CN1232373C - Method for processing microtantalum and/or niobium powder and powder made by said method - Google Patents
Method for processing microtantalum and/or niobium powder and powder made by said method Download PDFInfo
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- CN1232373C CN1232373C CN 03122325 CN03122325A CN1232373C CN 1232373 C CN1232373 C CN 1232373C CN 03122325 CN03122325 CN 03122325 CN 03122325 A CN03122325 A CN 03122325A CN 1232373 C CN1232373 C CN 1232373C
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Abstract
The present invention relates to a novel processing method for preparing superfine tantalum and/or niobium powder, particularly to a method for carrying out thermal processing and post-processing for superfine tantalum and/or niobium powder which is generated during the mixed reaction of tantalum and/or niobium halide and reducing metal in liquid ammonia in non-oxidation atmosphere at high temperature before the superfine tantalum and/or niobium powder contacts media with oxygen. The tantalum and/or niobium powder which is prepared according to the method of the present invention is superfine nanometer grade powder which is relatively stable.
Description
Technical field
The present invention relates to the processing method of a kind of freshly prepd fine tantalum and/or niobium powder, the halide of particularly a kind of tantalum and/or niobium and reducing metal fine tantalum that hybrid reaction generates in liquefied ammonia and/or niobium powder with processing method before oxygen-containing medium contacts.
Background technology
The similar performance of tantalum and niobium all is a refractory metal, and the inorganic acid except that hydrofluoric acid is had good chemical stability, but elements such as O, N, C are had very high activity.Tantalum, niobium or nitrogenous tantalum, niobium are used to make copper diffusion barrier layer of electrolytic capacitor, high temperature resistant and resistant material, superalloy, carbide alloy, spraying plating overcoat and integrated circuit etc.Particularly when being used as electrolytic capacitor, require it that fine particle size is arranged, just can obtain high volume specific volume.
Hongmin zhu (Zhu Hongmin) and D.R.Sadoway (D.R. Sa Dewei) are at J.MaterialRes., and Vol.16 discloses a kind of nanoscale tantalum and Nb among the No.9 (publication in September calendar year 2001)
3The preparation method of Al powder, this method comprises at least a halide of tantalum, the halide of niobium, halide and a kind of reducing agent of aluminium of being selected from, as alkali metal, be lower than under the condensing temperature of ammonia (34 ℃), partly or entirely be dissolved in the liquefied ammonia, to be dissolved with at least a halide of tantalum, the halide of niobium, halid ammonia solution and a kind of ammonia solution that is dissolved with reducing agent (as sodium) of aluminium of being selected from then mixes, generate the attritive powder of tantalum, niobium or its metallic compound, then with above-mentioned fine-powder and NaCl, NH
3, Na separates, and obtains purer tantalum, niobium powder, the about 20～60nm of primary partical particle diameter of this powder.This fine tantalum, niobium powder have very high activity, can rapid oxidation when contacting with oxygen-containing medium, can't long term exposure in air, therefore, do not have too big practical value.
In order to obtain stable fine tantalum and/or niobium metal powders with industrial utility value, the inventor finds through concentrating on studies, test the back, by the halide of tantalum and/or niobium and reducing metal are dissolved in react in the liquefied ammonia attritive powder that obtains with in non-oxidizing atmosphere, carry out high-temperature heat treatment and subsequent treatment before oxygen-containing medium contacts, can obtain stable tantalum and/or niobium powder.
Summary of the invention
The processing method that the purpose of this invention is to provide fine tantalum of a kind of new preparation and/or niobium metal powders.
According to the inventive method, the powder that makes fine tantalum and/or niobium with in non-oxidizing atmosphere, carry out high-temperature heat treatment and subsequent treatment before oxygen-containing medium contacts.
According to the powder of fine tantalum provided by the invention and/or niobium with in non-oxidizing atmosphere, carry out in the method for high-temperature heat treatment before oxygen-containing medium contacts, described fine tantalum and/or niobium powder are the halide that is selected from tantalum with at least a, the halide of niobium and a kind of reducing agent, as alkali metal, be lower than under the condensing temperature of ammonia (34 ℃), partly or entirely be dissolved in the liquefied ammonia, to be dissolved with at least a halide that is selected from tantalum then, the halid ammonia solution of niobium and a kind of ammonia solution that is dissolved with reducing agent mix, and generate tantalum and/or the niobium attritive powder of primary partical less than 100nm.
According to the powder of fine tantalum provided by the invention and/or niobium with in non-oxidizing atmosphere, carry out in the method for high-temperature heat treatment before oxygen-containing medium contacts, described heat-treatment temperature range is 200 ℃～1000 ℃, temperature retention time is 30～1440 minutes, preferred 500 ℃～900 ℃, temperature retention time is 60～720 minutes, and programming rate is had no particular limits.
In the processing method according to the powder of freshly prepd fine tantalum provided by the invention and/or niobium, before being included in described powder and oxygen-containing medium contacting, in non-oxidizing atmosphere, be 500 ℃～900 ℃ in temperature range and be incubated 60～720 minutes down, then cool to room temperature carries out Passivation Treatment, and wherein said nonoxidizing atmosphere is a vacuum, inert atmosphere, or the reducing atmosphere that in inert gas, has Ca, Mg, Li or Ce reducing metal element to exist.
According to the powder of fine tantalum provided by the invention and/or niobium with the method for in non-oxidizing atmosphere, heat-treating before oxygen-containing medium contacts in, described non-oxidizing atmosphere is to carry out under vacuum, the pressure of heat treatment vacuum chamber is lower than 1 torr, preferably is lower than 10
-2Torr is more preferably less than 10
-3Torr most preferably is lower than 10
-4Torr.
According to the powder of fine tantalum provided by the invention and/or niobium with the method for in non-oxidizing atmosphere, heat-treating before oxygen-containing medium contacts in, described non-oxidizing atmosphere is at inert atmosphere, as heat-treating under argon gas, helium.
According to the powder of fine tantalum provided by the invention and/or niobium with the method for in non-oxidizing atmosphere, heat-treating before oxygen-containing medium contacts in, described non-oxidizing atmosphere is the reducing atmosphere that has reducing metal elements such as Ca, Mg, Li, Ce to exist in inert gas, preferably heat-treats under the reducing atmosphere that has Ca, Mg reducing metal element to exist.
According to the powder of fine tantalum provided by the invention and/or niobium with the method for in non-oxidizing atmosphere, heat-treating before oxygen-containing medium contacts in, described non-oxidizing atmosphere is vacuum, inert gas and reducing atmosphere or their any combination.
According to the powder of fine tantalum provided by the invention and/or niobium with in non-oxidizing atmosphere, heat-treat before oxygen-containing medium contacts and the method for subsequent treatment in, according to well known to a person skilled in the art that method (for example making tantalum and/or niobium powder surface form the method for stable oxide film referring to WO 02/13998 is described by slow importing air) carries out Passivation Treatment, then sample is taken out from heat treatment container after after being heated to maximum temperature insulation, cooling to room temperature.If necessary, carry out pickling, washing and drying subsequently.Pickle can be with the inorganic acid of dilution, as nitric acid, hydrochloric acid, sulfuric acid, hydrofluoric acid and hydrogen peroxide or their any combination.Drying is generally carried out in atmosphere or vacuum, preferably carries out below 60 ℃ in a vacuum.
The fine tantalum that obtains according to the inventive method and/or the powder of niobium are porous groupization particles, and its primary partical size has good stability less than 100nm in air.
Description of drawings
For to further understanding of the present invention, the present invention is described in detail with drawings and Examples.These embodiment are explanations exemplary to the present invention, are not limitations of the present invention, and the present invention is limited by appended claim.
Accompanying drawing 1 is to use TaCl
5Be dissolved in the liquefied ammonia XRD figure spectrum of the tantalum powder that hybrid reaction then obtains respectively with Na.
Accompanying drawing 2 be according to Hongmin zhu (Zhu Hongmin) and D.R.Sadoway (D.R. Sa Dewei) at J.Material Res., Vol.16, transmission electron microscope (TEM) the pattern photo of the fine tantalum powder of disclosed method preparation among the No.9.
Accompanying drawing 3～6th is according to transmission electron microscope (TEM) the pattern photo of the fine tantalum powder that obtains after the inventive method processing.
The specific embodiment
A representative instance form of implementation of the present invention is to use TaCl
5Be dissolved in tantalum and/or the niobium powder that the back hybrid reaction obtains in the liquefied ammonia with Na, with the isolated environment of air under, for example in inert gas filled glove box, put in the container of sealing, for example, tantalum and/or niobium powder are packed in the tantalum crucible, again tantalum crucible is put in the quartz ampoule container that can seal, find time in the top of quartz ampoule container, inflation, the mouth of pipe of gaging pressure and exhaust pipe mouth insert the quartz ampoule that the sample crucible is housed in the resistance-heated furnace, and temperature survey and control are carried out in the position near sample, before heating, quartz container is found time, for example be evacuated to pressure and be lower than 1 torr, charge into argon gas, be evacuated to again and be lower than 10
-3Torr is warmed up to holding temperature with 5～30 ℃/minute speed then and is incubated, and insulation cools to room temperature after finishing, carry out Passivation Treatment by slow importing air then, how much determine time of passivation according to sample, general passivation 5～60 minutes is taken out washing and drying with sample after the passivation.Pickling if necessary places glass beaker with sample, adds an amount of dilute acid soln, as HNO
3: H
2The O volume ratio is 1/10, carries out diafiltration with deionized water then, is neutral up to filtrate, then 50 ℃ of vacuum drying.The attritive powder of the tantalum that obtains and/or niobium is carried out the morphology analysis of chemical composition analysis and X-ray diffraction analysis and transmission electron microscope, and the line space of going forward side by side gas exposes experiment.
To the chemical composition analysis of the powder of tantalum and/or niobium, Ta, Nb adopt HF acid sample dissolution among the present invention, and the evaporate to dryness posthydrolysis precipitates to be analyzed; TC-463H oxygen, nitrogen combined measuring instrument that O, N adopt Leco company to produce are analyzed; H adopts the analysis of RH-2 hydrogen determinator; Na, Mg adopt atomic absorption spectrography (AAS) to analyze; Transmission electron microscope (TEM) analysis adopts HIT to produce the H-800 analytic electron microscope; XRD analysis adopts the Japanese MAC Science product MXP21VAHF of company type X-ray diffractometer.
Comparative example
With 5.0 gram TaCl
5Be dissolved in respectively in the liquefied ammonia at-40 ℃ with 1.7 gram Na, generate the black tantalum powder after the hybrid reaction, then with above-mentioned tantalum powder and NaCl, NH
3, Na separates, and obtains fine tantalum powder.To carry out chemical analysis, result such as table 1 after the above-mentioned fine tantalum powder taking-up.The XRD analysis result of tantalum powder such as accompanying drawing 1.The TEM pattern photo of tantalum powder as shown in Figure 2.The tantalum powder is 20～35 ℃ in temperature, and relative humidity is just to have become linen powder after exposing 72 hours in 30%～80% the air, and the oxygen, the nitrogen content that record this powder change as table 2.
Embodiment 1
To in being filled with the glove box of argon gas, put in the tantalum crucible according to the fine tantalum powder that obtains with the identical method of above-mentioned comparative example, and place the quartz ampoule container to seal in the above-mentioned crucible that sample is housed, the quartz ampoule container will be taken out from glove box.The quartz ampoule container is inserted in the heating furnace vacuumizes, after being evacuated down to pressure and being lower than 1 torr, charge into argon gas to 1 atmospheric pressure, be evacuated down to 10 again
-3Torr was warmed up to 500 ℃ with 150 minutes, kept that pressure is lower than 10 in the quartz ampoule container
-3Torr, 500 ℃ of insulations of furnace temperature 360 minutes are cooled to room temperature then, and passivation after 20 minutes is taken out sample, obtains tantalum powder 2.2 grams.Analyze the chemical composition of tantalum powder, data are listed in the table 1.The TEM pattern photo of tantalum powder as shown in Figure 3.The tantalum powder is 20～35 ℃ in temperature, and relative humidity is to expose 48 hours oxygen, nitrogen content in 30%～80% the air to change as table 2.
Embodiment 2
With 4.0 gram NbCl
5Be dissolved in respectively in the liquefied ammonia at-40 ℃ with 1.8 gram Na, generate the black niobium powder after the hybrid reaction, then with above-mentioned niobium powder and NaCl, NH
3, Na separates, and obtains fine niobium powder.With above-mentioned fine niobium powder and embodiment 1 the same heat-treating, 700 ℃ of insulations 300 minutes and keep always that pressure is about 10 in the quartz ampoule container
-2Torr, cool to room temperature then, passivation after 20 minutes is taken out sample, spends after the deionised water 50 ℃ of vacuum drying, obtains niobium powder 1.2 grams.The chemical composition of analyzing Nb powder, data rows is in table 1.The TEM pattern photo of niobium powder as shown in Figure 4.
Embodiment 3
The same with embodiment 1, be evacuated to 10
-3Torr is warmed up to 300 ℃ and charges into and keep the argon gas circulation behind the argon gas, is warmed up to 900 ℃ of insulations 240 minutes again, obtains tantalum powder 2.1 grams.Analyze the chemical composition of tantalum powder, data are listed in the table 1.The TEM pattern photo of tantalum powder as shown in Figure 5.The tantalum powder is 20～35 ℃ in temperature, and relative humidity is to expose 48 hours oxygen content in 30%～80% the air to change as in the table 2.
Embodiment 4
The same with embodiment 3, but in the crucible of fine tantalum powder of packing into, add 0.30 gram metal magnesium powder, being warmed up to 800 ℃ of insulations and heat-treating in 300 minutes, the fine tantalum powder that obtains is used HNO earlier
3: H
2The O volume ratio is that 1/10 solution soaked 10 minutes, spends deionised water then, obtains tantalum powder 2.1 grams after the oven dry, analyzes the chemical composition of tantalum powder, and data are listed in the table 1.The TEM pattern photo of tantalum powder as shown in Figure 6.The tantalum powder is 20～35 ℃ in temperature, and relative humidity is to expose 48 hours oxygen content in 30%～80% the air to change as in the table 2.
Table 1: the chemical composition of tantalum, niobium powder (wt.%)
| Ta | Nb | O | N | Na | |
| Comparative example | 83.77 | -- | 2.93 | 11.82 | 0.81 |
| Example 1 | 90.66 | -- | 2.11 | 8.88 | 0.52 |
| Example 2 | -- | 81.02 | 3.28 | 12.05 | 2.71 |
| Example 3 | 91.71 | -- | 2.16 | 6.29 | 0.31 |
| Example 4 | 91.59 | -- | 1.94 | 7.86 | 0.049 |
Table 2: the tantalum powder exposes the variation of O after 72 hours, N content (wt.%) in air
| Before in air, exposing | After in air, exposing | |||
| O | N | O | N | |
| Comparative example | 2.93 | 11.82 | 16.40 | 12.10 |
| Example 1 | 2.11 | 8.88 | 2.39 | 9.31 |
| Example 3 | 2.16 | 6.29 | 3.58 | 8.13 |
| Example 4 | 1.94 | 7.86 | 3.14 | 7.88 |
From the data of accompanying drawing 3-6 and table 2 as can be seen, the tantalum powder and/or the niobium powder of the inventive method preparation are the porous agglomerated particles, and its primary partical is less than 100 nanometers.Different with the fine tantalum powder for preparing according to disclosed method in J.Material Res.Vol.16 No.9 is that the tantalum and/or the niobium powder that prepare according to the inventive method have good stability in air, therefore, have good industrial utility value.
Can obviously find out from above description, according to the present invention by the powder of fine tantalum and/or niobium with the tantalite niobite power end of in non-oxidizing atmosphere, carrying out the high-temperature heat treatment preparation before oxygen-containing medium contacts, be a kind of stable fine nanoscale tantalum and/or niobium powder.
Claims (11)
1, the processing method of the powder of freshly prepd fine tantalum and/or niobium, before this method is included in described powder and oxygen-containing medium contacts, in non-oxidizing atmosphere, be 500 ℃～900 ℃ in temperature range and be incubated 60～720 minutes down, then cool to room temperature carries out Passivation Treatment, and wherein said nonoxidizing atmosphere is a vacuum, inert atmosphere, or the reducing atmosphere that in inert gas, has Ca, Mg, Li or Ce reducing metal element to exist.
2, the method for claim 1 is characterized in that, described non-oxidizing atmosphere is the vacuum that pressure is lower than 1 torr.
3, method as claimed in claim 2 is characterized in that, described non-oxidizing atmosphere is that pressure is lower than 10
-2The vacuum of torr.
4, method as claimed in claim 3 is characterized in that, described non-oxidizing atmosphere is that pressure is lower than 10
-3The vacuum of torr.
5, method as claimed in claim 4 is characterized in that, described non-oxidizing atmosphere is that pressure is lower than 10
-4The vacuum of torr.
6, the method for claim 1 is characterized in that, described non-oxidizing atmosphere is argon gas or helium atmosphere.
7, the method for claim 1 is characterized in that, described non-oxidizing atmosphere is the reducing atmosphere that has Ca or Mg reducing metal element to exist in inert gas,
8, as each described method among the claim 1-7, it is characterized in that, described freshly prepd fine tantalum and/or niobium powder adopt following method preparation: with at least a halide of tantalum, halide and a kind of reducing agent of niobium of being selected from, be lower than under the condensing temperature of ammonia (34 ℃), partly or entirely be dissolved in the liquefied ammonia, to be dissolved with then and at least aly be selected from the halide of tantalum, halid ammonia solution and a kind of ammonia solution that is dissolved with reducing agent of niobium mixes, and generates described tantalum and/or the niobium attritive powder of primary partical less than 100nm.
9, the method described in claim 8 is characterized in that, described reducing agent is an alkali metal.
10, as each described method among the claim 1-7, it is characterized in that, after carrying out above-mentioned processing, also carry out following processing: after Passivation Treatment, sample is taken out from heat treatment container, carry out pickling, washing and drying subsequently.
11, a kind of fine tantalum stable in oxygen-containing atmosphere and/or the powder of niobium, it is a porous groupization particle, its primary partical size can be obtained by each method among the claim 1-10 less than 100nm.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102554215A (en) * | 2011-12-29 | 2012-07-11 | 中国兵器工业第五二研究所 | Thermal treatment method for nanometer tantalum powder |
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| GB2450669B (en) * | 2006-05-05 | 2012-03-21 | Cabot Corp | Tantalam powder and methods of manufacturing same |
| CN101182602B (en) * | 2006-11-14 | 2010-04-14 | 宁夏东方钽业股份有限公司 | Tantalum and/or niobium powder for powder metallurgy and method of producing the same |
| CN101574741B (en) | 2009-06-25 | 2011-05-18 | 宁夏东方钽业股份有限公司 | Preparation method of tantalum powder for capacitor |
| JP5774766B2 (en) * | 2011-03-23 | 2015-09-09 | ニンシア オリエント タンタル インダストリー カンパニー、 リミテッド | Method and apparatus for passivating the surface of tantalum metal |
| CN104493156B (en) * | 2014-12-12 | 2016-09-14 | 中国兵器科学研究院宁波分院 | The heat treatment method of nano-tantalum |
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| CN109266868B (en) * | 2018-11-22 | 2020-12-01 | 深圳技术大学 | Method for recovering cadmium in cadmium sulfide |
| CN113020617A (en) * | 2021-02-26 | 2021-06-25 | 宁夏德运创润钛业有限公司 | Method for preparing ultrafine high-purity refractory metal powder |
| CN113500204A (en) * | 2021-07-08 | 2021-10-15 | 安徽理工大学 | Method for preparing fine niobium powder by thermal reduction of niobium chloride through calcium in calcium chloride molten salt |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102554215A (en) * | 2011-12-29 | 2012-07-11 | 中国兵器工业第五二研究所 | Thermal treatment method for nanometer tantalum powder |
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