CN118064779B - Tungsten lanthanum rod and preparation method thereof - Google Patents
Tungsten lanthanum rod and preparation method thereof Download PDFInfo
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- CN118064779B CN118064779B CN202410498005.5A CN202410498005A CN118064779B CN 118064779 B CN118064779 B CN 118064779B CN 202410498005 A CN202410498005 A CN 202410498005A CN 118064779 B CN118064779 B CN 118064779B
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- FAYUQEZUGGXARF-UHFFFAOYSA-N lanthanum tungsten Chemical compound [La].[W] FAYUQEZUGGXARF-UHFFFAOYSA-N 0.000 title claims abstract description 67
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 134
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims abstract description 90
- 239000000843 powder Substances 0.000 claims abstract description 54
- 238000010438 heat treatment Methods 0.000 claims description 38
- 239000002245 particle Substances 0.000 claims description 38
- 238000005245 sintering Methods 0.000 claims description 27
- 238000002156 mixing Methods 0.000 claims description 22
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims description 13
- 239000001257 hydrogen Substances 0.000 claims description 13
- 239000011812 mixed powder Substances 0.000 claims description 12
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 claims description 12
- 238000003825 pressing Methods 0.000 claims description 12
- 229910001930 tungsten oxide Inorganic materials 0.000 claims description 12
- 239000002994 raw material Substances 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- 230000000694 effects Effects 0.000 description 11
- 229910052746 lanthanum Inorganic materials 0.000 description 8
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 229910052721 tungsten Inorganic materials 0.000 description 8
- 239000010937 tungsten Substances 0.000 description 8
- 229910001080 W alloy Inorganic materials 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 238000009826 distribution Methods 0.000 description 6
- 229910052761 rare earth metal Inorganic materials 0.000 description 6
- 239000013078 crystal Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- 238000007873 sieving Methods 0.000 description 4
- 238000010587 phase diagram Methods 0.000 description 3
- 238000010298 pulverizing process Methods 0.000 description 3
- 230000000630 rising effect Effects 0.000 description 3
- 238000000635 electron micrograph Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 150000002910 rare earth metals Chemical class 0.000 description 2
- 238000005728 strengthening Methods 0.000 description 2
- 238000012935 Averaging Methods 0.000 description 1
- 229910000975 Carbon steel Inorganic materials 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000010962 carbon steel Substances 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 238000010902 jet-milling Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 1
- DYIZHKNUQPHNJY-UHFFFAOYSA-N oxorhenium Chemical compound [Re]=O DYIZHKNUQPHNJY-UHFFFAOYSA-N 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 229910003449 rhenium oxide Inorganic materials 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C27/00—Alloys based on rhenium or a refractory metal not mentioned in groups C22C14/00 or C22C16/00
- C22C27/04—Alloys based on tungsten or molybdenum
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
- B22F1/052—Metallic powder characterised by the size or surface area of the particles characterised by a mixture of particles of different sizes or by the particle size distribution
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/12—Metallic powder containing non-metallic particles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/02—Compacting only
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/10—Sintering only
-
- 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
- C22C1/04—Making non-ferrous alloys by powder metallurgy
- C22C1/05—Mixtures of metal powder with non-metallic powder
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- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Powder Metallurgy (AREA)
Abstract
The invention relates to the technical field of tungsten lanthanum rods, in particular to a tungsten lanthanum rod and a preparation method thereof, wherein proper proportion of lanthanum oxide powder is doped into tungsten powder, and the tungsten powder is prepared by adopting high-particle-size tungsten powder and low-particle-size tungsten powder according to proper proportion, so that the density of the tungsten lanthanum rod is more than or equal to 18.5g/cm 3, and the performances such as the density of the tungsten lanthanum rod are improved.
Description
Technical Field
The invention relates to the technical field of tungsten lanthanum rods, in particular to a tungsten lanthanum rod and a preparation method thereof.
Background
The tungsten lanthanum rod is prepared by doping lanthanum metal element into tungsten alloy or tungsten alloy powder and then molding, has the characteristics of high density and excellent mechanical property, is widely applied to the fields of electronics, chemistry, medical treatment, aerospace and the like, is one of the raw materials for replacing pure tungsten rods to prepare high-strength tungsten wires, and enables a great deal of research on the tungsten lanthanum rod in the prior art.
For example: the patent application number 202310285290.8 discloses a lanthanum-containing tungsten rod blank, a preparation method and application thereof, wherein the tungsten alloy comprises 0.05% -0.5% of lanthanum oxide, the average grain size of the lanthanum-containing tungsten rod blank is more than 5000/mm 2, lanthanum is used as a strengthening element and added into the tungsten alloy, so that the growth of grains is effectively prevented, the control of the average grain size of the lanthanum-containing tungsten rod blank is realized, and the strength of tungsten alloy wires is high; meanwhile, the lanthanum element effectively relieves stress concentration of microcracks of the grain boundaries of the tungsten alloy, plays a role in strengthening particles, and improves the strength of the tungsten alloy.
However, with the rising application of high-strength tungsten wires to replace carbon steel diamond wires for photovoltaic cutting buses, in lanthanum-containing tungsten rod blanks for preparing high-strength tungsten wires, the distribution of lanthanum is unreasonable, the density of the rods is low, the distribution of crystal grains is not ideal, and the subsequent application effect of the tungsten lanthanum rods is not ideal.
Disclosure of Invention
In order to solve the technical problems in the prior art, the invention provides a tungsten lanthanum rod and a preparation method thereof, wherein the tungsten lanthanum rod has uniform crystal grains, the density is not less than 18.5g/cm 3, and the average grain size is 1000-3000 grains/mm 2.
The method is realized by the following technical scheme:
The invention provides a tungsten lanthanum rod, which comprises, by mass, 0.5-1.5 parts of lanthanum oxide powder and 96-103 parts of tungsten powder, wherein the tungsten powder is formed by mixing high-particle-size tungsten powder and low-particle-size tungsten powder, the particle size of Gao Lijing tungsten powder is 2-3 mu m, and the particle size of the low-particle-size tungsten powder is 0.5-0.8 mu m; the mass ratio of Gao Lijing tungsten powder to low-particle-size tungsten powder is 95-98:1-5.
The tungsten powder is mixed with proper proportion of lanthanum oxide powder, and is prepared by adopting high-grain-size tungsten powder and low-grain-size tungsten powder according to proper proportion, so that the density of the tungsten lanthanum rod is more than or equal to 18.5g/cm 3, the grain distribution is reasonable, and the density performance of the tungsten lanthanum rod is improved.
In order to improve the density of the tungsten lanthanum rod, preferably, the mass ratio of Gao Lijing tungsten powder to low-particle-size tungsten powder is 95:1. More preferably, the mass ratio of Gao Lijing tungsten powder to low-particle-size tungsten powder is 97:3. More preferably, the mass ratio of Gao Lijing tungsten powder to low-particle-size tungsten powder is 98:5.
In order to enable the lanthanum oxide powder to be added into the tungsten powder to improve the grain distribution effect and then improve the density of the tungsten lanthanum rod, the raw material components preferably comprise 1 part by mass of lanthanum oxide powder and 99 parts by mass of tungsten powder. More preferably, the raw material component comprises, by mass, 0.5 part of lanthanum oxide powder and 103 parts of tungsten powder.
In order to improve the uniformity and the dispersibility of the mixing of the lanthanum oxide powder and the tungsten powder and improve the mixing effect, the average particle size of the lanthanum oxide powder is preferably less than or equal to 1 mu m.
More preferably, the low-grain tungsten powder is prepared by placing tungsten oxide powder with specific surface area more than or equal to 10m 2/g into a three-belt heating full-automatic fifteen-tube reduction furnace, sequentially heating, controlling the temperature between 600 and 850 ℃, introducing hydrogen according to the flow rate more than or equal to 60m 3/h for reduction and crushing; the Gao Lijing tungsten powder is prepared by placing tungsten oxide powder with specific surface area less than or equal to 1m 2/g into a three-belt heating full-automatic fifteen-tube reduction furnace, sequentially heating, controlling the temperature between 800 and 950 ℃, introducing hydrogen according to the flow rate less than or equal to 25m 3/h for reduction and crushing.
The second object of the invention is to provide a method for preparing a tungsten lanthanum rod, comprising the following steps:
(1) Mixing: adding low-particle-size tungsten powder, high-particle-size tungsten powder and lanthanum oxide powder into a mixer, and mixing for 1-3 hours at the speed of 2000-2500r/min to obtain mixed powder;
(2) Pressing: pressing the mixed powder at 150-220MPa for 10-15min by adopting a cold isostatic press to obtain a green body;
(3) Sintering: and sintering the green body by adopting three sections of heating, wherein the first section is to uniformly heat from normal temperature to 1800 ℃ in 10-12h, the second section is to uniformly heat from 1800 ℃ to 2100 ℃ in 4-5h, and the third section is to uniformly heat from 2100 ℃ to 2500 ℃ in 2-3 h.
The mixing-pressing-sintering process is beneficial to improving the density of the tungsten lanthanum rod to more than 18.9g/cm 3 and improving the overall performance of the tungsten lanthanum rod.
In order to influence the distribution of crystal grains through the change of the temperature changing speed, the distribution of crystal grains in the tungsten lanthanum rod is promoted to be changed, the comprehensive performance of the tungsten lanthanum rod is promoted to be improved, and preferably, the three-stage temperature-rising sintering is continuous temperature rising.
The invention uses three-section continuous heating sintering treatment to realize low-temperature long-time sintering from normal temperature to 1800 ℃, promotes the internal moisture and low-melting point impurities to fully volatilize, then enters into a slower heating rate from 1800 ℃ to 2100 ℃ to promote the lanthanum oxide powder to be combined with low-grain-size tungsten powder, and then promotes the high-grain-size tungsten powder to remelt and crystallize to engulf the low-grain-size tungsten powder in a faster heating rate from 2100 ℃ to 2500 ℃, thereby leading the density of the tungsten lanthanum rod to reach more than 18.9g/cm 3.
Compared with the prior art, the invention has the technical effects that:
The invention combines proper preparation of lanthanum oxide powder and tungsten powder, and proper preparation of tungsten powder with low particle diameter and high particle diameter, so that the lanthanum oxide powder and tungsten powder are uniformly mixed, the mixing effect of the materials is enhanced, the density of the tungsten lanthanum rod is improved to more than 18.5g/cm 3, the number of crystal grains is between 1000 and 3000/mm 2, the density performance of the tungsten lanthanum rod is improved, and the comprehensive performance of the tungsten lanthanum rod is greatly improved. The invention has simple process flow and low manufacturing cost.
Drawings
FIG. 1 is a phase diagram of a lanthanum tungsten rod according to the invention of inventive example 1.
Fig. 2 is a phase diagram of a lanthanum tungsten rod according to inventive example 2.
Fig. 3 is a phase diagram of a lanthanum tungsten rod according to inventive example 3.
FIG. 4 is a photograph of a commercially available low particle size (0.5-0.8 μm) tungsten powder electron microscope.
FIG. 5 is an electron micrograph of a tungsten powder of low particle size (0.5-0.8 μm) according to the present invention.
FIG. 6 is a commercially available high particle size (2-3 μm) tungsten powder electron micrograph.
FIG. 7 is a photograph of a high particle size (2-3 μm) tungsten powder electron microscope created by the present invention.
Detailed Description
The technical scheme of the present invention is further defined below in conjunction with the specific embodiments, but the scope of the claimed invention is not limited to the description.
In certain embodiments, the lanthanum tungsten rod comprises, in parts by mass, 0.5-1.5 parts of lanthanum oxide powder, 96-103 parts of tungsten powder, for example: 0.5 part of lanthanum oxide powder and 96 parts of tungsten powder; for example: 1.5 parts of lanthanum oxide powder and 103 parts of tungsten powder; for example: 0.5 part of lanthanum oxide powder and 103 parts of tungsten powder; for example: 1.5 parts of lanthanum oxide powder and 96 parts of tungsten powder; for example: 1 part of lanthanum oxide powder and 97 parts of tungsten powder; for example: 1 part of lanthanum oxide powder and 99 parts of tungsten powder; for example: 1 part of lanthanum oxide powder, 103 parts of tungsten powder and the like, wherein the tungsten powder is formed by mixing high-particle-size tungsten powder and low-particle-size tungsten powder, the particle size of Gao Lijing tungsten powder is between 2 and 3 mu m, and the particle size of the low-particle-size tungsten powder is between 0.5 and 0.8 mu m; the mass ratio of Gao Lijing tungsten powder to low-particle-size tungsten powder is 95-98:1-5, such as ：95:1、95:2、95:3、95:4、19:1、96:1、48:1、32:1、24:1、96:5、97:1、97:2、97:3、97:4、97:5、98:1、49:1、98:3、49:2、98:5. The uniformity and object mixing effect of lanthanum oxide powder doped and mixed on the surface of tungsten powder are improved by mixing tungsten powder with the particle size of 2-3 mu m and tungsten powder with the particle size of 0.5-0.8 mu m, lanthanum oxide powder is promoted to be doped into tungsten powder, uniform distribution among tungsten powder is realized, and the density of tungsten lanthanum rods is improved.
In certain embodiments, the lanthanum oxide powder has a particle size of 1 μm or less, for example: 0.3 μm,0.4 μm,0.5 μm,0.6 μm,0.7 μm,0.8 μm,0.9 μm,1 μm, etc. The mixing effect with tungsten powder is enhanced, and the comprehensive performance of the tungsten lanthanum rod is improved. Of course, in certain embodiments, lanthanum oxide powder of a larger particle size, when properly used, has little effect on the overall performance of the lanthanum tungsten rod. Lanthanum oxide powder is prepared by jet milling lanthanum oxide.
In some embodiments, the low-particle-size tungsten powder is prepared by placing tungsten oxide powder with the specific surface area of more than or equal to 10m 2/g into a three-belt heating full-automatic fifteen-pipe reduction furnace, sequentially heating, controlling the temperature to be 600-850 ℃ (for example, one belt 600 ℃, two belts 720 ℃, three belts 850 ℃ and the like), introducing hydrogen according to the flow rate of more than or equal to 60m 3/h for reduction and crushing; the Gao Lijing tungsten powder is prepared by placing tungsten oxide powder with specific surface area less than or equal to 1m 2/g into a three-belt heating full-automatic fifteen-pipe reduction furnace, sequentially heating, controlling the temperature between 800 ℃ and 950 ℃ (for example, 800 ℃ in one belt, 870 ℃ in two belts, 950 ℃ in three belts and the like), introducing hydrogen for reduction according to the flow rate less than or equal to 25m 3/h, and crushing. In order to avoid oxidation, the reduction crushing is prepared by using jet crushing and sieving under the protection of nitrogen.
In order to make the comprehensive performance of the tungsten lanthanum rod more excellent and make the density of the prepared tungsten lanthanum rod reach more than 18.9g/cm 3, researchers created by the invention also research the tungsten lanthanum rod preparation process.
In certain embodiments, a method of preparing a lanthanum tungsten rod comprises the steps of:
(1) Mixing: adding low-particle-size tungsten powder, high-particle-size tungsten powder and lanthanum oxide powder into a mixer, and mixing for 1-3 hours at the speed of 2000-2500r/min to obtain mixed powder;
(2) Pressing: pressing the mixed powder at 150-220MPa for 10-15min by adopting a cold isostatic press to obtain a green body;
(3) Sintering: and sintering the green body by adopting three sections of heating, wherein the first section is to uniformly heat from normal temperature to 1800 ℃ in 10-12h, the second section is to uniformly heat from 1800 ℃ to 2100 ℃ in 4-5h, and the third section is to uniformly heat from 2100 ℃ to 2500 ℃ in 2-3 h.
In certain embodiments, the three-stage temperature-rising sintering is a continuous temperature rising.
In order to verify the technical effects brought by the technical scheme of the invention, the research team also carries out the following specific experimental study.
Example 1
The raw material components are lanthanum oxide powder (purchased on the market, with the particle size of 0.5-1 mu m) 0.5kg and tungsten powder 96kg, wherein the tungsten powder is formed by mixing high-particle-size tungsten powder (shown in figure 6) and low-particle-size tungsten powder (shown in figure 4), the particle size of Gao Lijing tungsten powder is 2-3 mu m, and the particle size of the low-particle-size tungsten powder is 0.5-0.8 mu m; the mass ratio of Gao Lijing tungsten powder to low-particle-size tungsten powder is 95:1.
The preparation method comprises the following steps:
(1) Adding low-particle-size tungsten powder, high-particle-size tungsten powder and lanthanum oxide powder into a mixer, and mixing for 1h at 2000r/min to obtain mixed powder, wherein the tap density is 7.5g/m 3;
(2) Pressing: pressing the mixed powder at 150MPa for 10min by adopting a cold isostatic press to obtain a green body (phi 20-28 mm) with the density of 12g/cm 3;
(3) Sintering: and sintering the green body by adopting three sections of continuous heating, wherein the first section is uniformly heated to 1800 ℃ from normal temperature in 10h, the second section is uniformly heated to 2100 ℃ from 1800 ℃ in 4h, and the third section is uniformly heated to 2500 ℃ from 2100 ℃ in 2h, so that the tungsten lanthanum rod shown in figure 1 is obtained.
Example 2
The raw material components are 1.5kg of lanthanum oxide powder (purchased in the market and with the particle size of 0.5-1 mu m) and 103kg of tungsten powder, wherein the tungsten powder is formed by mixing high-particle-size tungsten powder (shown in figure 6) and low-particle-size tungsten powder (shown in figure 4), the particle size of Gao Lijing tungsten powder is 2-3 mu m, and the particle size of the low-particle-size tungsten powder is 0.5-0.8 mu m; the mass ratio of Gao Lijing tungsten powder to low-particle-size tungsten powder is 98:5.
The preparation method comprises the following steps:
(1) Adding low-particle-size tungsten powder, high-particle-size tungsten powder and lanthanum oxide powder into a mixer, and mixing for 3 hours at 2500r/min to obtain mixed powder, wherein the tap density is 9.0g/m 3;
(2) Pressing: pressing the mixed powder at 220MPa for 15min by adopting a cold isostatic press to obtain a green body (phi 20-28 mm) with the density of 13g/cm 3;
(3) Sintering: and sintering the green body by adopting three sections of continuous heating, wherein the first section is to uniformly heat from normal temperature to 1800 ℃ in 12h, the second section is to uniformly heat from 1800 ℃ to 2100 ℃ in 5h, and the third section is to uniformly heat from 2100 ℃ to 2500 ℃ in 3h, so as to obtain the tungsten lanthanum rod shown in figure 2.
Example 3
1Kg of lanthanum oxide powder (purchased on the market, with the particle size of 0.5-1 mu m) and 99kg of tungsten powder, wherein the tungsten powder is formed by mixing high-particle-size tungsten powder (shown in figure 6) and low-particle-size tungsten powder (shown in figure 4), the particle size of Gao Lijing tungsten powder is 2-3 mu m, and the particle size of the low-particle-size tungsten powder is 0.5-0.8 mu m; the mass ratio of Gao Lijing tungsten powder to low-particle-size tungsten powder is 98:1.
The preparation method comprises the following steps:
(1) Adding low-particle-size tungsten powder, high-particle-size tungsten powder and lanthanum oxide powder into a mixer, and mixing for 2 hours at 2200r/min to obtain mixed powder, wherein the tap density is 8.2g/m 3;
(2) Pressing: pressing the mixed powder at 180MPa for 14min by adopting a cold isostatic press to obtain a green body (phi 20-28 mm) with the density of 13g/cm 3;
(3) Sintering: and sintering the green body by adopting three sections of continuous heating, wherein the first section is to uniformly heat from normal temperature to 1800 ℃ in 11h, the second section is to uniformly heat from 1800 ℃ to 2100 ℃ in 4.5h, and the third section is to uniformly heat from 2100 ℃ to 2500 ℃ in 2.5h, so as to obtain the tungsten lanthanum rod shown in figure 3.
Example 4
Based on the embodiment 1, the other materials are the same as the embodiment 1, as shown in fig. 5 and 7, the low-particle tungsten powder is prepared by placing tungsten oxide powder with the specific surface area of 10m 2/g into a three-belt heating full-automatic fifteen-tube reduction furnace, sequentially heating and controlling the temperature to be 600-850 ℃, introducing hydrogen to reduce according to the flow of 60m 3/h, and adopting an air flow pulverizer to perform air flow pulverization in an air flow pulverizer to pass through a 200-mesh sieve under the protection of nitrogen; the Gao Lijing tungsten powder is prepared by placing tungsten oxide powder with the specific surface area of 1m 2/g into a three-belt heating full-automatic fifteen-tube reduction furnace, sequentially heating, controlling the temperature to be 800-950 ℃, introducing hydrogen to reduce according to the flow of 25m 3/h, and crushing by adopting an air flow crusher under the protection of nitrogen and sieving by adopting a 160-mesh sieve.
Example 5
Based on the embodiment 1, the other materials are the same as the embodiment 1, as shown in fig. 5 and 7, the low-particle tungsten powder is prepared by placing tungsten oxide powder with the specific surface area of 13m 2/g into a three-belt heating full-automatic fifteen-tube reduction furnace, sequentially heating and controlling the temperature to be 600-850 ℃, introducing hydrogen to reduce according to the flow of 68m 3/h, and adopting an air flow pulverizer to perform air flow pulverization in an air flow pulverizer to pass through a 200-mesh sieve under the protection of nitrogen; the Gao Lijing tungsten powder is prepared by placing tungsten oxide powder with the specific surface area of 0.8m 2/g into a three-belt heating full-automatic fifteen-tube reduction furnace, sequentially heating, controlling the temperature to be 800-950 ℃, introducing hydrogen to reduce according to the flow of 20m 3/h, and adopting an air flow pulverizer to pulverize and sieving with a 160-mesh sieve under the protection of nitrogen.
Example 6
Based on the embodiment 1, the other materials are the same as the embodiment 1, as shown in fig. 5 and 7, the low-grain tungsten powder is prepared by placing tungsten oxide powder with the specific surface area of 15m 2/g into a three-belt heating full-automatic fifteen-pipe reduction furnace, sequentially heating, controlling the temperature to be 600-850 ℃, introducing hydrogen to reduce according to the flow of 70m 3/h, and adopting an air flow pulverizer to perform air flow pulverization in an air flow pulverizer to pass through a 200-mesh sieve under the protection of nitrogen; the Gao Lijing tungsten powder is prepared by placing tungsten oxide powder with the specific surface area of 0.5m 2/g into a three-belt heating full-automatic fifteen-tube reduction furnace, sequentially heating, controlling the temperature to be 800-950 ℃, introducing hydrogen to reduce according to the flow of 18m 3/h, and adopting an air flow pulverizer to pulverize and pass through a 160-mesh sieve under the protection of nitrogen.
Example 7
On the basis of example 1, the sintering was performed as described in example 1: and (3) heating, insulating and sintering the green body by three sections, wherein the first section is to uniformly heat from normal temperature to 1800 ℃ for 0.5h, the second section is to uniformly heat from 1800 ℃ to 2100 ℃ for 4.5h, the third section is to uniformly heat from 2100 ℃ to 2500 ℃ for 2.5h, and the heat is preserved for 0.5h, so that the tungsten lanthanum rod is obtained.
Example 8
On the basis of example 1, the sintering was performed as described in example 1: and (3) heating, insulating and sintering the green body by three sections, wherein the first section is to uniformly heat up to 1800 ℃ from normal temperature for 11h, the second section is to uniformly heat up to 2100 ℃ from 1800 ℃ for 4.5h, the third section is to uniformly heat up to 2500 ℃ from 2100 ℃ for 2.5h, and the heat is preserved for 1h, so that the tungsten lanthanum rod is obtained.
Example 9
On the basis of the embodiment 1, the sintering is performed in the same way as the embodiment 1, and the green body is sintered by three sections of heating and heat preservation, wherein the first section is to heat from normal temperature to 1100 ℃ for 1.5h; the second stage is to heat from 1100 ℃ to 2000 ℃ for 8 hours, and keep the temperature for 1.5 hours; and the third section is to heat from 2000 ℃ to 2400 ℃ for 3 hours and burn for 10 hours to obtain the tungsten lanthanum rod.
The sample lanthanum tungsten rods prepared in example 1-example 9 were subjected to measurement of density and average grain size (three times of averaging), and the results are shown in table 1 below.
TABLE 1 detection of tungsten lanthanum rod density and grain size
| Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 | Example 7 | Example 8 | Example 9 | |
| Density (g/cm 3) | 18.85 | 18.72 | 18.88 | 18.91 | 18.93 | 18.95 | 18.54 | 18.52 | 18.58 |
| Average grain size (. Times.10 3/mm 2) | 2.12 | 2.63 | 2.25 | 2.83 | 2.91 | 2.89 | 1.65 | 1.63 | 1.64 |
As can be seen from Table 1, the invention can make the density of the tungsten lanthanum rod reach more than 18.5g/cm 3 by controlling the dosage ratio of lanthanum oxide to tungsten powder and combining the control of low-grain size and high-grain size tungsten powder, and the average grain size is 1.6X10- 3/mm 2 to 3X 10- 3/mm 2, thus greatly improving the comprehensive performance of the tungsten lanthanum rod; meanwhile, as can be seen from table 1, the sintering process and the temperature control will affect the density and grain size of the lanthanum tungsten rod, resulting in a decrease in the number of grains per unit area, and a larger number of grains, which results in an effect on the mechanical properties and corrosion resistance of the lanthanum tungsten rod, and the sintering process with continuous temperature rise and temperature rate conversion greatly improves the density and grain size of the lanthanum tungsten rod, and the comprehensive properties of the lanthanum tungsten rod, so that the density of the lanthanum tungsten rod reaches more than 18.9g/cm 3.
The invention is characterized in that the temperature control treatment in the first stage is carried out to fully volatilize moisture and low-melting point impurities in the green body, then the temperature control treatment in the second stage is carried out to promote the lanthanum oxide powder to be combined with the low-particle-size tungsten powder, so that lanthanum oxide particles can be uniformly distributed on the surface of the high-particle-size tungsten powder, then the temperature control treatment in the third stage is carried out to lead the low-particle-size tungsten powder to be rapidly sintered and engulfed by the high-particle-size tungsten powder, and then a high-density tungsten lanthanum rod is formed, and the comprehensive performance of the tungsten lanthanum rod is greatly improved. In certain embodiments, the sintering is performed by sintering the green body under hydrogen protection using an intermediate frequency induction furnace. In some embodiments, the mixing is performed under the protection of nitrogen, so that oxidation of tungsten powder caused by the influence of air is avoided, and the comprehensive performance of the tungsten lanthanum rod is guaranteed.
In addition, the invention creates that in certain embodiments, small amounts of rare earth elements are added, such as: when several rare earth element oxide components are added, rhenium oxide components, cerium oxide components, yttrium oxide components, and the like, in a more excellent embodiment, equal mass ratios are used for addition. And by researching the influence condition of the comprehensive performance of the tungsten lanthanum rod by adding rare earth elements, the research shows that: after rare earth elements are added to form rare earth particles in the tungsten lanthanum rod, the rare earth particles should be controlled to be 20-50/mm 2, so that the comprehensive performance of the tungsten lanthanum rod can be improved.
The present invention creates other minor matters, and the person skilled in the art can refer to the prior art or the common general knowledge known to the person skilled in the art, and the conventional technical means are implemented, for example: for preparing the lanthanum oxide powder, a jet mill is adopted for grinding and sieving to prepare the lanthanum oxide powder.
The foregoing is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art will be able to apply equivalent substitutions or alterations to the present invention according to the technical scheme and the inventive concept thereof within the scope of the present disclosure, such as: it is within the scope of the present invention that proper expansion of the particle size ranges, such as tungsten powder particle size, lanthanum oxide powder particle size, temperature, etc., does not result in the resulting tungsten lanthanum rod having unexpected technical effects.
Claims (7)
1. The tungsten lanthanum rod is characterized by comprising, by mass, 0.5-1.5 parts of lanthanum oxide powder and 96-103 parts of tungsten powder, wherein the tungsten powder is formed by mixing high-particle-size tungsten powder and low-particle-size tungsten powder, the particle size of Gao Lijing tungsten powder is 2-3 mu m, and the particle size of the low-particle-size tungsten powder is 0.5-0.8 mu m; the mass ratio of Gao Lijing tungsten powder to low-particle-size tungsten powder is 95-98:1-5;
The preparation method comprises the following steps:
(1) Mixing: adding low-particle-size tungsten powder, high-particle-size tungsten powder and lanthanum oxide powder into a mixer, and mixing for 1-3 hours at the speed of 2000-2500r/min to obtain mixed powder;
(2) Pressing: pressing the mixed powder at 150-220MPa for 10-15min by adopting a cold isostatic press to obtain a green body;
(3) Sintering: heating and sintering the green body by three sections, wherein the first section is to uniformly heat from normal temperature to 1800 ℃ in 10-12h, the second section is to uniformly heat from 1800 ℃ to 2100 ℃ in 4-5h, and the third section is to uniformly heat from 2100 ℃ to 2500 ℃ in 2-3h, so that the green body is obtained; the three-stage heating sintering is continuous heating.
2. The lanthanum tungsten rod of claim 1, wherein the lanthanum oxide powder has an average particle size of 1 μm or less.
3. The tungsten lanthanum rod according to claim 1, wherein the low-grain tungsten powder is prepared by placing tungsten oxide powder with specific surface area more than or equal to 10m 2/g into a three-belt heating full-automatic fifteen-tube reduction furnace, sequentially heating, controlling the temperature between 600 ℃ and 850 ℃, introducing hydrogen according to the flow rate more than or equal to 60m 3/h for reduction and crushing; the Gao Lijing tungsten powder is prepared by placing tungsten oxide powder with specific surface area less than or equal to 1m 2/g into a three-belt heating full-automatic fifteen-tube reduction furnace, sequentially heating, controlling the temperature between 800 and 950 ℃, introducing hydrogen according to the flow rate less than or equal to 25m 3/h for reduction and crushing.
4. The tungsten lanthanum rod according to claim 1, wherein the raw material composition comprises 1 part by mass of lanthanum oxide powder and 99 parts by mass of tungsten powder.
5. The tungsten lanthanum rod according to claim 1, wherein the raw material composition comprises, by mass, 0.5 parts of lanthanum oxide powder and 103 parts of tungsten powder.
6. The lanthanum tungsten rod of claim 1 wherein the mass ratio of Gao Lijing tungsten powder to low particle size tungsten powder is 95:1.
7. The lanthanum tungsten rod of claim 1 wherein the mass ratio of Gao Lijing tungsten powder to low particle size tungsten powder is 98:5.
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| CN116275048A (en) * | 2023-03-22 | 2023-06-23 | 中钨稀有金属新材料(湖南)有限公司 | Lanthanum-containing tungsten rod blank and preparation method and application thereof |
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