CN103056372A - Preparation method of Wolfram-Nickel-Ferrum (W-Ni-Fe) alloy parts - Google Patents
Preparation method of Wolfram-Nickel-Ferrum (W-Ni-Fe) alloy parts Download PDFInfo
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Abstract
The invention discloses a preparation method of W-Ni-Fe alloy parts. The preparation method includes the steps of (1) material preparing by using reducted tungsten powder, hydroxy nickel powder and hydroxy iron powder as metal powder; (2) powder blending by weighing W powder, Fe powder and Ni powder in the proportion of 95:3.5:1.5; (3) binder preparation; (4) W-Ni-Fe materials mixing and feeding; (5) pelletizing; (6) injection molding; (7) solvent degreasing; (8) thermal debinding; (9) sintering; (10) thermal treating after sintering. By the preparation method, problem caused by using the present manufacturing process of W-Ni-Fe alloy is solved, so that product shapes are diversified, product design is liberated, mass production is implemented, manufacturing cost is reduced and the like.
Description
Technical field
The present invention relates to a kind of metal injection molded technology, particularly relate to a kind of method for preparing the tungsten nickel iron alloy parts.
Background technology
Tungsten nickel iron alloy is a kind of take tungsten as matrix (W content is 85%-98%), adds the alloy of a small amount of Ni, two kinds of elements compositions of Fe, and its density is up to 16.5-19.0g/cm
3, heavy metal or heavy alloy are otherwise known as.Tungsten nickel iron alloy has that density is high, intensity and hardness is high, physical and mechanical property and the serviceability of electric conductivity and a series of excellences such as thermal conductivity is good, thermal coefficient of expansion is little, anticorrosive and good in oxidation resistance, machining property and weldability are good, therefore tungsten nickel iron alloy all is widely used in national defense industry and civilian industry, particularly as injuring by force the warhead material, it is considered to replace the military new material of the potential feature of environmental protection of tool of depleted uranium bomb to the W-Ni-Fe alloy in national defense industry.
Metal injection molded (MIM) develops the most rapidly new technology in the field of powder metallurgy now, also is the new technology of metal forming, is called as " the 5th generation
"Has unique advantage aspect the metal forming method, even, the high performance nearly clean shape parts of, institutional framework complicated at geometrical shape making.The existing production method of tungsten nickel iron alloy mainly is powder metallurgy process, and this method has certain advantage to manufacturing simple shape, larger-size product, and the part complex-shaped, that structural change is large is had certain limitation.And through operations such as compacting, sintering, machining, annealing, raw-material waste has not only been wasted raw material but also increased many costs up to more than 40%.Adopt metal injection moulding can produce the high-performance, high-density tungsten nickel iron alloy complex-shaped, that size is little and draw ratio is large, greatly save material and reduce manufacturing procedure, and performance and microscopic structure all are better than adopting the tungsten nickel iron alloy of prior powder metallurgy production technology.Generally speaking, the MIM technology has unique advantage aspect geometrical shape making complexity, even, the high performance nearly clean shape parts of institutional framework.
Summary of the invention
The object of the present invention is to provide a kind ofly prepare that complex-shaped degree is high, excellent combination property, the method for preparing the tungsten nickel iron alloy parts that can be mass, solved that the shape of product that faces in the present tungsten nickel iron alloy production process is single, product design is restricted, be not suitable for batch production, production cost is crossed the problems such as high.
The present invention adopts following technical scheme:
A kind of method for preparing the tungsten nickel iron alloy parts is characterized in that: comprise the steps:
1) get the raw materials ready: used metal dust is reduction tungsten powder, hydroxyl nickel powder and carbonyl iron particles.The physical property of each powder is: the W content of tungsten powder＞99.95 %, granularity 3 ~ 5 μ m; The Ni content of nickel powder＞99.8%, granularity 3 ~ 5 μ m; The Fe content of iron powder＞99.5%, granularity 3 ~ 5 μ m;
2) join powder: W powder, Fe powder, Ni powder are proportionally taken by weighing, and its weight ratio is W:95, Ni:3.5, Fe:1.5; Mix 24h～48h in blender, rotating speed is 30 ~ 50r/min;
3) preparation of adhesive: used adhesive is paraffinic base multicomponent adhesive: 74PW-20EVA-5HDPE-1SA; Proportionally take by weighing the weight of each constituent element of adhesive during the preparation adhesive, with blender energising heating, at first add high molecular polymer HDPE, EVA, after high molecular polymer melts, add low molecule adhesive PW, then add couplant SA; After mixing 0.5 ~ 2h, stopped heating is poured out liquid adhesive, and is with the bag sealing, stand-by after the cooling;
4) mixed, the feeding of tungsten ferronickel: with W-Ni-Fe mixed-powder and prepared adhesive according to the quality percentage composition: W-Ni-Fe mixed-powder 51%, the ratio of adhesive 49% takes by weighing; First binding agent is joined in the torque rheometer device, after melting, add again the metal mixed powder; Mixture temperature is 100 ~ 170 ℃, and mixing time is 2h;
5) granulate: adopt extrusion device that feeding is extruded into band shape, strip, extruding rotating speed is 50r/min, and extrusion temperature is 110 ~ 160 ℃;
6) injection moulding: the feeding after will granulating adopts injection machine to inject the tungsten ferronickel injection base of various shapes, and injection temperature is 150 ~ 180 ℃, and injection pressure is 70 ~ 120Mpa;
7) solvent degreasing: before hot degreasing, will inject base and be immersed in the chloromethanes solvent to remove part solubility adhesive, and open the part space; The solvent degreasing temperature is 20 ~ 75 ℃, and the time is 0 ~ 40h; Behind the degreasing certain hour, take out alloy preform, drying;
8) hot degreasing;
9) sintering;
10) sintering after-baking.
As preferably, in the described step 8, hot skimming processes is as follows: the sample after solvent degreasing is placed in the vessel, adopts Al
2O
3Powder is worked as inserts, at H
2Middle degreasing; Hot skimming temp is: 80 ~ 700 ℃.
As preferably, in the described step 9, sintering process is as follows:
Sample after hot degreasing sintering in molybdenum wire furnace adopts two-step sintering technique with the distortion in the control sintering process, and then with the stove cooling, sintering process is at H
2Carry out under the atmosphere; Be divided into presintering, solid-phase sintering, liquid-phase sintering three phases, specific embodiment is as follows:
A) presintering: room temperature is warming up to 900 ℃, and times spent 4 h is at 900 ℃ of insulation 1 ~ 2h;
B) solid-phase sintering: be heated to 1400 ℃ from 900 ℃, time spent 6h is at 1400 ℃ of insulation 1 ~ 2h;
C) liquid-phase sintering: be heated to 1520 ℃ ~ 1530 ℃, time spent 1h, insulation 1 ~ 1.5h from 1400 ℃;
D) blowing out was come out of the stove after cooling a period of time, and be 9h cool time.
As preferably, in the described sintering step 10, heat treatment process is as follows: sintering gained tungsten nickel iron alloy base is carried out vacuum heat in 1200 ~ 1300 ℃ of lower vacuum sintering furnaces, finally can obtain tungsten nickel iron alloy parts finished product.
Beneficial effect of the present invention is:
Metal Injection Molding have once-forming complicated shape goods, product size precision high, need not machining, be easy to realize the characteristics such as the production automation and excellent product performance, be described as in the world " one of current the most popular parts forming technique ".The present invention combines the preparation of tungsten nickel iron alloy parts with metal injection moulding technique, thereby obtain the tungsten nickel iron alloy parts of high complexity, high accuracy, excellent combination property, and this process materials utilization rate is high, be fit to batch automatic production, can solve restriction and deficiency that the present preparation method of tungsten nickel iron alloy parts faces, for very large impetus has been played in the extensive use of tungsten nickel iron alloy.
Prepare tungsten nickel iron alloy by Metal Injection Molding and can effectively control alloying component and heterogeneous microstructure, thereby improve the tungsten nickel iron alloy performance.The uniformity of the performance of alloy and pore size, space distribution and microscopic structure is closely related.The microscopic structure of injection moulding alloy distributes more even, cohere phase γ (W-Ni-Fe) and extremely be evenly distributed between W interface and the particle, and hole little, be evenly distributed.Following table is the comparison of metal injection moulding (MIM) and two kinds of alloy properties of powder metallurgical technique (P/M).
The specific embodiment:
The invention will be further described below in conjunction with embodiment:
Embodiment 1:
Processing step of the present invention is as follows:
1) get the raw materials ready: used metal dust is reduction tungsten powder, hydroxyl nickel powder and carbonyl iron particles.The physical property of each powder is: the W content of tungsten powder＞99.95 %, granularity 3 ~ 5 μ m; The Ni content of nickel powder＞99.8%, granularity 3 ~ 5 μ m; The Fe content of iron powder＞99.5%, granularity 3 ~ 5 μ m.
2) join powder: W powder, Fe powder, Ni powder are proportionally taken by weighing, mix 24h in the V-arrangement blender, rotating speed is 50r/min;
A) at first in the working environment of cleaning on request weight ratio take by weighing the garbled tungsten powder of corresponding weight, iron powder, nickel powder, tungsten ferronickel weight ratio is W:95, Ni:3.5, Fe:1.5;
B) tungsten powder, nickel powder, iron powder are tentatively mixed in stainless steel disc, preliminary purpose of mixing is for next step mechanical mixture is more even, manually mixes in stainless container in the working environment of cleaning first: one deck tungsten powder one deck nickel powder one deck iron powder;
C) preliminary mixed alloyed powder is packed into batch mixer carries out mechanical mixture, and incorporation time is 24h.
3) preparation of adhesive: used adhesive is paraffinic base multicomponent adhesive: 74PW-20EVA-5HDPE-1SA; Proportionally take by weighing the weight of each constituent element of adhesive during the preparation adhesive, with blender energising heating.After the blender temperature is elevated to uniform temperature, at first add a certain amount of high molecular polymer HDPE, EVA, after high molecular polymer melts, add low molecule adhesive PW, then add couplant SA.After mixing 2h, stopped heating is poured out liquid adhesive, and is with the bag sealing, stand-by after the cooling.
4) mixed, the feeding of tungsten ferronickel: W-Ni-Fe mixed-powder and prepared adhesive are taken by weighing according to certain ratio, and its quality percentage composition is: W-Ni-Fe mixed-powder 51%, adhesive 49%.First binding agent is joined in the torque rheometer device, after melting, add again the metal mixed powder.Mixture temperature is 170 ℃, and mixing time is 2h.
5) granulate: adopt extrusion device that feeding is extruded into band shape, strip, extruding rotating speed is 50r/min, and extrusion temperature is 150 ℃.This step is so that adhesive and tungsten ferronickel powder distribution are more even.
6) injection moulding: the feeding after will granulating adopts injection machine to inject the tungsten ferronickel injection base of various shapes, and injection temperature is 170 ℃, and injection pressure is 100Mpa.
7) solvent degreasing: before hot degreasing, will inject base and be immersed in the chloromethanes solvent to remove part solubility adhesive, and open the part space.The solvent degreasing temperature is 65 ℃, and the time is 24h.Behind the degreasing certain hour, take out alloy preform, drying.
8) hot degreasing: the sample after solvent degreasing is placed in the vessel, adopts Al
2O
3Powder is worked as inserts, then according to certain degreasing process at H
2Middle degreasing.Hot skimming temp is: 500 ℃.
9) sintering: the sintering in molybdenum wire furnace of the sample after hot degreasing, adopt two-step sintering technique with the distortion in the control sintering process, then with the stove cooling, sintering process is at H
2Carry out under the atmosphere.Be divided into presintering, solid-phase sintering, liquid-phase sintering three phases, specific embodiment is as follows:
A) presintering: room temperature is warming up to 900 ℃, and times spent 4 h is at 900 ℃ of insulation 1 ~ 2h;
B) solid-phase sintering: be heated to 1400 ℃ from 900 ℃, time spent 6h is at 1400 ℃ of insulation 1 ~ 2h;
C) liquid-phase sintering: be heated to 1520 ℃ ~ 1530 ℃, time spent 1h, insulation 1 ~ 1.5h from 1400 ℃;
D) blowing out was come out of the stove after cooling a period of time, and be 9h cool time.
The concrete operation step of two-step sintering method is:
1) will wait the compressing tungsten nickel iron alloy base of static pressure to call in the intermediate frequency furnace, and arrange, mutual extruding can not be arranged, each the material between more than the spacing 10mm;
2) build bell, and the ON cycle cooling water, pass into hydrogen as protective atmosphere, then start the intermediate frequency furnace power supply and begin heating;
3) in operating process, rationally set heating current, strictly by the programming rate of technique initialization, and temperature retention time operate, carried out operation note in per 15 minutes;
4) close heating power supply after whole heating process is finished, but continue to pass into hydrogen and recirculated cooling water until room temperature.
In whole sintering process, after producing warm area in the stove, operating personnel carried out one time temperature detection at per 15 minutes, used leucoscope, instrument and meter for automation three factories in Shanghai produce: WGG2-201 measures, and is controlled at rational interval with control sintering stock heating curve.
10) sintering after-baking: sintering gained tungsten nickel iron alloy base is carried out vacuum heat in 1300 ℃ of lower vacuum sintering furnaces, finally can obtain tungsten nickel iron alloy parts finished product.
11) tungsten nickel iron alloy parts check.Its assay is:
A) alloy surface has metallic luster, does not have the defectives such as crackle, pore;
B) adopt draining check weighing method, detect tungsten nickel iron alloy plate Bear-grudge global density situation, density meets the GB/T26038-2010 standard-required after testing;
C) use the alloy analysis instrument to analyze the chemical composition of sintered alloy base different parts, analyze each position composition of demonstration identical;
C) check the texture of slab by the microscopic examination microsection, the assay texture evenly, do not have excessive or too small crystal grain, the tungsten metal metallographic test stone GB/T4197-84 of normative reference country, intergranule does not have the cavity.
Concrete step is as follows:
1. sampling: from tungsten nickel iron alloy front end reserved part, get the cube specimen that the length of side is approximately 10mm;
2. roughly grind: because the test specimen surface is uneven, tentatively polish with the surface of emery wheel with test specimen;
3. fine grinding: on the different sand paper of granularity, undertaken by order from coarse to fine;
4. polish: the test specimen after the fine grinding is placed on the polishing machine polishes;
5. corrode: the burnishing surface of test specimen is immersed in the aggressive agent, owing to the flour milling atom is dissolved in the aggressive agent, in dissolving, crystal grain and intergranule, the dissolution velocity between the grain and grain boundary is different, and microscopic structure just displays;
6. the microsection test specimen for preparing is placed on microscopically observe its texture evenly, do not have excessive or too small crystal grain, intergranule not to have the cavity;
D) by the ultrasonic nondestructive test Equipment Inspection, do not find that there is obvious crackle (crack length is less than 0.4mm) inside.
Metal injection moulding (MIM) is as follows with the comparison chart of two kinds of alloy properties of powder metallurgical technique (P/M):
Embodiment 2:
Processing step of the present invention is as follows:
1) get the raw materials ready: used metal dust is reduction tungsten powder, hydroxyl nickel powder and carbonyl iron particles.The physical property of each powder is: the W content of tungsten powder＞99.95 %, granularity 3 ~ 5 μ m; The Ni content of nickel powder＞99.8%, granularity 3 ~ 5 μ m; The Fe content of iron powder＞99.5%, granularity 3 ~ 5 μ m.
2) join powder: W powder, Fe powder, Ni powder are proportionally taken by weighing, mix 24h in the V-arrangement blender, rotating speed is 30r/min;
A) at first in the working environment of cleaning on request weight ratio take by weighing the garbled tungsten powder of corresponding weight, iron powder, nickel powder, tungsten ferronickel weight ratio is W:95, Ni:3.5, Fe:1.5;
B) tungsten powder, nickel powder, iron powder are tentatively mixed in stainless steel disc, preliminary purpose of mixing is for next step mechanical mixture is more even, manually mixes in stainless container in the working environment of cleaning first: one deck tungsten powder one deck nickel powder one deck iron powder;
C) preliminary mixed alloyed powder is packed into batch mixer carries out mechanical mixture, and incorporation time is 24h.
3) preparation of adhesive: used adhesive is paraffinic base multicomponent adhesive: 74PW-20EVA-5HDPE-1SA; Proportionally take by weighing the weight of each constituent element of adhesive during the preparation adhesive, with blender energising heating.After the blender temperature is elevated to uniform temperature, at first add a certain amount of high molecular polymer HDPE, EVA, after high molecular polymer melts, add low molecule adhesive PW, then add couplant SA.After mixing 1h, stopped heating is poured out liquid adhesive, and is with the bag sealing, stand-by after the cooling.
4) mixed, the feeding of tungsten ferronickel: W-Ni-Fe mixed-powder and prepared adhesive are taken by weighing according to certain ratio, and its quality percentage composition is: W-Ni-Fe mixed-powder 51%, adhesive 49%.First binding agent is joined in the torque rheometer device, after melting, add again the metal mixed powder.Mixture temperature is 110 ℃, and mixing time is 2h.
5) granulate: adopt extrusion device that feeding is extruded into band shape, strip, extruding rotating speed is 50r/min, and extrusion temperature is 120 ℃.This step is so that adhesive and tungsten ferronickel powder distribution are more even.
6) injection moulding: the feeding after will granulating adopts injection machine to inject the tungsten ferronickel injection base of various shapes, and injection temperature is 150 ℃, and injection pressure is 120Mpa.
7) solvent degreasing: before hot degreasing, will inject base and be immersed in the chloromethanes solvent to remove part solubility adhesive, and open the part space.The solvent degreasing temperature is 20 ℃, and the time is 35h.Behind the degreasing certain hour, take out alloy preform, drying.
8) hot degreasing: the sample after solvent degreasing is placed in the vessel, adopts Al
2O
3Powder is worked as inserts, then according to certain degreasing process at H
2Middle degreasing.Hot skimming temp is: 80 ℃.
9) sintering: the sintering in molybdenum wire furnace of the sample after hot degreasing, adopt two-step sintering technique with the distortion in the control sintering process, then with the stove cooling, sintering process is at H
2Carry out under the atmosphere.Be divided into presintering, solid-phase sintering, liquid-phase sintering three phases, specific embodiment is as follows:
A) presintering: room temperature is warming up to 900 ℃, and times spent 4 h is at 900 ℃ of insulation 1 ~ 2h;
B) solid-phase sintering: be heated to 1400 ℃ from 900 ℃, time spent 6h is at 1400 ℃ of insulation 1 ~ 2h;
C) liquid-phase sintering: be heated to 1520 ℃ ~ 1530 ℃, time spent 1h, insulation 1 ~ 1.5h from 1400 ℃;
D) blowing out was come out of the stove after cooling a period of time, and be 9h cool time.
The concrete operation step of two-step sintering method is:
1) will wait the compressing tungsten nickel iron alloy base of static pressure to call in the intermediate frequency furnace, and arrange, mutual extruding can not be arranged, each the material between more than the spacing 10mm;
2) build bell, and the ON cycle cooling water, pass into hydrogen as protective atmosphere, then start the intermediate frequency furnace power supply and begin heating;
3) in operating process, rationally set heating current, strictly by the programming rate of technique initialization, and temperature retention time operate, carried out operation note in per 15 minutes;
4) close heating power supply after whole heating process is finished, but continue to pass into hydrogen and recirculated cooling water until room temperature.
In whole sintering process, after producing warm area in the stove, operating personnel carried out one time temperature detection at per 15 minutes, used leucoscope, instrument and meter for automation three factories in Shanghai produce: WGG2-201 measures, and is controlled at rational interval with control sintering stock heating curve.
10) sintering after-baking: sintering gained tungsten nickel iron alloy base is carried out vacuum heat in 1200 ℃ of lower vacuum sintering furnaces, finally can obtain tungsten nickel iron alloy parts finished product.
11) tungsten nickel iron alloy parts check.Its assay is:
A) alloy surface has metallic luster, does not have the defectives such as crackle, pore;
B) adopt draining check weighing method, detect tungsten nickel iron alloy plate Bear-grudge global density situation, density meets the GB/T26038-2010 standard-required after testing;
C) use the alloy analysis instrument to analyze the chemical composition of sintered alloy base different parts, analyze each position composition of demonstration identical;
C) check the texture of slab by the microscopic examination microsection, the assay texture evenly, do not have excessive or too small crystal grain, the tungsten metal metallographic test stone GB/T4197-84 of normative reference country, intergranule does not have the cavity.
Explanation is at last, above embodiment is only unrestricted in order to technical scheme of the present invention to be described, other modifications that those of ordinary skills make technical scheme of the present invention or be equal to replacement, only otherwise break away from the spirit and scope of technical solution of the present invention, all should be encompassed in the middle of the claim scope of the present invention.
Claims (4)
1. a method for preparing the tungsten nickel iron alloy parts is characterized in that: comprise the steps:
1) get the raw materials ready: used metal dust is reduction tungsten powder, hydroxyl nickel powder and carbonyl iron particles, and the physical property of each powder is: the W content of tungsten powder＞99.95 %, granularity 3 ~ 5 μ m; The Ni content of nickel powder＞99.8%, granularity 3 ~ 5 μ m; The Fe content of iron powder＞99.5%, granularity 3 ~ 5 μ m;
2) join powder: W powder, Fe powder, Ni powder are proportionally taken by weighing, and its weight ratio is W:95, Ni:3.5, Fe:1.5; Mix 24h～48h in blender, rotating speed is 30 ~ 50r/min;
3) preparation of adhesive: used adhesive is paraffinic base multicomponent adhesive: 74PW-20EVA-5HDPE-1SA; Proportionally take by weighing the weight of each constituent element of adhesive during the preparation adhesive, with blender energising heating, at first add high molecular polymer HDPE, EVA, after high molecular polymer melts, add low molecule adhesive PW, then add couplant SA; After mixing 0.5 ~ 2h, stopped heating is poured out liquid adhesive, and is with the bag sealing, stand-by after the cooling;
4) mixed, the feeding of tungsten ferronickel: with W-Ni-Fe mixed-powder and prepared adhesive according to the quality percentage composition: W-Ni-Fe mixed-powder 51%, the ratio of adhesive 49% takes by weighing; First binding agent is joined in the torque rheometer device, after melting, add again the metal mixed powder; Mixture temperature is 100 ~ 170 ℃, and mixing time is 2h;
5) granulate: adopt extrusion device that feeding is extruded into band shape, strip, extruding rotating speed is 50r/min, and extrusion temperature is 110 ~ 160 ℃;
6) injection moulding: the feeding after will granulating adopts injection machine to inject the tungsten ferronickel injection base of various shapes, and injection temperature is 150 ~ 180 ℃, and injection pressure is 70 ~ 120Mpa;
7) solvent degreasing: before hot degreasing, will inject base and be immersed in the chloromethanes solvent to remove part solubility adhesive, and open the part space; The solvent degreasing temperature is 20 ~ 75 ℃, and the time is 0 ~ 40h; Behind the degreasing certain hour, take out alloy preform, drying;
8) hot degreasing;
9) sintering;
10) sintering after-baking.
2. a kind of method for preparing the tungsten nickel iron alloy parts according to claim 1, it is characterized in that: in the described step 8, hot skimming processes is as follows: the sample after solvent degreasing is placed in the vessel, adopts Al
2O
3Powder is worked as inserts, at H
2Middle degreasing; Hot skimming temp is: 80 ~ 700 ℃.
3. a kind of method for preparing the tungsten nickel iron alloy parts according to claim 1, it is characterized in that: in the described step 9, sintering process is as follows:
Sample after hot degreasing sintering in molybdenum wire furnace adopts two-step sintering technique with the distortion in the control sintering process, and then with the stove cooling, sintering process is at H
2Carry out under the atmosphere; Be divided into presintering, solid-phase sintering, liquid-phase sintering three phases, specific embodiment is as follows:
A) presintering: room temperature is warming up to 900 ℃, and times spent 4 h is at 900 ℃ of insulation 1 ~ 2h;
B) solid-phase sintering: be heated to 1400 ℃ from 900 ℃, time spent 6h is at 1400 ℃ of insulation 1 ~ 2h;
C) liquid-phase sintering: be heated to 1520 ℃ ~ 1530 ℃, time spent 1h, insulation 1 ~ 1.5h from 1400 ℃;
D) blowing out was come out of the stove after cooling a period of time, and be 9h cool time.
4. a kind of method for preparing the tungsten nickel iron alloy parts according to claim 1, it is characterized in that: in the described sintering step 10, heat treatment process is as follows: sintering gained tungsten nickel iron alloy base is carried out vacuum heat in 1200 ~ 1300 ℃ of lower vacuum sintering furnaces, finally can obtain tungsten nickel iron alloy parts finished product.
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| CN110108172B (en) * | 2019-05-14 | 2022-03-25 | 中国兵器科学研究院宁波分院 | Spherical prefabricated damaged element with double-layer composite structure and preparation method thereof |
| CN110883335A (en) * | 2019-11-05 | 2020-03-17 | 厦门虹鹭钨钼工业有限公司 | Preparation method of integrated tungsten alloy lure |
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| CN111485154A (en) * | 2020-04-16 | 2020-08-04 | 北京北冶功能材料有限公司 | Low-sintering-temperature tungsten-nickel-iron alloy for shielding material |
| CN112404429A (en) * | 2020-11-09 | 2021-02-26 | 山东金珠材料科技有限公司 | Metal powder injection molding MIM (metal injection molding) production process of novel fragile tungsten-based material |
| CN114523110A (en) * | 2020-11-09 | 2022-05-24 | 山东金珠材料科技有限公司 | H-shaped fragile tungsten-based MIM special feed |
| CN112404429B (en) * | 2020-11-09 | 2023-09-01 | 山东金珠材料科技有限公司 | Metal powder injection molding MIM production process of novel fragile tungsten-based material |
| CN112570710A (en) * | 2020-12-31 | 2021-03-30 | 江苏米莫金属股份有限公司 | Tungsten alloy powder casting processing method |
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