CN103290297A - Zirconium-molybdenum-magnesium-containing alloy and preparation technique thereof - Google Patents
Zirconium-molybdenum-magnesium-containing alloy and preparation technique thereof Download PDFInfo
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- CN103290297A CN103290297A CN2013102243075A CN201310224307A CN103290297A CN 103290297 A CN103290297 A CN 103290297A CN 2013102243075 A CN2013102243075 A CN 2013102243075A CN 201310224307 A CN201310224307 A CN 201310224307A CN 103290297 A CN103290297 A CN 103290297A
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Abstract
The invention discloses a zirconium-molybdenum-magnesium-containing alloy and a preparation technique thereof. The zirconium-molybdenum-magnesium-containing alloy comprises the following ingredients in percentage by weight: 26-38% of Mg, 23-34% of Mo, 4-5% of Nb, 2-4% of Zr, 2-6% of Ca, less than or equal to 0.05% of Fe, less than or equal to 0.05% of C, less than or equal to 0.05% of N, less than or equal to 0.05% of H, less than or equal to 0.06% of O, and the balance of Ni. By controlling the ingredients and machining mode of a material, the zirconium-molybdenum-magnesium-containing alloy not only has a high strength equivalent to that of the aluminum alloy, has good performance stability after being used at room temperature, and the strength of the zirconium-molybdenum-magnesium-containing alloy can also be improved by 1.5-3 times compared with the existing zirconium-molybdenum-magnesium-containing alloy.
Description
Technical field:
The invention belongs to the material field, relate to a kind of zirconium molybdenum magnesium alloy that contains, especially a kind of low impurity content contains zirconium molybdenum magnesium alloy and cold working and heat treating method
Background technology:
MAGNESIUM METAL is argenteous metal, and matter is hard, slightly ductility.Magnesium is mainly for the manufacture of light metal alloy, contain zirconium molybdenum magnesium alloy and have characteristics such as excellent toughness plasticity, solidity to corrosion, processibility, and low cost of manufacture, simultaneously, the alloy-free element adds environmentally compatible, is the structured material that is widely used in fields such as military project national defence, aerospace, medical treatment.Yet because it is lower to contain the intensity of zirconium molybdenum magnesium alloy, as structured material, range of application is restricted.
At present, in industrial application, improve that to contain the most ripe, the effective means of zirconium molybdenum magnesium alloy strength be to carry out refined crystalline strengthening.The principle of refined crystalline strengthening can be explained with the hall-Petch formula: because the crystal boundary resistance to deformation in the polycrystal is bigger, and the distortion of each crystal grain will be subjected to pining down of crystal grain on every side, so multicrystal room temperature strength always improves along with the refinement (being the increase of the crystal boundary total area) of crystal grain.The available hall-Petch formula of relation between polycrystal yield strength σ s and the average grain diameter d is described: σ
s=σ
0+ kd
-1/2The zirconium molybdenum magnesium alloy that contains with various grain sizes is example, and when grain-size was 7～8 grades, intensity was about 400Mpa, and when grain-size reached 11～12 grades, intensity can improve 70～100Mpa.This has proved absolutely that refined crystalline strengthening is effective for the lifting of the strength of materials.
Summary of the invention:
The objective of the invention is to overcome the shortcoming of above-mentioned prior art, a kind of zirconium molybdenum magnesium alloy and preparation technology thereof of containing is provided, contain zirconium molybdenum magnesium alloy and adopt the method in containing zirconium molybdenum magnesium alloy, add elements such as molybdenum, niobium, by cold working and heat treatment mode obtain to be higher than have 2～3 times of intensity now contain zirconium molybdenum magnesium alloy.
The objective of the invention is to solve by the following technical programs:
A kind of zirconium molybdenum magnesium alloy that contains, describedly contain Mg26-38wt%, Mo23-34wt%, Nb4-5wt%, Zr2-4wt%, Ca2-6wt%, Fe≤0.05wt%, C≤0.05wt%, N≤0.05wt%, H≤0.05wt%, O≤0.06wt% in the zirconium molybdenum magnesium alloy, all the other are Ni.
The described preparation technology who contains zirconium molybdenum magnesium alloy comprises the steps:
(1) melting: adopting magnesium powder, molybdenum powder, nickel powder, niobium powder, zirconium powder, calcium powder is raw material, melting in the good tungsten crucible of thermodynamic stability, the purity 〉=99.9wt% of tungsten crucible; Pack into after molybdenum powder, nickel powder, niobium powder and zirconium powder mixed in the tungsten crucible, magnesium powder and the calcium powder hopper of packing into added in the melting later stage; At first with pumping high vacuum in the body of heater, vacuum tightness is 1 * 10 in the stove
-1Pa, leak rate＜0.2Pa/min charges into argon gas, and making vacuum tightness is 0.1MPa; Energising, the molybdenum powder that melting mixes, nickel powder, niobium powder and zirconium powder treat that molybdenum powder, nickel powder, niobium powder and zirconium powder are all after the fusing, Turnover bunker adds magnesium powder and calcium powder, treats that magnesium powder and calcium powder are all after the fusing, left standstill 5-10 minute, and 2050-2150 degree centigrade of casting, obtained to contain zirconium molybdenum magnesium alloy.
The granularity of described magnesium powder, molybdenum powder, nickel powder, niobium powder, zirconium powder or calcium powder is the order into 100-300.
(2) cold working: adopt the mode of kicker annealing back room temperature drawing to process, annealing temperature is 750 ℃, time 1h, must not heat-treat in the middle of each drawing passes; Passage accumulation cold deformation 〉=70wt%;
(3) finished products thermal treatment: temperature≤400 ℃, time≤1h.
The described optimal way that contains zirconium molybdenum magnesium alloy preparation technology is:
The described rod silk material that zirconium molybdenum magnesium alloy is made, the diameter of phi≤12mm of described rod silk material, the tensile strength 〉=750Mpa of rod silk material, the unit elongation 〉=18wt% of containing.
The present invention makes to contain zirconium molybdenum magnesium alloy and not only have the high strength that is equivalent to aluminium alloy by composition and the processing mode of control material, at room temperature uses to have good stability, and its strength ratio is existing, and to contain zirconium molybdenum magnesium alloy high 1.5～3 times; The plasticity-of zirconium is good, and corrosion-resistant, added zirconium in the molybdenum magnesium alloy after, can improve its corrosion resistance, improve that it is moulding.
Embodiment:
Below the present invention is done and describes in further detail:
What the objective of the invention is to adopt low impurity content contains zirconium molybdenum magnesium alloy, contains zirconium molybdenum magnesium alloy by what suitable processing mode obtained to be higher than 1.5～3 times of existing intensity.This invention makes to contain zirconium molybdenum magnesium alloy and not only have quite high intensity by composition and the processing mode of control material, at room temperature uses to have good stability.
Along with the increase of deflection, contain and occurred a large amount of twin tissue and twin-plane boundary in the zirconium molybdenum magnesium alloy.Twin-plane boundary is similar to the mode of action and the crystal boundary of material reinforcement, and when having a large amount of twin-plane boundaries in the material structure, dislocation will be difficult to pass twin-plane boundary and be out of shape, cause filling at the interface long-pending a large amount of dislocation, cause stress concentration, cause work hardening, reach the purpose that promotes the strength of materials.Therefore, the deflection that contains zirconium molybdenum magnesium alloy is more big, mechanical twin is more many, and the twin size is more little, and the strength of materials will be more high.
The heat treating regime that adopts among the present invention is as follows:
Under the prerequisite of loss material intensity not, in order to improve the plasticity that contains zirconium molybdenum magnesium alloy, suitably improve the unit elongation that contains zirconium molybdenum magnesium alloy, can carry out low-temperature heat treatment.Thermal treatment is formulated: temperature≤400 ℃, time≤1h.
Embodiment 1:
A kind of zirconium molybdenum magnesium alloy that contains describedly contains Mg26wt%, Mo32wt%, Nb5wt%, Zr4wt%, Ca6wt%, Fe≤0.05wt%, C≤0.05wt%, N≤0.05wt%, H≤0.05wt%, O≤0.06wt% in the zirconium molybdenum magnesium alloy, and all the other are Ni.
Embodiment 2:
A kind of zirconium molybdenum magnesium alloy that contains describedly contains Mg38wt%, Mo34wt%, Nb4wt%, Zr2wt%, Ca2wt%, Fe≤0.05wt%, C≤0.05wt%, N≤0.05wt%, H≤0.05wt%, O≤0.06wt% in the zirconium molybdenum magnesium alloy, and all the other are Ni.
Embodiment 3:
A kind of zirconium molybdenum magnesium alloy that contains describedly contains Mg30wt%, Mo23wt%, Nb4.5wt%, Zr3wt%, Ca4wt%, Fe≤0.05wt%, C≤0.05wt%, N≤0.05wt%, H≤0.05wt%, O≤0.06wt% in the zirconium molybdenum magnesium alloy, and all the other are Ni.
Embodiment 4:
A kind of zirconium molybdenum magnesium alloy that contains describedly contains Mg32wt%, Mo30wt%, Nb4wt%, Zr2wt%, Ca5wt%, Fe≤0.05wt%, C≤0.05wt%, N≤0.05wt%, H≤0.05wt%, O≤0.06wt% in the zirconium molybdenum magnesium alloy, and all the other are Ni.
Embodiment 5:
A kind of zirconium molybdenum magnesium alloy that contains describedly contains Mg33wt%, Mo32wt%, Nb5wt%, Zr2wt%, Ca4wt%, Fe≤0.05wt%, C≤0.05wt%, N≤0.05wt%, H≤0.05wt%, O≤0.06wt% in the zirconium molybdenum magnesium alloy, and all the other are Ni.
Embodiment 6:
A kind of zirconium molybdenum magnesium alloy that contains describedly contains Mg28wt%, Mo24wt%, Nb5wt%, Zr4wt%, Ca6wt%, Fe≤0.05wt%, C≤0.05wt%, N≤0.05wt%, H≤0.05wt%, O≤0.06wt% in the zirconium molybdenum magnesium alloy, and all the other are Ni.
The described preparation technology who contains zirconium molybdenum magnesium alloy comprises the steps:
(1) melting: adopting magnesium powder, molybdenum powder, nickel powder, niobium powder, zirconium powder, calcium powder is raw material, melting in the good tungsten crucible of thermodynamic stability, the purity 〉=99.9wt% of tungsten crucible; Pack into after molybdenum powder, nickel powder, niobium powder and zirconium powder mixed in the tungsten crucible, magnesium powder and the calcium powder hopper of packing into added in the melting later stage; At first with pumping high vacuum in the body of heater, vacuum tightness is 1 * 10 in the stove
-1Pa, leak rate＜0.2Pa/min charges into argon gas, and making vacuum tightness is 0.1MPa; Energising, the molybdenum powder that melting mixes, nickel powder, niobium powder and zirconium powder treat that molybdenum powder, nickel powder, niobium powder and zirconium powder are all after the fusing, Turnover bunker adds magnesium powder and calcium powder, treats that magnesium powder and calcium powder are all after the fusing, left standstill 5-10 minute, and 2050-2150 degree centigrade of casting, obtained to contain zirconium molybdenum magnesium alloy.
The granularity of described magnesium powder, molybdenum powder, nickel powder, niobium powder, zirconium powder or calcium powder is the order into 100-300.
(2) cold working: adopt the mode of kicker annealing back room temperature drawing to process, annealing temperature is 750 ℃, time 1h, must not heat-treat in the middle of each drawing passes; Passage accumulation cold deformation 〉=70wt%;
(3) finished products thermal treatment: temperature≤400 ℃, time≤1h.
The above, it only is preferred embodiment of the present invention, be not that the present invention is done any pro forma restriction, though the present invention discloses as above with preferred embodiment, yet be not in order to limit the present invention, any those skilled in the art, in not breaking away from the technical solution of the present invention scope, when the method that can utilize above-mentioned announcement and technology contents are made a little change or be modified to the equivalent embodiment of equivalent variations, in every case be the content that does not break away from technical solution of the present invention, any simple modification that foundation technical spirit of the present invention is done above embodiment, equivalent variations and modification still belong in the scope of technical solution of the present invention.
Claims (6)
1. one kind contains zirconium molybdenum magnesium alloy, it is characterized in that: contain Mg26-38wt%, Mo23-34wt%, Nb4-5wt%, Zr2-4wt%, Ca2-6wt%, Fe≤0.05wt%, C≤0.05wt%, N≤0.05wt%, H≤0.05wt%, O≤0.06wt% described containing in the zirconium molybdenum magnesium alloy, and all the other are Ni.
2. contain zirconium molybdenum magnesium alloy according to claim 1, it is characterized in that: describedly contain Mg26wt%, Mo32wt%, Nb5wt%, Zr4wt%, Ca6wt%, Fe≤0.05wt%, C≤0.05wt%, N≤0.05wt%, H≤0.05wt%, O≤0.06wt% in the zirconium molybdenum magnesium alloy, all the other are Ni.
3. contain zirconium molybdenum magnesium alloy according to claim 1, it is characterized in that: describedly contain Mg38wt%, Mo34wt%, Nb4wt%, Zr2wt%, Ca2wt%, Fe≤0.05wt%, C≤0.05wt%, N≤0.05wt%, H≤0.05wt%, O≤0.06wt% in the zirconium molybdenum magnesium alloy, all the other are Ni.
4. contain zirconium molybdenum magnesium alloy preparation technology according to claim 1, it is characterized in that, comprise the steps:
(1) melting: adopting magnesium powder, molybdenum powder, nickel powder, niobium powder, zirconium powder, calcium powder is raw material, melting in the good tungsten crucible of thermodynamic stability, the purity 〉=99.9wt% of tungsten crucible; Pack into after molybdenum powder, nickel powder, niobium powder and zirconium powder mixed in the tungsten crucible, magnesium powder and the calcium powder hopper of packing into added in the melting later stage; At first with pumping high vacuum in the body of heater, vacuum tightness is 1 * 10 in the stove
-1Pa, leak rate＜0.2Pa/min charges into argon gas, and making vacuum tightness is 0.1MPa; Energising, the molybdenum powder that melting mixes, nickel powder, niobium powder and zirconium powder treat that molybdenum powder, nickel powder, niobium powder and zirconium powder are all after the fusing, Turnover bunker adds magnesium powder and calcium powder, treats that magnesium powder and calcium powder are all after the fusing, left standstill 5-10 minute, and 2050-2150 degree centigrade of casting, obtained to contain zirconium molybdenum magnesium alloy;
(2) cold working: adopt the mode of kicker annealing back room temperature drawing to process, annealing temperature is 750 ℃, time 1h, must not heat-treat in the middle of each drawing passes; Passage accumulation cold deformation 〉=70wt%;
(3) finished products thermal treatment: temperature≤400 ℃, time≤1h.
5. as described in claim 4, contain zirconium molybdenum magnesium alloy preparation technology, it is characterized in that: the described rod silk material that zirconium molybdenum magnesium alloy is made, the diameter of phi≤12mm of described rod silk material, the tensile strength 〉=750Mpa of rod silk material, the unit elongation 〉=18wt% of containing.
6. contain zirconium molybdenum magnesium alloy preparation technology as described in claim 4, it is characterized in that: the granularity of described magnesium powder, molybdenum powder, nickel powder, niobium powder, zirconium powder or calcium powder is the order into 100-300.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09272934A (en) * | 1996-02-05 | 1997-10-21 | Mitsubishi Materials Corp | Heat transfer tube for refuse incinerating waste heat boiler excellent in high temperature corrosion resistance |
| JPH10204563A (en) * | 1997-01-22 | 1998-08-04 | Mitsubishi Materials Corp | Composite heat exchanger tube for waste heat boiler using exhaust gas of refuse incinerator excellent in high temperature corrosion resistance |
| CN101600814A (en) * | 2006-12-29 | 2009-12-09 | 阿海珐核能公司 | To nickel-base alloy, in particular for fuel assembly for nuclear reactor and be used for heat treating method that the auxiliary cracking of environment of the nickel-base alloy of nuclear reactor desensitizes and with the parts of the alloy manufacturing of so handling |
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- 2013-06-06 CN CN201310224307.5A patent/CN103290297B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09272934A (en) * | 1996-02-05 | 1997-10-21 | Mitsubishi Materials Corp | Heat transfer tube for refuse incinerating waste heat boiler excellent in high temperature corrosion resistance |
| JPH10204563A (en) * | 1997-01-22 | 1998-08-04 | Mitsubishi Materials Corp | Composite heat exchanger tube for waste heat boiler using exhaust gas of refuse incinerator excellent in high temperature corrosion resistance |
| CN101600814A (en) * | 2006-12-29 | 2009-12-09 | 阿海珐核能公司 | To nickel-base alloy, in particular for fuel assembly for nuclear reactor and be used for heat treating method that the auxiliary cracking of environment of the nickel-base alloy of nuclear reactor desensitizes and with the parts of the alloy manufacturing of so handling |
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