CN108559898B - Low-cost high-toughness wrought magnesium alloy and preparation method thereof - Google Patents
Low-cost high-toughness wrought magnesium alloy and preparation method thereof Download PDFInfo
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- 229910000861 Mg alloy Inorganic materials 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title abstract description 13
- 239000011777 magnesium Substances 0.000 claims abstract description 28
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 20
- 229910052779 Neodymium Inorganic materials 0.000 claims abstract description 17
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 17
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 16
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 15
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 14
- 239000000956 alloy Substances 0.000 claims abstract description 14
- 239000012535 impurity Substances 0.000 claims abstract description 12
- 239000011572 manganese Substances 0.000 claims abstract description 12
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 11
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 10
- 238000001125 extrusion Methods 0.000 claims description 18
- 238000001816 cooling Methods 0.000 claims description 10
- 238000000265 homogenisation Methods 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- 238000009749 continuous casting Methods 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 238000005242 forging Methods 0.000 claims description 7
- 238000005520 cutting process Methods 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 5
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 5
- 238000007664 blowing Methods 0.000 claims description 5
- 229940099607 manganese chloride Drugs 0.000 claims description 5
- 235000002867 manganese chloride Nutrition 0.000 claims description 5
- 239000011565 manganese chloride Substances 0.000 claims description 5
- 238000005070 sampling Methods 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 230000032683 aging Effects 0.000 claims description 4
- 238000005266 casting Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 150000002910 rare earth metals Chemical class 0.000 abstract description 7
- 238000009776 industrial production Methods 0.000 abstract description 4
- 238000005275 alloying Methods 0.000 abstract description 3
- 238000005728 strengthening Methods 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 2
- 239000011159 matrix material Substances 0.000 abstract description 2
- 239000007787 solid Substances 0.000 abstract description 2
- 239000011701 zinc Substances 0.000 abstract description 2
- 239000007769 metal material Substances 0.000 description 4
- 229910001209 Low-carbon steel Inorganic materials 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical group [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- 230000002431 foraging effect Effects 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 238000009864 tensile test Methods 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- 230000005484 gravity Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 229910000914 Mn alloy Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- -1 ferrous metals Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C23/00—Alloys based on magnesium
- C22C23/04—Alloys based on magnesium with zinc or cadmium as the next major constituent
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
- C22C1/03—Making non-ferrous alloys by melting using master alloys
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/06—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of magnesium or alloys based thereon
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Powder Metallurgy (AREA)
- Extrusion Of Metal (AREA)
Abstract
the invention provides a low-cost high-toughness wrought magnesium alloy which consists of Zn, Y, Nd, La, Mn, Mg and inevitable impurities, wherein the sum of Y, Nd and La in percentage by mass is not more than 2.5% of the total mass fraction. According to the invention, Y, Nd and La three specific rare earth elements are used, the total mass percentage sum of the rare earth elements is controlled to be not more than 2.5% of the total mass fraction of the magnesium alloy, Zn, Mn and Mg are combined, the solid solubility of the elements in a matrix is reduced by the mutual influence among the elements through multi-element alloying, the yield and the utilization efficiency of the rare earth elements are improved, the strengthening effect of the alloy is obviously improved under the condition of less rare earth addition, the alloy has high strength and high toughness, the room temperature tensile strength is more than or equal to 420MPa, and the elongation after fracture is more than or equal to 7%. The preparation method is simple and suitable for industrial production.
Description
Technical Field
the invention belongs to the technical field of metal materials and metallurgy, and particularly relates to a low-cost high-toughness wrought magnesium alloy and a preparation method thereof.
Background
The magnesium alloy has the advantages of low density, high specific strength, lower rigidity, larger impact energy absorption, easy cutting processing, easy recycling and the like, is increasingly widely applied in the fields of automobiles, aerospace, electronics and the like at present, and is considered as an ideal material which effectively reduces the mass, saves energy, is environment-friendly and is beneficial to sustainable development. With the expansion of the application range of magnesium alloys, the demand of related industries on magnesium alloys is increasing. Although magnesium alloy has obvious advantage of light weight, the characteristic of low strength severely restricts the application range. In order to improve the strength of magnesium alloys, it is common in the industry of selection of alloying elements to obtain high-strength magnesium alloys by adding a large amount of rare earth elements. The high-strength magnesium alloy of Chinese patent CN101463441A (containing rare earth high-strength heat-resistant magnesium alloy and the preparation method thereof) comprises the following components: y is more than or equal to 3% and less than or equal to 16%, GD is more than or equal to 0% and less than or equal to 10%, CA is more than or equal to 0.3% and less than or equal to 5%, ZR is more than or equal to 0.1 and less than or equal to 1.5%, and the balance of MG and impurities; after heat treatment, the instantaneous ultimate tensile strength at 300 ℃ is 262 MPa. Chinese patent CN102732763A (a high-strength Mg-Gd-Y-Zn-Mn alloy), the components of the prepared high-strength magnesium alloy are as follows: gd is more than or equal to 8.2 and less than or equal to 10.2, Y is more than or equal to 5 and less than or equal to 6, Zn is more than or equal to 0.5 and less than or equal to 4, Mn is more than or equal to 0.5 and less than or equal to 0.8, and the balance is magnesium and inevitable impurities; after deformation and heat treatment, the room temperature strength of the alloy reaches over 496 MPa. Chinese patent CN105525179A (a method for preparing a large-size forging of rare earth magnesium alloy), wherein the high-strength magnesium alloy comprises the following components: gd is more than or equal to 7.5 and less than or equal to 9.5, Y is more than or equal to 3.5 and less than or equal to 5.0, Zn is more than or equal to 1.0 and less than or equal to 1.5, Mn is more than or equal to 0.3 and less than or equal to 0.6, impurities are less than or equal to 0.13%, and the balance is magnesium; after deformation and heat treatment, the room temperature strength of the forging reaches 430 MPa. The aging strengthening of Mg-15Gd-3Y extrusion alloy (Chinese non-ferrous metals bulletin 2010,20 (4): 600-605) in Zhangiei et al article has room temperature tensile strength of 446.67 MPa after the Mg-15Gd-3Y extrusion alloy is subjected to extrusion aging. The room-temperature tensile strength of the Mg-9Gd-4Y-0.6Zr alloy prepared by the article of Shayang et al, namely the performance of high-strength heat-resistant Mg-9Gd-4Y-0.6Zr alloy (proceedings of the university of south and middle, 2006,37 (5): 851 and 855) is 370 MPa. The high-strength magnesium alloy adopts rare earth elements with higher content, the rare earth elements are high in cost, the cost of the magnesium alloy is greatly increased, the specific gravity is high, the light weight advantage of the magnesium alloy cannot be fully exerted, and the requirement of large-scale industrial production cannot be met.
disclosure of Invention
in order to solve the problems in the prior art and widen the application range of the magnesium alloy, the first object of the present invention is to provide a magnesium alloy which has low rare earth content, good plastic formability, low cost and excellent performance.
The invention is realized by the following modes:
A magnesium alloy consisting of Zn, Y, Nd, La, Mn, Mg and inevitable impurities, characterized in that: the sum of the Y, Nd and La mass percent is not more than 2.5 percent of the total mass fraction.
In one embodiment, the mass percentage of the Zn element in the magnesium alloy of the present invention is 5.5 to 6.5% of the total mass fraction.
In one embodiment, the mass percentage of the Mn element in the magnesium alloy of the present invention is 0.5 to 0.8% of the total mass fraction.
In one embodiment, the mass percent of the Y element in the magnesium alloy is 0.7-1.4% of the total mass fraction; the mass percentage of the Nd element is 0.2-1.0% of the total mass fraction; the mass percentage of the La element is 0.2-1.0% of the total mass fraction.
in one embodiment, the magnesium alloy of the invention comprises the following components in percentage by mass: zn: 5.5-6.5%, Y: 0.7-1.4%, Nd: 0.2-1.0%, La: 0.2-1.0%, Mn: 0.5-0.8 percent, and the balance of Mg and inevitable impurities, and the sum of the mass percent of the rare earth element Y, Nd and the mass percent of La in the composition is not more than 2.5 percent of the total mass fraction.
The invention also aims to provide a preparation method of the magnesium alloy. The preparation method of the magnesium alloy comprises the following steps:
(1) Adding Mg and Zn into a crucible, protecting by using RJ-2 solvent, adding manganese chloride between the temperature of a solution and 750 ℃ and ~ 760 ℃ after the Mg and Zn are completely melted, adding Mg-30La, Mg-30Nd and Mg-30Y intermediate alloy when the temperature is raised to 780 ℃ and ~ 800 ℃, blowing Ar gas for 15 ~ 30min and purifying after the Mg and Zn are completely melted, adding RJ-6 solvent in the process, stirring, standing for 10min and ~ 20min, sampling components in front of the furnace, closing the crucible and standing after the components are qualified, setting the solution to be heat-preserved at 670 ℃ ~ 680 ℃, and semi-continuously casting when the temperature is lowered to 670 ℃ and ~ 680 ℃ to obtain magnesium alloy cast ingots;
(2) Removing the outer skin of the semi-continuous casting blank vehicle, preserving the heat for 8h ~ 14h at the temperature of 380 ℃ of ~ 410 ℃ for homogenization treatment, and cooling in air after the homogenization treatment is finished;
(3) keeping the homogenized cast ingot at 350 ℃ of ~ 410 ℃ for 3h ~ 6h, extruding, wherein the extrusion ratio is more than 4, and cooling by strong wind after the extrusion is finished;
(4) Cutting a blank on an extrusion rod according to the shape of a part, heating and insulating the blank at the temperature of 300 ℃ of ~ 410 ℃ for 3h ~ 6h, and then forging to obtain a formed piece;
(5) And (3) carrying out aging treatment on the magnesium alloy formed piece at 140 ℃ of ~ 180 ℃ for 16h ~ 28 h.
Has the advantages that:
Without intending to be bound by any theory, although the high-strength magnesium alloy can be obtained by adding a large amount of rare earth elements, the rare earth elements not only have high cost, but also have large specific gravity, and the lightweight advantage of the magnesium alloy is reduced on the basis of increasing the cost of the magnesium alloy, so that the requirement of large-scale industrial production cannot be met. The inventor carries out a large number of experiments and unexpectedly discovers that Y, Nd and La specific rare earth elements are used, the total mass percentage sum of the total mass of the rare earth elements is controlled to be not more than 2.5 percent of the total mass fraction of the magnesium alloy, Zn, Mn and Mg are combined, the solid solubility of the elements in a matrix is reduced by the mutual influence among the elements through multi-element alloying, the yield and the utilization efficiency of the rare earth elements are improved, the strengthening effect of the alloy is obviously improved under the condition of less rare earth addition, the alloy has high strength and high toughness, the room-temperature tensile strength is more than or equal to 420MPa, and the elongation after fracture is more than or equal to 7 percent; thereby preparing the magnesium alloy which can replace the widely used aluminum alloys such as 2A12 and the like at present and greatly expanding the application range of the magnesium alloy. The magnesium alloy has less total content of rare earth, the total content of the added rare earth is less than 2.5 percent, the preparation cost is low, the pressure processing forming performance is good, the types of products which can be produced are more, the application range is wide, and the magnesium alloy can be industrially produced in a large scale. The preparation method is simple and suitable for industrial production.
Detailed Description
The present invention is described in detail below with reference to specific examples, which are given for the purpose of further illustrating the invention and are not to be construed as limiting the scope of the invention, and the invention may be modified and adapted by those skilled in the art in light of the above disclosure. In the invention, the inevitable impurities are impurities in raw materials or impurities introduced in the preparation process, such as Si, Fe, Cu, Ni and the like, wherein Si is less than or equal to 0.05, Fe is less than or equal to 0.05, Cu is less than or equal to 0.05, and Ni is less than or equal to 0.005; the corresponding impurities can refer to the trade marks and chemical compositions of standard GB/T5153-2003 wrought magnesium and magnesium alloy. All the raw materials and reagents of the invention are commercial products.
Example 1
The magnesium alloy comprises the following components in percentage by mass: zn: 6.1%, Y: 1.0%, Nd: 0.5%, La: 0.4%, Mn: 0.5 percent and the balance of Mg, and the sum of the mass percentages of Y, Nd and La in the component composition is 1.9 percent of the total mass fraction.
The preparation process comprises the following steps:
(1) Adding preheated pure Mg and pure Zn into a low-carbon steel crucible, protecting by using a No. 2 solvent, after the pure Mg and the pure Zn are completely melted, adding manganese chloride at the temperature of 757 ℃, when the temperature is raised to 792 ℃, respectively adding Mg-30La, Mg-30Nd and Mg-30Y intermediate alloys, after the pure Mg and the pure Zn are completely melted, blowing Ar gas for 16min for pure purification treatment, adding the No. 6 solvent in the process for stirring, standing for 10min, sampling components in front of a furnace, ensuring that the components are qualified, closing the crucible for standing, setting the temperature of the solution to be 676 ℃, and when the temperature is lowered to the temperature, carrying out semi-continuous casting to obtain a magnesium alloy cast ingot;
(2) removing the outer skin of the semi-continuous casting blank vehicle, preserving heat for 12 hours at 400 ℃ for homogenization treatment, and cooling in air after the homogenization treatment is finished;
(3) keeping the homogenized cast ingot at 360 ℃ for 5h, then extruding with the extrusion ratio of 23, and cooling with strong wind after extrusion;
(4) Cutting a blank on an extrusion rod, heating and insulating the blank at 350 ℃ for 3h, and then forging to obtain a formed piece;
(5) and (3) preserving the heat of the magnesium alloy formed piece at 170 ℃ for 18h for aging treatment.
the properties of the high-strength magnesium alloy obtained in the embodiment are measured by using a part 1 room temperature test method of a GBT228.1-2010 metal material tensile test, and the room temperature tensile strength of the high-strength magnesium alloy prepared in the embodiment 1 is 436MPa, and the elongation after fracture is 9.0%.
Example 2
The magnesium alloy comprises the following components in percentage by mass: zn: 6.4%, Y: 0.9%, Nd: 0.6%, La: 0.6%, Mn: 0.6 percent of Mg, and the balance of Mg, wherein the sum of Y, Nd and La mass percent in the composition is 2.1 percent of the total mass fraction.
the preparation process comprises the following steps:
(1) Adding preheated pure Mg and pure Zn into a low-carbon steel crucible, protecting by using a No. 2 solvent, after the pure Mg and the pure Zn are completely melted, adding manganese chloride at the temperature of 750 ℃, respectively adding Mg-30La, Mg-30Nd and Mg-30Y intermediate alloys when the temperature is increased to 780 ℃, blowing Ar gas for 25min to carry out purification treatment after the pure Mg and the pure Zn are completely melted, adding the No. 6 solvent in the process, stirring, standing for 20min, then sampling components in front of a furnace, closing the crucible, standing, setting the temperature of the solution at 670 ℃, keeping the temperature, and carrying out semi-continuous casting when the temperature is reduced to the temperature range to obtain magnesium alloy cast ingots;
(2) Removing the outer skin of the semi-continuous casting blank vehicle, preserving heat for 9 hours at the temperature of 410 ℃ for homogenization treatment, and cooling in air after the homogenization treatment is finished;
(3) Keeping the homogenized cast ingot at 390 ℃ for 4h, extruding at an extrusion ratio of 15, and cooling by strong wind after extrusion;
(4) cutting a blank on an extrusion rod according to the shape of a part, heating and insulating the blank at 330 ℃ for 4 hours, and then forging to obtain a formed piece;
(5) and (3) preserving the heat of the magnesium alloy forming piece at 180 ℃ for 16h for aging treatment.
the properties of the high-strength magnesium alloy obtained in the embodiment are measured by using a room temperature test method of part 1 of a GBT228.1-2010 metal material tensile test, and the room temperature tensile strength of the high-strength magnesium alloy prepared in the embodiment 2 is 427MPa, and the elongation after fracture is 8.0%.
example 3
The magnesium alloy comprises the following components in percentage by mass: zn: 6.1%, Y: 0.8%, Nd: 0.7%, La: 0.6%, Mn: 0.5 percent, and the balance being Mg, and the sum of the mass percentages of Y, Nd and La in the component composition is 2.1 percent of the total mass fraction.
The preparation process comprises the following steps:
(1) adding preheated pure Mg and pure Zn into a low-carbon steel crucible, protecting by using a No. 2 solvent, after the pure Mg and the pure Zn are completely melted, adding manganese chloride at the temperature of 750 ℃, respectively adding Mg-30La, Mg-30Nd and Mg-30Y intermediate alloys when the temperature is raised to 800 ℃, blowing Ar gas for 20min for pure purification treatment after the pure Mg and the pure Zn are completely melted, adding the No. 6 solvent in the process for stirring, then standing for 18min, sampling components in front of a furnace, ensuring that the components are qualified, closing the crucible for standing, setting the temperature of the solution to be kept at 680 ℃, and performing semi-continuous casting when the temperature is lowered to the temperature to obtain a magnesium alloy cast ingot;
(2) removing the outer skin of the semi-continuous casting blank vehicle, preserving heat for 14 hours at 380 ℃ for homogenization treatment, and cooling in air after the homogenization treatment is finished;
(3) keeping the homogenized cast ingot at 390 ℃ for 3h, extruding with the extrusion ratio of 19, and cooling by strong wind after extrusion;
(4) cutting a blank on an extrusion rod, heating and insulating the blank at 330 ℃ for 3h, and then forging to obtain a formed piece;
(5) And (3) preserving the heat of the magnesium alloy formed piece at 150 ℃ for 28h for aging treatment.
the properties of the high-strength magnesium alloy obtained in the embodiment were measured by using the room temperature test method part 1 of the GBT228.1-2010 metal material tensile test, and the room temperature tensile strength of the high-strength magnesium alloy prepared in the embodiment 3 was 439MPa, and the elongation after fracture was 10%.
Claims (2)
1. a magnesium alloy consisting of Zn, Y, Nd, La, Mn, Mg and inevitable impurities, characterized in that: the magnesium alloy comprises the following components in percentage by mass: zn: 5.5-6.5%, Y: 0.7-1.4%, Nd: 0.2-1.0%, La: 0.2-1.0%, Mn: 0.5 to 0.8 percent of Mg and inevitable impurities as the rest, and the total mass percent of the rare earth element Y, Nd and the La in the composition is 1.9 to 2.1 percent of the total mass fraction.
2. the method for producing a magnesium alloy according to claim 1, comprising the steps of:
(1) adding Mg and Zn into a crucible, protecting by using RJ-2 solvent, adding manganese chloride between the temperature of a solution and 750 ℃ and ~ 760 ℃ after the Mg and Zn are completely melted, adding Mg-30La, Mg-30Nd and Mg-30Y intermediate alloy when the temperature is raised to 780 ℃ and ~ 800 ℃, blowing Ar gas for 15 ~ 30min and purifying after the Mg and Zn are completely melted, adding RJ-6 solvent in the process, stirring, standing for 10min and ~ 20min, sampling components in front of the furnace, closing the crucible and standing after the components are qualified, setting the solution to be heat-preserved at 670 ℃ ~ 680 ℃, and semi-continuously casting when the temperature is lowered to 670 ℃ and ~ 680 ℃ to obtain magnesium alloy cast ingots;
(2) Removing the outer skin of the semi-continuous casting blank vehicle, preserving the heat for 8h ~ 14h at the temperature of 380 ℃ of ~ 410 ℃ for homogenization treatment, and cooling in air after the homogenization treatment is finished;
(3) Keeping the homogenized cast ingot at 350 ℃ of ~ 410 ℃ for 3h ~ 6h, extruding, wherein the extrusion ratio is more than 4, and cooling by strong wind after the extrusion is finished;
(4) Cutting a blank on an extrusion rod according to the shape of a part, heating and insulating the blank at the temperature of 300 ℃ of ~ 410 ℃ for 3h ~ 6h, and then forging to obtain a formed piece;
(5) And (3) carrying out aging treatment on the magnesium alloy formed piece at 140 ℃ of ~ 180 ℃ for 16h ~ 28 h.
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Effective date of registration: 20240319 Address after: 400039 Chongqing Jiulongpo Yuzhou Road No. 33 Patentee after: Southwest Institute of technology and engineering of China Ordnance Equipment Group Country or region after: Zhong Guo Address before: 400039 Chongqing Jiulongpo Shiqiaopu Yuzhou Road No. 33 Patentee before: NO 59 Research Institute OF CHINA ORDNACE INDUSTRY Country or region before: Zhong Guo |