CN115229189A - Preparation method of uniform porous tungsten product - Google Patents
Preparation method of uniform porous tungsten product Download PDFInfo
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- CN115229189A CN115229189A CN202210737242.3A CN202210737242A CN115229189A CN 115229189 A CN115229189 A CN 115229189A CN 202210737242 A CN202210737242 A CN 202210737242A CN 115229189 A CN115229189 A CN 115229189A
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- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 229910052721 tungsten Inorganic materials 0.000 title claims abstract description 48
- 239000010937 tungsten Substances 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 33
- 239000011148 porous material Substances 0.000 claims abstract description 24
- 238000005049 combustion synthesis Methods 0.000 claims abstract description 20
- 239000002243 precursor Substances 0.000 claims abstract description 15
- 239000002245 particle Substances 0.000 claims abstract description 9
- 238000009766 low-temperature sintering Methods 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 238000005245 sintering Methods 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 12
- 239000000843 powder Substances 0.000 claims description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 229910002651 NO3 Inorganic materials 0.000 claims description 7
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 7
- 238000002490 spark plasma sintering Methods 0.000 claims description 7
- 239000004471 Glycine Substances 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims description 6
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 claims description 6
- 239000000779 smoke Substances 0.000 claims description 6
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 4
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 3
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 3
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 239000003929 acidic solution Substances 0.000 claims description 2
- 238000004090 dissolution Methods 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 238000005485 electric heating Methods 0.000 claims description 2
- 239000000446 fuel Substances 0.000 claims description 2
- 238000003760 magnetic stirring Methods 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 230000008569 process Effects 0.000 abstract description 6
- 229910052751 metal Inorganic materials 0.000 abstract description 4
- 239000002184 metal Substances 0.000 abstract description 4
- 239000003795 chemical substances by application Substances 0.000 abstract description 3
- 239000002131 composite material Substances 0.000 abstract description 3
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 239000007769 metal material Substances 0.000 abstract description 3
- 239000011159 matrix material Substances 0.000 abstract description 2
- 238000005260 corrosion Methods 0.000 abstract 1
- 230000007797 corrosion Effects 0.000 abstract 1
- 229910001960 metal nitrate Inorganic materials 0.000 abstract 1
- 239000002923 metal particle Substances 0.000 abstract 1
- 239000007800 oxidant agent Substances 0.000 abstract 1
- 230000001590 oxidative effect Effects 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 238000001816 cooling Methods 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229910044991 metal oxide Inorganic materials 0.000 description 4
- 150000004706 metal oxides Chemical class 0.000 description 4
- 238000004663 powder metallurgy Methods 0.000 description 4
- 238000002485 combustion reaction Methods 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000012702 metal oxide precursor Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
Classifications
-
- 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
- B22F3/11—Making porous workpieces or articles
- B22F3/1121—Making porous workpieces or articles by using decomposable, meltable or sublimatable fillers
- B22F3/1134—Inorganic fillers
-
- 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
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/14—Treatment of metallic powder
- B22F1/145—Chemical treatment, e.g. passivation or decarburisation
-
- 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
- B22F3/11—Making porous workpieces or articles
- B22F3/114—Making porous workpieces or articles the porous products being formed by impregnation
Abstract
A preparation method of a uniform porous tungsten product belongs to the field of porous metal material preparation. Solves the problems of coarse grains, compact sintered body, low porosity, uneven pore structure, poor mechanical property and the like of the porous tungsten product prepared by the prior method. According to the invention, tungsten powder is used as a tungsten source, metal nitrate is used as an oxidant and a pore-forming agent, a large amount of gas is generated by low-temperature combustion synthesis to form a metal-loaded porous tungsten composite precursor, the tungsten particles and the pore size can be adjusted and controlled by SPS low-temperature sintering, and finally the metal particles are removed by using the corrosion characteristic of metal, so that a large amount of pores are formed in a tungsten matrix for the second time, and the porosity is improved. The method has the advantages of simple process, good repeatability, low cost, low energy consumption, short period and the like, can prepare the porous tungsten product with the grain size being adjustable and controllable within the range of less than 1 mu m, the pore diameter being adjustable and controllable within the range of 0.1-2 mu m, the porosity being 15-45 percent, meets various use requirements, and has wide application prospect.
Description
Technical Field
The invention belongs to the technical field of porous metal material preparation, and particularly relates to a preparation method of a uniform porous tungsten product.
Background
The porous tungsten has the characteristics of high melting point (3420 ℃), low density, low thermal expansion coefficient, high strength and the like, is widely applied to the fields of aerospace, national defense engineering, constructional engineering, power electronics, metallurgical industry and the like, can be used as a base material of a reserve type diffusion tungsten hot cathode, or can be used as a framework for preparing a W-Cu composite material by an infiltration method, and can also be used as a high-temperature fluid filtering material and the like. In each application of the porous tungsten, the pore size and the porosity of the porous tungsten play a vital role in the service performance of the porous tungsten and the performance of manufacturing components. Powder Metallurgy (PM) is a process for preparing porous metal materials, composite materials and various types of products from metal powders (or mixtures of metal powders and non-metal powders) by molding and sintering, and has been commonly used for synthesizing porous tungsten products. However, the sintering temperature of this method is more than 1600 ℃, which inevitably results in coarse grains, densification of the sintered body, weakening of mechanical properties, reduction of porosity, and in the production of large-sized workpieces, expensive press equipment and dies are required.
The low-temperature combustion synthesis method has the advantages of self-maintenance of reaction, low energy consumption, horizontal mixing of reactant molecules, high speed, simple process and equipment, low economic cost, industrial scale production, high product purity, fineness, easy regulation and control of tissue morphology and the like, and is widely applied to the preparation of porous materials. However, at present, there are few reports of directly adopting a combustion synthesis method to prepare a porous tungsten material, and the method mainly stays in the preparation stage of the porous tungsten powder. Due to the limitations of the processing techniques, there has been no report on the in situ synthesis of porous tungsten articles of complex shape by combustion synthesis.
Disclosure of Invention
Aiming at the problems of the preparation of the porous tungsten product by the existing powder metallurgy method, the invention provides a solution technology for preparing the uniform porous tungsten product by combining a low-temperature combustion synthesis method with SPS low-temperature sintering and acid washing treatment.
A preparation method of a uniform porous tungsten product comprises the following specific steps:
(1) Mixing tungsten powder, fuel, nitrate and deionized water according to a certain proportion, heating in a water bath by using a magnetic stirrer while stirring to form a homogeneous aqueous solution, then placing the homogeneous aqueous solution on an electric heating plate, heating at a certain temperature to form sol, continuously heating for a period of time until the volume of the sol expands, generating a low-temperature combustion synthesis reaction along with generation of a large amount of dense smoke, and obtaining precursor powder after the reaction is finished;
(2) Placing the precursor powder prepared in the step (1) in a spark plasma sintering furnace to perform SPS low-temperature sintering reaction and forming;
(3) And (3) placing the product prepared in the step (2) in an acid solution, carrying out acid washing dissolution under a heating condition, then washing the sample with deionized water and ethanol, and completely drying to obtain the porous tungsten product with uniform pores and high porosity.
Further, the molar ratio of the tungsten powder to the glycine to the nitrate in the step (1) is (4.5-7): (1.5-3): (1-2).
Further, the granularity of the tungsten powder in the step (1) is 50-200 nm, and the purity is 99.9%.
Further, the nitrate in the step (1) is at least one of calcium nitrate, copper nitrate, zinc nitrate, manganese nitrate, nickel nitrate and chromium nitrate.
Further, the conditions of the water bath heating and magnetic stirring treatment in the step (1) are as follows: the water bath temperature is 60-90 ℃, and the stirring time is 20-40 min.
Further, the heating condition of the combustion synthesis in the step (1) is 250-400 ℃.
Further, the SPS low-temperature sintering conditions in the step (2) are as follows: the temperature is 800-1200 ℃, the time is 2-5 min, the heating rate is 50-120 ℃/min, the pressure is 10-40 MPa, the sintering vacuum degree is 1 multiplied by 10 -4 ～1×10 -2 Pa。
Further, the heating condition in the step (3) is 80-120 ℃ for 1-4 h.
Further, the acidic solution in the step (3) is at least one of sulfuric acid, hydrochloric acid, nitric acid and hydrofluoric acid, and the concentration is 5-15 wt%.
Furthermore, the grain size of the porous tungsten product prepared in the step (3) is less than 1 μm, the porosity is 15-45%, and the pore size is 0.1-2 μm.
The invention combines the characteristics of low-temperature combustion synthesis and porous materials, combines the combustion synthesis product with the preparation method of the porous materials, successfully prepares the porous tungsten product with high porosity, uniform pores, small pore diameter and high strength, and has certain practical significance and innovative significance. The porous tungsten product with porosity and pore diameter meeting the use requirements can be obtained by reasonably customizing the process parameters of low-temperature combustion synthesis, discharge plasma (SPS) low-temperature sintering, acid washing and the like, the grain size of the product can be regulated and controlled within the range of less than 1 mu m, the pore diameter can be regulated and controlled within the range of 0.1-2 mu m, the porosity is improved by more than 20 percent, and the performance of the porous tungsten material prepared by the powder metallurgy method can be obviously optimized.
The technique of the invention has the following advantages:
(1) The low-temperature combustion synthesis method of the invention utilizes the advantages of simple solution raw materials and easy realization of uniform mixing to prepare the precursor mixed at molecular level, and overcomes the problem of uneven mixing of the raw materials in the traditional powder metallurgy method.
(2) The invention provides a preparation method of a uniform porous tungsten product, which takes tungsten powder as a tungsten source and nitrate as a pore-forming agent and a dispersing agent, and utilizes self-heat release of combustion reaction to carry out combustion synthesis to prepare a porous tungsten/other metal oxide precursor. The combustion time is only 2-3 minutes, and other metal oxides in the precursor can effectively reduce the reaction thermodynamic temperature in the subsequent sintering process, and the sintering furnace is not required to be used for high-temperature long-time heat preservation sintering in the prior art, so that the method has the advantages of simple process, good repeatability, low cost, low energy consumption, short period and the like, and overcomes the defects of long period, low production efficiency and the like of the porous tungsten prepared by the traditional method.
(3) The invention can freely change the size and the number of the pore-forming metal oxide particles by controlling the types and the proportion of the nitrates, the combustion synthesis and the sintering conditions, thereby accurately controlling the pore size, the distribution and the porosity, and overcoming the defect that the pore structure of the porous tungsten prepared by the traditional method is difficult to control.
(4) The metal oxide particles serving as pore-forming agents exist all the time in the early combustion synthesis and SPS low-temperature sintering processes, the heat treatment deformation is small, the sizes of the metal oxide particles are increased along with the temperature rise, and the phenomena of excessive shrinkage and porosity reduction of a tungsten matrix caused by too high sintering temperature in the traditional porous tungsten preparation method can be effectively avoided, so that the performance of the porous tungsten product is improved, and the service life of the porous tungsten product is prolonged.
(5) The porous tungsten product prepared by the method has the advantages of regular shape, good surface quality, uniform and communicated pores, low impurity content, 200-900 nm of crystal grain size, 0.1-2 mu m of pore diameter and 15-45% of porosity, simple and easy preparation process, low cost, suitability for industrial mass production and wide application prospect.
Detailed Description
Example 1
3.27g of glycine, 4.83g of copper nitrate and 1.79g of manganese nitrate were weighed and placed in a 500ml beaker, and an appropriate amount of deionized water was added and stirred with a glass rod to prepare a solution. 22.08g of tungsten powder with the particle size of 50nm is added into the beaker, and the mixture is placed on a magnetic stirrer to be stirred for 30min under the water bath heating condition of 80 ℃ to form a homogeneous aqueous solution. And then, placing the beaker on an electric hot plate, heating at the temperature of 300 ℃ until sol is formed, continuing to heat for a period of time until the volume of the sol expands, generating a large amount of dense smoke along with low-temperature combustion synthesis reaction, and obtaining precursor powder. Placing the precursor in a spark plasma sintering furnace at a vacuum degree of 1 × 10 -2 Performing SPS sintering reaction in Pa environment at 80 deg.C/min under 30MPa at 1000 deg.C for 3min, and furnace cooling. Finally, the sample is placed in 8wt% sulfuric acid solution to be washed and dissolved for 4 hours under the heating condition of 80 ℃, deionized water and ethanol are used for washing the sample, and after the sample is completely dried, the porous tungsten product with the grain size of 420nm, the porosity of 38% and the pore size of 0.37 mu m is obtained.
Example 2
4.35g of glycine, 3.28g of calcium nitrate and 4.76g of chromium nitrate were weighed and placed in a 500ml beaker, and an appropriate amount of deionized water was added and stirred with a glass rod to prepare a solution. Adding 25.76g of tungsten powder with the particle size of 100nm into the beaker, placing the beaker on a magnetic stirrer, and stirring the beaker for 40min under the water bath heating condition of 60 ℃ to form a homogeneous aqueous solution. Then, the beaker is placed on an electric hot plate and heated at 350 ℃ until sol is formed, and the heating is continued for a period of time until the volume of the sol expands, and a low-temperature combustion synthesis reaction is carried out along with the generation of a large amount of dense smoke, so that precursor powder is obtained. Placing the precursor in a discharge plasma sintering furnace at a vacuum degree of 5 × 10 -3 Performing SPS sintering reaction in Pa environment at heating rate of 100 deg.C/min under 20MPa and 1200 deg.C for 2min, and cooling with furnace. Finally, the sample is put into 10wt% hydrochloric acid solution to be washed and dissolved for 2h under the heating condition of 100 ℃, deionized water and ethanol are used for washing the sample, and after the sample is completely dried, the porous tungsten product with the grain size of 977nm, the porosity of 16% and the pore size of 1.22 mu m is obtained.
Example 3
7.53g of glycine and 17.84g of zinc nitrate are weighed and placed in a 1000ml beaker, an appropriate amount of deionized water is added, and the mixture is stirred uniformly by a glass rod to prepare a solution. 46.37g tungsten powder with particle size of 150nm is added into a beaker, and the mixture is placed on a magnetic stirrer to be stirred for 30min under the water bath heating condition of 70 ℃ to form a homogeneous aqueous solution. Then, the beaker is placed on an electric hot plate and heated at the temperature of 250 ℃ until sol is formed, and the heating is continued for a period of time until the volume of the sol expands, and a large amount of dense smoke is generated along with the low-temperature combustion synthesis reaction, so that precursor powder is obtained. Placing the precursor in a spark plasma sintering furnace with the vacuum degree of 8 multiplied by 10 - 3 Performing SPS sintering reaction in Pa environment at heating rate of 90 deg.C/min under 40MPa and reaction temperature of 1100 deg.C for 4min, and cooling with furnace. Finally, the sample is placed in 15wt% sulfuric acid solution to be washed and dissolved for 3 hours under the heating condition of 90 ℃, deionized water and ethanol are used for washing the sample, and after the sample is completely dried, the porous tungsten product with the grain size of 610nm, the porosity of 26% and the pore size of 0.51 mu m is obtained.
Example 4
6.90g of glycine and 12.79g of nickel nitrate are weighed and placed in a 1000ml beaker, a proper amount of deionized water is added, and the mixture is uniformly stirred by a glass rod to prepare a solution. 38.64g tungsten powder with particle size of 80nm is added into a beaker, and the mixture is placed on a magnetic stirrer to be stirred for 20min under the water bath heating condition of 90 ℃ to form a homogeneous aqueous solution. Then, the beaker is placed on an electric hot plate and heated at the temperature of 400 ℃ until sol is formed, the heating is continued for a period of time until the volume of the sol expands, and a low-temperature combustion synthesis reaction is carried out along with the generation of a large amount of dense smoke, so that precursor powder is obtained. Placing the precursor in a spark plasma sintering furnace at a vacuum degree of 1 × 10 - 4 Performing SPS sintering reaction in Pa environment at heating rate of 120 deg.C/min under 10MPa at reaction temperature of 800 deg.C for 5min, and furnace cooling. Finally, the sample is placed in 12wt% sulfuric acid solution to be washed and dissolved for 1h under the heating condition of 120 ℃, deionized water and ethanol are used for washing the sample, and after the sample is completely dried, the porous tungsten product with the grain size of 230nm, the porosity of 43 percent and the pore size of 0.14 mu m is obtained.
Claims (10)
1. The preparation method of the uniform porous tungsten product is characterized by comprising the following preparation steps:
(1) Mixing tungsten powder, fuel, nitrate and deionized water according to a certain proportion, heating with a magnetic stirrer in a water bath and stirring to form a homogeneous aqueous solution, then placing the homogeneous aqueous solution on an electric heating plate, heating at a certain temperature to form sol, continuously heating for a period of time until the volume of the sol expands, generating low-temperature combustion synthesis reaction along with generation of a large amount of dense smoke, and obtaining precursor powder after the reaction is finished;
(2) Placing the precursor powder prepared in the step (1) in a spark plasma sintering furnace to perform SPS low-temperature sintering reaction and forming;
(3) And (3) placing the product prepared in the step (2) in an acid solution, carrying out acid washing dissolution under a heating condition, then washing the sample with deionized water and ethanol, and completely drying to obtain the porous tungsten product with uniform pores and high porosity.
2. The method for preparing a uniform porous tungsten product according to claim 1, wherein the molar ratio of the tungsten powder to the glycine to the nitrate in the step (1) is (4.5-7): (1.5-3): (1-2).
3. The method for preparing a uniform porous tungsten product according to claim 1 or 2, wherein the tungsten powder has a particle size of 50 to 200nm and a purity of 99.9%.
4. The method of claim 1 or 2, wherein the nitrate is at least one of calcium nitrate, copper nitrate, zinc nitrate, manganese nitrate, nickel nitrate, and chromium nitrate.
5. The method for preparing a uniform porous tungsten article according to claim 1, wherein the conditions of the water bath heating and magnetic stirring treatment in step (1) are as follows: the water bath temperature is 60-90 ℃, and the stirring time is 20-40 min.
6. The method for preparing a uniform porous tungsten product according to claim 1, wherein the combustion synthesis heating condition in step (1) is 250-400 ℃.
7. The method of claim 1, wherein the SPS low temperature sintering conditions in step (2) are: the temperature is 800-1200 ℃, the time is 2-5 min, the heating rate is 50-120 ℃/min, the pressure is 10-40 MPa, the sintering vacuum degree is 1 multiplied by 10 -4 ～1×10 -2 Pa。
8. The method for preparing a uniform porous tungsten product according to claim 1, wherein the heating condition in step (3) is 80-120 ℃ for 1-4 hours.
9. The method according to claim 1, wherein the acidic solution in step (3) is at least one of sulfuric acid, hydrochloric acid, nitric acid, and hydrofluoric acid, and has a concentration of 5-15 wt%.
10. The method of claim 1, wherein the porous tungsten article obtained in step (3) has a grain size of less than 1 μm, a porosity of 15 to 45%, and a pore size of 0.1 to 2 μm.
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