JP6751043B2 - Tantalum nitride manufacturing method - Google Patents
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- JP6751043B2 JP6751043B2 JP2017060803A JP2017060803A JP6751043B2 JP 6751043 B2 JP6751043 B2 JP 6751043B2 JP 2017060803 A JP2017060803 A JP 2017060803A JP 2017060803 A JP2017060803 A JP 2017060803A JP 6751043 B2 JP6751043 B2 JP 6751043B2
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- MZLGASXMSKOWSE-UHFFFAOYSA-N tantalum nitride Chemical compound [Ta]#N MZLGASXMSKOWSE-UHFFFAOYSA-N 0.000 title claims description 66
- 238000004519 manufacturing process Methods 0.000 title claims description 12
- 239000000463 material Substances 0.000 claims description 37
- 239000011575 calcium Substances 0.000 claims description 32
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 30
- 239000001301 oxygen Substances 0.000 claims description 30
- 229910052760 oxygen Inorganic materials 0.000 claims description 30
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 28
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 claims description 28
- 229910052791 calcium Inorganic materials 0.000 claims description 26
- -1 calcium nitride Chemical class 0.000 claims description 24
- 229910001936 tantalum oxide Inorganic materials 0.000 claims description 22
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 11
- BWKDLDWUVLGWFC-UHFFFAOYSA-N calcium;azanide Chemical compound [NH2-].[NH2-].[Ca+2] BWKDLDWUVLGWFC-UHFFFAOYSA-N 0.000 claims description 8
- 239000011260 aqueous acid Substances 0.000 claims description 6
- 238000005121 nitriding Methods 0.000 description 33
- 238000006243 chemical reaction Methods 0.000 description 19
- 239000000047 product Substances 0.000 description 19
- 238000004090 dissolution Methods 0.000 description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 229910021529 ammonia Inorganic materials 0.000 description 10
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 10
- 229910052500 inorganic mineral Inorganic materials 0.000 description 10
- 239000011707 mineral Substances 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 9
- 229910052715 tantalum Inorganic materials 0.000 description 8
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 8
- 239000002253 acid Substances 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 229910052788 barium Inorganic materials 0.000 description 6
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 6
- 239000000292 calcium oxide Substances 0.000 description 6
- 239000011777 magnesium Substances 0.000 description 6
- 229910052749 magnesium Inorganic materials 0.000 description 6
- 229910052712 strontium Inorganic materials 0.000 description 6
- 239000011941 photocatalyst Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 238000000634 powder X-ray diffraction Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 4
- 229920002554 vinyl polymer Polymers 0.000 description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000004907 flux Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- JENCOQNWECEFQI-UHFFFAOYSA-N azanide;barium(2+) Chemical compound [NH2-].[NH2-].[Ba+2] JENCOQNWECEFQI-UHFFFAOYSA-N 0.000 description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 150000003949 imides Chemical class 0.000 description 2
- PKMBLJNMKINMSK-UHFFFAOYSA-N magnesium;azanide Chemical compound [NH2-].[NH2-].[Mg+2] PKMBLJNMKINMSK-UHFFFAOYSA-N 0.000 description 2
- 150000004767 nitrides Chemical class 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 2
- YWMYPVCADAAQCE-UHFFFAOYSA-N strontium;azanide Chemical compound [NH2-].[NH2-].[Sr+2] YWMYPVCADAAQCE-UHFFFAOYSA-N 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- XCNGEWCFFFJZJT-UHFFFAOYSA-N calcium;azanidylidenecalcium Chemical compound [Ca+2].[Ca]=[N-].[Ca]=[N-] XCNGEWCFFFJZJT-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 230000002940 repellent Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002887 superconductor Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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Description
本発明は、窒化タンタルの製造法に関する。 The present invention relates to a method for producing tantalum nitride.
窒化タンタル（Ｔａ3Ｎ5）は、顔料、誘電体や超電導体などとして使用される金属窒化物である。さらに、近年では炭酸ガス排出削減、再生可能エネルギーの観点から、太陽光エネルギーを利用して、光触媒により水を分解して、水素や酸素を製造する技術に注目が集まっており、窒化タンタルは光触媒として利用可能である（特許文献１）。 Tantalum nitride (Ta 3 N 5 ) is a metal nitride used as a pigment, a dielectric, a superconductor, and the like. In addition, in recent years, from the viewpoint of reducing carbon dioxide emissions and renewable energy, attention has been focused on the technology of producing hydrogen and oxygen by using solar energy to decompose water with a photocatalyst. (Patent Document 1).
一方で、光触媒に含まれる酸素は忌避成分となり、水素の発生を阻害する。そこで、酸素を含まない高純度の窒化タンタルが求められている。
非特許文献１では、酸化タンタル（Ｔａ２Ｏ５）をアンモニアで８００℃で窒化反応させることにより、窒化タンタルを得ている。特許文献１では、酸化タンタル（Ｔａ2Ｏ5）をアンモニア気流中、８５０℃で２５時間窒化することで窒化タンタルを得て、光触媒に用いている。
特許文献２では、フラックスの存在下または不存在下で酸化タンタルとアンモニアを５００〜１１００℃で窒化反応をさせることにより、窒化タンタルを得ている。
On the other hand, oxygen contained in the photocatalyst becomes a repellent component and inhibits the generation of hydrogen. Therefore, there is a demand for high-purity tantalum nitride containing no oxygen.
In Non-Patent Document 1, tantalum nitride is obtained by nitriding tantalum oxide (Ta 2 O 5 ) with ammonia at 800° C. In Patent Document 1, tantalum oxide (Ta 2 O 5 ) is nitrided in an ammonia stream at 850° C. for 25 hours to obtain tantalum nitride, which is used as a photocatalyst.
In Patent Document 2, tantalum nitride is obtained by nitriding tantalum oxide and ammonia at 500 to 1100° C. in the presence or absence of flux.
非特許文献１では、酸化タンタルをアンモニアで８００℃で窒化反応させることにより、窒化タンタルを得ている。しかし、得られる窒化タンタルは、酸素を含む窒化タンタルであり、酸素含有量の低い窒化タンタルは得られない。また、特許文献１記載の酸化タンタルとアンモニアの製造方法を追試したところ、窒化タンタル以外に酸窒化タンタルが生成し、酸素含有量が多く、純度が低いことが判明した。
特許文献２は、添加する融剤が分解して酸素を放出するため、酸化タンタルの窒化反応に影響し、窒化タンタルを酸化するため、酸素量が多くなる。また、融剤が溶解して酸化タンタル表面に吸着、付着すると、窒化反応が妨げられて、未反応の酸化タンタルが残存する。これらにより、窒化タンタルのみを得ることはできない。
In Non-Patent Document 1, tantalum nitride is obtained by nitriding tantalum oxide with ammonia at 800°C. However, the obtained tantalum nitride is tantalum nitride containing oxygen, and tantalum nitride having a low oxygen content cannot be obtained. Further, when the method for producing tantalum oxide and ammonia described in Patent Document 1 was additionally tested, it was found that tantalum oxynitride was generated in addition to tantalum nitride, the oxygen content was large, and the purity was low.
In Patent Document 2, the flux to be added decomposes and releases oxygen, which affects the nitriding reaction of tantalum oxide and oxidizes tantalum nitride, resulting in a large amount of oxygen. Further, when the flux is dissolved and adsorbed and adhered to the surface of tantalum oxide, the nitriding reaction is hindered and unreacted tantalum oxide remains. Due to these, it is not possible to obtain only tantalum nitride.
従って、本発明の課題は、酸素含有量が少なく、かつ単一相の窒化タンタルの工業的な製造方法を提供することにある。 Therefore, an object of the present invention is to provide an industrial production method of single phase tantalum nitride having a low oxygen content.
そこで本発明者は、前記課題を解決すべく検討した結果、酸化タンタルと２族元素系材料を出発原料として用い、８００〜９５０℃という特定の温度でアンモニアガスで窒化反応させ、得られる生成物を酸水溶液で処理することにより２族元素系材料が溶解して除去できるため、酸素量が少なく、かつ単相の窒化タンタルが選択的に得られることを見出した。 Therefore, as a result of studies to solve the above problems, the present inventor uses tantalum oxide and a Group 2 element-based material as a starting material, and performs a nitriding reaction with ammonia gas at a specific temperature of 800 to 950° C. to obtain a product obtained. It was found that the group 2 element-based material can be dissolved and removed by treating the compound with an acid aqueous solution, so that a single-phase tantalum nitride having a small oxygen content can be selectively obtained.
すなわち、本発明は、次の〔１〕〜〔６〕を提供するものである。
〔１〕酸化タンタルと２族元素系材料との混合物を、８００〜９５０℃、アンモニアガス下で窒化後、酸水溶液処理することを特徴とする窒化タンタルの製造法。
〔２〕２族元素系材料が、カルシウム系材料、マグネシウム系材料、ストロンチウム系材料及びバリウム系材料から選ばれる材料である〔１〕記載の窒化タンタルの製造法。
〔３〕２族元素系材料が、窒化カルシウム、カルシウムアミド、カルシウムイミド、窒化マグネシウム、マグネシウムアミド、マグネシウムイミド、窒化ストロンチウム、ストロンチウムアミド、ストロンチウムイミド、窒化バリウム、バリウムアミド及びバリウムイミドから選ばれる材料である〔１〕又は〔２〕記載の窒化タンタルの製造法。
〔４〕酸化タンタルと２族元素系材料との混合比が、酸化タンタル１モルに対して２族元素系材料中の２族元素が３〜２０モルである〔１〕〜〔３〕のいずれかに記載の窒化タンタルの製造法。
〔５〕得られる窒化タンタルの酸素含有量が１質量％以下である〔１〕〜〔４〕のいずれかに記載の窒化タンタルの製造法。
〔６〕酸素含有量が１質量％以下である高純度窒化タンタル。
That is, the present invention provides the following [1] to [6].
[1] A method for producing tantalum nitride, which comprises nitriding a mixture of tantalum oxide and a Group 2 element-based material at 800 to 950° C. under ammonia gas and then treating with an aqueous acid solution.
[2] The method for producing tantalum nitride according to [1], wherein the Group 2 element-based material is a material selected from calcium-based materials, magnesium-based materials, strontium-based materials, and barium-based materials.
[3] The group 2 element-based material is a material selected from calcium nitride, calcium amide, calcium imide, magnesium nitride, magnesium amide, magnesium imide, strontium nitride, strontium amide, strontium imide, barium nitride, barium amide, and barium imide. The method for producing tantalum nitride according to [1] or [2].
[4] Any one of [1] to [3] in which the mixing ratio of the tantalum oxide and the Group 2 element-based material is 3 to 20 moles of the Group 2 element in the Group 2 element-based material with respect to 1 mole of tantalum oxide. The method for producing tantalum nitride according to claim 1.
[5] The method for producing tantalum nitride according to any one of [1] to [4], wherein the obtained tantalum nitride has an oxygen content of 1% by mass or less.
[6] High-purity tantalum nitride having an oxygen content of 1% by mass or less.
本発明方法によれば、酸素量が少なく高純度の窒化タンタルが工業的に有利に製造できる。また、本発明の窒化タンタルは、酸素含有量が少なく高純度であり、可視光で触媒作用を有する光触媒として有用である。 According to the method of the present invention, highly pure tantalum nitride containing a small amount of oxygen can be industrially advantageously produced. Further, the tantalum nitride of the present invention has a low oxygen content and high purity, and is useful as a photocatalyst having a catalytic action with visible light.
本発明の窒化タンタル（Ｔａ3Ｎ5）の製造方法は、酸化タンタル（Ｔａ2Ｏ5）と２族元素系材料と材料を出発原料として用い、８００〜９５０℃という特定の温度でアンモニアガスで窒化反応させ、得られる生成物を酸水溶液処理することを特徴とする。 The method for producing tantalum nitride (Ta 3 N 5 ) of the present invention uses tantalum oxide (Ta 2 O 5 ), a Group 2 element-based material and materials as starting materials, and uses ammonia gas at a specific temperature of 800 to 950° C. The nitriding reaction is performed, and the resulting product is treated with an aqueous acid solution.
本発明に用いる原料は、酸化タンタル（Ｔａ2Ｏ5）である。このような酸化タンタルを原料として用いるにもかかわらず、本発明においては、２族元素系材料と混合し、アンモニアと窒化反応することにより、高純度で酸素含有量の少ない窒化タンタルが得られる。
酸化タンタル（Ｔａ2Ｏ5）としては、粒子径１μｍ程度の通常の市販品を用いることができる。
The raw material used in the present invention is tantalum oxide (Ta 2 O 5 ). In spite of using such tantalum oxide as a raw material, in the present invention, tantalum nitride having a high purity and a low oxygen content can be obtained by mixing with a group 2 element material and nitriding with ammonia.
As tantalum oxide (Ta 2 O 5 ), a usual commercial product having a particle diameter of about 1 μm can be used.
２族元素系材料としては、カルシウム系材料、マグネシウム系材料、ストロンチウム系材料及びバリウム系材料から選ばれる１種以上を用いることができる。好ましくは酸水溶液による除去性の点から、２族元素窒化物、２族元素アミド又は２族元素イミドが挙げられる。具体的には、窒化カルシウム、カルシウムアミド、カルシウムイミド、窒化マグネシウム、マグネシウムアミド、マグネシウムイミド、窒化ストロンチウム、ストロンチウムアミド、ストロンチウムイミド、窒化バリウム、バリウムアミド及びバリウムイミドから選ばれる１種又は２種以上が挙げられ、このうち窒化カルシウム（Ｃａ3Ｎ2）、カルシウムアミド（Ｃａ（ＮＨ2）2）及びカルシウムイミド（ＣａＮＨ）から選ばれる１種以上を用いるのが経済性及び酸水溶液処理による除去性の点からより好ましい。 As the Group 2 element-based material, one or more selected from calcium-based materials, magnesium-based materials, strontium-based materials and barium-based materials can be used. From the viewpoint of removability with an aqueous acid solution, a Group 2 element nitride, a Group 2 element amide or a Group 2 element imide is preferable. Specifically, one or more selected from calcium nitride, calcium amide, calcium imide, magnesium nitride, magnesium amide, magnesium imide, strontium nitride, strontium amide, strontium imide, barium nitride, barium amide and barium imide. Among them, it is economical to use calcium nitride (Ca 3 N 2 ), calcium amide (Ca(NH 2 ) 2 ), and calcium imide (CaNH), and the removability by acid aqueous solution treatment is preferable. It is more preferable from the point.
これらの２族元素系材料（式ではカルシウム系材料の例）を用いることにより、式（１）〜式（３）に示すように酸化タンタルから窒化タンタルへの窒化反応で発生する酸素を２族元素系材料中の２族元素が安定な酸化２族元素（例えば酸化カルシウム）として固定して酸素濃度を低下させ、窒化タンタルの酸化を防止する。 By using these Group 2 element-based materials (in the formula, examples of calcium-based materials), oxygen generated in the nitriding reaction from tantalum oxide to tantalum nitride is converted into Group 2 as shown in Formulas (1) to (3). The Group 2 element in the elemental material is fixed as a stable Group 2 oxide element (for example, calcium oxide) to reduce the oxygen concentration and prevent the oxidation of tantalum nitride.
３Ｔａ２Ｏ５＋５Ｃａ３Ｎ２→２Ｔａ３Ｎ５＋１５ＣａＯ 式（１）
３Ｔａ２Ｏ５＋１５Ｃａ（ＮＨ２）２→
２Ｔａ３Ｎ５＋１５ＣａＯ＋２０ＮＨ３ 式（２）
３Ｔａ２Ｏ５＋１５ＣａＮＨ→２Ｔａ３Ｎ５＋１５ＣａＯ＋５ＮＨ３ 式（３）
3Ta 2 O 5 +5Ca 3 N 2 →2Ta 3 N 5 +15CaO Formula (1)
3Ta 2 O 5 +15Ca(NH 2 ) 2 →
2Ta 3 N 5 +15CaO+20NH 3 Formula (2)
3Ta 2 O 5 +15CaNH→2Ta 3 N 5 +15CaO+5NH 3 Formula (3)
また、カルシウムアミド（Ｃａ（ＮＨ２）２）、カルシウムイミド（ＣａＮＨ）等の２族元素系アミド、２族元素系イミドは、酸化タンタルから窒化タンタルへの窒化反応で発生する酸素を２族元素系材料中の２族元素が安定な酸化２族元素として固定するとき、アンモニアを発生し、アンモニア濃度を高くすることができる。そのため、窒化タンタルを安定して生成することができ、窒化反応に使用するアンモニアの量を減らすことができるため、より好ましい。 In addition, Group 2 element-based amides such as calcium amide (Ca(NH 2 ) 2 ) and calcium imide (CaNH), and Group 2 element-based imides generate oxygen generated by a nitriding reaction from tantalum oxide to tantalum nitride as a Group 2 element. When the Group 2 element in the system material is fixed as a stable Group 2 oxide element, ammonia is generated and the ammonia concentration can be increased. Therefore, tantalum nitride can be stably generated, and the amount of ammonia used in the nitriding reaction can be reduced, which is more preferable.
酸化タンタルと２族元素系材料の混合比（モル比）は、酸化タンタル（Ｔａ2Ｏ5）１モルに対して２族元素系材料中の２族元素が３〜２０モルが好ましく、より好ましくは４〜１０モル、さらに好ましくは５〜７モルである。混合比が３〜２０の範囲内であれば、これらの材料による酸素の固定が十分となり、窒化タンタルの酸化が防止でき酸素含有量が少なくなる。また、２族元素系材料の使用量が過剰にならず、製造できる窒化タンタルの量が多くなり、製造コストが抑制でき、酸水溶液による溶解工程と洗浄工程が短縮される。 The mixing ratio (molar ratio) of tantalum oxide and the Group 2 element-based material is preferably 3 to 20 moles of the Group 2 element in the Group 2 element-based material, and more preferably 1 mole of tantalum oxide (Ta 2 O 5 ). Is 4 to 10 mol, more preferably 5 to 7 mol. When the mixing ratio is in the range of 3 to 20, the fixation of oxygen by these materials is sufficient, the oxidation of tantalum nitride can be prevented, and the oxygen content decreases. In addition, the amount of the Group 2 element-based material used does not become excessive, the amount of tantalum nitride that can be manufactured increases, the manufacturing cost can be suppressed, and the dissolution process and the cleaning process using the acid aqueous solution can be shortened.
窒化する温度（加熱温度）は、８００℃以上９５０℃以下である。８００℃未満の場合、窒化が十分に進行しない。９５０℃超の場合、窒化タンタルから窒素が放出され金属タンタルとなるため高純度の窒化タンタルが得られない。より好ましい窒化温度は、８００℃以上９００℃以下である。 The nitriding temperature (heating temperature) is 800° C. or higher and 950° C. or lower. When the temperature is lower than 800°C, nitriding does not proceed sufficiently. If it exceeds 950° C., nitrogen is released from the tantalum nitride to form metal tantalum, so that high-purity tantalum nitride cannot be obtained. A more preferable nitriding temperature is 800° C. or higher and 900° C. or lower.
窒化する際のアンモニアガス量は、酸化タンタル１ｇあたり０．０１Ｌ／ｍｉｎ以上０．８Ｌ／ｍｉｎ以下が好ましい。さらに好ましくは、０．０２Ｌ／ｍｉｎ以上０．５Ｌ／ｍｉｎ以下である。アンモニアガス量がこの範囲であれば、窒化時間が短く、工業的に有利である。また、窒化に使用されないアンモニアガス量が抑制でき、製造コストを抑制できる。 The amount of ammonia gas at the time of nitriding is preferably 0.01 L/min or more and 0.8 L/min or less per 1 g of tantalum oxide. More preferably, it is 0.02 L/min or more and 0.5 L/min or less. When the amount of ammonia gas is within this range, the nitriding time is short, which is industrially advantageous. Further, the amount of ammonia gas not used for nitriding can be suppressed, and the manufacturing cost can be suppressed.
また、加熱時間は、加熱温度との関係で決定され、窒化を十分に進行させ、Ｔａ3Ｎ5を高純度で生成させる点から、加熱温度（℃）と加熱時間（ｈｒ）の積が、１００００〜２５０００になる時間が好ましい。この加熱時間が１００００未満の場合には、窒化が十分に進行しないおそれがある。より好ましい前記積は１２０００〜２００００であり、さらに好ましくは１６０００〜２００００である。
具体的な加熱時間は１３〜３０時間が好ましく、１５〜３０時間がより好ましい。なお、ここで加熱時間は、８００〜９５０℃の範囲に加熱されている時間である。
Further, the heating time is determined in relation to the heating temperature, and the product of the heating temperature (° C.) and the heating time (hr) is determined from the viewpoint that nitriding is sufficiently advanced and Ta 3 N 5 is produced with high purity. A time of 10,000 to 25,000 is preferable. If this heating time is less than 10,000, nitriding may not proceed sufficiently. The more preferable product is 12,000 to 20,000, and further preferably 16,000 to 20,000.
The specific heating time is preferably 13 to 30 hours, more preferably 15 to 30 hours. The heating time here is the time of heating in the range of 800 to 950°C.
反応装置は、１０００℃程度の熱に耐えられる装置であればよく、例えば、管状炉、電気炉、バッチ式キルン、ロータリーキルンを用いれば良い。 The reactor may be a device that can withstand heat of about 1000° C., and for example, a tubular furnace, an electric furnace, a batch kiln, or a rotary kiln may be used.
窒化反応により得られる生成物は、窒化タンタルと酸化２族元素であり、２族元素系材料の添加量によっては２族元素系材料が未反応として残存することである。
窒化タンタルは難溶解性物質であり、一方、２族元素酸化物、２族元素系材料は酸水溶液に溶解する。以下、カルシウム系材料を例にとって説明する。窒化タンタル、酸化カルシウム、未反応のカルシウム系材料を含む生成物は、塩酸、硝酸の酸水溶液により処理することで、酸化カルシウムとカルシウム系材料が溶解し、窒化タンタルは溶解しないため、粉末として分離できる。生成物を溶解する方法は、水に生成物を添加、撹拌してから、塩酸や硝酸を滴下して溶解する方法、水に塩酸や硝酸などの酸を混合して希釈した酸水溶液に生成物を添加、撹拌して溶解する方法がある。このとき使用する水は、イオン交換水、蒸留水などの不純物の少ないものが好ましい。
The product obtained by the nitriding reaction is tantalum nitride and a Group 2 oxide element, and the Group 2 element-based material remains unreacted depending on the addition amount of the Group 2 element-based material.
Tantalum nitride is a hardly soluble substance, while Group 2 element oxides and Group 2 element-based materials dissolve in aqueous acid solutions. Hereinafter, a calcium-based material will be described as an example. Products containing tantalum nitride, calcium oxide, and unreacted calcium-based material are treated as an aqueous acid solution of hydrochloric acid and nitric acid to dissolve calcium oxide and calcium-based materials, but not tantalum nitride. it can. The method of dissolving the product is to add the product to water, stir it, and then add hydrochloric acid or nitric acid dropwise to dissolve it, or to mix the acid such as hydrochloric acid or nitric acid with water to dilute the product. There is a method of adding, stirring and dissolving. The water used at this time is preferably water with few impurities such as ion-exchanged water and distilled water.
酸化カルシウムと未反応のカルシウム系材料は、水や空気と反応すると、発熱、アンモニアの発生などが起きる。窒化反応が終了し、冷却（室温程度）後、管状炉内に空気、炭酸ガス、水分を含むガスを吹き込み、水との反応性が穏やかな水酸化カルシウムや炭酸カルシウムとしてもよい。これらの化合物も、酸に溶解させること、窒化タンタルを分離することができる。
溶解処理後、窒化タンタルをろ過して、回収する。窒化タンタルにカルシウムが溶解した水溶液が付着しているため、水で洗浄し、付着しているカルシウムを除去する。洗浄後、粉末の窒化タンタルを回収、乾燥して、窒化タンタル粉末を得られる。
When a calcium-based material that has not reacted with calcium oxide reacts with water or air, heat is generated and ammonia is generated. After completion of the nitriding reaction and cooling (about room temperature), air, carbon dioxide gas, and a gas containing water may be blown into the tubular furnace to form calcium hydroxide or calcium carbonate having a mild reactivity with water. These compounds can also be dissolved in acid to separate tantalum nitride.
After the dissolution treatment, the tantalum nitride is filtered and collected. Since the aqueous solution in which calcium is dissolved adheres to tantalum nitride, it is washed with water to remove the adhered calcium. After washing, the powder of tantalum nitride is collected and dried to obtain tantalum nitride powder.
乾燥は、熱風式乾燥器、真空式乾燥器などの乾燥器であればよく、窒化タンタルに付着している水分を除去できればよい。 Drying may be performed using a dryer such as a hot air dryer or a vacuum dryer, as long as the moisture adhering to tantalum nitride can be removed.
得られる窒化タンタルは、窒化タンタルのみからなり、酸素含有量は１質量％以下が好ましく、０．８５質量％以下であるのがより好ましい。酸素含有量が、１質量％以下の窒化タンタルは光触媒として特に有用である。 The obtained tantalum nitride is composed of only tantalum nitride, and the oxygen content is preferably 1% by mass or less, more preferably 0.85% by mass or less. Tantalum nitride having an oxygen content of 1 mass% or less is particularly useful as a photocatalyst.
次に実施例を挙げて、本発明を詳細に説明する。
・使用した原料
酸化タンタル：三井金属鉱業(株)製、白色粉末
カルシウムアミド：太平洋セメント(株)製、金属カルシウムをアミド化したもの
カルシウムイミド：太平洋セメント(株)製、金属カルシウムをイミド化したもの
窒化カルシウム：太平洋セメント(株)製、金属カルシウムを窒化したもの
Next, the present invention will be described in detail with reference to examples.
・Raw materials used Tantalum oxide: Mitsui Mining & Smelting Co., Ltd., white powder Calcium amide: Taiheiyo Cement Co., Ltd., amidated calcium metal calcium imide: Taiheiyo Cement Co., Ltd., metallic calcium imidized Calcium nitride: Taiheiyo Cement Co., Ltd., nitriding metallic calcium
実施例１
グローブボックス内で、酸化タンタル２０ｇとカルシウムアミド２０ｇを計量し、ビニール袋で混合をした混合原料（Ｃａ／Ｔａ２Ｏ５モル比＝６．１）をアルミナボートに入れ、アルミナ製の炉芯管に入れ、両端をバルブ付きの蓋をして、取り出した。炉芯管を管状炉に設置し、９００℃、２０時間、アンモニアガス流量を１Ｌ／ｍｉｎ（０．０５Ｌ／ｍｉｎ・Ｔａ2Ｏ5−ｇ）で窒化反応を行った。冷却後、炉芯管から試料を取り出し、窒化反応後の生成物の鉱物組成を粉末Ｘ線回折（ＸＲＤ）で同定を行った結果、窒化タンタル（Ｔａ３Ｎ５）と酸化カルシウム（ＣａＯ）であり、窒化反応後の生成物のＸＲＤパターンを図１に示す。
試料１５ｇを０．５ｍｏｌ／Ｌの塩酸３００ｍＬに添加、撹拌し、溶解後、吸引ろ過を行い、窒化タンタルとカルシウムが溶解している水溶液と分離し、窒化タンタルを水で洗浄し、付着しているカルシウムを除去し、乾燥を行った。乾燥後、溶解後の試料の鉱物組成をＸＲＤで同定を行った結果、窒化タンタル（Ｔａ３Ｎ５）のみであった。溶解後の試料のＸＲＤパターンを図２に示す。
溶解後の試料の酸素含有量は、０．６質量％であった。
Example 1
In a glove box, 20 g of tantalum oxide and 20 g of calcium amide were weighed and mixed in a vinyl bag, and the mixed raw material (Ca/Ta 2 O 5 molar ratio=6.1) was put into an alumina boat to make a furnace core tube made of alumina. Then, the both ends were covered with a valve and removed. The furnace core tube was installed in a tubular furnace, and a nitriding reaction was performed at 900° C. for 20 hours at an ammonia gas flow rate of 1 L/min (0.05 L/min·Ta 2 O 5 -g). After cooling, the sample was taken out from the furnace core tube, and the mineral composition of the product after the nitriding reaction was identified by powder X-ray diffraction (XRD). As a result, tantalum nitride (Ta 3 N 5 ) and calcium oxide (CaO) were used. Yes, the XRD pattern of the product after the nitriding reaction is shown in FIG.
15 g of the sample was added to 300 mL of 0.5 mol/L hydrochloric acid, stirred, dissolved, and then suction filtered to separate the tantalum nitride and the calcium-dissolved aqueous solution from each other. The tantalum nitride was washed with water and attached. The remaining calcium was removed and drying was performed. After drying, the mineral composition of the sample after dissolution was identified by XRD, and as a result, it was only tantalum nitride (Ta 3 N 5 ). The XRD pattern of the sample after dissolution is shown in FIG.
The oxygen content of the sample after dissolution was 0.6% by mass.
実施例２
酸化タンタル２０ｇとカルシウムアミド１８ｇを計量し、ビニール袋で混合をした混合試料（Ｃａ／Ｔａ２Ｏ５モル比＝５．５）をアルミナボードに入れ、以下実施例１と同様に行った。
窒化反応後の生成物の鉱物組成は窒化タンタル（Ｔａ３Ｎ５）と酸化カルシウム（ＣａＯ）であり、溶解後の試料の鉱物組成は、窒化タンタル（Ｔａ３Ｎ５）のみであった。溶解後の試料の酸素含有量は、０．７質量％であった。
Example 2
20 g of tantalum oxide and 18 g of calcium amide were weighed and mixed in a vinyl bag, a mixed sample (Ca/Ta 2 O 5 molar ratio=5.5) was put into an alumina board, and the same procedure as in Example 1 was performed.
The mineral composition of the product after the nitriding reaction was tantalum nitride (Ta 3 N 5 ) and calcium oxide (CaO), and the mineral composition of the sample after dissolution was only tantalum nitride (Ta 3 N 5 ). The oxygen content of the sample after dissolution was 0.7% by mass.
実施例３
酸化タンタル２０ｇとカルシウムイミド１３ｇを計量し、ビニール袋で混合をした混合試料（Ｃａ／Ｔａ２Ｏ５モル比＝５．２）をアルミナボードに入れ、以下実施例１と同様に行った。
窒化反応後の生成物の鉱物組成は窒化タンタル（Ｔａ３Ｎ５）と酸化カルシウム（ＣａＯ）であり、溶解後の試料の鉱物組成は、窒化タンタル（Ｔａ３Ｎ５）のみであった。溶解後の試料の酸素含有量は、０．５質量％であった。
Example 3
20 g of tantalum oxide and 13 g of calcium imide were weighed and mixed in a vinyl bag, and a mixed sample (Ca/Ta 2 O 5 molar ratio=5.2) was put into an alumina board and the same procedure as in Example 1 was performed.
The mineral composition of the product after the nitriding reaction was tantalum nitride (Ta 3 N 5 ) and calcium oxide (CaO), and the mineral composition of the sample after dissolution was only tantalum nitride (Ta 3 N 5 ). The oxygen content of the sample after dissolution was 0.5% by mass.
実施例４
酸化タンタル２０ｇと窒化カルシウム１２ｇを計量し、ビニール袋で混合をした混合試料（Ｃａ／Ｔａ２Ｏ５モル比＝５．４）をアルミナボードに入れ、以下実施例１と同様に行った。
窒化反応後の生成物の鉱物組成は窒化タンタル（Ｔａ３Ｎ５）と酸化カルシウム（ＣａＯ）であり、溶解後の試料の鉱物組成は、窒化タンタル（Ｔａ３Ｎ５）のみであった。溶解後の試料の酸素含有量は、０．６質量％であった。
Example 4
20 g of tantalum oxide and 12 g of calcium nitride were weighed and mixed in a vinyl bag, and a mixed sample (Ca/Ta 2 O 5 molar ratio=5.4) was put into an alumina board and the same procedure as in Example 1 was performed.
The mineral composition of the product after the nitriding reaction was tantalum nitride (Ta 3 N 5 ) and calcium oxide (CaO), and the mineral composition of the sample after dissolution was only tantalum nitride (Ta 3 N 5 ). The oxygen content of the sample after dissolution was 0.6% by mass.
比較例１
グローブボックス内で、酸化タンタル２０ｇをアルミナボートに入れ、以下実施例１と同様に行った。
窒化反応後の生成物の鉱物組成は窒化タンタル（Ｔａ３Ｎ５）と酸窒化タンタル（ＴａＯＮ）であり、溶解後の試料の鉱物組成も窒化タンタル（Ｔａ３Ｎ５）と酸窒化タンタル（ＴａＯＮ）であった。溶解後の試料の酸素含有量は、２．５質量％であった。
Comparative Example 1
In the glove box, 20 g of tantalum oxide was placed in an alumina boat, and the same procedure as in Example 1 was performed.
The mineral composition of the product after the nitriding reaction is tantalum nitride (Ta 3 N 5 ) and tantalum oxynitride (TaON), and the mineral composition of the sample after dissolution is also tantalum nitride (Ta 3 N 5 ) and tantalum oxynitride (TaON). )Met. The oxygen content of the sample after dissolution was 2.5% by mass.
実施例１〜４は、窒化反応後の生成物は、窒化タンタルと酸化カルシウムであり、比較例１は、窒化タンタルと酸窒化タンタルであった。これらの生成物を０．５ｍｏｌ／Ｌの塩酸で溶解処理した結果、実施例１〜４は、酸化カルシウムが溶解し、酸素含有量が０．５〜０．７質量％と低い窒化タンタルのみが得られた。
しかし、比較例１は、０．５ｍｏｌ／Ｌの塩酸で溶解処理しても、酸窒化タンタルは溶解しないため、窒化タンタルと酸窒化タンタルの混合物であり、酸素含有量は２．５質量％と高かった。
In Examples 1 to 4, the products after the nitriding reaction were tantalum nitride and calcium oxide, and in Comparative Example 1, tantalum nitride and tantalum oxynitride. As a result of subjecting these products to dissolution treatment with 0.5 mol/L hydrochloric acid, in Examples 1 to 4, calcium oxide was dissolved, and only tantalum nitride having a low oxygen content of 0.5 to 0.7 mass% was used. Was obtained.
However, Comparative Example 1 is a mixture of tantalum oxynitride and tantalum oxynitride because the tantalum oxynitride does not dissolve even when subjected to dissolution treatment with 0.5 mol/L hydrochloric acid, and the oxygen content is 2.5% by mass. it was high.
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