cerium-rich mischmetal, La, Pr are difficult to solve; But; Through directly gross distortion hot-work and immediate quenching and ageing treatment after the homogenizing thermal treatment, solve the not high and problem of unstable of the strengthening effect of alloying element in MAGNESIUM METAL 99 such as Ce in the cerium-rich mischmetal, La, Pr from another angle.
The applicant finds when research contains the cerium-rich mischmetal magnesiumalloy; Through containing the cerium-rich mischmetal magnesiumalloy when the large plastometric set magnesiumalloy after the homogenizing processing; Undecomposed magnesium-cerium-rich mischmetal intermetallic compound fully is evenly distributed in the matrix after the fragmentation in plastic history in the magnesiumalloy; Intermetallic compound is the core of dynamic recrystallization forming core in the thermal deformation process, and these a large amount of equally distributed intermetallic compounds have played the effect of refinement dynamic recrystallization crystal grain, and through pinning crystal boundary and dislocation; Also play and suppress grain growth and hinder dislocation glide, thereby improve the intensity and the plasticity of magnesiumalloy simultaneously.Above-mentioned result of study provides thinking for the development and use REE that solid solubility is lower in magnesiumalloy; The magnesiumalloy that contains the cerium-rich mischmetal element; Because undecomposed strengthening phase has high melt point, this type of magnesiumalloy has higher room temperature and high-temperature behavior simultaneously through behind the large plastometric set.Therefore,, the present invention is directed to the comprehensive utilization of China's rare earth resources, with the alloy element of cerium-rich mischmetal as magnesium, development of new high-performance magnesium-alloy from another angle.
In the melting method of magnesiumalloy of the present invention, described shielding gas is preferably and contains 2~15 volume %SO 2N 2Be designated hereinafter simply as shielding gas (2~15%SO 2+ N 2).
Advantage of the present invention is: magnesiumalloy of the present invention can satisfy the requirement of higher mechanical property and high-temperature creep resistance, and its cutting be not easy the burning, the security during mechanical workout is more much higher than existing magnesiumalloy.
Embodiment
Embodiment 1:1000 kilogram Mg-6.5Y-0.7 cerium-rich mischmetal metal-0.4Zr magnesiumalloy (component content of this magnesiumalloy is: Y6.5wt%, and cerium-rich mischmetal 0.7wt%, Zr0.4wt%, all the other are Mg; Wherein, the component content of cerium-rich mischmetal is: Ce:50wt%; La:30wt%; Nd:15wt%; Pr:5wt%) and workpiece forging and pressing working method.
1, melting is prepared
Connect the power supply of preheating oven, smelting furnace, heat up.Preheating oven is warmed up to 160~260 ℃, smelting furnace is warmed up to 600~620 ℃, in smelting furnace, feed shielding gas (2~15%SO 2+ N 2).
2, pure Y ingot, rich norium ingot and Mg-30wt%Zr (Zr:30wt%, all the other are Mg) intermediate alloy ingot preheating
Adopt preheating oven that 915 kilograms of pure magnesium ingots of surface cleaning, 65 kilograms of pure Y ingots, 7 kilograms of rich norium ingots and 13 kilograms of Mg-30%Zr intermediate alloy ingot are preheating to 260~360 ℃; Wherein pure Y ingot, rich norium ingot and Mg-30%Zr intermediate alloy ingot are contained in and add in the charging basket, put into the preheating oven preheating together with adding charging basket.Add charging basket and adopt the thick Cr13 steel plate of 3mm to be processed into, on steel plate, get out the aperture of a large amount of Φ 5mm, make it into sieve-like.
3, pure magnesium ingot fusing
The pure magnesium ingot that at first adds 80~90 kilograms of surface cleanings makes it in aforementioned mixed gas protected fusing fully down, and the pure magnesium ingot that in batches will be preheating to design temperature then joins in the smelting furnace.Add about 25~40 kilograms the 1st time, concrete add-on is submerged in fully in the magnesium liquid with magnesium ingot and is as the criterion; Add the 2nd batch of preheated magnesium ingot until completely melted again, add-on still is submerged in fully in the magnesium liquid with magnesium ingot and is as the criterion; So repeatedly, reach 915 kilograms of preset values, after the fusing, the scum silica frost of molten surface is cleaned out fully, temperature is controlled at 760~800 ℃ with the spoon of skimming until the magnesium ingot add-on.
4, alloying
Pure Y ingot after the preheating, rich norium ingot and Mg-30%Zr intermediate alloy ingot are submerged in the magnesium melt together with the charging basket that adds that holds them; The magnesium melt temperature is controlled at 780~810 ℃; After treating that Y, rich norium and Mg-Zr master alloy dissolve fully; Under this temperature, be incubated 30~40 minutes again, the alloying element Y of adding, rich norium and Zr are evenly distributed in the magnesium melt;
5, cast
With the melt transfer pump above-mentioned magnesiumalloy liquation is transported in the mold, carries out semicontinuous casting, be prepared into the billet of forging and pressing processing usefulness;
6, homogenizing thermal treatment
Above-mentioned magnesium alloy ingot blank is carried out homogenizing thermal treatment, adopt the homogenizing heat treatment furnace that magnesium alloy ingot blank is heated to 490~520 ℃ of insulations 10~20 hours, alloying element Y, rich norium and Zr are evenly distributed in the matrix metal;
7, forging and pressing distortion
Magnesiumalloy billet after adopting forging press to homogenizing thermal treatment forges and presses deformation processing while hot and becomes magnesium alloy workpiece, and beginning to forge and press temperature is 490~500 ℃, and the forging and pressing end temp is 430~450 ℃, and accumulation forging and pressing deformation extent is greater than 50%;
8, immediate quenching is handled
The magnesium alloy workpiece that the forging and pressing deformation processing becomes is put into the water coolant container immediately, make the temperature of workpiece drop to room temperature rapidly, magnesium alloy workpiece is carried out immediate quenching handle;
9, ageing treatment
Adopt the magnesium alloy materials after aging oven is handled immediate quenching to carry out ageing treatment, be about to magnesium alloy materials and be heated to 240~250 ℃ of insulations 1~5 hour.
Mg-6.5Y-0.7 cerium-rich mischmetal metal of the present invention-0.4Zr magnesium alloy workpiece has following performance: the room temperature tensile strength sigma bBe 360~380MPa, ys σ 0.2Be 320~350MPa; Ys σ in the time of 250 ℃ bBe 220~230MPa; 250 ℃, 200MPa stress continue to load 10 hours, and the creep strain of generation is less than 0.2%.
Embodiment 2:1000 kilogram Mg-15Y-3 cerium-rich mischmetal metal-1.2Zr magnesiumalloy (component content of this magnesiumalloy is: Y15wt%, and cerium-rich mischmetal 3wt%, Zr1.2wt%, all the other are Mg; Wherein, the component content of cerium-rich mischmetal is: Ce:50wt%; La:30wt%; Nd:15wt%; Pr:5wt%) and the bar extruding method.
1, melting is prepared
Connect the power supply of preheating oven, smelting furnace, heat up.Preheating oven is warmed up to 420~460 ℃, smelting furnace is warmed up to 600~620 ℃, in smelting furnace, feed shielding gas (2~15%SO 2+ N 2).
2, pure Y ingot, rich norium ingot and Mg-30wt%Zr (Zr:30wt%, all the other are Mg) intermediate alloy ingot preheating
Adopt preheating oven that 780 kilograms of pure magnesium ingots of surface cleaning, 150 kilograms of pure Y ingots, 30 kilograms of rich norium ingots and 40 kilograms of Mg-30%Zr intermediate alloy ingot are preheating to 300~400 ℃; Wherein pure Y ingot, rich norium ingot and Mg-30%Zr intermediate alloy ingot are contained in and add in the charging basket, put into the preheating oven preheating together with adding charging basket.Add charging basket and adopt the thick Cr13 steel plate of 3mm to be processed into, on steel plate, get out the aperture of a large amount of Φ 5mm, make it into sieve-like.
3, pure magnesium ingot fusing
The pure magnesium ingot that at first adds 80~90 kilograms of surface cleanings makes it in aforementioned mixed gas protected fusing fully down, and the pure magnesium ingot that in batches will be preheating to design temperature then joins in the smelting furnace.Add about 25~40 kilograms the 1st time, concrete add-on is submerged in fully in the magnesium liquid with magnesium ingot and is as the criterion; Add the 2nd batch of preheated magnesium ingot until completely melted again, add-on still is submerged in fully in the magnesium liquid with magnesium ingot and is as the criterion; So repeatedly, reach 780 kilograms of preset values, after the fusing, the scum silica frost of molten surface is cleaned out fully, temperature is controlled at 790~830 ℃ with the spoon of skimming until the magnesium ingot add-on.
4, alloying
Pure Y ingot after the preheating, rich norium ingot and Mg-30%Zr intermediate alloy ingot are submerged in the magnesium melt together with the charging basket that adds that holds them; The magnesium melt temperature is controlled at 830~860 ℃; After treating that Y, rich norium and Mg-Zr master alloy dissolve fully; Under this temperature, be incubated 30~40 minutes again, the alloying element Y of adding, rich norium and Zr are evenly distributed in the magnesium melt;
5, cast
Above-mentioned magnesiumalloy liquation is poured in the permanent mold casting mould of abundant preheating and is frozen into the ingot blank that extrusion processing is used;
6, homogenizing thermal treatment
Above-mentioned magnesium alloy ingot blank is carried out homogenizing thermal treatment, adopt the homogenizing heat treatment furnace that magnesium alloy ingot blank is heated to 520~540 ℃ of insulations 30~60 hours, alloying element Y, rich norium and Zr are evenly distributed in the matrix metal;
7, crimp
Magnesiumalloy billet after adopting extrusion machine to homogenizing thermal treatment; Carry out crimp while hot and be processed into magnesium alloy rod; Extrusion ratio (promptly pushing the sectional area of ingot blank and the ratio of the sectional area of extruding rod) is 7~40; The container temperature is 430~500 ℃, and the extrusion mould temperature is 360~450 ℃, and extrusion speed is 0.5~3 mm/second;
8, immediate quenching is handled
Adopt the cool water shower device at extruder outlet place, the temperature of the magnesium alloy rod that is squeezed into is dropped to room temperature rapidly;
9, ageing treatment
Adopt aging oven that above-mentioned magnesium alloy rod is heated to 190~220 ℃ of insulations 15~30 hours.
Mg-15Y-3 cerium-rich mischmetal metal of the present invention-1.2Zr magnesium alloy rod has following performance: the room temperature tensile strength sigma bBe 420~450MPa, ys σ 0.2Be 390~420MPa; Ys σ in the time of 300 ℃ bBe 220~230MPa; 300 ℃, 200MPa stress continue to load 10 hours, and the creep strain of generation is less than 0.2%.
Embodiment 3:1000 kilogram Mg-7.5Y-2 cerium-rich mischmetal metal-0.7Zr (component content of this magnesiumalloy is: Y7.5wt%, and cerium-rich mischmetal 2wt%, Zr0.7wt%, all the other are Mg; Wherein, the component content of cerium-rich mischmetal is: Ce:50wt%; La:30wt%; Nd:15wt%; Pr:5wt%) magnesiumalloy and plate rolling working method thereof.
1, melting is prepared
Connect the power supply of preheating oven, smelting furnace, heat up.Preheating oven is warmed up to 260~360 ℃, smelting furnace is warmed up to 600~620 ℃, in smelting furnace, feed shielding gas (2~15%SO 2+ N 2).
2, pure Y ingot, rich norium ingot and Mg-30%Zr (Zr:30wt%, all the other are Mg) intermediate alloy ingot preheating
Adopt preheating oven that 882 kilograms of pure magnesium ingots of surface cleaning, 75 kilograms of pure Y ingots, 20 kilograms of rich norium ingots and 23 kilograms of Mg-30%Zr intermediate alloy ingot are preheating to 200~300 ℃; Wherein pure Y ingot, rich norium ingot and Mg-30%Zr intermediate alloy ingot are contained in and add in the charging basket, put into the preheating oven preheating together with adding charging basket.Add charging basket and adopt the thick Cr13 steel plate of 3mm to be processed into, on steel plate, get out the aperture of a large amount of Φ 5mm, make it into sieve-like.
3, pure magnesium ingot fusing
The pure magnesium ingot that at first adds 80~90 kilograms of surface cleanings makes it in aforementioned mixed gas protected fusing fully down, and the pure magnesium ingot that in batches will be preheating to design temperature then joins in the smelting furnace.Add about 25~40 kilograms the 1st time, concrete add-on is submerged in fully in the magnesium liquid with magnesium ingot and is as the criterion; Add the 2nd batch of preheated magnesium ingot until completely melted again, add-on still is submerged in fully in the magnesium liquid with magnesium ingot and is as the criterion; So repeatedly, reach 882 kilograms of preset values, after the fusing, the scum silica frost of molten surface is cleaned out fully, temperature is controlled at 780~830 ℃ with the spoon of skimming until the magnesium ingot add-on.
4, alloying
Pure Y ingot after the preheating, rich norium ingot and Mg-30%Zr intermediate alloy ingot are submerged in the magnesium melt together with the charging basket that adds that holds them; The magnesium melt temperature is controlled at 820~850 ℃; After treating that Y, rich norium and Mg-Zr master alloy dissolve fully; Under this temperature, be incubated 30~40 minutes again, the alloying element Y of adding, rich norium and Zr are evenly distributed in the magnesium melt;
5, cast
With the melt transfer pump above-mentioned magnesiumalloy liquation is transported in the mold, carries out semicontinuous casting, be prepared into the billet that rolling deformation is used;
6, homogenizing thermal treatment
Above-mentioned magnesium alloy ingot blank is carried out homogenizing thermal treatment, adopt the homogenizing heat treatment furnace that magnesium alloy ingot blank is heated to 515~535 ℃ of insulations 25~50 hours, alloying element Y, rich norium and Zr are evenly distributed in the matrix metal;
7, rolling deformation
Magnesiumalloy billet after adopting milling train to homogenizing thermal treatment is rolled deformation processing while hot and becomes magnesium alloy plate, and the beginning rolling temperature is 510~530 ℃, and rolling end temp is 435~470 ℃, and accumulation rolling deformation degree is greater than 50%;
8, immediate quenching is handled
Adopt the cool water shower device in milling train exit, the temperature of the magnesium alloy plate that is rolled into is dropped to room temperature rapidly;
9, ageing treatment
Adopt aging oven that above-mentioned magnesium alloy plate is heated to 210~230 ℃ of insulations 5~15 hours.
Mg-7.5Y-2 cerium-rich mischmetal metal of the present invention-0.7Zr magnesium alloy plate has following performance: the room temperature tensile strength sigma bBe 390~430MPa, ys σ 0.2Be 350~370MPa; Ys σ in the time of 250 ℃ bBe 230~250MPa; 250 ℃, 200MPa stress continue to load 10 hours, and the creep strain of generation is less than 0.17%.
Embodiment 4:1000 kilogram Mg-9.5Y-1 cerium-rich mischmetal metal-0.5Zr (component content of this magnesiumalloy is: Y9.5wt%, and cerium-rich mischmetal 1wt%, Zr0.5wt%, all the other are Mg; Wherein, the component content of cerium-rich mischmetal is: Ce:50wt%; La:30wt%; Nd:15wt%; Pr:5wt%) magnesiumalloy and section bar forging and pressing-extruding method thereof.
1, melting is prepared
Connect the power supply of preheating oven, smelting furnace, heat up.Preheating oven is warmed up to 300~400 ℃, smelting furnace is warmed up to 600~620 ℃, in smelting furnace, feed shielding gas (2~15%SO 2+ N 2).
2, pure Y ingot, rich norium ingot and Mg-30%Zr (Zr:30wt%, all the other are Mg) intermediate alloy ingot preheating
Adopt preheating oven that 878 kilograms of pure magnesium ingots of surface cleaning, 95 kilograms of pure Y ingots, 10 kilograms of rich norium ingots and 17 kilograms of Mg-30%Zr intermediate alloy ingot are preheating to 260~350 ℃; Wherein pure Y ingot, rich norium ingot and Mg-30%Zr intermediate alloy ingot are contained in and add in the charging basket, put into the preheating oven preheating together with adding charging basket.Add charging basket and adopt the thick Cr13 steel plate of 3mm to be processed into, on steel plate, get out the aperture of a large amount of Φ 5mm, make it into sieve-like.
3, pure magnesium ingot fusing
The pure magnesium ingot that at first adds 80~90 kilograms of surface cleanings makes it in aforementioned mixed gas protected fusing fully down, and the pure magnesium ingot that in batches will be preheating to design temperature then joins in the smelting furnace.Add about 25~40 kilograms the 1st time, concrete add-on is submerged in fully in the magnesium liquid with magnesium ingot and is as the criterion; Add the 2nd batch of preheated magnesium ingot until completely melted again, add-on still is submerged in fully in the magnesium liquid with magnesium ingot and is as the criterion; So repeatedly, reach 878 kilograms of preset values, after the fusing, the scum silica frost of molten surface is cleaned out fully, temperature is controlled at 780~830 ℃ with the spoon of skimming until the magnesium ingot add-on.
4, alloying
Pure Y ingot after the preheating, rich norium ingot and Mg-30%Zr intermediate alloy ingot are submerged in the magnesium melt together with the charging basket that adds that holds them; The magnesium melt temperature is controlled at 820~850 ℃; After treating that Y, rich norium and Mg-Zr master alloy dissolve fully; Under this temperature, be incubated 30~40 minutes again, the alloying element Y of adding, rich norium and Zr are evenly distributed in the magnesium melt;
5, cast
With the melt transfer pump above-mentioned magnesiumalloy liquation is transported in the mold, carries out semicontinuous casting, be prepared into the billet that forging and pressing-crimp is used;
6, homogenizing thermal treatment
Above-mentioned magnesium alloy ingot blank is carried out homogenizing thermal treatment, adopt the homogenizing heat treatment furnace that magnesium alloy ingot blank is heated to 515~535 ℃ of insulations 25~50 hours, alloying element Y, rich norium and Zr are evenly distributed in the matrix metal;
7, forging and pressing distortion
Magnesiumalloy billet after adopting forging press to homogenizing thermal treatment forges and presses deformation processing while hot, and beginning to forge and press temperature is 510~530 ℃, and the forging and pressing end temp is 465~505 ℃, and accumulation forging and pressing deformation extent is greater than 50%;
8, crimp
Magnesiumalloy billet after adopting extrusion machine to the forging and pressing deformation processing; Carry out crimp while hot and be processed into magnesium alloy profiles; Extrusion ratio (promptly pushing the sectional area of ingot blank and the ratio of the sectional area of extruded section) is 7~30; The container temperature is 460~500 ℃, and the extrusion mould temperature is 400~450 ℃, and extrusion speed is 0.5~2 mm/second;
9, immediate quenching is handled
Adopt the cold wind blower at extruder outlet place, the temperature of the magnesium alloy profiles that is squeezed into is dropped to room temperature rapidly;
10, ageing treatment
Adopt aging oven that above-mentioned magnesium alloy profiles is heated to 210~230 ℃ of insulations 5~12 hours.
Mg-9.5Y-1 cerium-rich mischmetal metal of the present invention-0.5Zr magnesium alloy profiles has following performance: the room temperature tensile strength sigma bBe 390~430MPa, ys σ 0.2Be 350~370MPa; Ys σ in the time of 250 ℃ bBe 230~250MPa; 250 ℃, 200MPa stress continue to load 10 hours, and the creep strain of generation is less than 0.17%.
Embodiment 5:1000 kilogram Mg-8.5Y-1.2 cerium-rich mischmetal metal-0.6Zr magnesiumalloy (component content of this magnesiumalloy is: Y8.5wt%, and cerium-rich mischmetal 1.2wt%, Zr0.6wt%, all the other are Mg; Wherein, the component content of cerium-rich mischmetal is: Ce:50wt%; La:30wt%; Nd:15wt%; Pr:5wt%) and sheet material forging and pressing-rolling working method.
1, melting is prepared
Connect the power supply of preheating oven, smelting furnace, heat up.Preheating oven is warmed up to 300~400 ℃, smelting furnace is warmed up to 600~620 ℃, in smelting furnace, feed shielding gas (2~15%SO 2+ N 2).
2, pure Y ingot, rich norium ingot and Mg-30%Zr (Zr:30wt%, all the other are Mg) intermediate alloy ingot preheating
Adopt preheating oven that 883 kilograms of pure magnesium ingots of surface cleaning, 85 kilograms of pure Y ingots, 12 kilograms of rich norium ingots and 20 kilograms of Mg-30%Zr intermediate alloy ingot are preheating to 260~350 ℃; Wherein pure Y ingot, rich norium ingot and Mg-30%Zr intermediate alloy ingot are contained in and add in the charging basket, put into the preheating oven preheating together with adding charging basket.Add charging basket and adopt the thick Cr13 steel plate of 3mm to be processed into, on steel plate, get out the aperture of a large amount of Φ 5mm, make it into sieve-like.
3, pure magnesium ingot fusing
The pure magnesium ingot that at first adds 80~90 kilograms of surface cleanings makes it in aforementioned mixed gas protected fusing fully down, and the pure magnesium ingot that in batches will be preheating to design temperature then joins in the smelting furnace.Add about 25~40 kilograms the 1st time, concrete add-on is submerged in fully in the magnesium liquid with magnesium ingot and is as the criterion; Add the 2nd batch of preheated magnesium ingot until completely melted again, add-on still is submerged in fully in the magnesium liquid with magnesium ingot and is as the criterion; So repeatedly, reach 883 kilograms of preset values, after the fusing, the scum silica frost of molten surface is cleaned out fully, temperature is controlled at 780~830 ℃ with the spoon of skimming until the magnesium ingot add-on.
4, alloying
Pure Y ingot after the preheating, rich norium ingot and Mg-30%Zr intermediate alloy ingot are submerged in the magnesium melt together with the charging basket that adds that holds them; The magnesium melt temperature is controlled at 820~850 ℃; After treating that Y, rich norium and Mg-Zr master alloy dissolve fully; Under this temperature, be incubated 30~40 minutes again, the alloying element Y of adding, rich norium and Zr are evenly distributed in the magnesium melt;
5, cast
With the melt transfer pump above-mentioned magnesiumalloy liquation is transported in the mold, carries out semicontinuous casting, be prepared into the billet that forging and pressing-crimp is used;
6, homogenizing thermal treatment
Above-mentioned magnesium alloy ingot blank is carried out homogenizing thermal treatment, adopt the homogenizing heat treatment furnace that magnesium alloy ingot blank is heated to 515~535 ℃ of insulations 25~50 hours, alloying element Y, rich norium and Zr are evenly distributed in the matrix metal;
7, forging and pressing distortion
Magnesiumalloy billet after adopting forging press to homogenizing thermal treatment forges and presses deformation processing while hot, and beginning to forge and press temperature is 510~530 ℃, and the forging and pressing end temp is 465~505 ℃, and accumulation forging and pressing deformation extent is greater than 50%;
8, rolling deformation
Magnesiumalloy billet after adopting milling train to the forging and pressing deformation processing is rolled deformation processing while hot and becomes magnesium alloy plate, and the beginning rolling temperature is 460~500 ℃, and rolling end temp is 435~470 ℃, and accumulation rolling deformation degree is greater than 50%;
8, immediate quenching is handled
Adopt the cool water shower device in milling train exit, the temperature of the magnesium alloy plate that is rolled into is dropped to room temperature rapidly;
9, ageing treatment
Adopt aging oven that above-mentioned magnesium alloy plate is heated to 210~230 ℃ of insulations 5~15 hours.
Mg-7.5Y-2 cerium-rich mischmetal metal of the present invention-0.7Zr magnesium alloy plate has following performance: the room temperature tensile strength sigma bBe 390~430MPa, ys σ 0.2Be 350~370MPa; Ys σ in the time of 250 ℃ bBe 230~250MPa; 250 ℃, 200MPa stress continue to load 10 hours, and the creep strain of generation is less than 0.17%.

Claims (5)

1. high-strength heat-resistant magnesium alloy, it is characterized in that: the component content of this magnesiumalloy is: Y6.5~15wt%, cerium-rich mischmetal 0.7~3.0wt%, Zr0.4~1.2wt%, all the other are Mg; Wherein, the component content at cerium-rich mischmetal is: Ce:50 ± 5wt%; La:30 ± 3wt%; Nd:15 ± 2wt%; Pr:5 ± 1wt%.
2. high-strength heat-resistant magnesium alloy according to claim 1 is characterized in that: the content of described Y is 7.5~9.5wt%, and the content of cerium-rich mischmetal metal is 1~2wt%, and the content of Zr is 0.5~0.7wt%.
3. high-strength heat-resistant magnesium alloy according to claim 1 and 2 is characterized in that: described high-strength heat-resistant magnesium alloy is magnesium alloy workpiece or material.
4. high-strength heat-resistant magnesium alloy according to claim 3 is characterized in that: described magnesium alloy workpiece or material be be equipped with according to the weight percent of above-mentioned magnesiumalloy composition raw material process the magnesiumalloy liquation; The magnesiumalloy liquation is poured into magnesium alloy ingot blank; Perhaps the magnesiumalloy liquation is carried out continuously or semicontinuous casting becomes magnesium alloy ingot blank; Again magnesium alloy ingot blank is carried out homogenizing thermal treatment; Be about to magnesium alloy ingot blank and be heated to 490~540 ℃ of insulations 10~60 hours, alloying element Y, rich norium and Zr are evenly distributed in the matrix metal, process through thermal distortion then; Immediate quenching processing and ageing treatment are made.
5. described preparation working method that contains the high-strength heat-resisting magnesium alloy of cerium-rich mischmetal metal of claim 1, it is characterized in that: this method comprises the steps:
(1), gets the raw materials ready by the weight percent of the composition of the described magnesiumalloy of claim 1; And preheating pure magnesium ingot and the pure Y ingot of preheating, rich norium ingot and Mg-Zr master alloy; Melting preheated pure magnesium ingot is a magnesium melt; Pure Y ingot after the preheating, rich norium ingot and Mg-Zr intermediate alloy ingot are dissolved in magnesium melt, process the magnesiumalloy liquation; The magnesiumalloy liquation is poured into magnesium alloy ingot blank; Perhaps the magnesiumalloy liquation is carried out continuously or semicontinuous casting becomes magnesium alloy ingot blank;
(2), magnesium alloy ingot blank is carried out homogenizing thermal treatment, be about to magnesium alloy ingot blank and be heated to 490~540 ℃ of insulations 10~60 hours, alloying element Y, rich norium and Zr are evenly distributed in the matrix metal;
(3), the magnesiumalloy billet after the homogenizing thermal treatment is carried out magnesium alloy workpiece or the material that various sizes is processed in thermal distortion; Thermal distortion processing comprises conventional crimp, forging and pressing distortion, rolling deformation and their combination or other deformation processing; The beginning texturing temperature is 490~540 ℃, and the distortion end temp is 430~530 ℃;
(4), to magnesium alloy workpiece or material that thermal distortion is processed into, carry out immediate quenching immediately and handle, after immediate quenching is handled and is exactly the thermal distortion process finishing, make the temperature of workpiece or material drop to room temperature rapidly with water coolant or blowing immediately;
(5), magnesium alloy workpiece or material after immediate quenching handled carry out ageing treatment, is about to magnesium alloy workpiece or material and is heated to 190~250 ℃ of insulations 1~30 hour, promptly obtains magnesium alloy workpiece of the present invention or material.
CN2010105809211A 2010-12-03 2010-12-03 Cerium-rich mischmetal-containing high-strength heat-resisting magnesium alloy and preparation method thereof Pending CN102485928A (en)

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102865354A (en) * 2012-10-16 2013-01-09 山东银光钰源轻金属精密成型有限公司 Automobile reduction gearbox casing and preparation process of casing
CN104087801A (en) * 2014-07-10 2014-10-08 重庆大学 Corrosion-resistant magnesium alloy and method for improving corrosion resistance of corrosion-resistant magnesium alloy
CN104818415A (en) * 2015-06-01 2015-08-05 河南科技大学 High-strength heat-resistant magnesium alloy
CN108085627A (en) * 2017-11-22 2018-05-29 北京有色金属研究总院 A kind of deformation heat treatment method of Mg-Al systems precipitation strength type magnesium alloy
CN108660347A (en) * 2018-07-30 2018-10-16 上海交通大学 A kind of tough Mg-Li-Al-Y alloys of height and preparation method thereof containing rich Ce mischmetals
CN111230014A (en) * 2018-11-29 2020-06-05 有研工程技术研究院有限公司 Preparation and processing method of high-strength and low-stress magnesium alloy forging

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GB1067915A (en) * 1963-10-26 1967-05-10 Fuchs Ges Mit Beschraenkter Ha Process for improving the strength properties and oxidation resistance of zirconium-containing magnesium alloys and alloys produced by the process
CN101078080A (en) * 2007-07-04 2007-11-28 北京有色金属研究总院 Creep resistance magnesium alloy and preparation method thereof
CN101113504A (en) * 2007-09-06 2008-01-30 北京有色金属研究总院 Heat conductive magnesium alloy and method for preparing same

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GB1067915A (en) * 1963-10-26 1967-05-10 Fuchs Ges Mit Beschraenkter Ha Process for improving the strength properties and oxidation resistance of zirconium-containing magnesium alloys and alloys produced by the process
CN101078080A (en) * 2007-07-04 2007-11-28 北京有色金属研究总院 Creep resistance magnesium alloy and preparation method thereof
CN101113504A (en) * 2007-09-06 2008-01-30 北京有色金属研究总院 Heat conductive magnesium alloy and method for preparing same

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102865354A (en) * 2012-10-16 2013-01-09 山东银光钰源轻金属精密成型有限公司 Automobile reduction gearbox casing and preparation process of casing
CN102865354B (en) * 2012-10-16 2015-01-14 山东银光钰源轻金属精密成型有限公司 Automobile reduction gearbox casing and preparation process of casing
CN104087801A (en) * 2014-07-10 2014-10-08 重庆大学 Corrosion-resistant magnesium alloy and method for improving corrosion resistance of corrosion-resistant magnesium alloy
CN104818415A (en) * 2015-06-01 2015-08-05 河南科技大学 High-strength heat-resistant magnesium alloy
CN108085627A (en) * 2017-11-22 2018-05-29 北京有色金属研究总院 A kind of deformation heat treatment method of Mg-Al systems precipitation strength type magnesium alloy
CN108660347A (en) * 2018-07-30 2018-10-16 上海交通大学 A kind of tough Mg-Li-Al-Y alloys of height and preparation method thereof containing rich Ce mischmetals
CN111230014A (en) * 2018-11-29 2020-06-05 有研工程技术研究院有限公司 Preparation and processing method of high-strength and low-stress magnesium alloy forging

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