JP5618364B2 - Method for producing ultrafine and homogeneous titanium carbonitride solid solution powder - Google Patents
Method for producing ultrafine and homogeneous titanium carbonitride solid solution powder Download PDFInfo
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Description
チタン系炭窒化物は高硬度・高融点でありであり導電性を有し、高温構造材料として期待されると共に、セラミックス基複合材料もしくは金属基複合材料のフィラーあるいは、導電性ポリマーの分散相として期待されている。
この発明は、チタン系炭窒化物固溶体の微粒粉末の製造方法に関わるものである。
Titanium carbonitride has high hardness and high melting point, has conductivity, is expected as a high-temperature structural material, and is used as a filler of ceramic-based composite materials or metal-based composite materials, or as a dispersed phase of conductive polymers Expected.
The present invention relates to a method for producing a fine powder of a titanium-based carbonitride solid solution.
従来、チタン炭窒化物粉末の製造法としては、チタンの窒化物粉末とチタンの炭化物粉末との混合粉末を固溶化熱処理して得る方法が知られているが、この製造法では、炭素および窒素の拡散を十分行わせるためには長時間を有するため、効率的な反応が行われず、また、チタン水素化物粉末と炭素粉末を原料粉末とし、この混合粉末を、窒素気流中あるいは水素−窒素混合気流中で、１４００℃以下で熱処理し、さらに、１４００〜１７００℃での熱処理（二段階での熱処理）を行うことによって、チタン炭窒化物粉末を得る方法も知られているが、この製造法においても、熱処理時に窒素ガスを多く吸収した領域とそうでない領域のアンバランスが生じるため、炭素含有量および窒素含有量の変動が大きく、均一組成のチタン炭窒化物粉末を得ることは非常に困難であり、これを解消するには、長時間かけた緩やかな窒化処理を行わざるを得なかった（特許文献１参照）。
応用面から考えた場合、チタン系炭窒化物粉末は、高硬度、高融点、導電性を有するセラミックスという点で種々の材料において微量添加物もしくはフィラーとしての適用が可能である。しかし、上述のような既存粉末は、粒子が粗大化もしくは焼結現象を起こしているため、強粉砕が必要となる。その結果得られる粉末は粗粒微粒粉が混在して粒径分布が大きく、かつ平均粒径も１μｍ以上である。このため、チタン系炭窒化物固有の優れた特性にもかかわらず、応用分野が限られていた。
Conventionally, as a method for producing titanium carbonitride powder, a method is known in which a mixed powder of titanium nitride powder and titanium carbide powder is subjected to solution heat treatment, but in this production method, carbon and nitrogen are used. Since it takes a long time to sufficiently diffuse the material, an efficient reaction is not performed, and titanium hydride powder and carbon powder are used as raw material powder, and this mixed powder is mixed in a nitrogen stream or hydrogen-nitrogen mixed. There is also known a method of obtaining titanium carbonitride powder by heat treatment at 1400 ° C. or less in an air stream and further heat treatment at 1400 to 1700 ° C. (two-step heat treatment). In this case, the carbon content and the nitrogen content vary greatly, and the titanium carbonitride powder having a uniform composition has a large variation. That is very difficult to obtain, to solve this, had to perform gradual nitriding treatment over a long time (see Patent Document 1).
From the viewpoint of application, titanium-based carbonitride powder can be applied as a trace additive or filler in various materials in terms of ceramics having high hardness, high melting point, and conductivity. However, the existing powder as described above needs to be strongly pulverized because the particles are coarsened or sintered. The resulting powder has a mixture of coarse and fine particles, a large particle size distribution, and an average particle size of 1 μm or more. For this reason, the field of application has been limited despite the excellent characteristics inherent in titanium-based carbonitrides.
例えば、サーメット用粉末としての応用を念頭に、１００ｎｍ以下のナノサイズを有するＴｉを含んだ炭窒化物固溶体粉末が提案されている（特許文献２）。しかし、当該特許においては、単にチタンを含む遷移金属からなる炭窒化物粉末の炭素熱還元合成を示したに過ぎず、実施例に示される粉末のＳＥＭ写真からも、粉末は粗大な粒を含んでおり、粒子径分布の均一性、微粒化という点で従来の知見と大きく変わる技術ではない。また、微粒化するメカニズムに関してはいっさい言及されておらず、技術の新規性・進歩性という点でも不十分である。 For example, a carbonitride solid solution powder containing Ti having a nano size of 100 nm or less has been proposed in consideration of application as a cermet powder (Patent Document 2). However, in this patent, only the carbothermal reduction synthesis of carbonitride powder made of transition metal containing titanium is shown, and the powder contains coarse particles from the SEM photographs of the powder shown in the examples. However, it is not a technology that greatly differs from conventional knowledge in terms of uniformity of particle size distribution and atomization. In addition, no mention is made of the mechanism of atomization, and the novelty and inventive step of the technology is insufficient.
本発明は、チタン系炭窒化物固溶体粉末の製造方法として、より一層微粒かつ均粒であって、しかも、均質な固溶体組織を有する超微粒かつ均質なチタン系炭窒化物固溶体粉末の製造方法を提供することを目的とする。 The present invention provides a method for producing a titanium-based carbonitride solid solution powder as a method for producing a titanium-based carbonitride solid solution powder that is finer and more uniform and has a homogeneous solid solution structure. The purpose is to provide.
本発明者らは、前記課題を解決すべく、炭窒化チタン粉末を製造する際の原料粉末及びその製造工程について、鋭意研究を行なったところ、以下の知見を得たのである。 In order to solve the above-mentioned problems, the present inventors have earnestly studied the raw material powder and the production process for producing the titanium carbonitride powder, and obtained the following knowledge.
炭窒化チタン粉末製造用の原料粉末として、チタン酸化物粉末と炭素粉末、さらに、モリブデン酸化物粉末およびタングステン酸化物粉末の１種または２種の粉末からなる粉末とを混合し、この混合粉末を、非窒化性かつ非酸化性雰囲気（例えば、アルゴン雰囲気）中で１４００℃まで加熱昇温し、その後、雰囲気を窒素雰囲気に切り替え、該窒素雰囲気中において、１４００〜１６００℃の温度範囲で熱処理することにより、超微粒かつ均粒であって、しかも、均質な固溶体組織を有するチタン系炭窒化物固溶体粉末を製造し得ることを見出したのである。
また、上記の混合粉末に、さらに、バナジウム酸化物粉末、クロム酸化物粉末、ジルコニウム酸化物粉末、ニオブ酸化物粉末、タンタル酸化物粉末、ハフニウム酸化物粉末のうちの１種または２種以上を添加した混合粉末を用いた場合にも、超微粒かつ均粒であって、しかも、均質な固溶体組織を有するチタン系炭窒化物固溶体粉末を製造し得ることを見出したのである。
As a raw material powder for producing titanium carbonitride powder, titanium oxide powder and carbon powder, and further, a powder composed of one or two kinds of molybdenum oxide powder and tungsten oxide powder are mixed. Then, the temperature is raised to 1400 ° C. in a non-nitriding and non-oxidizing atmosphere (for example, argon atmosphere), then the atmosphere is switched to a nitrogen atmosphere, and heat treatment is performed in the nitrogen atmosphere at a temperature range of 1400 to 1600 ° C. Thus, it has been found that a titanium carbonitride solid solution powder that is ultrafine and uniform and has a homogeneous solid solution structure can be produced.
Further, one or more of vanadium oxide powder, chromium oxide powder, zirconium oxide powder, niobium oxide powder, tantalum oxide powder and hafnium oxide powder are added to the above mixed powder. It has been found that even when the mixed powder is used, it is possible to produce a titanium-based carbonitride solid solution powder that is ultrafine and uniform and has a homogeneous solid solution structure.
上記アルゴン雰囲気等の非窒化性かつ非酸化性雰囲気中で１４００℃まで昇温することにより、混合粉末中のチタン酸化物は、還元されると同時に炭化されてチタン炭化物を生成し、次いで、窒素雰囲気中、１４００〜１６００℃の温度範囲で熱処理されることによって上記チタン炭化物が窒化されてチタン炭窒化物が生成する。
そして、この発明では、原料粉末として所定含有割合のモリブデン粉末、タングステン酸化物粉末を加えていることから、モリブデン化合物、タングステン化合物が気相を通してチタン酸化物の表面に新たな化合物として析出し、炭窒化反応前のチタン酸化物の粒成長を抑制し、結果としてチタン系炭窒化物の粒子径は均一で微細なものとなる。すなわち、蒸気圧が高くなりかつ、最終的にチタン炭窒化物に固溶する金属を含む酸化物（不活性雰囲気中１０００℃でその酸化物上での金属種を含むガス相の平衡蒸気圧が１０−１０ａｔｍ以上となる金属元素）を選択することが本技術の中心となる。
さらに、チタン系炭窒化物の一次粒子径が小さいため、チタン以外の金属元素が固溶するための拡散距離が短くなり、従来に比べ低い温度での固溶化反応が容易になる。すなわち、微粒化することで合成温度を従来に比べ低くすることが可能となり、結果として後工程で強粉砕が必要となるような焼結現象はほとんど現れない。
上記原理を発現させるためには、原料となるチタン酸化物が微細であることが必要となる。また、炭素も主原料であるチタン酸化物と同程度の細かさが必要とされる。また、Ｍｏ、Ｗがチタン炭窒化物への固溶限があり、その上限はおよそ３０ｍｏｌ％である。また、実験により、本メカニズムを発現させるために必要なＭｏもしくはＷ量は２ｍｏｌ％であった。
本発明で得られた一次粒子の平均粒径が２００ｎｍ以下の超微粒であって、かつ５００ｎｍ以上の粒子を含まない均粒粉末が得られる。
さらに、Ｘ線回折装置による結晶相評価の結果、得られた粉末はＮａＣｌ型の回折パターンのみを示しており、ほぼ単相粉末であることが確認された。上記チタン炭窒化物は、均質な固溶体組織を有するチタンとモリブデンの炭窒化物、均質な固溶体組織を有するチタンとタングステンの炭窒化物、あるいは、均質な固溶体組織を有するチタンとモリブデンとタングステンの炭窒化物（以下、チタン系炭窒化物という）固溶体粉末として形成されていることが確認される。
また、混合粉末として、さらに、バナジウム酸化物粉末、クロム酸化物粉末、ジルコニウム酸化物粉末、ニオブ酸化物粉末、タンタル酸化物粉末、ハフニウム酸化物粉末のうちの１種または２種以上を添加した場合でも、チタン系炭窒化物粉の平均粒径は２２０ｎｍ以下の超微粒であって、かつ５００ｎｍ以上の粒子を含まない均粒粉末が得られる。
By raising the temperature to 1400 ° C. in a non-nitriding and non-oxidizing atmosphere such as the argon atmosphere, the titanium oxide in the mixed powder is reduced and simultaneously carbonized to form titanium carbide, and then nitrogen. The titanium carbide is nitrided by being heat-treated in a temperature range of 1400 to 1600 ° C. in an atmosphere to produce titanium carbonitride.
In the present invention, since molybdenum powder and tungsten oxide powder having a predetermined content ratio are added as raw material powders, the molybdenum compound and tungsten compound are precipitated as new compounds on the surface of titanium oxide through the gas phase, and carbon Grain growth of the titanium oxide before the nitriding reaction is suppressed, and as a result, the particle diameter of the titanium carbonitride becomes uniform and fine. That is, an oxide containing a metal whose vapor pressure becomes high and finally dissolves in titanium carbonitride (the equilibrium vapor pressure of a gas phase containing a metal species on the oxide at 1000 ° C. in an inert atmosphere is The center of the present technology is to select a metal element that is 10 −10 atm or more.
Furthermore, since the primary particle diameter of the titanium-based carbonitride is small, the diffusion distance for dissolving a metal element other than titanium is shortened, so that a solid solution reaction at a lower temperature than conventional is facilitated. That is, by making the particles fine, the synthesis temperature can be lowered as compared with the conventional case, and as a result, a sintering phenomenon that requires strong pulverization in the subsequent process hardly appears.
In order to develop the above principle, it is necessary that the titanium oxide as a raw material is fine. Carbon is also required to be as fine as titanium oxide, which is the main raw material. Moreover, Mo and W have a solid solubility limit in titanium carbonitride, and the upper limit is about 30 mol%. In addition, the amount of Mo or W necessary for developing this mechanism was 2 mol% by experiments.
The average particle diameter of the primary particles obtained in the present invention is an ultrafine particle having a particle size of 200 nm or less, and a uniform-sized powder containing no particles having a particle size of 500 nm or more is obtained.
Furthermore, as a result of crystal phase evaluation by an X-ray diffractometer, the obtained powder showed only a NaCl-type diffraction pattern, and it was confirmed that it was almost a single-phase powder. The titanium carbonitride is composed of titanium and molybdenum carbonitride having a homogeneous solid solution structure, titanium and tungsten carbonitride having a homogeneous solid solution structure, or titanium, molybdenum and tungsten carbon having a homogeneous solid solution structure. It is confirmed that it is formed as a nitride (hereinafter referred to as titanium-based carbonitride) solid solution powder.
Further, when one or more of vanadium oxide powder, chromium oxide powder, zirconium oxide powder, niobium oxide powder, tantalum oxide powder and hafnium oxide powder are added as a mixed powder However, the average particle diameter of the titanium-based carbonitride powder is an ultrafine particle having a particle size of 220 nm or less, and a uniform powder having no particles of 500 nm or more is obtained.
すなわち、この発明によれば、アルゴン雰囲気等の非窒化性非酸化性雰囲気中でのチタン酸化物の還元と炭化、また、これに続く高温窒素雰囲気中での窒化によって、均質な固溶体組織を有し、同時に、超微粒かつ均粒であるチタン系炭窒化物固溶体粉末を得ることができ、さらには従来に比べ合成温度を下げることができることを見出したのである。 That is, according to the present invention, a homogeneous solid solution structure is obtained by reduction and carbonization of titanium oxide in a non-nitriding non-oxidizing atmosphere such as an argon atmosphere, and subsequent nitriding in a high-temperature nitrogen atmosphere. At the same time, it was found that a titanium carbonitride solid solution powder that is ultrafine and uniform can be obtained, and that the synthesis temperature can be lowered as compared with the conventional one.
この発明は、上記知見に基づいてなされたものであって、
「（１） 平均粒径がそれぞれ１０〜２００ｎｍのチタン酸化物粉末、炭素粉末、および、モリブデン酸化物粉末もしくはタングステン酸化物粉末の１種または２種の粉末からなる混合粉末を、０．１ａｔｍ以上のアルゴン雰囲気中において、１４００℃まで加熱昇温し、その後、雰囲気を窒素雰囲気に切り替え、該窒素雰囲気中において、１４００〜１６００℃の温度範囲で６０〜１２０分間熱処理することを特徴とする組成式（Ｔｉ１−ＸＭ１Ｘ）ＣＮ（但し、Ｍ１は、ＭｏとＷのうちの１種または２種。Ｘは原子比で、０．０２≦Ｘ≦０．３）で表され、一次粒子の平均粒径が２００ｎｍ以下の超微粒であって、かつ、５００ｎｍ以上の粒子を含まない均粒粉末であり、さらに、均質な固溶体組織を有する超微粒かつ均質なチタン系炭窒化物固溶体粉末の製造方法。
（２） 平均粒径がそれぞれ１０〜２００ｎｍのチタン酸化物粉末、炭素粉末、および、モリブデン酸化物粉末もしくはタングステン酸化物粉末の１種または２種の粉末、さらに、バナジウム酸化物粉末、クロム酸化物粉末、ジルコニウム酸化物粉末、ニオブ酸化物粉末、タンタル酸化物粉末、ハフニウム酸化物粉末のうちの１種以上の酸化物粉末からなる混合粉末を、０．１ａｔｍ以上のアルゴン雰囲気中において、１４００℃まで加熱昇温し、その後、雰囲気を窒素雰囲気に切り替え、該窒素雰囲気中において、１４００〜１６００℃の温度範囲で６０〜１２０分間熱処理することを特徴とする組成式（Ｔｉ１−Ｘ−ＹＭ１ＸＭ２Ｙ）ＣＮ（但し、Ｍ１は、ＭｏとＷのうちの１種または２種。Ｍ２は、Ｖ，Ｃｒ，Ｚｒ，Ｎｂ，Ｔａ，Ｈｆのうちの１種または２種以上。Ｘ，Ｙは、いずれも原子比で、Ｘ＝０．０２〜０．３，０＜Ｙ＜０．１）で表され、一次粒子の平均粒径が２２０ｎｍ以下の超微粒であって、かつ、５００ｎｍ以上の粒子を含まない均粒粉末であり、さらに、均質な固溶体組織を有する超微粒かつ均質なチタン系炭窒化物固溶体粉末の製造方法。」
に特徴を有するものである。
This invention has been made based on the above findings,
“(1) A mixed powder composed of titanium oxide powder, carbon powder, and molybdenum oxide powder or tungsten oxide powder each having an average particle diameter of 10 to 200 nm is 0.1 atm or more. In an argon atmosphere, the composition is heated to 1400 ° C. , then the atmosphere is switched to a nitrogen atmosphere, and heat treatment is performed in the nitrogen atmosphere at a temperature range of 1400 to 1600 ° C. for 60 to 120 minutes. (Ti 1-X M1 X) CN ( where, M1 is at one or .X atomic ratio of Mo and W, 0.02 ≦ X ≦ 0.3) is represented by, the primary particles an average particle size of less 200nm ultrafine and a Hitoshitsubu powder containing no 500nm or more particles, and further, ultrafine, homogeneous titanium-based with a homogeneous solid solution structure Method of manufacturing a nitride solid-solution powder.
(2) Titanium oxide powder, carbon powder, and one or two kinds of molybdenum oxide powder or tungsten oxide powder each having an average particle diameter of 10 to 200 nm , vanadium oxide powder, and chromium oxide A mixed powder composed of one or more oxide powders among powder, zirconium oxide powder, niobium oxide powder, tantalum oxide powder, and hafnium oxide powder is heated to 1400 ° C. in an argon atmosphere of 0.1 atm or more. After heating and raising temperature, the atmosphere is switched to a nitrogen atmosphere, and heat treatment is performed in the nitrogen atmosphere at a temperature range of 1400 to 1600 ° C. for 60 to 120 minutes (Ti 1-XY M1 X M2 Y) CN (where, M1 is one or two .M2 of Mo and W, V, Cr, Zr, Nb , Ta, H .X 1 or two or more of, Y are both atomic ratio is expressed by X = 0.02~0.3,0 <Y <0.1) , an average particle diameter of primary particles A method for producing an ultrafine and homogeneous titanium-based carbonitride solid solution powder that is ultrafine particles of 220 nm or less and does not contain particles of 500 nm or more, and further has a homogeneous solid solution structure . "
It has the characteristics.
以下に、本発明について、より具体的かつ詳細に説明する。 Hereinafter, the present invention will be described more specifically and in detail.
まず、チタン系炭窒化物固溶体粉末の一例として、チタンとモリブデンの炭窒化物固溶体粉末の製造法について述べる。
本発明では、チタン系炭窒化物固溶体粉末を製造するに当たり、いずれも平均粒径が２００ｎｍ以下であるチタン酸化物（例えば、ＴｉＯ２）粉末、炭素粉末、モリブデン酸化物（ＭｏＯ２，ＭｏＯ３）粉末の混合粉末を原料粉末として用い、これを、非窒化性かつ非酸化性雰囲気（好ましくは、アルゴン雰囲気）中で１４００℃まで昇温速度１０〜４０℃／ｍｉｎで昇温する。この昇温時に、チタン酸化物は、炭素粉末による還元および炭化が進行し、チタン炭化物が形成される。さらに、チタン酸化物の一部は、炭素粉末、モリブデン酸化物粉末が共存していることにより、部分的に、チタンとモリブデンとの酸化物固溶体を形成し、また、形成された酸化物固溶体の還元および炭化が進行し、チタンとモリブデンとの炭化物固溶体が形成される。しかも、ここで形成されるチタンとモリブデンとの炭化物固溶体は、粒成長が抑制され、微粒状態を維持したままである。
上記還元、炭化反応を１４００℃までの昇温時に行わせるのは、１４００℃を超える温度にまで昇温した場合には、粒が粗大化し、均質な固溶体組織を形成できなるばかりか、このような粉末で焼結体を作製した場合に、焼結体の硬度、靭性の向上が期待できなくなるからである。
また、１４００℃まで昇温速度を１０℃／ｍｉｎ未満とした場合には、還元反応前にチタン酸化物粉末およびモリブデン酸化物粉末が粒成長しやすくなり、所望の粒度の超微粒固溶体粉末を得ることができなくなる。一方、昇温速度が４０℃／ｍｉｎを超えると、出発原料にＭｏＯ３を使用した場合に、ＭｏＯ３の還元よりも早くＭｏＯ３が昇華してしまい、狙い組成の固溶体粉末を得ることが困難になることから、１４００℃まで昇温速度は１０〜４０℃／ｍｉｎの範囲内とすることが望ましい。
First, as an example of a titanium-based carbonitride solid solution powder, a method for producing a carbonitride solid solution powder of titanium and molybdenum will be described.
In the present invention, when producing titanium-based carbonitride solid solution powder, titanium oxide (for example, TiO 2 ) powder, carbon powder, molybdenum oxide (MoO 2 , MoO 3 ) each having an average particle diameter of 200 nm or less. A mixed powder of powder is used as a raw material powder, and this is heated to 1400 ° C. at a heating rate of 10 to 40 ° C./min in a non-nitriding and non-oxidizing atmosphere (preferably an argon atmosphere). At the time of this temperature increase, the titanium oxide undergoes reduction and carbonization by the carbon powder, and titanium carbide is formed. Furthermore, a part of the titanium oxide partially forms an oxide solid solution of titanium and molybdenum due to the coexistence of carbon powder and molybdenum oxide powder, and the oxide solid solution of the formed oxide solid solution. Reduction and carbonization proceed, and a carbide solid solution of titanium and molybdenum is formed. And the carbide | carbonized_material solid solution of titanium and molybdenum formed here suppresses grain growth and maintains a fine grain state.
The above reduction and carbonization reactions are performed when the temperature is raised to 1400 ° C. When the temperature is raised to a temperature exceeding 1400 ° C., the grains become coarse and a homogeneous solid solution structure cannot be formed. This is because when a sintered body is produced with a simple powder, improvement in hardness and toughness of the sintered body cannot be expected.
Moreover, when the heating rate is less than 10 ° C./min up to 1400 ° C., the titanium oxide powder and the molybdenum oxide powder easily grow before the reduction reaction, and an ultrafine solid solution powder having a desired particle size is obtained. I can't do that. On the other hand, when the heating rate exceeds 40 ° C. / min, when using MoO 3 as the starting material, it will be sublimated quickly MoO 3 than the reduction of MoO 3, difficult to obtain a solid solution powder aim composition Therefore, it is desirable that the temperature rising rate is up to 1400 ° C. within the range of 10-40 ° C./min.
上記混合粉末の配合割合は、例えば、チタン酸化物粉末を５１．１〜６８．２重量部、炭素粉末を２５．９〜２７．５重量部、モリブデン酸化物粉末を４．３〜２３．０重量部とし、しかも、チタンとの合量に占めるモリブデンの配合割合が５〜２０原子％となるようにすることができる。
チタン酸化物粉末、炭素粉末およびモリブデン酸化物粉末の配合割合が、上記数値範囲を外れる場合には、組成式（Ｔｉ１−ＸＭ１Ｘ）ＣＮ（但し、Ｍ１は、ＭｏとＷのうちの１種または２種。Ｘは、原子比で、０．０２≦Ｘ≦０．３）を満足する所望の組成・粒度のチタンとモリブデンの炭窒化物固溶体粉末を得ることができず、またこれら粉末を使用し作製したサーメット合金の特性向上を図ることができなくなることから望ましくない。
つまり、チタンとの合量に占めるモリブデンの配合割合が２原子％未満であると、粉末形成時の粒成長抑制効果の低下により粒子が粗大化してしまい、一方、モリブデンの配合割合が３０原子％を超えると、形成される固溶体粉末が単一相でなく未固溶相が出現し均質な固溶体粉末を得ることが困難であるから、チタンとの合量に占めるモリブデンの配合割合は２〜３０原子％とすることが必要である。
The mixing ratio of the mixed powder is, for example, 51.1 to 68.2 parts by weight of titanium oxide powder, 25.9 to 27.5 parts by weight of carbon powder, and 4.3 to 33.0 of molybdenum oxide powder. Furthermore, it is possible to make the blending ratio of molybdenum to 5 to 20 atomic% in the total amount with titanium.
When the mixing ratio of the titanium oxide powder, the carbon powder, and the molybdenum oxide powder is out of the above numerical range, the composition formula (Ti 1-X M1 X ) CN (where M1 is one of Mo and W) Species or two, where X is a carbonitride solid solution powder of titanium and molybdenum having a desired composition and particle size satisfying an atomic ratio of 0.02 ≦ X ≦ 0.3), and these powders It is not desirable because it is impossible to improve the characteristics of the cermet alloy produced by using the material.
In other words, if the blending ratio of molybdenum in the total amount with titanium is less than 2 atomic%, the particles become coarse due to a decrease in the effect of suppressing grain growth during powder formation, while the blending ratio of molybdenum is 30 atomic%. If the solid solution powder exceeds 1, the solid solution powder formed is not a single phase but an unsolid solution phase appears, and it is difficult to obtain a homogeneous solid solution powder. Therefore, the blending ratio of molybdenum in the total amount with titanium is 2-30. It is necessary to make it atomic%.
１４００℃までの昇温過程で、上記チタンとモリブデンとの炭化物固溶体、あるいは、チタンの炭化物を形成した後、非窒化性かつ非酸化性雰囲気（例えば、アルゴン雰囲気）から窒素雰囲気に切り替え、該窒素雰囲気中において、１４００〜１６００℃の温度範囲で、好ましくは、６０〜１２０分間熱処理を行う。
上記窒素雰囲気中での熱処理により、上記チタンとモリブデンとの炭化物固溶体あるいは上記チタン炭化物が窒化され、チタンとモリブデンの炭窒化物固溶体が形成される。
ここで、窒素雰囲気中における熱処理温度が１４００℃未満では、チタンの酸化物粉末の還元反応が進み難くなるためであり、一方、１６００℃を超える熱処理温度では、粉末の粒子成長が進み、所望の粒度の粉末を得ることができなくなることから、窒化反応を行わせる熱処理温度は、１４００〜１６００℃と定めた。また、この温度範囲における熱処理時間が６０分未満では、窒化反応が十分に進行せず所望の窒素量の粉末を得ることができず、また不均質なＣ／Ｎ組成の粉末となってしまい、一方、１２０分を超えると窒化反応が進み過ぎてしまい、窒素含有量の高い粉末となり、また長時間の処理は粒子の粗大化を引き起こすこと
から、熱処理時間は６０〜１２０分とすることが望ましい。
After forming the carbide solid solution of titanium and molybdenum or the titanium carbide in the temperature raising process up to 1400 ° C., the nitrogen is switched from a non-nitriding and non-oxidizing atmosphere (for example, argon atmosphere) to the nitrogen atmosphere. In the atmosphere, heat treatment is preferably performed in a temperature range of 1400 to 1600 ° C. for 60 to 120 minutes.
By the heat treatment in the nitrogen atmosphere, the carbide solid solution of titanium and molybdenum or the titanium carbide is nitrided to form a carbonitride solid solution of titanium and molybdenum.
Here, when the heat treatment temperature in the nitrogen atmosphere is less than 1400 ° C., the reduction reaction of the titanium oxide powder is difficult to proceed. On the other hand, when the heat treatment temperature exceeds 1600 ° C., the particle growth of the powder proceeds and the desired temperature is reached. Since it becomes impossible to obtain a powder having a particle size, the heat treatment temperature for performing the nitriding reaction was set to 1400 to 1600 ° C. In addition, if the heat treatment time in this temperature range is less than 60 minutes, the nitriding reaction does not proceed sufficiently and a powder having a desired nitrogen amount cannot be obtained, and the powder has a heterogeneous C / N composition. On the other hand, if it exceeds 120 minutes, the nitriding reaction proceeds too much, resulting in a powder having a high nitrogen content, and long-time treatment causes coarsening of the particles, so the heat treatment time is preferably 60 to 120 minutes. .
本発明で製造した上記チタン系炭窒化物固溶体粉末について、走査型電子顕微鏡で観察測定したところ、一次粒子の平均粒径は２００ｎｍ以下の超微粒粉末が得られることを確認した。
また、比表面積測定結果から求めた等価粒子径が約０．１３μｍであり、ＳＥＭ観察結果とほぼ同じであることなどから、粉末全体がほぼ同じ粒子径であることが分かる。
For the titanium-based carbonitride solid solution powder prepared in the present invention, was observed and measured with a scanning electron microscope, the average particle diameter of primary particles was confirmed that the obtained the following ultrafine powder 200 nm.
Moreover, since the equivalent particle diameter calculated | required from the specific surface area measurement result is about 0.13 micrometer, and it is substantially the same as a SEM observation result, it turns out that the whole powder is substantially the same particle diameter.
チタン系炭窒化物固溶体粉末を、組成式（Ｔｉ１−ＸＭ１Ｘ）ＣＮで表した場合、Ｍ１成分としてＭｏを選択したチタンとモリブデンの炭窒化物固溶体粉末の製造については上記したとおりであるが、Ｍ１成分として、Ｗ単独添加の場合あるいはＭｏとＷの両者を添加した場合についても、前記と同様、超微粒かつ均粒であって、しかも、タングステン成分、モリブデン成分の偏析がなく均質な固溶体組織を有するチタン系炭窒化物固溶体粉末を製造することができる。
Ｍ１成分としてＷ単独添加した場合、ＭｏとＷの両者を添加した場合も、Ｍ１成分としてＭｏを選択した場合と同様に、Ｔｉに対するＭ１成分の含有割合を表すＸの値（原子比）は、０．０２〜０．３であることが必要であり、Ｘの値がこの数値範囲を外れると、粉末形成時の粒成長抑制効果の低下による粒子の粗大化あるいは形成される固溶体粉末が単一相でなく未固溶相が出現し均質な固溶体粉末を得ることが困難となる。
When the titanium-based carbonitride solid solution powder is represented by the composition formula (Ti 1-X M1 X ) CN, the production of the titanium and molybdenum carbonitride solid solution powder with Mo selected as the M1 component is as described above. However, even when W alone is added as the M1 component or when both Mo and W are added, it is ultrafine and uniform in size as described above, and further, the tungsten component and the molybdenum component are not segregated and are homogeneous. Titanium carbonitride solid solution powder having a solid solution structure can be produced.
When W is added alone as the M1 component, even when both Mo and W are added, as in the case where Mo is selected as the M1 component, the value (atomic ratio) of X representing the content ratio of the M1 component with respect to Ti is: When the value of X is out of this numerical range, the particles become coarse due to a decrease in the effect of suppressing grain growth at the time of powder formation or a solid solution powder is formed. It is difficult to obtain a homogeneous solid solution powder because an unsolid solution phase appears instead of a phase.
本願の請求項２では、チタン系炭窒化物固溶体粉末について、これを組成式（Ｔｉ１−Ｘ−ＹＭ１ＸＭ２Ｙ）ＣＮで表した場合、Ｍ２成分として、Ｖ，Ｃｒ，Ｚｒ，Ｎｂ，Ｔａ，Ｈｆのうちの１種または２種以上を、０＜Ｙ＜０．１の範囲内で添加するとしているが、Ｍ２成分の添加によって、チタン系炭窒化物固溶体粉末の微粒化、均粒性、固溶体としての均質性に悪影響を及ぼすことはない。
むしろ、Ｖ添加は熱伝導率の向上、Ｃｒ添加は耐摩耗性の向上、Ｚｒ添加は溶融温度の上昇、Ｎｂ添加はヤング率の向上、Ｔａ添加はヤング率の向上と溶融温度の上昇、Ｈｆ添加は硬度の向上と溶融温度の上昇という、チタン系炭窒化物固溶体粉末の特性を改善するという効果がある。
In claim 2 of the present application, when the titanium-based carbonitride solid solution powder is represented by a composition formula (Ti 1-XY M1 X M2 Y ) CN, V, Cr, Zr, Nb, One or more of Ta and Hf are added within the range of 0 <Y <0.1. By adding the M2 component, the titanium carbonitride solid solution powder is atomized and uniformed. And homogeneity as a solid solution.
Rather, V addition improves thermal conductivity, Cr addition improves wear resistance, Zr addition increases melting temperature, Nb addition improves Young's modulus, Ta addition improves Young's modulus and melting temperature, Hf Addition has the effect of improving the properties of the titanium-based carbonitride solid solution powder, that is, increasing the hardness and increasing the melting temperature.
本発明の超微粒かつ均質なチタン系炭窒化物固溶体粉末の製造方法によれば、超微粒かつ均粒であって、しかも、Ｍｏ、ＷからなるＭ１成分、また、Ｖ，Ｃｒ，Ｚｒ，Ｎｂ，Ｔａ，ＨｆからなるＭ２成分の偏析がなく均質な固溶体組織を有するチタン系炭窒化物固溶体粉末を製造することができ、さらに、本発明により製造したチタン系炭窒化物固溶体粉末を用いることによって、例えば、すぐれた特性を備えるサーメット、超硬合金、セラミックス等焼結材料を得ることができるので、工業的な価値は非常に大きい。 According to the production method of the ultrafine and homogeneous titanium-based carbonitride solid solution powder of the present invention, the M1 component which is ultrafine and uniform and is composed of Mo and W, and V, Cr, Zr and Nb. Titanium carbonitride solid solution powder having a homogeneous solid solution structure with no segregation of M2 component consisting of Ti, Ta and Hf can be produced, and further, by using the titanium carbonitride solid solution powder produced according to the present invention Since, for example, sintered materials such as cermets, cemented carbides and ceramics having excellent characteristics can be obtained, the industrial value is very large.
以下に、本発明について、実施例を用いて説明する Hereinafter, the present invention will be described using examples.
《実施例１》
表１に示す平均粒径２０ｎｍのチタン酸化物（ＴｉＯ２）粉末、平均粒径５０ｎｍの炭素粉末、モリブデン酸化物（ＭｏＯ３）粉末、タングステン酸化物（ＷＯ３）粉末を、表１に示すチタン系炭窒化物固溶体組成となるように原料配合・混合して、混合粉末１〜５を用意した。
Example 1
Titanium oxide (TiO 2 ) powder having an average particle diameter of 20 nm, carbon powder having an average particle diameter of 50 nm, molybdenum oxide (MoO 3 ) powder, and tungsten oxide (WO 3 ) powder shown in Table 1 are shown in Table 1. The mixed powders 1 to 5 were prepared by mixing and mixing the raw materials so as to have a solid carbonitride solid solution composition.
混合粉末１〜５（１００ｇ）を電気炉内に装入し、アルゴン雰囲気中で、所定の昇温速度で所定の温度まで昇温加熱し、その後、雰囲気を窒素雰囲気に切り替え、該窒素雰囲気中において、所定の温度で所定時間熱処理し、熱処理終了後室温にまで徐冷することにより、チタンとモリブデン，タングステンの炭窒化物固溶体超微粒粉末からなる本発明のチタン系炭窒化物固溶体粉末（以下、本発明粉末という）１〜５を作製した。
表２に、処理条件を示す。
The mixed powders 1 to 5 (100 g) were charged into an electric furnace, heated to a predetermined temperature at a predetermined temperature increase rate in an argon atmosphere, and then switched to a nitrogen atmosphere. In the present invention, the titanium-based carbonitride solid solution powder of the present invention (hereinafter referred to as the titanium-carbonitride solid solution powder of the present invention consisting of a carbonitride solid solution ultrafine powder of titanium, molybdenum and tungsten is annealed to a room temperature after the heat treatment is completed for a predetermined time. 1 to 5).
Table 2 shows the processing conditions.
上記方法で作製した本発明粉末１〜５について、以下の測定法で、粒径、粒度分布、固溶体の均質性を測定し、また、Ｍｏ，Ｗの含有割合を測定し、Ｘ値を算出した。
粒径：平均粒径は比表面積測定結果から等価粒子径を計算により求めた。
粒度分布：ＳＥＭによる画像解析処理で５００ｎｍ以上の粒子を含まないことを確認した。
固溶体の均質性：Ｘ線回折装置により（Ｔｉ，Ｍ）ＣＮの回折パターンとＭｏ２Ｃ、ＷＣの回折パターンから其々の最強線強度から，Ｉ[Ｍｏ２Ｃ＋ＷＣ]／Ｉ[（Ｔｉ，Ｍ）ＣＮ] 比を算出し、その強度比が０．０５以下であることを確認した。
Ｍｏ，Ｗの含有割合：それぞれＩＣＰ発光分光分析装置によりＭｏ、Ｗ含有割合を測定した。
なお、Ｃ，Ｎの含有割合についても、赤外線吸収法で炭素含有割合を、また、熱伝導法で窒素含有割合を測定した。
これらの値を表３に示す。
About this invention powders 1-5 produced by the above method, the particle size, particle size distribution, and homogeneity of the solid solution were measured by the following measurement methods, and the content ratios of Mo and W were measured, and the X value was calculated. .
Particle size: The average particle size was obtained by calculating the equivalent particle size from the measurement result of the specific surface area.
Particle size distribution: It was confirmed by image analysis processing with SEM that particles of 500 nm or more were not included.
Homogeneity of solid solution: I [Mo2C + WC] / I [(Ti, M) CN from the strongest line intensity from the diffraction pattern of (Ti, M) CN and the diffraction pattern of Mo 2 C, WC by X-ray diffractometer ] Ratio was calculated and it was confirmed that the intensity ratio was 0.05 or less.
Mo and W content ratios: The Mo and W content ratios were measured with an ICP emission spectroscopic analyzer, respectively.
In addition, also about the content rate of C and N, the carbon content rate was measured by the infrared absorption method, and the nitrogen content rate was measured by the heat conduction method.
These values are shown in Table 3.
表３に示すように、本発明の製造方法によれば、一次粒子の平均粒径が２００ｎｍ以下の超微粒であって、かつ、５００ｎｍ以上の粒子を含まない均粒粉末であり、さらに、均質な固溶体組織を有する超微粒かつ均質なチタン系炭窒化物固溶体粉末を得られることがわかる。 As shown in Table 3, according to the production method of the present invention, the primary particles are ultrafine particles having an average particle size of 200 nm or less and do not contain particles of 500 nm or more, and are homogeneous. It can be seen that an ultrafine and homogeneous titanium-based carbonitride solid solution powder having a solid solution structure can be obtained.
《比較例１》
比較のために、表１に示す平均粒径のチタン酸化物（ＴｉＯ２）粉末、炭素粉末および金属酸化物（例えば、ＭｏＯ２，ＷＯ３，Ｖ２Ｏ５，Ｃｒ２Ｏ３，Ｎｂ２Ｏ５，Ｔａ２Ｏ５）粉末を、表１に示すチタン系炭窒化物固溶体組成となるように原料配合・混合して、混合粉末６〜１３を用意した。
ついで、混合粉末６〜１３（１００ｇ）を電気炉内に装入し、所定の雰囲気中で、所定の昇温速度で所定の温度にまで昇温加熱し、その後、所定の雰囲気中で、所定の温度で所定時間熱処理し、熱処理終了後室温にまで徐冷することにより、比較例のチタン系炭窒化物粉末（以下、比較例粉末という）６〜１３を作製した。
表２に、処理条件を示す。
ついで、本発明粉末１〜５と同様にして、一次粒子の平均粒径および粉末中におけるＴｉとの合量に占めるＭ１成分（但し、Ｍ１は、ＭｏあるいはＷ）の含有割合（Ｍ１／（Ｔｉ＋Ｍ１））を求めた。
これらの値を表３に示す。
<< Comparative Example 1 >>
For comparison, titanium oxide (TiO 2 ) powder, carbon powder and metal oxide (for example, MoO 2 , WO 3 , V 2 O 5 , Cr 2 O 3 , Nb 2 O) having an average particle diameter shown in Table 1 5 , Ta 2 O 5 ) powder was mixed and mixed so as to have a titanium-based carbonitride solid solution composition shown in Table 1 to prepare mixed powders 6 to 13.
Subsequently, the mixed powders 6 to 13 (100 g) are charged into an electric furnace, heated to a predetermined temperature at a predetermined temperature increase rate in a predetermined atmosphere, and then predetermined in the predetermined atmosphere. The titanium-based carbonitride powders (hereinafter referred to as “comparative example powders”) 6 to 13 of comparative examples were produced by heat-treating for a predetermined time at the above temperature and gradually cooling to room temperature after completion of the heat treatment.
Table 2 shows the processing conditions.
Next, in the same manner as in the powders 1 to 5 of the present invention, the content ratio (M1 / (Ti + M1) of the M1 component (where M1 is Mo or W) in the average particle diameter of the primary particles and the total amount of Ti in the powder. )).
These values are shown in Table 3.
表３に示されるように、比較例の製造方法によって得た比較例粉末６では昇温中の雰囲気による微粒化の効果が、比較例粉末７，８，１０，１１では平均粒径２００ｎｍ以下の超微粒粉末を合成するための適正処理温度とＭ１金属の適正添加量、また微細原料粉末の有効性を確認することができる。また、比較例粉末９，１２，１３では超微粒粉末を合成するためにはＭｏ，Ｗ添加が有効であることを確認することができる。
As shown in Table 3, the comparative example powder 6 obtained by the manufacturing method of the comparative example has an effect of atomization by the atmosphere during the temperature increase, and the comparative example powders 7, 8, 10, and 11 have an average particle size of 200 nm or less. It is possible to confirm the appropriate processing temperature for synthesizing the ultrafine powder, the appropriate amount of M1 metal added, and the effectiveness of the fine raw material powder. In addition, it can be confirmed that the addition of Mo and W is effective for synthesizing the ultrafine powder in the comparative example powders 9, 12, and 13.
《実施例２》
平均粒径２０ｎｍのチタン酸化物（ＴｉＯ２）粉末、平均粒径５０ｎｍの炭素粉末、モリブデン酸化物（ＭｏＯ３）粉末、タングステン酸化物（ＷＯ３）粉末に対して、さらに、Ｍ２成分の酸化物粉末（即ち、Ｖ，Ｃｒ，Ｎｂ，Ｔａの各酸化物粉末）を、表４に示すチタン系炭窒化物固溶体組成となるように原料配合・混合して、混合粉末１４〜１７を用意した。
Example 2
In addition to titanium oxide (TiO 2 ) powder having an average particle diameter of 20 nm, carbon powder having an average particle diameter of 50 nm, molybdenum oxide (MoO 3 ) powder, and tungsten oxide (WO 3 ) powder, an oxide of M2 component Powders (that is, oxide powders of V, Cr, Nb, and Ta) were mixed and mixed so as to have a titanium-based carbonitride solid solution composition shown in Table 4 to prepare mixed powders 14 to 17.
混合粉末１４〜１７（１００ｇ）を電気炉内に装入し、アルゴン雰囲気中で、所定の昇温速度で所定の温度まで昇温加熱し、その後、雰囲気を窒素雰囲気に切り替え、該窒素雰囲気中において、所定の温度で所定時間熱処理し、熱処理終了後室温にまで徐冷することにより、チタンとＭ１成分とＭ２成分の炭窒化物固溶体超微粒粉末からなる本発明のチタン系炭窒化物固溶体粉末（以下、本発明粉末という）１４〜１７を作製した。
表５に、処理条件を示す。
The mixed powders 14 to 17 (100 g) were charged into an electric furnace, heated to a predetermined temperature at a predetermined temperature increase rate in an argon atmosphere, and then the atmosphere was switched to a nitrogen atmosphere. The titanium-based carbonitride solid solution powder of the present invention consisting of titanium, M1 component, and M2 component carbonitride solid solution ultrafine powder by heat treatment at a predetermined temperature for a predetermined time, and gradually cooling to room temperature after the heat treatment is completed 14-17 (henceforth this invention powder) were produced.
Table 5 shows the processing conditions.
上記方法で作製した本発明粉末１４〜１７について、以下の測定法で、粒径、粒度分布、固溶体の均質性を測定し、また、Ｍ１成分，Ｍ２成分の含有割合を測定し、Ｘ値，Ｙ値を算出した。
粒径：平均粒径は比表面積測定結果から等価粒子径を計算により求めた。
粒度分布：ＳＥＭによる画像解析処理で５００ｎｍ以上の粒子を含まないことを確認した。
固溶体の均質性：Ｘ線回折装置により（Ｔｉ，Ｍ１，Ｍ２）ＣＮの回折パターンとＭ１成分の炭化物相（Ｍｏ２Ｃ、ＷＣ）、Ｍ２成分の炭化物相（ＶＣ、Ｃｒ３Ｃ２、ＮｂＣ、ＴａＣ等）の回折パターンから其々の最強線強度から，Ｉ[Ｍ１Ｃ＋Ｍ２Ｃ]／Ｉ[（Ｔｉ，Ｍ１、Ｍ２）ＣＮ] 比を算出し、その強度比が０．０５以下であることを確認した。
Ｍ１成分，Ｍ２成分の含有割合：ＩＣＰ発光分光分析装置によりＭ１、Ｍ２含有割合を測定した。
なお、Ｃ，Ｎの含有割合についても、赤外線吸収法で炭素含有割合を、また、熱伝導法で窒素含有割合を測定した。
これらの値を表６に示す。
For the inventive powders 14 to 17 produced by the above method, the particle size, particle size distribution, and homogeneity of the solid solution are measured by the following measurement methods, and the content ratios of the M1 component and M2 component are measured. Y value was calculated.
Particle size: The average particle size was obtained by calculating the equivalent particle size from the measurement result of the specific surface area.
Particle size distribution: It was confirmed by image analysis processing with SEM that particles of 500 nm or more were not included.
Solid solution homogeneity: (Ti, M1, M2) CN diffraction pattern, M1 component carbide phase (Mo 2 C, WC), M2 component carbide phase (VC, Cr3C2, NbC, TaC, etc.) From the diffraction pattern, the I [M1C + M2C] / I [(Ti, M1, M2) CN] ratio was calculated from each strongest line intensity, and it was confirmed that the intensity ratio was 0.05 or less.
Content ratio of M1 component and M2 component: M1 and M2 content ratios were measured with an ICP emission spectroscopic analyzer.
In addition, also about the content rate of C and N, the carbon content rate was measured by the infrared absorption method, and the nitrogen content rate was measured by the heat conduction method.
These values are shown in Table 6.
表６に示すように、本発明の製造方法によれば、一次粒子の平均粒径が２２０ｎｍ以下の超微粒であって、かつ、５００ｎｍ以上の粒子を含まない均粒粉末であり、さらに、均質な固溶体組織を有する超微粒かつ均質なチタン系炭窒化物固溶体粉末を得られることがわかる。
As shown in Table 6, according to the production method of the present invention, the primary particles are ultrafine particles having an average particle size of 220 nm or less and containing no particles of 500 nm or more, and It can be seen that an ultrafine and homogeneous titanium-based carbonitride solid solution powder having a homogeneous solid solution structure can be obtained.
《比較例２》
比較のために、表４に示す平均粒径４００ｎｍのチタン酸化物（ＴｉＯ２）粉末、平均粒径８０ｎｍの炭素粉末、モリブデン酸化物（ＭｏＯ３）粉末、タングステン酸化物（ＷＯ３）粉末に対して、さらに、Ｍ２成分の酸化物粉末（即ち、Ｖ，Ｃｒ，Ｎｂ，Ｔａの各酸化物粉末）を、表４に示すチタン系炭窒化物固溶体組成となるように原料配合・混合して、混合粉末１４〜１７を用意した。
ついで、混合粉末１４〜１７（１００ｇ）を電気炉内に装入し、所定の雰囲気中で、所定の昇温速度で所定の温度にまで昇温加熱し、その後、所定の雰囲気中で、所定の温度で所定時間熱処理し、熱処理終了後室温にまで徐冷することにより、比較例のチタン系炭窒化物粉末（以下、比較例粉末という）１８〜２１を作製した。
表５に、処理条件を示す。
ついで、本発明粉末１４〜１７と同様にして、一次粒子の平均粒径および粉末中におけるＴｉとの合量に占めるＭ１成分、Ｍ２成分の含有割合（Ｍ１／（Ｔｉ＋Ｍ１＋Ｍ２），Ｍ２／（Ｔｉ＋Ｍ１＋Ｍ２）。但し、原子比）を求めた。
これらの値を表６に示す。
<< Comparative Example 2 >>
For comparison, with respect to titanium oxide (TiO 2 ) powder having an average particle diameter of 400 nm, carbon powder having an average particle diameter of 80 nm, molybdenum oxide (MoO 3 ) powder, and tungsten oxide (WO 3 ) powder shown in Table 4 Further, the M2 component oxide powder (that is, each oxide powder of V, Cr, Nb, Ta) is mixed and mixed with the raw materials so as to have the titanium-based carbonitride solid solution composition shown in Table 4, Mixed powders 14 to 17 were prepared.
Subsequently, the mixed powders 14 to 17 (100 g) are charged into an electric furnace, heated to a predetermined temperature at a predetermined temperature increase rate in a predetermined atmosphere, and then predetermined in the predetermined atmosphere. The titanium-based carbonitride powders (hereinafter referred to as “comparative example powders”) 18 to 21 of comparative examples were produced by heat-treating at a temperature of a predetermined time and gradually cooling to room temperature after completion of the heat treatment.
Table 5 shows the processing conditions.
Subsequently, in the same manner as the powders 14 to 17 of the present invention, the average particle size of the primary particles and the content ratio of the M1 component and the M2 component in the total amount with Ti in the powder (M1 / (Ti + M1 + M2), M2 / (Ti + M1 + M2) However, the atomic ratio) was determined.
These values are shown in Table 6.
表６に示されるように、比較例の製造方法によって得た比較例粉末１８〜２１では、一次粒子の平均粒径は約１．５μｍ以上であって、本発明粉末１４〜１７の平均粒径２２０ｎｍ以下と比較して平均粒径が大きく粗粒である。
また、本発明粉末１４〜１７は、ＴｉとＭ１，Ｍ２成分が均質な固溶体組織を有するのに対して、比較例粉末１８〜２１では、粉末中におけるＴｉとＭ１，Ｍ２成分との固溶体組織は均質であるとはいえない。
As shown in Table 6, in Comparative Example powders 18 to 21 obtained by the production method of the Comparative Example, the average particle size of the primary particles is about 1.5 μm or more, and the average particle size of the inventive powders 14 to 17 Compared to 220 nm or less , the average particle size is large and coarse.
In addition, the inventive powders 14 to 17 have a solid solution structure in which Ti, M1, and M2 components are homogeneous, whereas in the comparative example powders 18 to 21, the solid solution structure of Ti and M1, M2 components in the powder is It cannot be said to be homogeneous.
以上のとおり、本発明の製造方法によれば、超微粒で均粒、しかも、均質な固溶体組織を有するチタン系炭窒化物固溶体粉末を製造し得るものである。
そして、本発明により得たチタン系炭窒化物固溶体粉末を、例えば、金属基複合材料、セラミックス材料の特性改善のための分散材、あるいは、サーメット製造用の原料粉末等として用いることによって、すぐれた特性を備える複合材料、セラミックス、サーメット等を得ることができるので、本発明の工業的な価値は非常に大きい。
As described above, according to the production method of the present invention, it is possible to produce a titanium-based carbonitride solid solution powder having ultrafine particles, uniform particles, and a homogeneous solid solution structure.
The titanium-based carbonitride solid solution powder obtained according to the present invention is excellent by using, for example, a metal matrix composite material, a dispersion material for improving the characteristics of ceramic materials, or a raw material powder for cermet production. Since composite materials, ceramics, cermets and the like having characteristics can be obtained, the industrial value of the present invention is very large.
Claims (2)
One or two kinds of titanium oxide powder, carbon powder, molybdenum oxide powder or tungsten oxide powder each having an average particle diameter of 10 to 200 nm , vanadium oxide powder, chromium oxide powder, zirconium A mixed powder composed of one or more oxide powders of oxide powder, niobium oxide powder, tantalum oxide powder, and hafnium oxide powder is heated to 1400 ° C. in an argon atmosphere of 0.1 atm or more. Then, the atmosphere is switched to a nitrogen atmosphere, and heat treatment is performed in the nitrogen atmosphere at a temperature range of 1400 to 1600 ° C. for 60 to 120 minutes (Ti 1-XY M1 X M2 Y ) CN (where M1 is one or two of Mo and W. M2 is V, Cr, Zr, Nb, Ta, Hf) .X 1 or two or more, Y are both atomic ratio is expressed by X = 0.02~0.3,0 <Y <0.1) , an average primary particle diameter of 220nm or less A method for producing ultrafine and homogeneous titanium-based carbonitride solid solution powder having a uniform solid solution structure, and a uniform powder having no ultrafine particles of 500 nm or more .
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