CN111926282B - Hydrogenation method for tantalum material and niobium material - Google Patents
Hydrogenation method for tantalum material and niobium material Download PDFInfo
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- CN111926282B CN111926282B CN202010604803.3A CN202010604803A CN111926282B CN 111926282 B CN111926282 B CN 111926282B CN 202010604803 A CN202010604803 A CN 202010604803A CN 111926282 B CN111926282 B CN 111926282B
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- niobium
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- alkaline earth
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- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 69
- 239000010955 niobium Substances 0.000 title claims abstract description 66
- 229910052758 niobium Inorganic materials 0.000 title claims abstract description 66
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 title claims abstract description 66
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 229910052715 tantalum Inorganic materials 0.000 title claims abstract description 57
- 239000000463 material Substances 0.000 title claims abstract description 42
- 238000000034 method Methods 0.000 title claims abstract description 35
- 239000001257 hydrogen Substances 0.000 claims abstract description 49
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 49
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 40
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 24
- 150000001342 alkaline earth metals Chemical class 0.000 claims abstract description 24
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 19
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 19
- 238000007599 discharging Methods 0.000 claims abstract description 16
- 238000010438 heat treatment Methods 0.000 claims abstract description 14
- 238000001816 cooling Methods 0.000 claims abstract description 12
- 150000002431 hydrogen Chemical class 0.000 claims abstract description 9
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 7
- 229910052708 sodium Inorganic materials 0.000 claims description 7
- 239000011734 sodium Substances 0.000 claims description 7
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 5
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 5
- 229910052791 calcium Inorganic materials 0.000 claims description 5
- 239000011575 calcium Substances 0.000 claims description 5
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 4
- 229910052788 barium Inorganic materials 0.000 claims description 4
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 4
- 238000011049 filling Methods 0.000 claims description 4
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- 239000011777 magnesium Substances 0.000 claims description 4
- 229910052700 potassium Inorganic materials 0.000 claims description 4
- 239000011591 potassium Substances 0.000 claims description 4
- 229910052712 strontium Inorganic materials 0.000 claims description 4
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 4
- 230000000694 effects Effects 0.000 abstract description 11
- 239000000126 substance Substances 0.000 abstract description 4
- 230000007797 corrosion Effects 0.000 abstract description 3
- 238000005260 corrosion Methods 0.000 abstract description 3
- 239000003638 chemical reducing agent Substances 0.000 abstract description 2
- 238000011282 treatment Methods 0.000 description 17
- 229910052751 metal Inorganic materials 0.000 description 15
- 239000002184 metal Substances 0.000 description 15
- 239000002253 acid Substances 0.000 description 6
- 230000004913 activation Effects 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 238000011068 loading method Methods 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 150000004678 hydrides Chemical class 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000004901 spalling Methods 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 230000003749 cleanliness Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 230000003628 erosive effect Effects 0.000 description 2
- 239000012634 fragment Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000002821 niobium Chemical class 0.000 description 2
- -1 niobium metal oxide Chemical class 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 150000003481 tantalum Chemical class 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000004071 soot Substances 0.000 description 1
- WTKKCYNZRWIVKL-UHFFFAOYSA-N tantalum Chemical compound [Ta+5] WTKKCYNZRWIVKL-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C8/06—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
- C23C8/08—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases only one element being applied
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
Abstract
The invention relates to a hydrogenation method of tantalum and niobium. The method is characterized by comprising the following steps of: taking tantalum or niobium with clean surface; charging the obtained tantalum material or niobium material into a crucible of a hydrogenation furnace, and adding a certain amount of alkali metal or alkaline earth metal around the crucible, wherein Be is not included in the alkaline earth metal; vacuumizing the hydrogenation furnace for the first time, charging high-purity hydrogen until the pressure reaches 0.1-2MPa, heating to 300-600 ℃, preserving heat for 2-6h, vacuumizing for the second time, continuously heating to 600-1000 ℃ and preserving heat for 2-6h, charging high-purity hydrogen until the pressure reaches 0.1-2MPa, then powering off and cooling, evacuating and replacing after the temperature is reduced to less than 60 ℃, discharging redundant hydrogen, and discharging. The method adds the strong reducing agent on the conventional process, does not need early chemical corrosion, and economically and environmentally improves the hydrogenation effect of tantalum/niobium ingots, sintered rods, blocks and the like.
Description
Technical Field
The invention relates to a hydrogenation method of tantalum and niobium.
Background
The hydrogen embrittlement characteristic of tantalum/niobium metal after hydrogen absorption is utilized, and then the tantalum/niobium powder with certain granularity range and purity can be prepared through crushing, dehydrogenation and purification treatment. Compact metals such as tantalum/niobium sintered bars and smelting ingots are oxidized on the surfaces of the compact metals during crystallization or when the compact metals are placed in air for a long time to generate protective oxide films, and the oxide films can obstruct hydrogen to permeate into the metal and reduce the hydrogen absorption amount, so that the hydrogenation effect of the final metal is affected, and the tantalum/niobium ingots after hydrogenation can show phenomena of blocky crystals, unobvious layering, insufficient intermediate hydrogenation and the like, thereby causing barriers to subsequent powder preparation.
In the prior art, the activation treatment is needed before hydrogenation, and one is vacuum high-temperature activation treatment, namely, before hydrogenation, the material to be hydrogenated is firstly heated to high temperature (1200 ℃ -1500 ℃) under the hydrogen atmosphere or under vacuum, so that the oxide film on the metal surface has defects, thereby facilitating the diffusion of hydrogen into the metal; the other is chemical treatment, i.e. soaking with an acid solution such as HF with a certain concentration, so as to remove or reduce the oxide film on the metal surface to increase the hydrogen absorption amount of the metal. The first treatment method has higher equipment requirement, high energy consumption and uneconomical; the second treatment method uses HF acid with a certain concentration, is not environment-friendly, and can easily generate a new oxide film on the surface of the niobium ingot due to different acid erosion degrees or erosion time and other differences, thus preventing hydrogen permeation in the heating hydrogenation process and causing unsatisfactory hydrogenation effect. In order to ensure the hydrogenation effect, in chinese patent CN103147050B, tantalum ingots are cut into blocks of 5-10 mm x 5-10 mm in advance and then hydrogenated; chinese patent CN106216695A is to crush tantalum rod into 2-5mm fragments by a crusher and then to dehydrogenate the fragments to prepare powder. The above-described prior cutting or crushing operations introduce new impurities and increase material loss.
Disclosure of Invention
The invention aims to provide a hydrogenation method of tantalum and niobium, which can economically and environmentally improve the hydrogenation effect of tantalum and niobium without the need of early chemical corrosion.
A hydrogenation method of tantalum and niobium is characterized by comprising the following steps:
(1) Taking tantalum or niobium with clean surface;
(2) Charging the obtained tantalum material or niobium material into a crucible of a hydrogenation furnace, and adding a certain amount of alkali metal or alkaline earth metal around the crucible, wherein Be is not included in the alkaline earth metal;
(3) Vacuumizing the hydrogenation furnace for the first time, charging high-purity hydrogen until the pressure reaches 0.1-2MPa, heating to 300-600 ℃, preserving heat for 2-6h, vacuumizing for the second time, continuously heating to 600-1000 ℃ and preserving heat for 2-6h, charging high-purity hydrogen until the pressure reaches 0.1-2MPa, then powering off and cooling, evacuating and replacing after the temperature is reduced to less than 60 ℃, discharging redundant hydrogen, and discharging.
The form of the alkali metal or alkaline earth metal in the step (2) is stable at normal temperature, and the added amount is 0.02% -0.1% of the weight of the tantalum material or the niobium material.
In the step (2), the alkali metal is potassium or sodium, and the alkaline earth metal is magnesium, calcium, strontium or barium.
And (3) vacuumizing to 0-100 MPa in the first vacuumizing and the second vacuumizing in the step (3).
A hydrogenation method of tantalum and niobium is characterized by comprising the following steps:
(1) Taking tantalum or niobium with clean surface;
(2) Charging the obtained tantalum material or niobium material into a crucible of a hydrogenation furnace, and adding a certain amount of alkali metal or alkaline earth metal around the crucible, wherein Be is not included in the alkaline earth metal;
(3) Heating the hydrogenation furnace to 600-1000 ℃, vacuumizing the hydrogenation furnace, preserving heat for 2-6h at 600-1000 ℃, then filling 0.1-2MPa high-purity hydrogen, preserving heat for 2-6h at 600-1000 ℃, then stopping power supply and cooling, evacuating and replacing after the temperature is reduced to less than 60 ℃, discharging redundant hydrogen, and discharging.
The form of the alkali metal or alkaline earth metal in the step (2) is stable at normal temperature, and the added amount is 0.02% -0.1% of the weight of the tantalum material or the niobium material.
In the step (2), the alkali metal is potassium or sodium, and the alkaline earth metal is magnesium, calcium, strontium or barium.
And (3) vacuumizing to 0-100 MPa in the step (3).
The hydrogenation method solves the problem of poor hydrogenation effect of tantalum/niobium materials on the premise of not carrying out activation treatment. The hydrogenation method is applied to the hydrogenation treatment of tantalum/niobium/titanium ingots, tantalum/niobium/titanium sintered rods and tantalum/niobium/titanium billets. The hydrogenation method reduces the activation treatment in the earlier stage, can avoid the use of HF acid in the earlier stage and can also avoid high-temperature heating treatment, so the hydrogenation method is more environment-friendly and economical. The method adds the strong reducing agent on the conventional process, does not need early chemical corrosion, and economically and environmentally improves the hydrogenation effect of tantalum/niobium ingots, sintered rods, blocks and the like.
Detailed Description
The prior art has the defects that: on the one hand, the activation treatment before hydrogenation has high equipment requirement, high energy consumption and poor economical efficiency, and on the other hand, the use of HF is not environment-friendly; the cutting and crushing treatment before hydrogenation not only increases the impurity content of the raw materials, but also increases the loss of materials. The method solves the problem of poor hydrogenation effect of the tantalum/niobium material in the prior art. In order to enhance the hydrogenation effect of tantalum/niobium materials in practice, it is necessary to subject the valve metal surface to an activation treatment or to subject it to a plurality of hydrogenation treatments before the tantalum/niobium materials are hydrogenated.
In the step (1) of the method, the surface purification treatment of the tantalum/niobium material is an independent treatment mode selected according to the surface cleanliness degree of the tantalum/niobium material, if the surface cleanliness degree is high, the surface can be not treated or only the surface of compressed air is used for soot blowing, if impurities such as greasy dirt and the like exist on the surface, HCL or nitric acid with a certain concentration can be selected for treatment, and the surface can be washed and dried by pure water, and the method belongs to the conventional technology in the field.
When hydrogen is added into the step (3) and heated to 300-600 ℃, alkali metal or alkaline earth metal (except Be) can directly react with the hydrogen to generate ionic hydride MH x (M=alkali metal, x= 1;M =alkaline earth metal, x=2;) while MH x has strong reducibility, under the conditions of vacuumizing and 600-1000 ℃, MH x presents a gaseous state, MH x can reduce tantalum/niobium metal oxide, so that an oxide film on the surface of tantalum/niobium material is damaged, the hydrogen permeation into the metal is promoted in the power failure cooling process, the hydrogen absorption effect of tantalum/niobium metal is enhanced, and the oxygen content of tantalum/niobium material after hydrogenation is further reduced.
Example 1:
After the surface of a 1 cylindrical niobium ingot with the diameter of 120mm and the weight of 100kg is blown into ash by using compressed air, the cylindrical niobium ingot is filled into a crucible of a hydrogenation furnace, 100g of sodium blocks are added around the crucible, the hydrogenation furnace is pumped out to be evacuated (-2 MPa), then high-purity hydrogen with the pressure of 1.0MPa is filled (actually, hydrogen is filled until the pressure reaches 1.0 MPa), the temperature is raised to 600 ℃ for 2 hours, the hydrogenation furnace is pumped out again to be continuously heated to 950 ℃ for 4 hours, then high-purity hydrogen with the pressure of 1.2MPa is filled (actually, hydrogen is filled until the pressure reaches 1.2 MPa), then the power is cut off, natural cooling is carried out, the niobium ingot can fully absorb hydrogen and react with the hydrogen, the hydrogen is pumped out of the hydrogenation furnace after the temperature is reduced to be less than 60 ℃, and finally, the hydrogenated niobium ingot is obviously layered, easy to peel off and has no sandwich phenomenon.
The invention also relates to a method step (3), which comprises the steps of evaporating alkali metal or alkaline earth metal (except Be) under the conditions of vacuumizing and reaching 600-1000 ℃, attaching the alkali metal or alkaline earth metal to materials to Be hydrogenated such as tantalum/niobium ingots, sintering rods and the like, reacting the corresponding alkali metal or alkaline earth metal (except Be) with hydrogen to produce ionic hydride MHx (M=alkali metal, x= 1;M =alkaline earth metal and x=2) with strong reducibility after adding hydrogen, and reducing tantalum/niobium metal oxide by the hydride generated at the temperature of 600-1000 ℃, so that an oxide film on the surface of the tantalum/niobium material is damaged, the hydrogen permeation into the metal is promoted in the process of power failure cooling, the hydrogen absorption effect of the tantalum/niobium metal is enhanced, and the oxygen content of the tantalum/niobium material after hydrogenation is further reduced.
Example 2:
The method comprises the steps of using compressed air to blow ash on the surface of 1 cylindrical niobium ingot with the diameter of 120mm and the weight of 100kg, loading the cylindrical niobium ingot into a crucible of a hydrogenation furnace, adding 100g of sodium blocks around the crucible, heating the hydrogenation furnace to 900 ℃, vacuumizing to the pressure of < -60MPa, preserving heat for 2 hours at the temperature of 900 ℃, then introducing high-purity hydrogen with the pressure of 1.0MPa into the hydrogenation furnace (actually filling hydrogen to the pressure of 1.0 MPa), preserving heat for 6 hours at the temperature of 900 ℃, then naturally cooling after power failure, evacuating and discharging hydrogen in the hydrogenation furnace after the temperature is reduced to the temperature of less than 60 ℃, and finally obtaining the hydrogenated niobium ingot with obvious layering, easy spalling and no sandwich phenomenon.
Example 3:
After the surface of 1 cylindrical niobium sintered rod with the diameter of 120mm and the weight of 100kg is blown with ash by using compressed air, the cylindrical niobium sintered rod is put into a crucible of a hydrogenation furnace, 20g of sodium blocks are added around the crucible, the hydrogenation furnace is heated to 900 ℃, the vacuum pumping is carried out until the pressure is less than-60 MPa, the temperature is kept for 2 hours at the temperature of 900 ℃, then high-purity hydrogen with the pressure of 1.0MPa (actually hydrogen is filled until the pressure reaches 1.0 MPa) is introduced into the hydrogenation furnace, the temperature is kept for 6 hours at the temperature of 900 ℃, then the power is cut, the temperature is naturally reduced, the hydrogen in the hydrogenation furnace is exhausted after the temperature is reduced to less than 60 ℃, and finally, the hydrogenated niobium rod is obviously layered, easy to peel and free from sandwich phenomenon is obtained.
Example 4:
The method comprises the steps of using compressed air to blow ash on the surface of 1 cylindrical tantalum ingot with the diameter of 120mm and the weight of 100kg, loading the tantalum ingot into a crucible of a hydrogenation furnace, adding 100g of calcium blocks around the crucible, heating the hydrogenation furnace to 950 ℃, vacuumizing to the pressure of < -60MPa, preserving heat for 2 hours at the temperature of 950 ℃, then introducing high-purity hydrogen with the pressure of 1.0MPa into the hydrogenation furnace (actually, filling hydrogen to the pressure of 1.0 MPa), preserving heat for 6 hours at the temperature of 950 ℃, then naturally cooling after power failure, evacuating and discharging hydrogen in the hydrogenation furnace after the temperature is reduced to the temperature of less than 60 ℃, and finally obtaining the hydrogenated tantalum ingot with obvious layering, easy spalling and no sandwich phenomenon after discharging.
Example 5:
The method comprises the steps of using compressed air to blow ash on the surface of 1 cylindrical tantalum rod with the diameter of 120mm and the weight of 100kg, loading the tantalum rod into a crucible of a hydrogenation furnace, adding 20g of magnesium powder around the crucible, heating the hydrogenation furnace to 900 ℃, vacuumizing to the pressure of < -60MPa, preserving heat for 2 hours at the temperature of 900 ℃, then introducing high-purity hydrogen with the pressure of 1.0MPa into the hydrogenation furnace, continuously preserving heat for 6 hours at the temperature of 900 ℃, then cutting off power and cooling, evacuating and discharging the hydrogen in the hydrogenation furnace after the temperature is reduced to less than 60 ℃, and finally obtaining the hydrogenated tantalum ingot with obvious layering, easy spalling and no sandwich phenomenon after discharging.
Comparative example 1:
firstly, soaking a niobium ingot with the diameter of 120mm and the weight of 100kg for 8 hours by using 30% HF acid, so that the acid erodes the outer surface, then washing and drying the niobium ingot by using pure water, then, loading the niobium ingot into a crucible of a hydrogenation furnace, vacuumizing the hydrogenation furnace to the pressure of < -60MPa, heating the furnace to 900 ℃ for 2 hours, then, introducing high-purity hydrogen with the pressure of 0.8MPa into the hydrogenation furnace, continuously preserving the heat for 6 hours, then, cooling by power failure, evacuating the hydrogen in the hydrogenation furnace after the temperature is reduced to less than 60 ℃, and finally, discharging the niobium ingot after hydrogenation, wherein the niobium ingot presents the phenomena of insufficient hydrogenation such as massive crystals, insignificant layering and the like, and causes barriers to subsequent powder preparation.
Claims (8)
1. A method for hydrogenating tantalum and niobium, comprising the steps of:
(1) Taking tantalum or niobium with clean surface;
(2) Charging the obtained tantalum material or niobium material into a crucible of a hydrogenation furnace, and adding a certain amount of alkali metal or alkaline earth metal around the crucible, wherein Be is not included in the alkaline earth metal;
(3) Vacuumizing the hydrogenation furnace for the first time, charging high-purity hydrogen until the pressure reaches 0.1-2MPa, heating to 300-600 ℃, preserving heat for 2-6h, vacuumizing for the second time, continuously heating to 600-1000 ℃ and preserving heat for 2-6h, charging high-purity hydrogen until the pressure reaches 0.1-2MPa, then powering off and cooling, evacuating and replacing after the temperature is reduced to less than 60 ℃, discharging redundant hydrogen, and discharging.
2. A method of hydrogenating tantalum and niobium materials according to claim 1 wherein: the form of the alkali metal or alkaline earth metal in the step (2) is stable at normal temperature, and the added amount is 0.02% -0.1% of the weight of the tantalum material or the niobium material.
3. A method of hydrogenating tantalum and niobium materials according to claim 1 wherein: in the step (2), the alkali metal is potassium or sodium, and the alkaline earth metal is magnesium, calcium, strontium or barium.
4. A method of hydrogenating tantalum and niobium materials according to claim 1 wherein: and (3) vacuumizing to 0-100 MPa in the first vacuumizing and the second vacuumizing in the step (3).
5. A method for hydrogenating tantalum and niobium, comprising the steps of:
(1) Taking tantalum or niobium with clean surface;
(2) Charging the obtained tantalum material or niobium material into a crucible of a hydrogenation furnace, and adding a certain amount of alkali metal or alkaline earth metal around the crucible, wherein Be is not included in the alkaline earth metal;
(3) Heating the hydrogenation furnace to 600-1000 ℃, vacuumizing the hydrogenation furnace, preserving heat for 2-6h at 600-1000 ℃, then filling 0.1-2MPa high-purity hydrogen, preserving heat for 2-6h at 600-1000 ℃, then stopping power supply and cooling, evacuating and replacing after the temperature is reduced to less than 60 ℃, discharging redundant hydrogen, and discharging.
6. A method of hydrogenating tantalum and niobium materials according to claim 5 wherein: the form of the alkali metal or alkaline earth metal in the step (2) is stable at normal temperature, and the added amount is 0.02% -0.1% of the weight of the tantalum material or the niobium material.
7. A method of hydrogenating tantalum and niobium materials according to claim 5 wherein: in the step (2), the alkali metal is potassium or sodium, and the alkaline earth metal is magnesium, calcium, strontium or barium.
8. A method of hydrogenating tantalum and niobium materials according to claim 5 wherein: and (3) vacuumizing to 0-100 MPa in the step (3).
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1305227A (en) * | 1961-11-13 | 1962-09-28 | Union Carbide Corp | New tantalum powder and its manufacturing process |
| DE19831280A1 (en) * | 1998-07-13 | 2000-01-20 | Starck H C Gmbh Co Kg | Acidic earth metal, specifically tantalum or niobium, powder for use, e.g., in capacitor production is produced by two-stage reduction of the pentoxide using hydrogen as the first stage reducing agent for initial suboxide formation |
| FR2897608A1 (en) * | 2006-02-23 | 2007-08-24 | Centre Nat Rech Scient | Making powdery metallic composite material, useful for reversible storage of hydrogen, comprises preparing, hydrogenating and fragmentizing the metallic composite material e.g. of titanium, vanadium, zirconium and nickel |
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