JP5294458B2 - Composite powder and method for producing the same - Google Patents
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この発明は、すぐれた強度、靭性、硬さを有し、例えば、これをサーメット製切削工具等の原料粉末に用いた場合に、優れた工具特性を発揮するサーメット製切削工具製造用複合粉末及びその製造方法に関する。
The present invention has excellent strength, toughness, hardness, and, for example, a composite powder for producing a cermet cutting tool that exhibits excellent tool characteristics when used as a raw material powder such as a cermet cutting tool, and the like. It relates to the manufacturing method.
従来、一般的に、サーメット製品の製造用原料粉末として用いられるチタン系粉末（例えば、炭化チタン、窒化チタン及び炭窒化チタンの何れか１種または２種以上からなる粉末。以下、Ｔｉ系粉末で示す。）及びその製造法としては、例えば、窒化チタン粉末と炭化チタン粉末との混合粉末を熱処理して固溶化した炭窒化チタン粉末を得ることが知られている。 Conventionally, titanium-based powders that are generally used as raw material powders for producing cermet products (for example, powders composed of one or more of titanium carbide, titanium nitride, and titanium carbonitride. Hereinafter, Ti-based powders are used. And a manufacturing method thereof, for example, it is known to obtain a titanium carbonitride powder obtained by solidifying a mixed powder of a titanium nitride powder and a titanium carbide powder by heat treatment.
また、特許文献１に開示されているように、例えば、３価のチタンイオンと錯化剤を含む水溶液に、Ｔｉ系粉末を加え攪拌し、該液をアルカリ性にした後に、コバルトイオン等の鉄族イオンを加えて攪拌することにより、Ｔｉ系粉末表面にコバルト等の鉄族金属をコーティングした複合粉末も知られている。
しかし、窒化チタン粉末と炭化チタン粉末との混合粉末を熱処理して固溶化する上記従来技術においては、炭素、窒素等の拡散を十分行わせるためには長時間を要するため、効率的な反応が行われるとはいえず、また、所望均一組成のＴｉ系粉末を得ることは非常に困難であるため均質な特性を備えたサーメット製品を得ることは困難であった。
また、Ｔｉ系粉末表面にコバルト等の鉄族金属をコーティングする上記従来技術においても、コーティング量の調整が難しく、そのため、硬さ−強度−靭性バランスのとれたサーメット製品を得ることが困難であった。
そこで、本発明は、サーメット製切削工具等のすぐれた特性を備えたサーメット製品を製造するのに好適なＴｉ系の複合粉末を提供することを目的とし、またこのようなＴｉ系の複合粉末を簡易な方法で製造することができる製造方法を提供することを目的とする。
However, in the above-described prior art in which a mixed powder of titanium nitride powder and titanium carbide powder is heat-treated to form a solid solution, it takes a long time to sufficiently diffuse carbon, nitrogen, etc. It is difficult to obtain a cermet product having uniform characteristics because it is very difficult to obtain a Ti-based powder having a desired uniform composition.
Further, even in the above-described conventional technique in which the surface of the Ti-based powder is coated with an iron group metal such as cobalt, it is difficult to adjust the coating amount, and thus it is difficult to obtain a cermet product having a balance of hardness-strength-toughness. It was.
Then, this invention aims at providing the Ti type composite powder suitable for manufacturing the cermet product provided with the outstanding characteristics, such as a cutting tool made from cermet, Moreover, such a Ti type composite powder is provided. It aims at providing the manufacturing method which can be manufactured by a simple method.
本発明者らは、サーメット製品の原料粉末として用いた場合にすぐれた強度、靭性、硬さを示す新たなＴｉ系粉末について鋭意研究を行い、この要請に適う新たな組織構造を有するＴｉ系複合粉末とその製造方法を見出した。
即ち、Ｔｉ系粉末と、Ｃｏ及び／又はＮｉを含有する水溶性塩の溶液とを混合・乾燥して原料混合物を調整し、これを不活性ガス雰囲気中で熱処理し、水溶性塩の熱分解処理を行った後還元処理を行うことにより、個々のＴｉ系粉末の表面には、Ｃｏ及び／又はＮｉの微細粒子粉末が付着する形態で複合化している新たな組織構造の複合粉末を得ることができること、そして、この複合粉末を用いて、例えば、サーメット製切削工具を製造すると、該サーメット製切削工具は、高硬度、高靭性を備え、長期の使用にわたって、すぐれた耐欠損性と耐摩耗性を発揮すること。
The present inventors have earnestly studied a new Ti-based powder exhibiting excellent strength, toughness, and hardness when used as a raw material powder of a cermet product, and a Ti-based composite having a new structure that meets this requirement The powder and its manufacturing method were found.
That is, a raw material mixture is prepared by mixing and drying a Ti-based powder and a solution of a water-soluble salt containing Co and / or Ni, heat-treated in an inert gas atmosphere, and thermal decomposition of the water-soluble salt. After the treatment is performed, a reduction treatment is performed to obtain a composite powder having a new structure structure in which fine particles of Co and / or Ni are adhered to the surface of each Ti-based powder. When, for example, a cermet cutting tool is manufactured using this composite powder, the cermet cutting tool has high hardness and high toughness, and has excellent fracture resistance and wear resistance over a long period of use. To demonstrate sexuality.
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０．５〜２．５μｍの窒化チタン及び炭窒化チタンの何れか１種または２種からなるチタン系粉末と、平均粒径３７ｎｍ以下のコバルト及びニッケルの何れか１種または２種からなる微細粒子粉末が複合化された複合粉末において、
（ａ）上記コバルト及びニッケルの何れか１種または２種からなる微細粒子粉末は、上記チタン系粉末の表面に付着する形で複合化しており、
（ｂ）上記コバルト及びニッケルの何れか１種または２種からなる微細粒子粉末の全粉末に対する含有割合は５〜３０重量％であり、
（ｃ）上記複合粉末の比表面積（ＢＥＴ値）は、４．５２ｍ２／ｇ以上であり、
（ｄ）上記複合粉末中の酸素含有量は、４．０重量％以下である、
ことを特徴とするサーメット製切削工具製造用複合粉末。
（２） 前記（１）に記載のサーメット製切削工具製造用複合粉末の製造方法において、
窒化チタン及び炭窒化チタンの何れか１種または２種からなるチタン系粉末と、コバルト及びニッケルの何れか１種または２種を含有する水溶性塩の溶液とを混合し、その後乾燥することによって、前記窒化チタン及び炭窒化チタンの何れか１種または２種からなるチタン系粉末が、コバルト及びニッケルの何れか１種または２種を含有する水溶性塩を担持してなる原料混合物を調整し、
上記原料混合物を不活性ガス雰囲気中にて２００〜５００℃の温度で熱処理することによって、コバルト及びニッケルの何れか１種または２種を含有する水溶性塩の熱分解処理を行い、窒化チタン及び炭窒化チタンの何れか１種または２種からなるチタン系粉末と熱分解反応生成物の混合物を形成し、
次いで、チタン系粉末と熱分解反応生成物からなる上記混合物を水素雰囲気中にて２００〜９００℃の温度で還元処理する、
ことを特徴とする前記（１）に記載のサーメット製切削工具製造用複合粉末の製造方法。」
に特徴を有するものである。
This invention has been made based on the above findings,
"(1) any average particle size and either one or two or Ranaru titanium-based powders nitrided titanium and titanium carbonitride of 0.5 to 2.5 .mu.m, average particle size below 37 nm of cobalt and nickel In a composite powder in which fine particle powder composed of 1 type or 2 types is combined,
(A) The fine particle powder consisting of any one or two of the cobalt and nickel is compounded in a form that adheres to the surface of the titanium-based powder,
(B) The content ratio of the fine particle powder composed of any one or two of cobalt and nickel to the total powder is 5 to 30% by weight,
(C) The specific surface area (BET value) of the composite powder is 4.52 m 2 / g or more,
(D) The oxygen content in the composite powder is 4.0% by weight or less.
A composite powder for producing a cermet cutting tool .
(2) In the method for producing a composite powder for producing a cermet cutting tool according to (1),
One or the two or Ranaru titanium-based powder either nitrided titanium and titanium carbonitride, with a solution of cobalt and soluble salts containing either one or nickel are mixed, then dried by any one or any Ranaru titanium-based powder before Ki窒 titanium and titanium carbonitride is formed by carrying a water-soluble salt containing either one or two of cobalt and nickel Adjust the raw material mixture,
By heat treatment at a temperature of 200 to 500 ° C. The above raw material mixture in an inert gas atmosphere, subjected to thermal decomposition treatment of the water-soluble salts containing either one or two of cobalt and nickel, nitrogen, titanium and forming a mixture of any one or two or Ranaru titanium-based powder and the thermal decomposition reaction products of titanium carbonitride,
Next, the mixture comprising the titanium-based powder and the thermal decomposition reaction product is subjected to reduction treatment at a temperature of 200 to 900 ° C. in a hydrogen atmosphere.
The method for producing a composite powder for producing a cermet cutting tool as described in (1) above. "
It has the characteristics.
以下に、本発明について説明する。 The present invention will be described below.
図１には、本発明の複合粉末の製造フローの一例を示す。
まず、図１にしたがって、本発明の製造方法の概略について説明する。
（イ）この例においては、Ｔｉ系粉末として炭窒化チタン粉末（以下、ＴｉＣＮ粉末で示す）を用い、また、コバルト及びニッケルの何れか１種または２種を含有する水溶性塩の溶液として、硝酸Ｃｏ水溶液及び／又は硝酸Ｎｉ水溶液を用い、
（ロ）Ｔｉ系粉末と硝酸Ｃｏ水溶液及び／又は硝酸Ｎｉ水溶液とを、例えば、ボールミル中で５時間混合し、１５０℃で乾燥した後解砕し、ＴｉＣＮ粉末表面に硝酸Ｃｏ及び／又は硝酸Ｎｉを担持する原料混合物を調整し、
（ハ）次いで、上記原料混合物を、例えば、窒素雰囲気中にて、３００℃×１時間熱処理して、ＴｉＣＮ粉末表面の硝酸Ｃｏ及び／又は硝酸Ｎｉを熱分解させ、ＴｉＣＮ粉末表面に熱分解反応生成物（例えば、酸化Ｃｏ及び／又は酸化Ｎｉ）が生成したＴｉＣＮ粉末と熱分解反応生成物の混合物を形成し、
（ニ）次いで、上記混合物を、水素雰囲気中にて、例えば、３００℃×１時間熱処理して、ＴｉＣＮ粉末表面の熱分解反応生成物を還元することにより、
ＴｉＣＮ粉末表面に、Ｃｏ及び／又はＮｉの微細粒子粉末が付着する形で複合化した新たな組織構造を有するＴｉ系複合粉末を得ることができる。
FIG. 1 shows an example of the production flow of the composite powder of the present invention.
First, the outline of the production method of the present invention will be described with reference to FIG.
(A) In this example, titanium carbonitride powder (hereinafter referred to as TiCN powder) is used as the Ti-based powder, and as a solution of a water-soluble salt containing one or two of cobalt and nickel, Using Ni nitrate aqueous solution and / or Ni nitrate aqueous solution,
(B) Ti-based powder and aqueous Ni nitrate solution and / or Ni nitrate aqueous solution are mixed in, for example, a ball mill for 5 hours, dried at 150 ° C. and then crushed, and CoNi nitrate and / or Ni nitrate on the surface of TiCN powder. Adjusting the raw material mixture carrying
(C) Next, the raw material mixture is heat-treated in, for example, a nitrogen atmosphere at 300 ° C. for 1 hour to thermally decompose Co nitrate and / or Ni nitrate on the surface of the TiCN powder, thereby causing a thermal decomposition reaction on the surface of the TiCN powder. Forming a mixture of TiCN powder and pyrolysis reaction product produced by product (eg, Co oxide and / or Ni oxide);
(D) Next, the mixture is heat-treated in a hydrogen atmosphere, for example, at 300 ° C. for 1 hour to reduce the thermal decomposition reaction product on the surface of the TiCN powder,
A Ti-based composite powder having a new structure in which Co and / or Ni fine particles adhere to the surface of the TiCN powder can be obtained.
図２には、本発明の製造方法によって得られた上記Ｔｉ系複合粉末の走査電子顕微鏡写真を示すが、この図からもわかるとおり、ＴｉＣＮ粉末の表面には、Ｃｏ及びＮｉの微細粒子粉末が付着する形で複合化した新たな組織構造が形成されていることが観察される。 FIG. 2 shows a scanning electron micrograph of the Ti-based composite powder obtained by the production method of the present invention. As can be seen from this figure, fine particles of Co and Ni are present on the surface of the TiCN powder. It is observed that a new tissue structure complexed in the form of adhering is formed.
次に、まず、本発明の複合粉末について、より具体的かつ詳細に説明する。
本発明のサーメット製造用複合粉末は、平均粒径０．５〜２．５μｍの窒化チタン及び炭窒化チタンの何れか１種または２種からなるＴｉ系粉末の表面に、平均粒径３７ｎｍ以下のＣｏ及び／又はＮｉの微細粒子粉末が付着する形で複合化した組織構造を有する複合粉末であるが、まず、上記Ｔｉ系粉末の平均粒径が０．５μｍ未満では原料Ｔｉ系粉末の酸素値が高くなり、その結果、複合粉末の酸素含有量が４．０％を超えてしまい、焼結後の焼結密度の低下、ひいては合金特性に悪影響を及ぼすためであり、一方、平均粒径が２．５μｍを超えると、焼結後の組織が粗大になり、強度や靭性の低下を招くことから、Ｔｉ系粉末の平均粒径を０．５〜２．５μｍと定めた。
また、Ｔｉ系粉末の表面に付着・複合化するＣｏ及び／又はＮｉの微細粒子粉末の平均粒径が１００ｎｍを超えると、Ｔｉ系粉末表面への分散性が低下し、焼結後のサーメットの強度、靭性の低下を招くことから、Ｃｏ及び／又はＮｉの微細粒子粉末の平均粒径は１００ｎｍ以下とすることが必要であり、本発明では３７ｎｍ以下と定めた。
Next, the composite powder of the present invention will be described more specifically and in detail.
Cermet prepared composite powder of the present invention, either one or two or Ranaru Ti system surface of the powder having an average particle diameter of nitrided titanium and titanium carbonitride of 0.5 to 2.5 .mu.m, the mean particle size of 37 It is a composite powder having a textured structure in which fine particle powders of Co and / or Ni of less than nm are adhered. First, if the average particle size of the Ti powder is less than 0.5 μm, the raw material Ti powder As a result, the oxygen content of the composite powder exceeds 4.0%, resulting in a decrease in the sintered density after sintering, and thus adversely affecting the alloy characteristics. If the particle size exceeds 2.5 μm, the structure after sintering becomes coarse and the strength and toughness are reduced. Therefore, the average particle size of the Ti-based powder is determined to be 0.5 to 2.5 μm.
Further, when the average particle size of the Co and / or Ni fine particle powder adhering to and complexed with the surface of the Ti-based powder exceeds 100 nm, the dispersibility on the surface of the Ti-based powder is lowered, and the sintered cermet Since the strength and toughness are reduced, the average particle size of the Co and / or Ni fine particle powder is required to be 100 nm or less . In the present invention, it is determined to be 37 nm or less.
さらに、本発明では、Ｃｏ及び／又はＮｉからなる微細粒子粉末の付着割合（重量％で、（Ｃｏ粉末＋Ｎｉ粉末）／全粉末×１００）が５重量％未満であると、結合成分であるＣｏ、Ｎｉの量が少なすぎるためサーメットの焼結性が低下し、一方、３０重量％を超えると、結合成分であるＣｏ、Ｎｉの量が多くなりすぎサーメット焼結体の硬度、強度が低下するので、微細粒子粉末の全粉末に占める含有割合は５〜３０重量％と定めた。 Furthermore, in the present invention, when the adhesion ratio (by weight%, (Co powder + Ni powder) / total powder × 100) of the fine particle powder made of Co and / or Ni is less than 5% by weight, Co which is a binding component Since the amount of Ni is too small, the sinterability of the cermet is reduced. On the other hand, when it exceeds 30% by weight, the amount of Co and Ni as binding components is excessively increased and the hardness and strength of the cermet sintered body are reduced. Therefore, the content ratio of the fine particle powder in the total powder is determined to be 5 to 30% by weight.
さらに、本発明では、Ｔｉ系粉末の表面にＣｏ及び／又はＮｉの微細粒子粉末が付着・複合化した複合粉末の比表面積（ＢＥＴ値）を４．５２ｍ２／ｇ以上と定めたが、これは、Ｔｉ系粉末の表面へのＣｏ及び／又はＮｉの微細粒子粉末の分散性を高め、もって、焼結後のサーメットの強度、靭性の向上を図るという理由によるものである。
Furthermore, in the present invention, the specific surface area (BET value) of the composite powder in which the fine particles of Co and / or Ni are adhered and combined on the surface of the Ti-based powder is set to 4.52 m 2 / g or more. This is because the dispersibility of the Co and / or Ni fine particle powder on the surface of the Ti-based powder is enhanced, thereby improving the strength and toughness of the cermet after sintering.
次に、本発明の複合粉末の製造方法について、より具体的かつ詳細に説明する。
（イ）まず、窒化チタン及び炭窒化チタンの何れか１種または２種からなるＴｉ系粉末と、Ｃｏ及び／又はＮｉを含有する水溶性塩の溶液、例えば、硝酸Ｃｏ（Ｃｏ（ＮＯ３）２）水溶液及び／又は硝酸Ｎｉ（Ｎｉ（ＮＯ３）２）水溶液、とを混合し、その後乾燥することによって、前記Ｃｏ及び／又はＮｉを含有する水溶性塩（例えば、硝酸Ｃｏ，硝酸Ｎｉ）が前記Ｔｉ系粉末の表面に担持されてなる原料混合物を形成し、この原料混合乾燥物の塊を粒径が１．５ｍｍ以下となるように解砕する。
Next, the method for producing the composite powder of the present invention will be described more specifically and in detail.
(A) First, with any one or any Ranaru Ti-based powders nitrided titanium and titanium carbonitride, a solution of a water-soluble salt containing Co and / or Ni, for example, nitrate Co (Co (NO 3 ) 2 ) An aqueous solution and / or an aqueous solution of Ni nitrate (Ni (NO 3 ) 2 ), and then dried to obtain a water-soluble salt containing Co and / or Ni (for example, Co nitrate, nitric acid) Ni) is formed on the surface of the Ti-based powder to form a raw material mixture, and the mass of the raw material mixed dried product is crushed so that the particle diameter is 1.5 mm or less.
Ｃｏ及び／又はＮｉを含有する水溶性塩の溶液としては、硝酸Ｃｏ（Ｃｏ（ＮＯ３）２）水溶液及び／又は硝酸Ｎｉ（Ｎｉ（ＮＯ３）２）水溶液が好適であるが、これに限らず、乾燥後のＴｉ系粉末の表面に、Ｃｏ，Ｎｉの塩が担持されるようなＣｏ及び／又はＮｉを含有する水溶性塩の溶液であれば、いかなるものでも使用することができる。
また、上記の混合は、Ｔｉ系粉末の表面を、上記水溶性塩の溶液で十分に濡らすために、例えば、ボールミル等による５時間程度攪拌することにより行なわれ、さらに、その後の乾燥は、粉末に付着している余分な水分を除去するとともに、Ｔｉ系粉末表面に上記水溶性塩（例えば、硝酸コバルト及び／又は硝酸ニッケル）を均一に担持するため、１５０℃前後の温度で行なわれる。
As the solution of the water-soluble salt containing Co and / or Ni, an aqueous solution of Co (Co (NO 3 ) 2 ) nitrate and / or an aqueous solution of Ni (Ni (NO 3 ) 2 ) nitrate is preferable, but not limited thereto. Any water-soluble salt solution containing Co and / or Ni in which a Co and Ni salt is supported on the surface of the Ti-based powder after drying can be used.
Further, the above mixing is performed by, for example, stirring for about 5 hours with a ball mill or the like in order to sufficiently wet the surface of the Ti-based powder with the solution of the water-soluble salt. In order to remove excess water adhering to the surface and uniformly support the water-soluble salt (for example, cobalt nitrate and / or nickel nitrate) on the surface of the Ti-based powder, the process is performed at a temperature of about 150 ° C.
（ロ）次に、上記原料混合物を、窒素、アルゴン等の不活性ガス雰囲気中で、２００〜５００℃の温度範囲で熱処理することによって、過度の酸化を避けつつ、Ｔｉ系粉末の表面に担持されるＣｏ及び／又はＮｉの水溶性塩の熱分解処理を行い、Ｔｉ系粉末と熱分解反応生成物の混合物を形成する。 (B) Next, the raw material mixture is heat-treated in an inert gas atmosphere such as nitrogen or argon in a temperature range of 200 to 500 ° C., and is supported on the surface of the Ti-based powder while avoiding excessive oxidation. The water-soluble salt of Co and / or Ni is thermally decomposed to form a mixture of the Ti-based powder and the thermal decomposition reaction product.
上記熱分解処理によって、原料混合物中のＴｉ系粉末表面に担持されていたＣｏ及び／又はＮｉの水溶性塩（例えば、硝酸コバルト及び／又は硝酸ニッケル）の熱分解が生じると同時に、Ｔｉ系粉末表面の一部には、例えば、酸化コバルト及び／又は酸化ニッケルのような酸化物が形成されるが、Ｔｉ系粉末の酸化物の形成を極力避けるために、窒素、アルゴン等の不活性ガス雰囲気中で熱処理を行い、かつ、熱処理温度も２００〜５００℃という比較的低温の温度範囲で熱処理を行うことにより、Ｔｉ系粉末の過度の酸化を避けつつ、Ｔｉ系粉末と熱分解反応生成物の混合物を形成する。 The thermal decomposition treatment causes thermal decomposition of a water-soluble salt of Co and / or Ni (for example, cobalt nitrate and / or nickel nitrate) supported on the surface of the Ti powder in the raw material mixture, and at the same time, Ti powder. For example, an oxide such as cobalt oxide and / or nickel oxide is formed on a part of the surface, but in order to avoid the formation of an oxide of Ti-based powder as much as possible, an inert gas atmosphere such as nitrogen or argon is used. Heat treatment in a relatively low temperature range of 200 to 500 ° C., and avoiding excessive oxidation of the Ti powder, while the Ti powder and the pyrolysis reaction product A mixture is formed.
（ハ）次に、Ｔｉ系粉末と熱分解反応生成物からなる上記混合物を、水素雰囲気中で、２００〜９００℃の温度範囲で熱処理することによって、前記熱分解処理で一部に形成された酸化コバルト及び／又は酸化ニッケルのような酸化物の還元を行い、Ｔｉ系粉末表面にＣｏ及び／又はＮｉからなる微細粒子粉末が付着・複合化する複合粉末を形成する。 (C) Next, the mixture composed of the Ti-based powder and the thermal decomposition reaction product was heat-treated in a hydrogen atmosphere at a temperature range of 200 to 900 ° C., and thus partially formed by the thermal decomposition treatment. An oxide such as cobalt oxide and / or nickel oxide is reduced to form a composite powder in which fine particle powder made of Co and / or Ni adheres to and is combined with the surface of the Ti-based powder.
上記（イ）〜（ハ）からなる製造方法によって、
平均粒径０．５〜２．５μｍのＴｉ系粉末と、平均粒径３７ｎｍ以下のＣｏ及び／又はＮｉからなる微細粒子粉末が複合化され、
（ａ）前記Ｃｏ及び／又はＮｉからなる微細粒子粉末は、前記Ｔｉ系粉末の表面に付着する形で複合化しており、
（ｂ）前記Ｃｏ及び／又はＮｉからなる微細粒子粉末の全粉末に対する含有割合は５〜３０重量％であり、
（ｃ）前記複合粉末の比表面積（ＢＥＴ値）は、４．５２ｍ２／ｇ以上であり、
（ｄ）前記複合粉末中の酸素含有量は、４．０重量％以下である、
という本発明のサーメット製切削工具製造用複合粉末を得ることができる。
By the manufacturing method consisting of (i) to (c) above,
A Ti-based powder having an average particle size of 0.5 to 2.5 μm and a fine particle powder composed of Co and / or Ni having an average particle size of 37 nm or less are combined,
(A) The fine particle powder made of Co and / or Ni is combined in a form that adheres to the surface of the Ti-based powder,
(B) The content ratio of the fine particle powder made of Co and / or Ni to the total powder is 5 to 30% by weight,
(C) The specific surface area (BET value) of the composite powder is 4.52 m 2 / g or more,
(D) The oxygen content in the composite powder is 4.0% by weight or less.
A composite powder for producing a cermet cutting tool of the present invention can be obtained.
そして、この複合粉末を原料粉末として、サーメット製品、例えば、サーメット製切削工具を焼結により製造したところ、この切削工具は、高硬度、高靭性、高強度を備え、長期の使用にわたってすぐれた耐欠損性と耐摩耗性を発揮するものであった。 Then, when this composite powder is used as a raw material powder, a cermet product, for example, a cermet cutting tool is manufactured by sintering. Demonstrate and wear resistance were exhibited.
本発明によれば、本発明のサーメット製切削工具製造用複合粉末は、Ｔｉ系粉末と、その表面に付着・複合化するＣｏ及び／又はＮｉからなる微細粒子粉末との新たな組織構造を有し、そのため、この複合粉末を用いて製造されたサーメット製品は、高硬度、高靭性及び高強度を備え、例えば、この複合粉末を用いて製造されたサーメット製切削工具においては、長期の使用にわたって、すぐれた耐欠損性及び耐摩耗性を発揮し、工具性能の向上ばかりか、工具の長寿命化が図られる。
According to the present invention, the composite powder for producing a cermet cutting tool of the present invention has a new structure of a Ti-based powder and a fine particle powder composed of Co and / or Ni that adheres to and is combined with the surface thereof. Therefore, a cermet product manufactured using this composite powder has high hardness, high toughness, and high strength. For example, in a cermet cutting tool manufactured using this composite powder, It exhibits excellent chipping resistance and wear resistance, and improves tool performance as well as prolongs tool life.
以下に、本発明を実施例に基づいて詳細に説明する。 Hereinafter, the present invention will be described in detail based on examples.
Ｔｉ系粉末として、炭素と窒素の含有割合が原子比で１：１である炭窒化チタン（ＴｉＣ０．５Ｎ０．５）粉末を以下の方法で製造した。
まず、酸化チタンとカーボンブラックを混合した後、窒素雰囲気中で１８００℃で熱処理することで、炭素と窒素の含有割合が原子比で１：１であり、平均粒径が１．３１μｍの炭窒化チタン粉末（ＴｉＣ０．５Ｎ０．５粉末）を得た。
As the Ti-based powder, a titanium carbonitride (TiC 0.5 N 0.5 ) powder having a carbon / nitrogen content ratio of 1: 1 by atomic ratio was produced by the following method.
First, after mixing titanium oxide and carbon black, heat treatment is performed at 1800 ° C. in a nitrogen atmosphere, so that the carbon / nitrogen content ratio is 1: 1 by atomic ratio and the average particle size is 1.31 μm. Titanium powder (TiC 0.5 N 0.5 powder) was obtained.
次に、上記ＴｉＣ０．５Ｎ０．５粉末を、２．５ｍｏｌ／ＬＣｏ及び２．５ｍｏｌ／ＬＮｉを含有する（Ｃｏ（ＮＯ３）２＋Ｎｉ（ＮＯ３）２）水溶液と混合し、ホールミル中で５時間混合した後、１５０℃で５時間乾燥し、これを解砕し、平均粒径１．５ｍｍ以下の原料混合物を形成した。
次いで、この原料混合物を、窒素ガス雰囲気中で３００℃×１時間加熱して、熱分解処理を行い、ＴｉＣ０．５Ｎ０．５粉末と熱分解反応生成物（酸化Ｃｏ，酸化Ｎｉ等）の混合物を形成した。
その後、上記ＴｉＣ０．５Ｎ０．５粉末と熱分解反応生成物の混合物を、水素ガス雰囲気中で３００℃×１時間加熱して、還元処理を行うことにより、本発明の複合粉末（以下、本発明粉末１という）を製造した。
Next, the TiC 0.5 N 0.5 powder is mixed with an aqueous solution containing 2.5 mol / LCo and 2.5 mol / LNi (Co (NO 3 ) 2 + Ni (NO 3 ) 2 ) For 5 hours and then dried at 150 ° C. for 5 hours, and crushed to form a raw material mixture having an average particle size of 1.5 mm or less.
Next, this raw material mixture is heated in a nitrogen gas atmosphere at 300 ° C. for 1 hour to perform thermal decomposition treatment, and TiC 0.5 N 0.5 powder and a thermal decomposition reaction product (Co oxide, Ni oxide, etc.) Formed a mixture.
Thereafter, the mixture of the TiC 0.5 N 0.5 powder and the thermal decomposition reaction product is heated in a hydrogen gas atmosphere at 300 ° C. for 1 hour to perform a reduction treatment, whereby the composite powder of the present invention (hereinafter referred to as the composite powder) Inventive powder 1) was produced.
また、上記本発明粉末１の製造において、ＴｉＣ０．５Ｎ０．５粉末と混合する（Ｃｏ（ＮＯ３）２＋Ｎｉ（ＮＯ３）２）水溶液のＣｏ濃度を１．３５ｍｏｌ／Ｌに変更し、さらに、Ｎｉ濃度を１．３５ｍｏｌ／Ｌに変更し、それ以外は、上記本発明粉末１の製造工程と全く同じ工程で、本発明の複合粉末（以下、本発明粉末２という）を製造した。 In the production of the powder 1 of the present invention, the Co concentration of the aqueous solution (Co (NO 3 ) 2 + Ni (NO 3 ) 2 ) mixed with the TiC 0.5 N 0.5 powder was changed to 1.35 mol / L. Further, the Ni concentration was changed to 1.35 mol / L, and the composite powder of the present invention (hereinafter referred to as the present invention powder 2) was produced in the same process as the production process of the present invention powder 1 except that. .
上記本発明粉末１の製造において、ＴｉＣ０．５Ｎ０．５粉末と混合する（Ｃｏ（ＮＯ３）２＋Ｎｉ（ＮＯ３）２）水溶液のＣｏ濃度を０．５６ｍｏｌ／Ｌに変更し、さらに、Ｎｉ濃度を０．５６ｍｏｌ／Ｌに変更し、それ以外は、上記本発明粉末１の製造工程と全く同じ工程で、本発明の複合粉末（以下、本発明粉末３という）を製造した。 In the production of the powder 1 of the present invention, the Co concentration of the aqueous solution (Co (NO 3 ) 2 + Ni (NO 3 ) 2 ) mixed with the TiC 0.5 N 0.5 powder is changed to 0.56 mol / L, and The composite powder of the present invention (hereinafter referred to as the present invention powder 3) was produced in the same process as the production process of the present invention powder 1 except that the Ni concentration was changed to 0.56 mol / L.
上記本発明粉末１の製造において、ＴｉＣ０．５Ｎ０．５粉末と混合する（Ｃｏ（ＮＯ３）２＋Ｎｉ（ＮＯ３）２）水溶液を、０．５６ｍｏｌ／ＬのＣｏを含有するＣｏ（ＮＯ３）２水溶液に変更し、それ以外は、上記本発明粉末１の製造工程と全く同じ工程で、本発明の複合粉末（以下、本発明粉末４という）を製造した。 In the production of the powder 1 of the present invention, an aqueous solution (Co (NO 3 ) 2 + Ni (NO 3 ) 2 ) mixed with the TiC 0.5 N 0.5 powder is used as a Co (containing 0.56 mol / L Co ( The composite powder of the present invention (hereinafter referred to as the present invention powder 4) was produced in the same process as the production process of the present invention powder 1 except that the aqueous solution was changed to a NO 3 ) 2 aqueous solution.
上記本発明粉末１〜４について、それぞれの複合粉末中のＣｏ含有割合、Ｎｉ含有割合を原子吸光光度法で測定し、それぞれの粉末の平均粒径をフィシャー法（ＡＳＴＭＢ３３０）で測定し、複合粉末の比表面積（ＢＥＴ値）をＢＥＴ法で、また、酸素含有量を赤外吸収法で測定した。
これらの測定値を表１に示す。
For the present invention powders 1 to 4, the Co content and Ni content in each composite powder were measured by atomic absorption photometry, the average particle size of each powder was measured by Fischer method (ASTMB330), and composite powder The specific surface area (BET value) was measured by the BET method, and the oxygen content was measured by the infrared absorption method.
These measured values are shown in Table 1.
さらに、本発明粉末１と本発明粉末２について、それぞれの複合粉末の組織を走査型電子顕微鏡で観察した。
図２に、本発明粉末１のＳＥＭ写真を示すが、粒径１．３μｍのＴｉＣ０．５Ｎ０．５粉末（中央部分）の表面に、粒径１０〜２００ｎｍのＣｏ、Ｎｉの微細粒子粉末が付着した粒子形態を有することがわかる。また、本発明粉末２についても、図２と同様な粒子形態組織構造を有することを確認している。
Furthermore, regarding the powder 1 and the
FIG. 2 shows an SEM photograph of the powder 1 of the present invention. Co and Ni fine particles having a particle size of 10 to 200 nm are formed on the surface of a TiC 0.5 N 0.5 powder (central portion) having a particle size of 1.3 μm. It can be seen that the powder has an attached particle morphology. It has also been confirmed that the
比較のため、ＴｉＣ０．５Ｎ０．５粉末の表面に、Ｃｏ、Ｎｉの微細粒子粉末をその表面に付着・複合化していない上記通常のＴｉＣ０．５Ｎ０．５粉末（以下、比較例粉末という）について、上記本発明粉末１、本発明粉末２と同様に、粉末の比表面積（ＢＥＴ値）、平均粒径、酸素含有量を測定した。これらの測定値を表１に示す。
For comparison, the surface of TiC 0.5 N 0.5 powder, Co, the conventional TiC 0.5 unattached, composite fine particle powder of Ni on the surface thereof N 0.5 powder (hereinafter, comparative Example powders) were measured for the specific surface area (BET value), average particle diameter, and oxygen content of the powders in the same manner as in the
次に、原料粉末として、１．００〜２．００μｍの平均粒径を有する上記本発明粉末１〜４以外に、ＴｉＣ粉末、ＴｉＮ粉末、ＴａＣ粉末、ＮｂＣ粉末、ＷＣ粉末、Ｍｏ２Ｃ粉末、Ｃｏ粉末およびＮｉ粉末を用意し、これら原料粉末を、表２に示される配合組成に配合し、ボールミルで２４時間湿式混合し、乾燥した。その後、１００ＭＰａの圧力で圧粉体にプレス成形し、この圧粉体を２ｋＰａの窒素雰囲気中、温度：１５００℃に１時間保持の条件で焼結した。その後、切れ刃部分にＲ：０．０３のホーニング加工を施してＩＳＯ規格・ＣＮＭＧ１２０４０８−ＳＨのチップ形状をもった炭窒化チタン基サーメットからなる切削工具（以下、本発明工具という）１〜６を製造した。 Next, as the raw material powder, in addition to the present invention powders 1 to 4 having an average particle diameter of 1.00 to 2.00 μm, TiC powder, TiN powder, TaC powder, NbC powder, WC powder, Mo 2 C powder, Co powder and Ni powder were prepared, these raw material powders were blended in the blending composition shown in Table 2, wet-mixed with a ball mill for 24 hours, and dried. Thereafter, the green compact was press-molded at a pressure of 100 MPa, and the green compact was sintered in a nitrogen atmosphere of 2 kPa at a temperature of 1500 ° C. for 1 hour. After that, cutting tools (hereinafter referred to as the tool of the present invention) 1 to 6 made of titanium carbonitride-based cermet having a chip shape of ISO standard / CNMG120408-SH by performing a honing process of R: 0.03 on the cutting edge portion. Manufactured.
比較のため、上記本発明粉末１〜４を用いる代わりに上記比較例粉末を使用して、本発明工具１〜６とそれぞれＴｉＣ０．５Ｎ０．５、Ｎｉ、Ｃｏ含有量が同量となるように配合を行い、同じ条件で同じチップ形状をもった炭窒化チタン基サーメットからなる切削工具（以下、比較例工具という）１〜６を製造した。 For comparison, instead of using the powders of the present invention 1 to 4, the powders of the comparative examples were used, and the contents of TiC 0.5 N 0.5 , Ni and Co were the same as those of the tools 1 to 6 of the present invention. Then, cutting tools (hereinafter referred to as comparative example tools) 1 to 6 made of titanium carbonitride-based cermet having the same chip shape under the same conditions were manufactured.
また、上記本発明工具１〜６と上記比較例工具１〜６について、焼結体としての表面硬度、内部硬度を、ロックウェル硬さ試験機を用いたロックウェル硬さ試験方法（ＪＩＳ Ｚ２２４５）、靭性値をビッカース硬さ試験機を用いた圧子挿入法（ＪＩＳ Ｒ１６０７）によりそれぞれ測定した。その測定値を表２に示す。 Moreover, about the said invention tools 1-6 and the said comparative example tools 1-6, the Rockwell hardness test method (JIS Z2245) which used the Rockwell hardness tester for the surface hardness and internal hardness as a sintered compact. The toughness value was measured by an indenter insertion method (JIS R1607) using a Vickers hardness tester. The measured values are shown in Table 2.
さらに、この本発明切削工具１〜６と比較例工具１〜６とを、いずれも工具鋼製バイトの先端部に固定治具にてネジ止めした状態で、以下の条件Ａ、Ｂにて合金鋼の乾式切削加工試験を行った。 Further, the cutting tools 1 to 6 of the present invention and the comparative tools 1 to 6 are all alloyed under the following conditions A and B in a state where they are screwed to the tip of the tool steel tool with a fixing jig. A steel dry cutting test was performed.
[切削条件Ａ]
被削材： ＪＩＳ・ＳＮＣＭ４３９の丸棒
切削速度： ２００ ｍ／ｍｉｎ
切り込み： １．０ ｍｍ
送り： ０．２０ ｍｍ／ｒｅｖ
切削時間： １０ 分
[切削条件Ｂ]
被削材： ＪＩＳ・ＳＣＭ４４０の丸棒
切削速度： ２００ ｍ／ｍｉｎ
切り込み： １．０ ｍｍ
送り： ０．２０ ｍｍ／ｒｅｖ
切削時間： １０ 分
[Cutting conditions A]
Work material: JIS / SNCM439 round bar Cutting speed: 200 m / min
Cutting depth: 1.0 mm
Feeding: 0.20 mm / rev
Cutting time: 10 minutes
[Cutting conditions B]
Work material: JIS / SCM440 round bar Cutting speed: 200 m / min
Cutting depth: 1.0 mm
Feeding: 0.20 mm / rev
Cutting time: 10 minutes
上記切削条件Ａ、Ｂにて１０分切削後の逃げ面摩耗幅を測定し、その値を表３に示す。切削途中で欠損に至った場合は、欠損に至るまでの切削時間を示す。 The flank wear width after 10 minutes of cutting was measured under the above cutting conditions A and B, and the values are shown in Table 3. When a defect is reached in the middle of cutting, the cutting time until the defect is reached is indicated.
表３に示す切削条件Ａの結果より、本発明工具は比較例工具に比して摩耗幅が１０〜２０％程度小さく、耐摩耗性が非常に優れていることがわかる。
また、切削条件Ｂの結果より、欠損することなく正常に摩耗しており、耐欠損性においても非常に優れることがわかる。
From the results of cutting conditions A shown in Table 3, it can be seen that the tool of the present invention has a wear width of about 10 to 20% smaller than that of the comparative example tool, and is extremely excellent in wear resistance.
Further, it can be seen from the result of cutting condition B that the wear is normally made without any defects and the defect resistance is very excellent.
以上のとおり、本発明サーメット製切削工具製造用複合粉末は、優れた高硬度、高靭性、高強度を有し、これを用いてサーメット製品、例えば、サーメット製切削工具を製造した場合には、該サーメット製切削工具は、優れた耐欠損性、耐摩耗性を備え、長期の使用にわたって優れた切削性能を発揮する。
また、本発明のサーメット製切削工具製造用複合粉末の製造方法は、簡易かつ緩条件下ですぐれた特性を備える複合粉末を製造し得るものである。
したがって、本発明の工業的な価値は非常に高い。
As described above, the composite powder for manufacturing a cermet cutting tool of the present invention has excellent high hardness, high toughness, and high strength, and when a cermet product, for example, a cermet cutting tool is manufactured using this, The cermet cutting tool has excellent chipping resistance and wear resistance, and exhibits excellent cutting performance over a long period of use.
Moreover, the manufacturing method of the composite powder for cermet cutting tool manufacture of this invention can manufacture the composite powder provided with the outstanding characteristic on simple and gentle conditions.
Therefore, the industrial value of the present invention is very high.
Claims (2)
（ａ）上記コバルト及びニッケルの何れか１種または２種からなる微細粒子粉末は、上記チタン系粉末の表面に付着する形で複合化しており、
（ｂ）上記コバルト及びニッケルの何れか１種または２種からなる微細粒子粉末の全粉末に対する含有割合は５〜３０重量％であり、
（ｃ）上記複合粉末の比表面積（ＢＥＴ値）は、４．５２ｍ２／ｇ以上であり、
（ｄ）上記複合粉末中の酸素含有量は、４．０重量％以下である、
ことを特徴とするサーメット製切削工具製造用複合粉末。 And any one or any Ranaru titanium-based powders nitrided titanium and titanium carbonitride having an average particle size of 0.5 to 2.5 .mu.m, any one of an average particle diameter of 37 nm or less of cobalt and nickel or In a composite powder in which two kinds of fine particle powders are combined,
(A) The fine particle powder consisting of any one or two of the cobalt and nickel is compounded in a form that adheres to the surface of the titanium-based powder,
(B) The content ratio of the fine particle powder composed of any one or two of cobalt and nickel to the total powder is 5 to 30% by weight,
(C) The specific surface area (BET value) of the composite powder is 4.52 m 2 / g or more,
(D) The oxygen content in the composite powder is 4.0% by weight or less.
A composite powder for producing a cermet cutting tool .
窒化チタン及び炭窒化チタンの何れか１種または２種からなるチタン系粉末と、コバルト及びニッケルの何れか１種または２種を含有する水溶性塩の溶液とを混合し、その後乾燥することによって、前記窒化チタン及び炭窒化チタンの何れか１種または２種からなるチタン系粉末が、コバルト及びニッケルの何れか１種または２種を含有する水溶性塩を担持してなる原料混合物を調整し、
上記原料混合物を不活性ガス雰囲気中にて２００〜５００℃の温度で熱処理することによって、コバルト及びニッケルの何れか１種または２種を含有する水溶性塩の熱分解処理を行い、窒化チタン及び炭窒化チタンの何れか１種または２種からなるチタン系粉末と熱分解反応生成物の混合物を形成し、
次いで、チタン系粉末と熱分解反応生成物からなる上記混合物を水素雰囲気中にて２００〜９００℃の温度で還元処理する、
ことを特徴とする請求項１に記載のサーメット製切削工具製造用複合粉末の製造方法。
In the manufacturing method of the composite powder for cermet cutting tool manufacture according to claim 1,
One or the two or Ranaru titanium-based powder either nitrided titanium and titanium carbonitride, with a solution of cobalt and soluble salts containing either one or nickel are mixed, then dried by any one or any Ranaru titanium-based powder before Ki窒 titanium and titanium carbonitride is formed by carrying a water-soluble salt containing either one or two of cobalt and nickel Adjust the raw material mixture,
By heat treatment at a temperature of 200 to 500 ° C. The above raw material mixture in an inert gas atmosphere, subjected to thermal decomposition treatment of the water-soluble salts containing either one or two of cobalt and nickel, nitrogen, titanium and forming a mixture of any one or two or Ranaru titanium-based powder and the thermal decomposition reaction products of titanium carbonitride,
Next, the mixture comprising the titanium-based powder and the thermal decomposition reaction product is subjected to reduction treatment at a temperature of 200 to 900 ° C. in a hydrogen atmosphere.
The manufacturing method of the composite powder for cermet cutting tool manufacture of Claim 1 characterized by the above-mentioned.
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