CN101532106A - Heat resisting casting rare earth magnesium alloy and preparation method thereof - Google Patents
Heat resisting casting rare earth magnesium alloy and preparation method thereof Download PDFInfo
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- CN101532106A CN101532106A CN200910064625A CN200910064625A CN101532106A CN 101532106 A CN101532106 A CN 101532106A CN 200910064625 A CN200910064625 A CN 200910064625A CN 200910064625 A CN200910064625 A CN 200910064625A CN 101532106 A CN101532106 A CN 101532106A
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Abstract
The invention discloses a heat resisting casting rare earth magnesium alloy, in particular to a magnesium alloy with compositions of Mg, Gd, Y, Sm and Zr. The alloy consists of the following compositions in percentage by weight: 7 to 14 percent of Gd, 2 to 5 percent of Y, 0.3 to 5 percent of Sm, 0.2 to 0.6 percent of Zr, less than 0.02 percent of gross amount of impurity elements, namely Si, Fe, Cu and Ni, and the balance being Mg. The invention also discloses a method for preparing the heat resisting casting rare earth magnesium alloy. The heat resisting casting rare earth magnesium alloy has high tensile strength, in a range between room temperature and 250 DEG C, the tensile strength of the alloy has anomalous temperature effect, which means that the tensile strength rises along with rise of tensile temperature. The heat resisting casting rare earth magnesium alloy has the highest tensile strength reaching 330MPa at 250 DEG C. Compared with WE series commercial magnesium alloy, the rare earth magnesium alloy has more excellent room temperature strength, instant high temperature strength and other mechanical performances, and has good application prospect in aero-space, automobile industry, weaponry and other fields.
Description
Technical field
The present invention relates to a kind of heat-resistant cast rare earth magnesium alloy, also related to a kind of preparation method of this magnesium alloy simultaneously.
Background technology
Magnesium is the lightest structural metallic materials, uses increasing on automobile.The every loss of weight 100Kg of automobile, then 100Km fuel-economizing 0.5L has reduced exhaust emissions simultaneously, and therefore carrying out the Mg Alloy Research exploitation has significance for save energy, inhibition environmental pollution.But, its application in aerospace, military project, automobile and other industry of the not good serious obstruction of the intensity of magnesium alloy and thermotolerance, therefore improve magnesium alloy intensity and heat-resisting be the important topic of development magnesium alloy materials.
Existing heat-resistant cast rare earth magnesium alloy is mainly started with from restriction dislocation motion and reinforcement crystal boundary, by suitable alloying, by introduce the second high phase of thermostability, reduce element in magnesium matrix rate of diffusion or improve the purpose that means such as grain boundary structure state and tissue morphology realize improving magnesium alloy heat resistance and high temperature creep drag.At present, in all alloying elements, rare earth (RE) is to improve the most effective alloying element of magnesium alloy resistance toheat, except having degasification, removal of impurities, raising casting fluidity, corrosion resisting property, most of rare earth element has bigger solid solubility limit to rare earth element in magnesium simultaneously in magnesium alloy; And descend with temperature, solid solubility sharply reduces, and can obtain bigger degree of supersaturation, thus in ag(e)ing process subsequently diffusion-precipitation, dystectic rare earth compound phase; The all right crystal grain thinning of rare earth element, raising room temperature strength, and be distributed in intracrystalline and crystal boundary (mainly being crystal boundary) disperse, the high-melting-point rare earth compound, still can pinning intracrystalline dislocation and crystal boundary slippage when high temperature, thereby improved the hot strength of magnesium alloy, the rate of diffusion of RE element in magnesium matrix is slower simultaneously, and this makes the Mg-RE alloy be suitable for long term operation under the comparatively high temps environment.Mg-RE (as Mg-Gd system) alloy is important refractory alloy system, has higher high temperature strength and good creep property.It is alloy that current magnesium alloy component in 200～300 ℃ of following long term operations are Mg-RE, because electronic structure that rare earth is special and the significant strengthening effect in magnesium alloy are tied to form to developing an important alloy system of high strength heat resistant cast rare earth magnesium alloy Mg-RE.
As rare earth resources first big country, China is that the research of alloy is on the increase in recent years and is goed deep into about Mg-RE, and the successful research and development of magnesium-rare earth alloy will help us to utilize this advantage.Present commercial heat resistance magnesium alloy such as WE54, its deficiency that mainly exists is: strength degradation is still more during high temperature, in the time of can't satisfying it fully and in aerospace, military project, automobile and other industry, use under the high temperature to the higher requirement of intensity.
Summary of the invention
The purpose of this invention is to provide a kind of high-strength heat-resistant cast rare earth magnesium alloy.
Another object of the present invention provides a kind of preparation method of this heat-resistant cast rare earth magnesium alloy.
In order to realize above purpose, the technical scheme that heat-resistant cast rare earth magnesium alloy of the present invention adopted is: a kind of heat-resistant cast rare earth magnesium alloy, form by following component by mass percent: 7～14%Gd, 2～5%Y, 0.3～5%Sm, 0.2～0.6%Zr, impurity element Si, Fe, Cu and Ni total amount are less than 0.02%, and surplus is Mg.
Described Gd, Y, the mass percent sum of Sm is 13～18%.
Described heat-resistant cast rare earth magnesium alloy is by magnesium and master alloy Mg-Gd, Mg-Y, and Mg-Sm, Mg-Zr forms for the raw material melting.
The preparation method of heat-resistant cast rare earth magnesium alloy of the present invention comprises the steps:
1. with magnesium, master alloy Mg-Gd, Mg-Y, Mg-Sm and Mg-Zr preheating;
2. with magnesium at SF
6+ CO
2Mixed gas protected fusing down in 720～740 ℃ of adding master alloy Mg-Gd, Mg-Y, Mg-Sm, rises to 740～760 ℃ with temperature and adds the Mg-Zr master alloys;
3. after Mg-Zr fusing, remove surface scum, stop to heat up after temperature is risen to 770～780 ℃;
4. cast after cooling the temperature to 690～730 ℃, obtain cast alloy;
5. obtain heat-resistant cast rare earth magnesium alloy after cast alloy being heat-treated.
The 1. described preheating temperature of step is 150～220 ℃.
Described thermal treatment is that cast alloy is carried out solution treatment and ageing treatment successively.
The treatment temp of described solution treatment is 490～540 ℃, and the treatment time is 4～15 hours.
The treatment temp of described ageing treatment is 180～230 ℃, and the treatment time is 6～40 hours.
During described casting casting die is preheated to 180～250 ℃.
Alloy compositions of the present invention is Mg-Gd-Y-Sm-Zr.It is first component that the present invention adopts Gd, the maximum solid solution degree of Gd in Mg sosoloid is 20.3wt%, 200 ℃ of solid solubility in Mg sosoloid are 3.8wt%, for guaranteeing that alloy obtains good timeliness precipitation strength and solid solution strengthening effect, the add-on of Gd is not less than 7wt%, and too many for fear of the alloy density increase, and the undue embrittlement of alloy, therefore Gd add-on of the present invention is not higher than 14wt%; Adopting Y is second component, and adopting Sm is the 3rd component, and Y, Sm can reduce the solid solubility of Gd in Mg, thereby increases the timeliness precipitation strength effect of Gd; The maximum solid solution degree of Sm in Mg is 5.7wt%, and therefore Sm add-on of the present invention is not higher than 5wt%; Adopt Zr as grain-refining agent, with toughness that improves alloy and the processing performance of improving alloy.
Under the prerequisite of the precipitation strength of taking all factors into consideration alloying element and solution strengthening, assisted and strengthened element Zr can obviously not influence the performance of main reinforced rare earth element strengthening effect, and the content of Zr is controlled at 0.2%～0.6%, mainly plays crystal grain thinning.Heavy rare earth Gd and the Y maximum solid solution degree in magnesium is respectively 20.3wt% and 11.5wt%, and Gd and Y are the bigger elements of solid solubility in the rare earth element.In magnesium-rare earth binary alloy, the hot strength of Mg-Gd and creep property performance are the most remarkable, secondly are Mg-Y.The equilibrium phase of separating out of two kinds of alloys is respectively Mg
5Gd and Mg
24Y
5, have high melt point, alloy at room temperature and mechanical behavior under high temperature are produced strengthening effect preferably.Sm can produce good solution strengthening and ageing strengthening effect in magnesium, Sm solid solubility in magnesium is changed to: 540 ℃, and 5.7wt%, 200 ℃, 0.4wt%.The equilibrium phase that Sm and magnesium generate is Mg
41Sm
5, can remain to higher temperature to the strengthening effect of matrix.Y, Gd solid solubility in magnesium is changed to: Y (550 ℃, 11.5wt%, 200 ℃, 2.2wt%), Gd (540 ℃, 20.3wt%, 200 ℃, 3.8wt%).Therefore, a small amount of Sm has in magnesium alloy and is higher than the precipitating reinforcing effect that Y, Gd with its equivalent can reach, the weight of corresponding reduction alloy and cost, and the precipitate of main strengthening element is higher than auxilliary strengthening element to the contribution of raising alloy use temperature simultaneously.
Heat-resistant cast rare earth magnesium alloy of the present invention has an outstanding feature on mechanical property, in room temperature to 250 ℃ scope, tensile strength of alloys has the abnormal temperature effect, promptly along with the raising of draft temperature, tensile strength also improves thereupon, in the time of 250 ℃, tensile strength can reach 330MPa.Heat-resistant cast rare earth magnesium alloy of the present invention is example with Mg-14Gd-2Y-0.5Sm-0.6Zr, its tensile strength is 291MPa after solution treatment and ageing treatment, and unit elongation is that 3.4%, 200 ℃ of tensile strength is 309MPa, 250 ℃ of tensile strength are 318Mpa, and 300 ℃ of tensile strength are 286Mpa.And the room temperature tensile strength of WE54 magnesium alloy is 280MPa under the same conditions, and unit elongation is that 4.0%, 200 ℃ of tensile strength is 241MPa, and 250 ℃ of tensile strength are 230MPa.Heat-resistant cast rare earth magnesium alloy of the present invention is compared with commercial magnesium alloy WE54, has mechanical properties such as excellent more room temperature strength and TRANSIENT HIGH TEMPERATURE intensity.Therefore at aspects such as aerospace, automobile, weaponrys extraordinary application prospect is arranged.
Embodiment
The raw material Mg that relates in the embodiment of the invention, Mg-Gd, Mg-Sm, Mg-Y is the commercially available prod.The purity of described marketable material is: 99.9% Mg, 99.5% Mg-25.26%Gd, 99.5% Mg-24.54%Y, 99.5% Mg-25.11%Sm, 99.5% Mg-30.00%Zr.
Embodiment 1
The heat-resistant cast rare earth magnesium alloy of present embodiment is made up of following component by mass percent: 7%Gd, and 5%Y, 5%Sm, 0.2%Zr, impurity element Si, Fe, Cu and Ni total amount are less than 0.02%, and surplus is Mg.Its middle-weight rare earths total content is 17%.
Press the mentioned component alloyage, its founding is: adopt corundum crucible, medium-frequency induction furnace melting.Earlier magnesium, master alloy Mg-Gd, Mg-Y, Mg-Sm and Mg-Zr are preheating to 200 ℃, magnesium are put into be preheating to 500 ℃ crucible then, at CO
2+ SF
6Mixed gas protected down, high-power rapid heating fusing, treat the magnesium fusing after, add Mg-Gd, Mg-Y master alloy at 740 ℃, small power slowly heats, and treats that its fusing back and magnesium liquid temp add the Mg-Sm master alloy again when ging up to 740 ℃; Be warmed up to 760 ℃ and add the Mg-Zr master alloy, treat its fusing back removal surface scum, temperature is risen to 770 ℃ again, close governor circuit, leave standstill; Treat that magnesium liquid is cooled to 710 ℃ and casts, steel die used during casting is heated to 200 ℃ in advance, obtains the Mg-7Gd-5Y-5Sm-0.2Zr as-cast magnesium alloy.The thermal treatment of as-cast magnesium alloy: 515 ℃ of solution treatment 8 hours, 210 ℃ of isothermal agings were handled 20 hours.
The stretching test method of present embodiment heat-resistant cast rare earth magnesium alloy: the sample after solid solution aging is handled, be processed into 5 times of standard tensile samples according to standard GB 6397-86 " metal stretching experimental sample ".Tension specimen at high temperature need be in the requirement of sample two ends machining screw with the clamping device that satisfies the drawing by high temperature sample.Electronics is stretching on the accurate universal testing machine of day island proper Tianjin AG-I250kN and carries out, and draw speed is 1mm/min.During drawing by high temperature, to tension specimen insulation 15 minutes, temperature fluctuation ± 1 ℃ stretched then under relevant temperature.
The heat-resistant cast rare earth magnesium alloy of present embodiment gained, its room temperature tensile strength is 300MPa, and unit elongation is that 3.4%, 200 ℃ tensile strength is 312MPa, and 250 ℃ tensile strength is 313Mpa, and 300 ℃ of tensile strength are 316MPa.The tensile strength of this example heat-resistant cast rare earth magnesium alloy improves along with the rising of draft temperature in room temperature to 300 ℃, still has very high tensile strength under 300 ℃ of high temperature, has satisfied its requirement in aerospace, military project, automobile and other industry.
Embodiment 2
The heat-resistant cast rare earth magnesium alloy of present embodiment is made up of following component by mass percent: 10%Gd, and 2.0%Y, 1.5%Sm, 0.4%Zr, impurity element Si, Fe, Cu and Ni total amount are less than 0.02%, and surplus is Mg.Its middle-weight rare earths total content is 13.5%.
Press the mentioned component alloyage, its founding is: adopt corundum crucible, medium-frequency induction furnace melting.Earlier magnesium, master alloy Mg-Gd, Mg-Y, Mg-Sm and Mg-Zr are preheating to 150 ℃, magnesium are put into be preheating to 500 ℃ crucible then, at CO
2+ SF
6Mixed gas protected down, high-power rapid heating fusing, treat the magnesium fusing after, add Mg-Gd, Mg-Y master alloy at 720 ℃, small power slowly heats, and treats that its fusing back and magnesium liquid temp add the Mg-Sm master alloy again when ging up to 720 ℃; Be warmed up to 740 ℃ and add the Mg-Zr master alloy, treat its fusing back removal surface scum, temperature is risen to 780 ℃ again, close governor circuit, leave standstill; Treat that magnesium liquid is cooled to 730 ℃ and casts, casting is heated to 250 ℃ in advance with steel die.Obtain the Mg-10Gd-2Y-1.5Sm-0.4Zr as-cast magnesium alloy at last.The thermal treatment of as-cast magnesium alloy: 540 ℃ of solution treatment 4 hours, 230 ℃ of isothermal agings were handled 6 hours.
The stretching test method of present embodiment heat-resistant cast rare earth magnesium alloy is with embodiment 1.
The heat-resistant cast rare earth magnesium alloy of present embodiment gained, its room temperature tensile strength is 278MPa, and unit elongation is that 2.8%, 200 ℃ tensile strength is 304MPa, and 250 ℃ tensile strength is 330MPa, and 300 ℃ of tensile strength are 296MPa.The tensile strength of this example heat-resistant cast rare earth magnesium alloy improves along with the rising of draft temperature in room temperature to 250 ℃, warm relative superiority or inferiority at 300 ℃ still has very high tensile strength, has satisfied its requirement in aerospace, military project, automobile and other industry.
Embodiment 3
The heat-resistant cast rare earth magnesium alloy of present embodiment is made up of following component by mass percent: 14.0%Gd, and 2.0%Y, 0.5%Sm, 0.6%Zr, the total amount of impurity element Si, Fe, Cu and Ni is less than 0.02%, and surplus is Mg.Its middle-weight rare earths total content is 16.5%.
Press the mentioned component alloyage, its founding is: adopt corundum crucible, medium-frequency induction furnace melting.Earlier magnesium, master alloy Mg-Gd, Mg-Y, Mg-Sm and Mg-Zr are preheating to 220 ℃, magnesium are put into be preheating to 500 ℃ crucible then, at CO
2+ SF
6Mixed gas protected down, high-power rapid heating fusing, treat the magnesium fusing after, add Mg-Gd, Mg-Y master alloy at 730 ℃, small power slowly heats, and treats that its fusing back and magnesium liquid temp add the Mg-Sm master alloy again when ging up to 730 ℃; Be warmed up to 750 ℃ and add the Mg-Zr master alloy, treat its fusing back removal surface scum, temperature is risen to 775 ℃ again, close governor circuit, leave standstill; Treat that magnesium liquid is cooled to 690 ℃ and casts, used steel die is heated to 180 ℃ in advance during casting, obtains the Mg-14Gd-2Y-0.5Sm-0.6Zr as-cast magnesium alloy at last.The thermal treatment of as-cast magnesium alloy: 490 ℃ of solution treatment 15 hours, 180 ℃ of isothermal agings were handled 40 hours.
The stretching test method of present embodiment heat-resistant cast rare earth magnesium alloy is with embodiment 1.
The heat-resistant cast rare earth magnesium alloy of present embodiment gained, its room temperature tensile strength is 291MPa, and unit elongation is that 3.4%, 200 ℃ of tensile strength is 309MPa, and 250 ℃ of tensile strength are 318Mpa, and 300 ℃ of tensile strength are 286Mpa.The tensile strength of this example heat-resistant cast rare earth magnesium alloy improves along with the rising of draft temperature in room temperature to 250 ℃, still has very high tensile strength 300 ℃ warm relative superiority or inferiority.
It should be noted last that, above example only is illustrative rather than definitive thereof technical scheme of the present invention, although the present invention is had been described in detail with reference to the foregoing description, those of ordinary skill in the art is to be understood that, still can make amendment or be equal to replacement the present invention, and not breaking away from any modification or partial replacement of the spirit and scope of the present invention, it all should be encompassed in the middle of the claim scope of the present invention.
Claims (9)
1, a kind of heat-resistant cast rare earth magnesium alloy is characterized in that: be made up of following component by mass percent: 7～14% Gd, 2～5% Y, 0.3～5% Sm, 0.2～0.6% Zr, impurity element Si, Fe, Cu and Ni total amount are less than 0.02%, and surplus is Mg.
2, heat-resistant cast rare earth magnesium alloy according to claim 1 is characterized in that: described Gd, and Y, the mass percent sum of Sm is 13～18%.
3, heat-resistant cast rare earth magnesium alloy according to claim 1 and 2 is characterized in that: this heat-resistant cast rare earth magnesium alloy is by magnesium and master alloy Mg-Gd, Mg-Y, and Mg-Sm, Mg-Zr forms for the raw material melting.
4, a kind of preparation method of heat-resistant cast rare earth magnesium alloy according to claim 1 is characterized in that: comprise the steps:
1. with magnesium, master alloy Mg-Gd, Mg-Y, Mg-Sm and Mg-Zr preheating;
2. with magnesium at SF
6+ CO
2Mixed gas protected fusing down in 720～740 ℃ of adding master alloy Mg-Gd, Mg-Y, Mg-Sm, rises to 740～760 ℃ with temperature and adds the Mg-Zr master alloys;
3. after Mg-Zr fusing, remove surface scum, stop to heat up after temperature is risen to 770～780 ℃;
4. cast after cooling the temperature to 690～730 ℃, obtain cast alloy;
5. obtain heat-resistant cast rare earth magnesium alloy after cast alloy being heat-treated.
5, according to the preparation method of the described heat-resistant cast rare earth magnesium alloy of claim 4, it is characterized in that: the 1. described preheating temperature of step is 150～220 ℃.
6, according to the preparation method of the described heat-resistant cast rare earth magnesium alloy of claim 4, it is characterized in that: described thermal treatment is that cast alloy is carried out solution treatment and ageing treatment successively.
7, according to the preparation method of the described heat-resistant cast rare earth magnesium alloy of claim 6, it is characterized in that: the treatment temp of described solution treatment is 490～540 ℃, and the treatment time is 4～15 hours.
8, according to the preparation method of the described heat-resistant cast rare earth magnesium alloy of claim 6, it is characterized in that: the treatment temp of described ageing treatment is 180～230 ℃, and the treatment time is 6～40 hours.
9, according to the preparation method of the described heat-resistant cast rare earth magnesium alloy of claim 4, it is characterized in that: during described casting casting die is preheated to 180～250 ℃.
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