JP2539712B2 - Nitride powder - Google Patents
Nitride powderInfo
- Publication number
- JP2539712B2 JP2539712B2 JP3269037A JP26903791A JP2539712B2 JP 2539712 B2 JP2539712 B2 JP 2539712B2 JP 3269037 A JP3269037 A JP 3269037A JP 26903791 A JP26903791 A JP 26903791A JP 2539712 B2 JP2539712 B2 JP 2539712B2
- Authority
- JP
- Japan
- Prior art keywords
- powder
- nitride
- grain size
- crystal grain
- nitrogen gas
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 239000000843 powder Substances 0.000 title claims description 95
- 150000004767 nitrides Chemical class 0.000 title claims description 46
- 239000013078 crystal Substances 0.000 claims description 36
- 239000010936 titanium Substances 0.000 claims description 35
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 33
- 239000010955 niobium Substances 0.000 claims description 31
- 229910052751 metal Inorganic materials 0.000 claims description 28
- 239000002184 metal Substances 0.000 claims description 28
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 26
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 23
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 21
- 239000012298 atmosphere Substances 0.000 claims description 19
- 239000002159 nanocrystal Substances 0.000 claims description 17
- 229910052758 niobium Inorganic materials 0.000 claims description 16
- 229910052782 aluminium Inorganic materials 0.000 claims description 14
- 229910052719 titanium Inorganic materials 0.000 claims description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 8
- 229910052742 iron Inorganic materials 0.000 claims description 7
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 6
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 6
- 238000005245 sintering Methods 0.000 description 20
- 239000000463 material Substances 0.000 description 14
- 238000000034 method Methods 0.000 description 14
- 238000010521 absorption reaction Methods 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 9
- 239000010935 stainless steel Substances 0.000 description 7
- 229910001220 stainless steel Inorganic materials 0.000 description 7
- 229910010037 TiAlN Inorganic materials 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 239000002131 composite material Substances 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 238000001000 micrograph Methods 0.000 description 4
- 239000011812 mixed powder Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229910018509 Al—N Inorganic materials 0.000 description 2
- 102220479482 Puromycin-sensitive aminopeptidase-like protein_C21D_mutation Human genes 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 238000007545 Vickers hardness test Methods 0.000 description 2
- 238000005275 alloying Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000010574 gas phase reaction Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 229910002593 Fe-Ti Inorganic materials 0.000 description 1
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000005280 amorphization Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 238000007542 hardness measurement Methods 0.000 description 1
- 238000007373 indentation Methods 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 238000005551 mechanical alloying Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 238000005121 nitriding Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- -1 titanium-aluminum-nitrogen Chemical compound 0.000 description 1
- 239000011882 ultra-fine particle Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/06—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
- C01B21/0602—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron with two or more other elements chosen from metals, silicon or boron
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/06—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
- C01B21/076—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron with titanium or zirconium or hafnium
Description
【０００１】[0001]
【産業上の利用分野】本発明は、極めて微細な結晶組織
乃至非晶質組織を有する窒化物粉体に関する。さらに詳
しくは、超微細粒組織を有し、圧粉焼結によるセラミッ
クスや金属ーセラミックス複合焼結材の作製に好適な窒
化物粉体に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a nitride powder having an extremely fine crystal structure or amorphous structure. More specifically, the present invention relates to a nitride powder having an ultrafine grain structure and suitable for producing a ceramic or a metal-ceramic composite sintered material by powder compaction sintering.
【０００２】[0002]
【従来の技術】金属窒化物は高硬度・高耐食性・高温耐
久性等を有するため、超硬工具やその他各種の材料とし
て広い用途を有するものである。従って金属窒化物を粉
体として大量に得ることは、それの焼結体を経て上記用
途に提供できる点で非常に重要なこととなる。従来、金
属窒化物粉体は、窒化物形成金属元素の粉末原料を、高
温・高圧の窒素ガス雰囲気下に保持して製造する方法が
用いられている。この方法は、主として窒化チタンのよ
うな二元窒化物を製造する方法であり、例えば特開昭61
-132505号公報には、プラズマ、アークなどの任意の熱
源によりＴｉ材を溶解し、溶融Ｔｉを窒素ガスで噴霧す
ることにより、ＴｉＮ粉末を製造する方法が開示されて
いる。2. Description of the Related Art Since metal nitrides have high hardness, high corrosion resistance, high temperature durability, etc., they have wide applications as cemented carbide tools and various other materials. Therefore, it is very important to obtain a large amount of metal nitride as a powder in that it can be provided for the above-mentioned use via the sintered body thereof. Conventionally, a method of manufacturing a metal nitride powder by holding a powder material of a nitride-forming metal element in a nitrogen gas atmosphere at high temperature and high pressure has been used. This method is mainly a method for producing a binary nitride such as titanium nitride.
-132505 discloses a method for producing TiN powder by melting a Ti material with an arbitrary heat source such as plasma or arc and spraying molten Ti with nitrogen gas.
【０００３】しかしながら、上記のような方法では例え
ばチタンーアルミニウムー窒素のような三元窒化物を製
造することは困難である。一方上記三元窒化物の製造に
関しては、例えば特開昭60-171271号公報に開示されて
いる方法やマグネトロンスパッタリング法を利用した特
殊な方法が公知であるが、前者の方法ではＴi2ＡlＮ粉
末を製造できるが高温での耐酸化性が非常に良好とされ
ているＴiＡlＮ粉末を製造することはできないものであ
る。また後者の方法ではＴiＡlＮを得ることはできるも
のの、装置がおおげさになる上、窒化物は対象物にスパ
ッタリングされた薄膜状であり、これを剥離して微粉末
化しても極く微量しか得られず、コスト的に非常に高価
なものになるという欠点があった。However, it is difficult to produce a ternary nitride such as titanium-aluminum-nitrogen by the above method. On the other hand, regarding the production of the ternary nitride, a method disclosed in, for example, JP-A-60-171271 and a special method utilizing a magnetron sputtering method are known, but in the former method, Ti 2 AlN powder is used. However, TiAlN powder, which is said to have very good oxidation resistance at high temperature, cannot be produced. In addition, although TiAlN can be obtained by the latter method, the apparatus is overwhelming and the nitride is in the form of a thin film sputtered on the object. Even if it is peeled off and made into fine powder, only a very small amount can be obtained. However, there is a drawback that the cost becomes very expensive.
【０００３】上記述べた従来の方法により得られる窒化
物の粉体の致命的な欠点は、その結晶粒径が数ミクロン
メータのオーダーのものであって粒径が非常に大きく、
焼結体とするときの焼結温度は約１４００℃以上と非常
に高い温度を必要とするばかりか、得られる焼結体も粗
大結晶粒であるために非常に脆く、クラックの発生も甚
だしくて靭性に乏しいものであった。The fatal drawback of the nitride powder obtained by the above-mentioned conventional method is that the crystal grain size is on the order of several micrometers, and the grain size is very large.
The sintering temperature required for forming a sintered body is about 1400 ° C. or higher, which is extremely high, and the sintered body obtained is also very brittle because of its coarse crystal grains, and cracks are not very serious. It was poor in toughness.
【０００４】[0004]
【発明が解決しようとする課題】本発明の解決しようと
する課題は、結晶粒径が非常に小さく乃至非晶質で、か
つ均質な窒化物粉体を安価且つ大量に提供することであ
る。SUMMARY OF THE INVENTION An object of the present invention is to provide a large amount of inexpensive and uniform nitride powder having a very small crystal grain size or an amorphous grain size.
【０００５】[0005]
【課題を解決するための手段】本発明の発明者は、特定
の金属塊又はその粉末を窒素ガス雰囲気下で振動させる
ことにより固相ー気相反応を行わせ、この結果、結晶粒
径が数10ｎｍ以下の超微細粒組織を有する窒化物粉体を
得るに至った。本発明の窒化物粉体における上記超微細
粒組織は、最高でも60〜70ｎｍ程度の結晶粒径で、大部
分の結晶粒径は数ｎｍにあるものであり、該粉体１粒子
中の結晶構造がすべて数10ｎｍ以下の結晶粒径にあるも
の、及びこの粒径範囲にある非晶質構造をいう。本願発
明の窒化物粉体を得るための振動としては、通常、固相
反応による合金化を対象とするメカニカルアロイング
（以下ＭＡと略す）法が好適に利用できる。 尚、ＭＡ
法とは、加振装置(通常は、高エネルギーボールミル)中
に所定の材料をボールと共に入れて加振し、材料に強度
の振動エネルギーを与えて材料を微粉化すると同時に材
料の表面を活性化し、高温に加熱することなく材料同士
の活性表面同士の接触による合金化を行う方法で、本発
明の場合は雰囲気ガスの吸収による化合物を生成すると
いう方法である。The inventor of the present invention causes a solid-gas phase reaction by vibrating a specific metal block or its powder in a nitrogen gas atmosphere, and as a result, the crystal grain size is reduced. A nitride powder having an ultrafine grain structure of several tens nm or less has been obtained. The above-mentioned ultrafine grain structure in the nitride powder of the present invention has a crystal grain size of about 60 to 70 nm at the maximum, and most of the crystal grain size is several nm. All of the structures have a crystal grain size of several tens of nm or less, and an amorphous structure in this grain size range. As the vibration for obtaining the nitride powder of the present invention, a mechanical alloying (hereinafter abbreviated as MA) method, which is generally intended for alloying by a solid phase reaction, can be suitably used. Incidentally, MA
The method is to put a specified material together with a ball into a vibration device (usually a high-energy ball mill) and vibrate it to give strong vibration energy to the material to atomize it and at the same time activate the surface of the material. A method of alloying by contacting active surfaces of materials with each other without heating to a high temperature, and in the case of the present invention, a compound is generated by absorption of atmospheric gas.
【０００６】すなわち、『請求項１』に係る発明は、
『チタン金属塊又はその粉末を窒素ガス雰囲気下で振動
させることにより得られる、結晶粒径数10ｎｍ以下のナ
ノクリスタル構造を有するＴｉＮからなる窒化物粉体』
を要旨とする。That is, the invention according to claim 1 is
"Nitride powder made of TiN having a nanocrystal structure with a crystal grain size of several 10 nm or less, which is obtained by vibrating a titanium metal block or its powder in a nitrogen gas atmosphere"
Is the gist.
【０００７】また『請求項２』に係る発明は、『チタン
金属塊もしくはその粉末及びアルミニウム金属塊もしく
はその粉末を、窒素ガス雰囲気下で振動させることによ
り得られる、結晶粒径数10ｎｍ以下のナノクリスタル構
造を有する(Ｔｉ，Ａｌ)Ｎからなる窒化物粉体』を要旨
とする。ここで、「(Ｔｉ，Ａｌ)Ｎ」とは、ＴｉとＡｌ
とが任意の割合で合金化したものの窒化物を意味する。The invention according to "Claim 2" is a "nanoparticle having a crystal grain size of 10 nm or less, which is obtained by vibrating a titanium metal block or its powder and an aluminum metal block or its powder in a nitrogen gas atmosphere. A nitride powder made of (Ti, Al) N having a crystal structure ”is a gist. Here, “(Ti, Al) N” means Ti and Al
Means a nitride of an alloy in an arbitrary ratio.
【０００８】また『請求項３』に係る発明は、『チタン
金属塊もしくはその粉末、鉄塊もしくはその粉末及びア
ルミニウム金属塊もしくはその粉末を、窒素ガス雰囲気
下で振動させることにより得られる、結晶粒径数10ｎｍ
以下のナノクリスタル構造を有するＦｅ−ＴｉＮからな
る窒化物粉体』を要旨とする。ここで、「Ｆｅ−Ｔｉ
Ｎ」とは、超微細粒のＴｉ窒化物に同じく超微細粒のＦ
ｅが混在しているものを意味する。この場合、鉄塊もし
くはその粉末は積極的に加えても良いし、ステンレス鋼
製のボールミルやボールから剥離したＦｅ分を利用して
も良い。The invention according to "claim 3" is a crystal grain obtained by vibrating a "titanium metal block or powder thereof, an iron block or powder thereof and an aluminum metal block or powder thereof in a nitrogen gas atmosphere. Diameter number 10 nm
The following is a summary of "nitride powder made of Fe-TiN having a nanocrystal structure". Here, "Fe-Ti
“N” means ultra-fine-grained Ti nitride as well as ultra-fine-grained F
It means a mixture of e. In this case, the iron ingot or the powder thereof may be positively added, or the Fe content separated from the stainless steel ball mill or the balls may be used.
【０００９】また『請求項４』に係る発明は、『ニオブ
金属塊又はその粉末を窒素ガス雰囲気下で振動させるこ
とにより得られる、結晶粒径数10ｎｍ以下のナノクリス
タル構造乃至非晶質構造を有するＮｂＮからなる窒化物
粉体』を要旨とする。なお、非晶質構造で得られる上記
窒化物粉体は、これを適宜加熱することによって、結晶
粒径数10ｎｍ以下のナノクリスタル構造の窒化物粉体と
する事ができる。The invention according to "claim 4" provides a nanocrystal structure or an amorphous structure having a crystal grain size of 10 nm or less, which is obtained by vibrating a niobium metal block or its powder in a nitrogen gas atmosphere. The nitride powder made of NbN is included. The above-mentioned nitride powder obtained with an amorphous structure can be made into a nitride powder having a nanocrystal structure with a crystal grain size of several tens of nm or less by appropriately heating it.
【００１０】また『請求項５』に係る発明は、『ニオブ
金属塊もしくはその粉末及びアルミニウム金属塊もしく
はその粉末を、窒素ガス雰囲気下で振動させることによ
り得られる、結晶粒径数10ｎｍ以下のナノクリスタル構
造乃至非晶質構造を有する(Ｎｂ，Ａｌ)Ｎからなる窒化
物粉体』を要旨とするものである。ここで、「(Ｎｂ，
Ａｌ)Ｎ」とは、ＮｂとＡｌとが任意の割合で合金化し
たものの窒化物を意味する。なおこの場合でも前述のよ
うに、非晶質構造で得られる上記窒化物粉体は、これを
適宜加熱することによって、結晶粒径数10ｎｍ以下のナ
ノクリスタル構造の窒化物粉体とする事ができる。The invention according to "Claim 5" is a nanoparticle having a crystal grain size of 10 nm or less, which is obtained by vibrating a "niobium metal block or powder thereof and an aluminum metal block or powder thereof in a nitrogen gas atmosphere. A nitride powder made of (Nb, Al) N having a crystal structure or an amorphous structure ”is a gist. Here, "(Nb,
"Al) N" means a nitride of Nb and Al alloyed at an arbitrary ratio. Even in this case, as described above, the nitride powder obtained in the amorphous structure may be appropriately heated to be a nitride powder having a nanocrystal structure with a crystal grain size of several tens of nm or less. it can.
【００１１】また『請求項６』に係る発明は、『ニオブ
金属塊もしくはその粉末、鉄塊もしくはその粉末及びア
ルミニウム金属塊もしくはその粉末を、窒素ガス雰囲気
下で振動させることにより得られる、結晶粒径数10ｎｍ
以下のナノクリスタル構造乃至非晶質構造を有するＦｅ
−(Ｎｂ，Ａｌ)Ｎからなる窒化物粉体』を要旨とする。
ここで「Ｆｅ−(Ｎｂ，Ａｌ)Ｎ」とは、超微細粒の
(Ｎｂ，Ａｌ)Ｎに同じく超微細粒のＦｅが混在している
ものを意味する。この場合も前述のように鉄塊もしくは
その粉末は積極的に加えても良いし、ステンレス鋼製の
ボールミルやボールから剥離したＦｅ分を利用しても良
い。さらに前述のように、非晶質構造で得られる上記窒
化物粉体は、これを適宜加熱することによって、結晶粒
径数10ｎｍ以下のナノクリスタル構造の窒化物粉体とす
る事ができる。The invention according to "claim 6" is a crystal grain obtained by vibrating a "niobium metal block or powder thereof, an iron block or powder thereof and an aluminum metal block or powder thereof in a nitrogen gas atmosphere. Diameter number 10 nm
Fe having the following nanocrystal structure or amorphous structure
-Nitride powder consisting of (Nb, Al) N ".
Here, "Fe- (Nb, Al) N" means ultrafine particles.
It also means that (Nb, Al) N is mixed with ultrafine grain Fe. Also in this case, the iron ingot or the powder thereof may be positively added as described above, or the Fe component separated from the stainless steel ball mill or the balls may be used. Further, as described above, the above-mentioned nitride powder obtained in an amorphous structure can be made into a nanocrystal structure nitride powder having a crystal grain size of several tens of nm or less by appropriately heating it.
【００１２】上記各発明において、用いられる各金属塊
は、振動により固相ー気相反応が進行するに十分な任意
の大きさで用いられるが、ことに、上記したＭＡ法に用
いる高エネルギーボールミルを利用できる大きさが好ま
しく、さらに、均質な窒化物粉体を得る点からは、金属
塊よりも金属粉末として用いることが好ましく、通常10
0〜400メッシュ程度の粉末が好ましいが、これに限定さ
れない。また、上記各発明において、各金属塊又はその
粉末は、純度が95％以上のものが適し、さらに98％以上
のものがＭＡ処理時間等の点から好ましいが、これに限
定されない。In each of the above inventions, each of the metal ingots used is of an arbitrary size sufficient for the solid phase-gas phase reaction to proceed by vibration. In particular, the high energy ball mill used in the MA method described above is used. It is preferable to use as a metal powder rather than a metal lump, from the viewpoint of obtaining a homogeneous nitride powder, usually 10
A powder of about 0 to 400 mesh is preferable, but not limited to this. Further, in each of the above inventions, each of the metal ingots or the powder thereof preferably has a purity of 95% or more, and more preferably 98% or more in terms of MA treatment time, etc., but is not limited thereto.
【００１３】上記各発明において、最終的に得る窒化物
粉体における各元素成分相の割合は、振動条件ことにＭ
Ａ処理条件及び原料金属の組成を調節することにより任
意の割合に調整できる。例えば三元窒化物であるＴｉ−
Ａｌ−Ｎにおいては、（Ｔi0.5Ａl0.5）Ｎが得られ、Ｎ
は50at.％まで吸収できる。Ｔｉの量がＡｌ量より多い
場合には（ＴixＡl1-x）Ｎが、逆にＴｉの量がＡｌ量よ
り少ない場合にはＡｌと（Ｔi0.5Ａl0.5）Ｎからなる金
属−窒化物複合粉末が得られる。三元窒化物（ＴixＡl
1-x）Ｎは、極めて優れた高温耐食性を示す事が知られ
ている。In each of the above inventions, the ratio of each elemental component phase in the finally obtained nitride powder is M
It can be adjusted to an arbitrary ratio by adjusting the treatment condition A and the composition of the raw material metal. For example, ternary nitride Ti-
In Al-N, (Ti 0.5 Al 0.5 ) N is obtained,
Can absorb up to 50 at.%. When the amount of Ti is larger than the amount of Al, (Ti x Al 1-x ) N, and when the amount of Ti is smaller than the amount of Al, the metal-nitride composed of Al and (Ti 0.5 Al 0.5 ) N. A composite powder is obtained. Ternary nitride (Ti x Al
1-x ) N is known to exhibit extremely high temperature corrosion resistance.
【００１４】またＮｂ−Ａｌ−Ｎの三元窒化物において
は、ＮｂとＡｌとの混合比が１：１の場合、Ｎは最終的
に50at.％まで吸収できるが、ＮｂとＡｌとの混合比が
６：４の場合、Ｎは40at.％の吸収となり、Ｎｂ量が20a
t.％以下になると吸収されるＮ量が急激に低下する。上
記各発明において、最終的に得られる窒化物粉体は、粒
径(即ち、粉体の直径)が数10μｍ程度のものが焼結用粉
末として用いる場合には好ましい。結晶粒の大きさは10
ｎｍ以下のナノクリスタル構造乃至非晶質構造である。Further, in the Nb-Al-N ternary nitride, when the mixing ratio of Nb and Al is 1: 1, N can finally be absorbed up to 50 at.%, But Nb and Al are mixed. When the ratio is 6: 4, the absorption of N is 40at.% And the amount of Nb is 20a.
When it becomes less than t.%, the amount of N absorbed is drastically reduced. In each of the above inventions, the finally obtained nitride powder preferably has a particle size (that is, a diameter of the powder) of about several tens of μm when used as the sintering powder. Crystal grain size is 10
It has a nanocrystal structure of nm or less or an amorphous structure.
【００１５】本発明の各実施例において得られる窒化物
粉体は、室温で所定の形状に圧粉し、これを加熱焼成し
て焼結体とする事ができるが、この場合、結晶構造がナ
ノクリスタル構造乃至非晶質構造であるため、５００Ｋ
の比較的低温から焼結する事ができる。The nitride powder obtained in each of the examples of the present invention can be pressed into a predetermined shape at room temperature and heated and sintered to obtain a sintered body. In this case, the crystal structure is 500K due to the nanocrystal structure or amorphous structure
It can be sintered at a relatively low temperature.
【００１６】上記各発明において、振動をＭＡ法で行う
場合、該ＭＡ法に用いられるボールミルとしては例えば
高エネルギー振動型ボールミル（ＳＰＥＸ−８０００；
スペックス社製）、振動型ボールミル（ＹＡＭＰ−２Ｓ
ＮＤ；安川商事社製）等が挙げられる。なお、上記ボー
ルミル自身の構成金属が試料金属に混入することを避け
る必要がある場合には、試料金属と同じ金属製のボール
ミル及びボールを用いることが要求される。In the above inventions, when the vibration is performed by the MA method, the ball mill used in the MA method is, for example, a high energy vibration type ball mill (SPEX-8000;
Specs, vibrating ball mill (YAMP-2S)
ND; manufactured by Yasukawa Shoji Co., Ltd.) and the like. When it is necessary to avoid mixing the constituent metal of the ball mill itself into the sample metal, it is required to use a ball mill and balls made of the same metal as the sample metal.
【００１７】[0017]
【作用】この発明によれば、窒素ガス雰囲気下で、窒化
材料として窒化物形成元素の金属塊又はその粉末、複合
材料の場合には少なくともその内の１種類が窒化物形成
元素からなる単体金属塊もしくはその粉末を、振動処理
に付すことにより、結晶粒径が数10ｎｍ以下のナノクリ
スタル構造乃至非晶質構造を有する窒化物粉体が得られ
ることとなる。According to the present invention, in a nitrogen gas atmosphere, a metal lump of a nitride-forming element or a powder thereof as a nitriding material, and in the case of a composite material, at least one of them is a single-element metal composed of a nitride-forming element. By subjecting the lump or its powder to a vibration treatment, a nitride powder having a nanocrystal structure or an amorphous structure with a crystal grain size of several tens of nm or less can be obtained.
【００１８】[0018]
【実施例】以下、本発明を図示実施例に従って詳述する
が、これによって本発明が限定されるものではない。 …ＴｉＮ又はＴｉＡｌＮの製造… ＴｉＮの製造の場合には、原料粉末として純度98％のＴ
ｉ粉末（ 325ッシュ）を、ＴｉＡｌＮの製造の場合に
は、同Ｔｉ粉末及び純度99.8％のＡｌ粉末（ 200メッシ
ュ）を用意した。一方、ＭＡ処理に用いるボールミルと
して、スペックス−８０００(容量9.2×10-5m3のSUS316
ステンレス製バイアル、径12.7mmのSUS304ステンレス製
ボール、ガス溜め容量：6.6×10-3m3 スペックス社
製)、及びＹＡＭＰ−２ＳＮＤ（容量1.3×10-3m3のSUS3
16ステンレス製バイアル、径12.7mmのSUS304ステンレス
製ボール、ガス溜め容量：3.4×10-2m3 安川商事製）
を用いた。バイアルに上記原料を、ボールと原料粉末と
の重量比が前者のボールミルでは１３：１、後者のボー
ルミルでは４５−９０：１の割合となるように充填した
後、バイアルにガス溜めを接続し、これに圧力ゲージを
取付け、バイアル及びガス溜めを窒素ガス置換した後、
ＭＡ処理を開始した。該処理中の粉末への窒素ガス吸収
量は、窒素ガス圧の低下量から求めた。ＭＡ処理した粉
末粒子の組織をＸ線回析、透過顕微鏡観察及び走査顕微
鏡観察により調べた。また、圧粉体を種々の温度で焼結
し、組織観察を行うと共に焼結材の機械的性質をマイク
ロビッカース硬度測定により調べた。The present invention will be described in detail below with reference to the illustrated embodiments, but the present invention is not limited thereto. ... Production of TiN or TiAlN ... In the case of production of TiN, T having a purity of 98% is used as a raw material powder.
i powder (325sh), in the case of manufacturing TiAlN, the same Ti powder and Al powder (200 mesh) having a purity of 99.8% were prepared. On the other hand, as a ball mill used for MA treatment, Spex-8000 (SUS316 with a capacity of 9.2 × 10 -5 m 3
Stainless steel vial, SUS304 stainless steel ball with a diameter of 12.7 mm, gas reservoir capacity: 6.6 × 10 -3 m 3 made by Spex), and YAMP-2SND (capacity 1.3 × 10 -3 m 3 SUS 3 )
16 stainless steel vials, 12.7 mm diameter SUS304 stainless steel balls, gas storage capacity: 3.4 × 10 -2 m 3 Yasukawa Shoji)
Was used. After filling the vial with the above raw material so that the weight ratio of the ball and the raw material powder was 13: 1 in the former ball mill and 45-90: 1 in the latter ball mill, a gas reservoir was connected to the vial, After attaching a pressure gauge to this and replacing the vial and gas reservoir with nitrogen gas,
MA treatment started. The amount of nitrogen gas absorbed into the powder during the treatment was determined from the amount of decrease in nitrogen gas pressure. The structure of the MA-treated powder particles was examined by X-ray diffraction, transmission microscope observation and scanning microscope observation. Further, the green compact was sintered at various temperatures, the structure was observed, and the mechanical properties of the sintered material were examined by micro Vickers hardness measurement.
【００１９】図１、図２は、Ｔｉ粉末を窒素ガス雰囲気
中でＭＡ処理した時の加振時間と窒素吸収量との関係を
示すグラフで、図１での使用ボールミルはＹＡＭＰ−２
ＳＮＤであり、図２の使用ボールミルはスペックス−８
０００である。図１によると２００時間程度の加振で窒
素吸収量が飽和し、図２(イ)によると５０時間程度の加
振で窒素吸収量が飽和し、いずれもＮが約50at.％のＴ
ｉＮ粉末となった。ＭＡ処理による加振時間の相違は、
ボールミルの能力によって相違するが、いずれの場合の
でもＮは約50at.％に到達する。又、ここでは、ボール
ミルのバイアル並びにボールにステンレス鋼を使用した
ので、加振時に大量のＦｅ成分がＴｉ粉末中に混入し
た。Ｆｅ成分の混入を防止するにはボールとバイアルと
をＴｉ又はＴｉコーティング材とすれば良い。1 and 2 are graphs showing the relationship between the vibration time and the nitrogen absorption amount when Ti powder is subjected to MA treatment in a nitrogen gas atmosphere. The ball mill used in FIG. 1 is YAMP-2.
It is an SND, and the ball mill used in FIG. 2 is Spex-8.
000. According to Fig. 1, the nitrogen absorption amount is saturated after about 200 hours of vibration, and according to Fig. 2 (a), the nitrogen absorption amount is saturated after about 50 hours of vibration.
It became iN powder. The difference in excitation time due to MA processing is
In all cases, N reaches about 50 at.%, Although it depends on the ball mill's ability. Also, here, since stainless steel was used for the vial and balls of the ball mill, a large amount of Fe component was mixed in the Ti powder during vibration. In order to prevent the Fe component from being mixed, the ball and the vial may be made of Ti or a Ti coating material.
【００２０】このＴｉＮ粉末を圧粉体とし、焼結した場
合の焼結温度と密度、マイクロビッカース硬度、平均粒
径との関係を図３に示す。図３によると、１３００Ｋ〜
１４００Ｋの焼結温度では、粉末の平均粒径は0.04〜0.
05μｍであって焼結による結晶粒の成長はみられず、マ
イクロビッカース硬度も 400程度で加工することができ
る程度の硬さである。図３では焼結温度を１３００Ｋの
手前から取っているが、実際は図４に示すように５００
Ｋ付近から焼結が始まっている。FIG. 3 shows the relationship between the sintering temperature and the density, the micro Vickers hardness, and the average particle diameter when this TiN powder is used as a green compact. According to FIG. 3, 1300K ~
At a sintering temperature of 1400K, the average particle size of the powder is 0.04-0.
The grain size is 05 μm, no growth of crystal grains due to sintering is observed, and the micro Vickers hardness is about 400, which is a hardness that can be processed. In FIG. 3, the sintering temperature is taken before 1300K, but as shown in FIG.
Sintering starts near K.
【００２１】図４はＴｉＮ圧粉体の焼結温度と直線収縮
率(ΔL/L0)の関係を示すグラフで５００ＫからＴｉＮ圧
粉体の収縮が開始し、焼結が始まっている。(通常の焼
結温度は１３００Ｋ付近から開始する。) 焼結体の結晶構造はＮaＣl型である。また、この場合、
ＴｉＮ粉末中には、前述の理由により、Ｆｅ分が混在し
ており、厳密に言えば、金属−窒化物複合材であり、Ｆ
ｅ分が混在している事により、靭性の向上が図られると
考えられる。又、Ｆｅ分を積極的に混入するために鉄塊
又は鉄粉を添加してもよい。FIG. 4 is a graph showing the relationship between the sintering temperature of the TiN green compact and the linear shrinkage ratio (ΔL / L 0 ). The shrinkage of the TiN green compact starts at 500 K and the sintering starts. (The normal sintering temperature starts around 1300 K.) The crystal structure of the sintered body is the NaCl type. Also in this case,
For the above-mentioned reason, Fe content is mixed in the TiN powder, and strictly speaking, it is a metal-nitride composite material, and
It is considered that the toughness is improved due to the mixture of the e component. Further, an iron ingot or iron powder may be added to positively mix the Fe content.
【００２２】図５はＴｉＮの格子像の透過電子顕微鏡写
真（ 700万倍）、図６〜８はそれぞれ、（１２７３Ｋ，
５時間）、（１５７３Ｋ，５時間）及び（１７７３Ｋ，
５時間）で焼結したときの走査顕微鏡写真である。図５
にはＴｉＮ（１１１）面の幅2.44Å（＝0.244nm）の像
が観察され、全体として 5〜10ｎｍの結晶粒径が観察さ
れる。また、図６及び図７の中央に観察される菱形の窪
みはマイクロビッカースの圧痕である。焼結温度の上昇
と共に結晶粒も成長し、又、密度並びにマイクロビッカ
ース硬度も上昇して焼結温度が１６００Ｋ以上になると
マイクロビッカース硬度が1000程度に上昇する。しかし
ながら、本発明にかかるＴｉＮ焼結体では焼結体の結晶
粒がナノ組織と非常に微細なので靭性が高く、マイクロ
ビッカースの圧痕周辺にクラックが生じていない。（従
来法によるＴｉＮ粉を使用した焼結体では、結晶粒が数
ミクロンと粗大であるため脆弱でマイクロビッカースの
圧痕の周囲には微細なクラックが発生していた。）FIG. 5 is a transmission electron micrograph (7 million times) of a TiN lattice image, and FIGS. 6 to 8 are (1273K,
5 hours), (1573K, 5 hours) and (1773K,
It is a scanning micrograph at the time of sintering for 5 hours. Figure 5
An image with a TiN (111) plane width of 2.44 Å (= 0.244 nm) is observed on the surface, and a crystal grain size of 5 to 10 nm is observed as a whole. The diamond-shaped depression observed in the center of FIGS. 6 and 7 is an indentation of micro-Vickers. Crystal grains grow as the sintering temperature rises, and the density and the micro Vickers hardness also rise, and the micro Vickers hardness rises to about 1000 when the sintering temperature reaches 1600K or higher. However, in the TiN sintered body according to the present invention, since the crystal grains of the sintered body are very fine and have a nanostructure, the toughness is high and no cracks are formed around the micro Vickers indentations. (In the sintered body using the TiN powder according to the conventional method, the crystal grains are coarse with a size of several microns, so that the sintered body is fragile and fine cracks are generated around the micro Vickers indentation.)
【００２３】ＴｉＡｌＮの製造の場合に付いて言えば、
Ｔｉ：Ａｌ＝１：１の場合には（Ｔi0.5Ａl0.5）Ｎが得
られる。Ｔｉの量がＡｌ量より多い場合には（ＴixＡl
1-x）Ｎが、逆にＴｉの量がＡｌ量より少ない場合には
Ａｌと（Ｔi0.5Ａl0.5）Ｎからなる金属−窒化物複合粉
末が得られる。三元窒化物（ＴixＡl1-x）Ｎは、極めて
優れた高温耐食性を示す。In the case of manufacturing TiAlN,
When Ti: Al = 1: 1, (Ti 0.5 Al 0.5 ) N is obtained. If the amount of Ti is larger than the amount of Al, (Ti x Al
When 1-x ) N, and conversely the amount of Ti is smaller than the amount of Al, a metal-nitride composite powder consisting of Al and (Ti 0.5 Al 0.5 ) N is obtained. Ternary nitride (Ti x Al 1-x) N indicates an extremely excellent high temperature corrosion resistance.
【００２４】…ＮｂＮ又はＮｂＡｌＮの製造… Ｎｂ粉末（9.5％，325メッシュ）及びＡｌ粉末（99.8
％，200メッシュ）を用い、Ｎｂ単独及びＮｂ量を変え
たＡｌ−Ｎｂ混合粉末をＮ2雰囲気中で最大５０時間Ｍ
Ａを行った（使用ボールミルはスペックス−８００
０）。ＭＡ処理中のＮ吸収量を連続的に測定すると共に
ＭＡ後のＸ線回析（図９参照）、透過顕微鏡観察及び走
査顕微鏡観察を行った。ＭＡ処理方法は、ＴｉＮの場合
と同一である。Manufacture of NbN or NbAlN Nb powder (9.5%, 325 mesh) and Al powder (99.8)
%, 200 mesh), and Nb alone and Al-Nb mixed powders with different amounts of Nb are used for up to 50 hours in an N 2 atmosphere.
A was performed (The ball mill used is Spex-800.
0). The N absorption amount during MA treatment was continuously measured, and X-ray diffraction after MA (see FIG. 9), transmission microscope observation and scanning microscope observation were performed. The MA treatment method is the same as that for TiN.
【００２５】Ｎｂ単独の場合、ＭＡ処理の進行と共に多
量のＮをＮｂが吸収し、最終的に50at.％吸収した。
（３０時間後） Ｎの吸収と共にＮｂ4Ｎ3及びＮｂＮの生成がＸ線的に確
認された。In the case of Nb alone, a large amount of N was absorbed by Nb with the progress of MA treatment, and finally 50 at.% Was absorbed.
(After 30 hours) The absorption of N and the formation of Nb 4 N 3 and NbN were confirmed by X-ray.
【００２６】Ａl50Ｎb50混合粉末の場合も最終的に約50
at.％のＮを吸収し（５０時間後）、アモルファス化の
後、（Ｎｂ，Ａｌ）Ｎと考えられる窒化物が生成した。
Ａl60Ｎb40混合粉末の場合も約40at.％のＮを吸収した
が、Ａｌ−Ｎｂ混合粉末中のＮｂ量が20at.％以下にな
ると吸収されるＮ量が急減した。この場合も前述の理由
でＦｅ分がＮｂＮ粉末中に混入している。In the case of the Al 50 Nb 50 mixed powder, the final value is about 50.
After absorption of at.% N (after 50 hours) and amorphization, a nitride considered to be (Nb, Al) N was formed.
The Al 60 Nb 40 mixed powder also absorbed about 40 at.% Of N, but when the amount of Nb in the Al-Nb mixed powder was 20 at.% Or less, the absorbed N amount decreased sharply. Also in this case, the Fe content is mixed in the NbN powder for the above-mentioned reason.
【００２７】本発明にかかるＴｉＮ、ＴｉＡｌＮ、Ｎｂ
Ｎ及びＮｂＡｌＮは、粉末の場合の用途としては、例え
ば、従来使用されていたアルミナ粉末に代わる耐熱塗料
用材料としての用途が考えられ、焼結体の用途として
は、ドリル先端に固定される切削刃物、高融点金型材
料、核融合炉のＴｉＣ皮膜蒸着第１炉壁の代わりとなる
炉壁ブロック材などが例として考えられる。TiN, TiAlN, Nb according to the present invention
N and NbAlN may be used as a heat-resistant paint material in place of the conventionally used alumina powder as an application in the case of powder, and as a use of a sintered body, cutting fixed to a drill tip. Examples include blades, high melting point mold materials, furnace wall block materials that substitute for the TiC film deposition first furnace wall of a fusion reactor, and the like.
【発明の効果】本発明にかかる窒化物粉体は、結晶粒径
10ｎｍ以下のナノクリスタル構造又は非晶質構造を有す
るので、焼結温度を５００Ｋと従来の粉体に比べて大幅
に低くする事が出来るだけでなく、高強度、高靭性、高
耐熱性、超塑性など優れた性質を発現させることが出来
る。The nitride powder according to the present invention has a crystal grain size of
Since it has a nanocrystal structure or amorphous structure of 10 nm or less, the sintering temperature can be 500 K, which is much lower than that of conventional powder, and it also has high strength, high toughness, high heat resistance, and super heat resistance. Excellent properties such as plasticity can be expressed.
【図１】ＹＡＭＰ−２ＳＮＤにてＴｉ粉末を窒素ガス雰
囲気中でＭＡ処理した時の加振時間と窒素吸収量との関
係を示すグラフFIG. 1 is a graph showing a relationship between a vibration time and a nitrogen absorption amount when MA treatment is performed on Ti powder by YAMP-2SND in a nitrogen gas atmosphere.
【図２】スペックス−８０００にてＴｉ粉末、（Ｔ
i0.5，Ａl0.5）Ｎ粉末、並びに（Ｔi0.5，Ｆｅ0.5）Ｎ
を窒素ガス雰囲気中でＭＡ処理した時の加振時間と窒素
吸収量との関係を示すグラフFIG. 2: Ti powder, (T
i 0.5, Al 0.5) N powder, and (Ti 0. 5, Fe 0.5 ) N
Graph showing the relationship between vibration time and nitrogen absorption amount when MA treatment was performed in a nitrogen gas atmosphere
【図３】Ｆｅ分を含むＴｉＮの焼結温度とマイクロビッ
カース硬度、密度並びに平均結晶粒径の関係を示すグラ
フFIG. 3 is a graph showing the relationship between the sintering temperature of TiN containing Fe and the micro Vickers hardness, density, and average crystal grain size.
【図４】ＴｉＮ圧粉体の焼結温度と直線収縮率（ΔL/
L0）の関係を示すグラフ[Fig. 4] Sintering temperature and linear shrinkage ratio (ΔL /
Graph showing the relationship of L 0 ).
【図５】本発明のＴｉＮ粉体の透過電子顕微鏡写真FIG. 5 is a transmission electron micrograph of the TiN powder of the present invention.
【図６】本発明のＴｉＮの焼結温度が１２７３Ｋでの走
査顕微鏡写真FIG. 6 is a scanning micrograph showing the sintering temperature of TiN of the present invention at 1273K.
【図７】本発明のＴｉＮの焼結温度が１５７３Ｋでの走
査顕微鏡写真FIG. 7: Scanning micrograph of TiN of the present invention at a sintering temperature of 1573K.
【図８】本発明のＴｉＮの焼結温度が１７７３Ｋでの走
査顕微鏡写真FIG. 8: Scanning micrograph of TiN of the present invention at a sintering temperature of 1773K.
【図９】本発明のＮｂを窒素ガス雰囲気中でＭＡ処理し
た場合のＸ線回析変化グラフFIG. 9 is an X-ray diffraction change graph when Nb of the present invention is MA-treated in a nitrogen gas atmosphere.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｃ０１Ｇ 49/00 Ｃ０１Ｇ 49/00 Ａ Ｃ２１Ｄ 1/74 Ｃ２１Ｄ 1/74 Ｊ ─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. 6 Identification code Internal reference number FI Technical display location C01G 49/00 C01G 49/00 A C21D 1/74 C21D 1/74 J
Claims (6)
ガス雰囲気中で振動させることにより得られる、結晶粒
径数10ｎｍ以下のナノクリスタル構造を有するＴｉＮか
らなる窒化物粉体。1. A nitride powder made of TiN having a nanocrystal structure having a crystal grain size of several 10 nm or less, which is obtained by vibrating a titanium metal block or a powder thereof in a nitrogen gas atmosphere.
びアルミニウム金属塊もしくはその粉末を、窒素ガス雰
囲気中で振動させることにより得られる、結晶粒径数10
ｎｍ以下のナノクリスタル構造を有する(Ｔｉ，Ａｌ)Ｎ
からなる窒化物粉体。2. A crystal grain size of 10 obtained by vibrating a titanium metal block or its powder and an aluminum metal block or its powder in a nitrogen gas atmosphere.
(Ti, Al) N having nanocrystal structure of nm or less
Nitride powder consisting of.
鉄塊もしくはその粉末及びアルミニウム金属塊もしくは
その粉末を、窒素ガス雰囲気下で振動させることにより
得られる、結晶粒径数10ｎｍ以下のナノクリスタル構造
を有するＦｅ−ＴｉＮからなる窒化物粉体。3. A titanium metal block or a powder thereof,
A nitride powder made of Fe-TiN having a nanocrystal structure having a crystal grain size of 10 nm or less, which is obtained by vibrating an iron ingot or its powder and an aluminum metal ingot or its powder in a nitrogen gas atmosphere.
ガス雰囲気下で振動させることにより得られる、結晶粒
径数10ｎｍ以下のナノクリスタル構造乃至非晶質構造を
有するＮｂＮからなる窒化物粉体。4. A nitride powder made of NbN having a nanocrystal structure or an amorphous structure having a crystal grain size of 10 nm or less, which is obtained by vibrating a niobium metal lump or a powder thereof in a nitrogen gas atmosphere.
びアルミニウム金属塊もしくはその粉末を、窒素ガス雰
囲気下で振動させることにより得られる、結晶粒径数10
ｎｍ以下のナノクリスタル構造乃至非晶質構造を有する
(Ｎｂ，Ａｌ)Ｎからなる窒化物粉体。5. A crystal grain size of 10 obtained by vibrating a niobium metal block or its powder and an aluminum metal block or its powder in a nitrogen gas atmosphere.
Has a nanocrystal structure or an amorphous structure of nm or less
Nitride powder composed of (Nb, Al) N.
鉄塊もしくはその粉末及びアルミニウム金属塊もしくは
その粉末を、窒素ガス雰囲気下で振動させることにより
得られる、結晶粒径数10ｎｍ以下のナノクリスタル構造
乃至非晶質構造を有するＦｅ−(Ｎｂ，Ａｌ)Ｎからなる
窒化物粉体。6. A niobium metal lump or a powder thereof,
Fe- (Nb, Al) having a nanocrystal structure or an amorphous structure having a crystal grain size of 10 nm or less, which is obtained by vibrating an iron ingot or its powder and an aluminum metal ingot or its powder in a nitrogen gas atmosphere. Nitride powder made of N.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3269037A JP2539712B2 (en) | 1991-09-19 | 1991-09-19 | Nitride powder |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3269037A JP2539712B2 (en) | 1991-09-19 | 1991-09-19 | Nitride powder |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0578107A JPH0578107A (en) | 1993-03-30 |
| JP2539712B2 true JP2539712B2 (en) | 1996-10-02 |
Family
ID=17466797
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3269037A Expired - Fee Related JP2539712B2 (en) | 1991-09-19 | 1991-09-19 | Nitride powder |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2539712B2 (en) |
Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10182234A (en) * | 1996-12-25 | 1998-07-07 | Agency Of Ind Science & Technol | Cubic boron nitride-base sintered material and its production |
| JPH10182233A (en) * | 1996-12-25 | 1998-07-07 | Agency Of Ind Science & Technol | Titanium aluminum nitride-base sintered material and its production |
| US6277740B1 (en) * | 1998-08-14 | 2001-08-21 | Avery N. Goldstein | Integrated circuit trenched features and method of producing same |
| KR100456797B1 (en) * | 2002-05-01 | 2004-11-10 | 한국과학기술연구원 | FABRICATION METHOD OF NANOCRYSTALLINE TiN/Ti-M COMPOSITE POWDER VIA REACTION MILLING |
| KR100524529B1 (en) * | 2002-11-30 | 2005-10-31 | 김진권 | Preparation Method of Nano-sized Metal Nitride Particle |
| JP5093433B2 (en) * | 2005-11-11 | 2012-12-12 | 学校法人同志社 | Method for producing a bulk body of Al-added TiN |
| KR100959931B1 (en) * | 2008-03-07 | 2010-05-26 | 한국과학기술연구원 | Method of forming titanium nitride powders |
| JP4997542B2 (en) * | 2008-05-20 | 2012-08-08 | 独立行政法人物質・材料研究機構 | TiN-based crystalline nanoparticles and method for producing the same, and aggregates of TiN-based crystalline nanoparticles and method for producing the same |
| JP4997541B2 (en) * | 2008-05-20 | 2012-08-08 | 独立行政法人物質・材料研究機構 | TiN-based crystalline nanoparticles and method for producing the same |
| US10029948B2 (en) | 2014-08-29 | 2018-07-24 | Sumitomo Electric Industries, Ltd. | Sintered material, tool including sintered material, and sintered material production method |
| JP6571275B2 (en) * | 2016-04-08 | 2019-09-04 | 富士フイルム株式会社 | Composition, method for producing composition, cured film, color filter, light-shielding film, solid-state imaging device, and image display device |
| KR102639978B1 (en) * | 2018-03-23 | 2024-02-22 | 닛신 엔지니어링 가부시키가이샤 | Composite particles and methods for producing composite particles |
| CN110205452B (en) * | 2019-04-24 | 2020-10-27 | 西北大学 | Hydrophobic steel plate with micron octahedron/nano needle-shaped structure and preparation method thereof |
| CN113652630B (en) * | 2021-08-18 | 2022-10-28 | 合肥工业大学 | Method for preparing nitrogen-containing modified layer on surface of magnesium-lithium alloy at room temperature |
-
1991
- 1991-09-19 JP JP3269037A patent/JP2539712B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0578107A (en) | 1993-03-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA2158048C (en) | Densified micrograin refractory metal or solid solution (mixed metal) carbide ceramics | |
| JP2606967B2 (en) | Ceramic composite material | |
| US4909840A (en) | Process of manufacturing nanocrystalline powders and molded bodies | |
| JP2539712B2 (en) | Nitride powder | |
| Koc et al. | Sintering properties of submicron TiC powders from carbon coated titania precursor | |
| JP2005239472A (en) | High strength and high wear resistance diamond sintered compact and its production method | |
| JPH01208401A (en) | Roduction of secondary powder particle having sealed particle surface and nano crystallizable structure, secondary powder and molded body having texture of nano crystallizable structure | |
| JPS6362474B2 (en) | ||
| JPH06500601A (en) | Method for producing metal carbide objects and composites containing metal carbides | |
| EP1420076A1 (en) | Hard alloy and W-based composite carbide powder used as starting material | |
| JP2004517025A (en) | Powdered ceramic material | |
| JP2004142993A (en) | Hexagonal composite carbide, and production method therefor | |
| JP3038371B2 (en) | Silicon carbide nanoparticle-encapsulated carbon nanoparticle structure | |
| JP2002249801A (en) | Method for manufacturing corrosion resistant magnesium alloy and material | |
| JPH07278719A (en) | Particulate plate crystal cemented carbide containing wc and its production | |
| JPH11139882A (en) | Composite silicon nitride powder and its production | |
| JPH05339659A (en) | Production of sintered hard alloy having sheet-like tungsten carbide and coated sintered hard alloy | |
| JP3032818B2 (en) | Titanium boride dispersed hard material | |
| KR100818572B1 (en) | High-strength and highly-wear-resistant sintered diamond object and manufacturing method of the same | |
| JP3305527B2 (en) | Polyhedral shaped chip made of crystal-oriented cemented carbide and method of manufacturing the same | |
| JP3213903B2 (en) | Tantalum carbide based sintered body and method for producing the same | |
| JP2802587B2 (en) | Manufacturing method of plate-shaped WC-containing cemented carbide | |
| JP2000144301A (en) | Tungsten carbide sintered body and its production | |
| JP4165850B2 (en) | Plate-like tungsten carbide-containing powder and method for producing the same | |
| JP2612016B2 (en) | Method for producing low oxygen aluminum nitride powder |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |