JP2001294969A - Cemented carbide - Google Patents
Cemented carbideInfo
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- JP2001294969A JP2001294969A JP2000116105A JP2000116105A JP2001294969A JP 2001294969 A JP2001294969 A JP 2001294969A JP 2000116105 A JP2000116105 A JP 2000116105A JP 2000116105 A JP2000116105 A JP 2000116105A JP 2001294969 A JP2001294969 A JP 2001294969A
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- Prior art keywords
- cemented carbide
- carbide
- amount
- cemented
- range
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Abstract
Description
【０００１】[0001]
【発明の属する技術分野】この発明は、ＷＣを主成分と
する超硬合金に係り、特に、高強度で耐摩耗性に優れる
と共に耐食性にも優れ、切削工具、耐摩耗性工具、耐食
性工具及び各種の部品に好適に使用される超硬合金に関
するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a cemented carbide mainly composed of WC, and more particularly to a cutting tool, a wear-resistant tool, a corrosion-resistant tool, which has high strength, excellent wear resistance and excellent corrosion resistance. The present invention relates to a cemented carbide suitably used for various parts.
【０００２】[0002]
【従来の技術】従来、ＷＣを主成分とする超硬合金とし
ては、ＷＣ−Ｃｏ系超硬合金等が存在しているが、一般
にＷＣ−Ｃｏ系超硬合金等は耐食性が十分でないという
問題があった。2. Description of the Related Art Conventionally, as a cemented carbide mainly composed of WC, there is a WC-Co cemented carbide or the like, but generally, the WC-Co cemented carbide or the like has a problem that corrosion resistance is not sufficient. was there.
【０００３】このため、結合相を構成するＣｏの一部又
は全部を、Ｃｏより耐食性に優れたＮｉに置換させたＷ
Ｃ−Ｃｏ−Ｎｉ系超硬合金やＷＣ−Ｎｉ系超硬合金が用
いられるようになった。[0003] For this reason, W in which a part or all of Co constituting the binder phase is replaced by Ni having better corrosion resistance than Co is used.
C-Co-Ni-based cemented carbides and WC-Ni-based cemented carbides have come to be used.
【０００４】しかし、このようなＷＣ−Ｃｏ−Ｎｉ系超
硬合金やＷＣ−Ｎｉ系超硬合金においても、依然として
十分な耐食性が得られなかった。[0004] However, even with such WC-Co-Ni-based cemented carbides and WC-Ni-based cemented carbides, sufficient corrosion resistance has not yet been obtained.
【０００５】さらに、近年においては、特公平５−７６
５３１号公報に示されるように、ＷＣを主成分とする超
硬合金において、Ｎｉと共にＣｒを所定量加え、その耐
食性を向上させるようにしたものが提案されている。Further, in recent years, Japanese Patent Publication No. 5-76
As disclosed in Japanese Patent No. 531, there has been proposed a cemented carbide containing WC as a main component, in which a predetermined amount of Cr is added together with Ni to improve its corrosion resistance.
【０００６】しかし、超硬合金に対するＣｒの添加量が
少ないと、超硬合金の耐食性を十分に向上させることが
できず、過酷な腐食環境下において使用する場合、例え
ば、腐食性を有する木材等の切削を行う場合には十分な
耐食性が得られず、また、逆にクロムの添加量が多くな
ると、超硬合金の焼結性が悪くなって、超硬合金の強度
が低下し、また十分に焼結させるために焼結温度を高く
した場合には、粒成長が生じて、超硬合金の強度が低下
するという問題があった。However, if the amount of Cr added to the cemented carbide is small, the corrosion resistance of the cemented carbide cannot be sufficiently improved, and when used in a severely corrosive environment, for example, corrosive wood, etc. In the case of cutting, sufficient corrosion resistance cannot be obtained, and when the addition amount of chromium is large, the sinterability of the cemented carbide deteriorates, the strength of the cemented carbide decreases, and When the sintering temperature is increased for sintering, there is a problem that grain growth occurs and the strength of the cemented carbide decreases.
【０００７】[0007]
【発明が解決しようとする課題】この発明は、ＷＣを主
成分とする超硬合金における上記のような様々な問題を
解決することを課題とするものであり、高硬度で耐摩耗
性に優れると共に耐食性にも優れ、切削工具，耐摩耗性
工具，耐食性工具及び各種の部品に好適に使用できる超
硬合金を提供することを課題とするものである。SUMMARY OF THE INVENTION It is an object of the present invention to solve the above-mentioned various problems in a cemented carbide containing WC as a main component, and has high hardness and excellent wear resistance. It is another object of the present invention to provide a cemented carbide having excellent corrosion resistance and suitable for use in cutting tools, wear-resistant tools, corrosion-resistant tools, and various parts.
【０００８】[0008]
【課題を解決するための手段】この発明においては、上
記のような課題を解決するため、ＷＣを主成分とする超
硬合金において、この超硬合金中に結合相を構成するＮ
ｉを１０〜２５重量％、金属の硼化物を０．２〜５．０
重量％の範囲で含有させると共に、Ｃｒの炭化物を結合
相を構成する上記のＮｉに対して５０〜１５０重量％の
範囲で含有させるようにしたのである。According to the present invention, in order to solve the above-mentioned problems, in a cemented carbide containing WC as a main component, the N-phase forming a bonding phase in the cemented carbide is specified.
i is 10 to 25% by weight, and a metal boride is 0.2 to 5.0%.
In addition to being contained in the range of 50% by weight, Cr carbide is contained in the range of 50 to 150% by weight with respect to the above-mentioned Ni constituting the binder phase.
【０００９】ここで、この発明における超硬合金におい
て、Ｎｉは硬質成分を結合させるものであり、このＮｉ
を超硬合金中に１０〜２５重量％の範囲で含有させるよ
うにしたのは、上記のようにＣｒの炭化物を多量に含有
させる場合において、Ｎｉの量が１０重量％未満になる
と、硬質成分の結合性が著しく低下し、強度や靭性が低
下する一方、Ｎｉの量が２５重量％を超えると、超硬合
金の硬度が低くなりすぎて、超硬合金の耐摩耗性や耐塑
性変形性が低下すると共に、耐食性も低下するためであ
る。Here, in the cemented carbide according to the present invention, Ni binds a hard component.
Is contained in the cemented carbide in the range of 10 to 25% by weight. When the amount of Ni is less than 10% by weight when the carbide of Cr is contained in a large amount as described above, the hard component is hardened. When the amount of Ni exceeds 25% by weight, the hardness of the cemented carbide becomes too low, and the wear resistance and plastic deformation resistance of the cemented carbide become excessively low. This is because, as well as the corrosion resistance decreases.
【００１０】また、Ｃｒの炭化物を含有させるのは超硬
合金の耐食性を向上させるためであり、このＣｒの炭化
物を結合相を構成する上記のＮｉに対して５０〜１５０
重量％の範囲で含有させるようにしたのは、Ｃｒの炭化
物の量がＮｉに対して５０重量％未満になると、超硬合
金の耐食性を十分に向上させることができなくなる一
方、Ｃｒの炭化物の量がＮｉに対して１５０重量％を越
えると、合金組織中にＮｉとＣｒとの化合物が析出して
脆化相が形成されると共に、超硬合金中におけるＷＣの
量が少なくなって、超硬合金の強度や靭性も低下するた
めである。The inclusion of Cr carbide is for improving the corrosion resistance of the cemented carbide, and the Cr carbide is added to the above-mentioned Ni constituting the binder phase in an amount of 50 to 150%.
The content of the carbide in the range of weight% is such that when the amount of the carbide of Cr is less than 50% by weight with respect to Ni, the corrosion resistance of the cemented carbide cannot be sufficiently improved, while the carbide of the Cr If the amount exceeds 150% by weight with respect to Ni, a compound of Ni and Cr precipitates in the alloy structure to form an embrittlement phase, and the amount of WC in the cemented carbide decreases. This is because the strength and toughness of the hard alloy also decrease.
【００１１】また、金属の硼化物を含有させるのは、上
記のようにＷＣとＣｒ炭化物とＮｉとを含む超硬合金に
おける焼結性を改善して緻密な焼結体が得られるように
するためであり、金属の硼化物を超硬合金中に０．２〜
５．０重量％の範囲で含有させるようにしたのは、この
金属の硼化物の量が０．２重量％未満であると、超硬合
金における焼結性を十分に向上させることができなくな
る一方、金属の硼化物の量が５．０重量％を越えると、
この金属の硼化物とＮｉやＣｒやＷとの化合物が析出し
て、超硬合金の強度が低下するためである。The inclusion of a metal boride improves the sinterability of a cemented carbide containing WC, Cr carbide and Ni, as described above, so that a dense sintered body can be obtained. For this reason, the metal boride is added to the cemented carbide in an amount of 0.2 to
The reason for including the content in the range of 5.0% by weight is that if the amount of the boride of the metal is less than 0.2% by weight, the sinterability of the cemented carbide cannot be sufficiently improved. On the other hand, if the amount of the metal boride exceeds 5.0% by weight,
This is because a compound of this metal boride and Ni, Cr or W precipitates, and the strength of the cemented carbide decreases.
【００１２】ここで、金属の硼化物を含有させた場合
に、超硬合金における焼結性が改善されて緻密な焼結体
が得られる理由は定かではないが、金属の硼化物が上記
の超硬合金の成分であるＮｉと反応して共晶物ができて
融点が下がると共に、この共晶物によりＣｒの炭化物と
の濡れ性がよくなるためであると考えられる。The reason why the sinterability of a cemented carbide is improved and a dense sintered body can be obtained when a metal boride is contained is not clear. This is considered to be because eutectic is formed by reacting with Ni which is a component of the cemented carbide to lower the melting point, and the eutectic improves the wettability of Cr with carbide.
【００１３】そして、上記の金属の硼化物には各種の金
属硼化物を用いることができ、例えば、ＷＢ，Ｃｒ
Ｂ2 ，ＮｉＢ，ＴＩＢ2 等を用いることができる。Various borides of metal can be used as the above-mentioned borides of metals, for example, WB, Cr
B 2 , NiB, TIB 2 or the like can be used.
【００１４】また、この発明における上記の超硬合金に
おいて、その強度を高めるため、結合相を構成するＮｉ
の一部をＣｏで置換させることが可能である。しかし、
Ｎｉの一部をＣｏで置換させるにあたり、Ｃｏの量が多
くなってＮｉの量が減少すると、得られる超硬合金にお
ける耐食性が低下するため、請求項２に示すように、Ｃ
ｏで置換させるＮｉの割合を４０％以下にすることが好
ましい。Further, in the above-mentioned cemented carbide according to the present invention, in order to increase the strength, Ni which constitutes the binder phase is used.
Can be partially replaced with Co. But,
In substituting a part of Ni with Co, if the amount of Co increases and the amount of Ni decreases, the corrosion resistance of the resulting cemented carbide decreases.
It is preferable that the ratio of Ni substituted by o be 40% or less.
【００１５】また、この発明における上記の超硬合金に
おいては、焼結により上記のＣｒの炭化物が主としてＣ
ｒ3 Ｃ2 とＣｒ7 Ｃ3 になる。そして、この超硬合金に
おける合金炭素量が多くなると、上記のように焼結した
場合に、Ｃｒの炭化物におけるＣｒ3 Ｃ2 の割合が多く
なって、超硬合金の強度が高くなるが、超硬合金中に遊
離炭素が出現すると、超硬合金の強度が著しく低下す
る。このため、請求項３に示すように、超硬合金におけ
る合金炭素量を、遊離炭素が出現し始める合金炭素量の
９０％以上、１００％未満の範囲にすることが好まし
い。Further, in the above-mentioned cemented carbide according to the present invention, the above-mentioned carbide of Cr is mainly converted to C by sintering.
r 3 C 2 and Cr 7 C 3 . When the amount of alloy carbon in the cemented carbide increases, the ratio of Cr 3 C 2 in the carbide of Cr increases when sintered as described above, and the strength of the cemented carbide increases. When free carbon appears in the hard alloy, the strength of the cemented carbide decreases significantly. For this reason, as described in claim 3, it is preferable that the amount of alloy carbon in the cemented carbide be in the range of 90% or more and less than 100% of the amount of alloy carbon in which free carbon starts to appear.
【００１６】なお、この発明における超硬合金は、上記
のようにＷＣを主成分とするものであるが、一般に行わ
れているように、このＷＣの一部を周期律表の第４ａ
族、第５ａ族、第６ａ族の金属の炭化物や窒化物で置換
させるようにしてもよい。また、この発明における超硬
合金の表面に、ＰＶＤ法やＣＶＤ法によって硬質を被膜
を形成することも可能であり、このように硬質を被膜を
形成すると、耐摩耗性や耐食性がさらに向上する。The cemented carbide according to the present invention contains WC as a main component as described above, and as is generally practiced, a part of the WC is formed in the 4a of the periodic table.
The metal may be replaced with a carbide or nitride of a Group 5, 5a, or 6a metal. Further, it is also possible to form a hard coating on the surface of the cemented carbide according to the present invention by a PVD method or a CVD method. When such a hard coating is formed, the wear resistance and the corrosion resistance are further improved.
【００１７】[0017]
【実施例】以下、この発明の実施例に係る超硬合金につ
いて説明すると共に、比較例を挙げて、この発明の実施
例に係る超硬合金が優れていることを明らかにする。The cemented carbide according to the examples of the present invention will be described below, and comparative examples will be given to clarify that the cemented carbides according to the examples of the present invention are excellent.
【００１８】ここで、以下の実施例及び比較例において
は、超硬合金の原料として、平均粒度が０．８μｍのＷ
Ｃ粉、平均粒度が１．５μｍのＮｉ粉、平均粒度が１．
５μｍのＣｏ粉、平均粒度が１．５μｍのＣｒ3 Ｃ
2 粉、平均粒度が１．５μｍのＮｉＢ粉、平均粒度が
１．５μｍのＷＢ粉、平均粒度が３．０μｍのＣｒＢ2
粉、平均粒度が１．５μｍのＴｉＢ2 粉を用いると共
に、超硬合金における合金炭素量を調整するために、金
属タングステン粉やカーボンブラックを用いるようにし
た。なお、上記のＷＣ粉やＣｒ3 Ｃ2 粉としては、任意
の粒度のものを用いることができるが、粒度の細かいも
のを用いる方が耐摩耗性に優れた超硬合金が得られるよ
うになり、特に、ＷＣ粉の粒度が細かいと、Ｃｒの炭化
物の粒成長も抑えられて、硬度の高い超硬合金が得られ
るようになる。Here, in the following Examples and Comparative Examples, as a raw material of a cemented carbide, W having an average particle size of 0.8 μm was used.
C powder, Ni powder having an average particle size of 1.5 μm, and average particle size of 1.
5 μm Co powder, Cr 3 C with an average particle size of 1.5 μm
2 powder, NiB powder having an average particle size of 1.5 μm, WB powder having an average particle size of 1.5 μm, CrB 2 having an average particle size of 3.0 μm
Powder and TiB 2 powder having an average particle size of 1.5 μm were used, and metal tungsten powder and carbon black were used to adjust the amount of alloy carbon in the cemented carbide. The WC powder and Cr 3 C 2 powder can be of any particle size. However, the use of finer particle size makes it possible to obtain a cemented carbide having excellent wear resistance. In particular, when the particle size of the WC powder is small, the grain growth of the carbide of Cr is suppressed, and a cemented carbide having high hardness can be obtained.
【００１９】（実施例１〜１３及び比較例１〜８）これ
らの実施例１〜１３及び比較例１〜８においては、上記
の各原料を下記の表１に示す組成になるように配合し、
これらを湿式混合した後、プレス成形し、真空空中にお
いて窒素ガス等の不活性ガスを僅かに流入させながら、
同表に示す焼結温度で焼結して、各超硬合金を得た。な
お、下記の表１において、Ｃｒ3 Ｃ 2 粉の量について
は、結合相を構成するＮｉの量又はＮｉとこれを置換し
たＣｏの合計量に対する重量％を括弧内に示した。(Examples 1 to 13 and Comparative Examples 1 to 8)
In Examples 1 to 13 and Comparative Examples 1 to 8,
Are blended so as to have the composition shown in Table 1 below,
These are wet-mixed, press-molded, and placed in vacuum air.
While slightly flowing an inert gas such as nitrogen gas,
Each cemented carbide was obtained by sintering at the sintering temperatures shown in the same table. What
In Table 1 below,ThreeC TwoAbout the amount of powder
Is the amount of Ni constituting the binder phase or
The percentages by weight based on the total amount of Co are shown in parentheses.
【００２０】[0020]
【表１】 [Table 1]
【００２１】そして、上記のようにして得た実施例１〜
１３及び比較例１〜８の各超硬合金について、それぞれ
機械的特性及び耐食性を調べた。Examples 1 to 5 obtained as described above
The mechanical properties and corrosion resistance of each of the cemented carbides 13 and Comparative Examples 1 to 8 were examined.
【００２２】ここで、機械的特性については、ＪＩＳ
Ｚ ２２４４−1998に準拠してビッカース（Ｈｖ）硬度
を、ＪＩＳ Ｒ １６０７−1995に準拠して破壊靱性値
を、ＣＩＳ ０２６−1983に準拠して抗折力を求め、こ
れらの結果を下記の表２に示した。Here, mechanical properties are described in JIS.
The Vickers (Hv) hardness was determined in accordance with Z2244-1998, the fracture toughness value in accordance with JIS R 1607-1995, and the transverse rupture strength in accordance with CIS 226-1983. 2 is shown.
【００２３】また、耐食性については、それぞれ液温が
７０℃になった２０％のＨＮＯ3 溶液、２０％のＨ2 Ｓ
Ｏ4 溶液、２０％のＨＣｌ溶液、２０％のＮａＯＨ溶液
に上記の各超硬合金を浸漬させ、超音波振動を加えなが
ら１０時間放置した時の単位時間当たりの腐食減量を求
め、単位時間当たりの腐食減量が０．１ｇ／ｍ2 ・ｈｒ
以下の場合を◎、０．１〜１．０ｇ／ｍ2 ・ｈｒの場合
を○、１．０〜１０ｇ／ｍ2 ・ｈｒの場合を△、１０ｇ
／ｍ2 ・ｈｒ以上の場合を×として下記の表２に示し
た。As for the corrosion resistance, a 20% HNO 3 solution and a 20% H 2 S
Each of the above-mentioned cemented carbides was immersed in an O 4 solution, a 20% HCl solution, and a 20% NaOH solution, and the corrosion loss per unit time when allowed to stand for 10 hours while applying ultrasonic vibration was determined. 0.1g / m 2 · hr
In the following cases: ◎, in the case of 0.1~1.0g / m 2 · hr ○, the case of 1.0~10g / m 2 · hr △, 10g
Table 2 below shows the case where the ratio was not less than / m 2 · hr.
【００２４】[0024]
【表２】 [Table 2]
【００２５】この結果から明らかなように、この発明の
条件を満たす実施例１〜１３の各超硬合金においては、
この発明の条件を満たさない比較例１〜８の各超硬合金
に比べて耐食性が向上しており、またその機械的特性が
低下するということもなかった。As is clear from the results, in each of the cemented carbides of Examples 1 to 13 satisfying the conditions of the present invention,
The corrosion resistance was improved as compared with each of the cemented carbides of Comparative Examples 1 to 8 that did not satisfy the conditions of the present invention, and the mechanical properties did not decrease.
【００２６】（実施例１４〜１６）これらの実施例１４
〜１６においては、上記のＷＣ粉とＮｉ粉とＣｒ3 Ｃ2
粉とＷＢ粉とを下記の表３に示す組成になるよう配合す
ると共に、金属タングステン粉とカーボンブラックを用
いて超硬合金における合金炭素量の調整するようにし、
その後は、上記の場合と同様に、これらを湿式混合した
後、プレス成形し、窒素ガス等の不活性雰囲気中におい
て、同表に示す焼結温度で焼結して、各超硬合金を得
た。(Examples 14 to 16) These examples 14
No. 16 to No. 16, the above WC powder, Ni powder and Cr 3 C 2
The powder and the WB powder are mixed so as to have the composition shown in Table 3 below, and the amount of alloy carbon in the cemented carbide is adjusted using metal tungsten powder and carbon black,
After that, in the same manner as described above, these are wet-mixed, then press-molded, and sintered at a sintering temperature shown in the same table in an inert atmosphere such as nitrogen gas to obtain each cemented carbide. Was.
【００２７】[0027]
【表３】 [Table 3]
【００２８】そして、このようにして得た実施例１４〜
１６の各超硬合金についても、上記の場合と同様にし
て、それぞれ機械的特性及び耐食性を調べ、その結果を
下記の表４に示した。Then, the thus obtained Examples 14 to 14
The mechanical properties and corrosion resistance of each of the sixteen cemented carbides were examined in the same manner as described above, and the results are shown in Table 4 below.
【００２９】[0029]
【表４】 [Table 4]
【００３０】この結果から明らかなように、上記の実施
例１４〜１６の超硬合金を比較すると、超硬合金におけ
る合金炭素量が増加するに連れて、その機械的特性が向
上していた。As is evident from the results, when the cemented carbides of Examples 14 to 16 were compared, the mechanical properties were improved as the amount of alloy carbon in the cemented carbide was increased.
【００３１】[0031]
【発明の効果】以上詳述したように、この発明において
は、ＷＣを主成分とする超硬合金において、結合相を構
成するＮｉを１０〜２５重量％、金属の硼化物を０．２
〜５．０重量％の範囲で含有させると共に、Ｃｒの炭化
物を結合相を構成する上記のＮｉに対して５０〜１５０
重量％の範囲で含有させるようにしたため、高硬度で耐
摩耗性に優れると共に耐食性にも優れた超硬合金が得ら
れた。As described above in detail, according to the present invention, in a cemented carbide containing WC as a main component, 10-25% by weight of Ni constituting a binder phase and 0.2% of boride of a metal are used.
To 5.0 wt%, and a Cr carbide of 50 to 150 wt.
Since it was contained in the range of weight%, a cemented carbide having high hardness, excellent wear resistance and excellent corrosion resistance was obtained.
【００３２】この結果、耐食性を必要とする耐摩耗性部
品や、樹脂切削のような腐食摩耗の激しい切削工具材料
等として、この発明における超硬合金を好適に使用する
ことができた。As a result, the cemented carbide according to the present invention could be suitably used as a wear-resistant part requiring corrosion resistance, a cutting tool material with severe corrosion wear such as resin cutting, and the like.
Claims (3)
この超硬合金中に結合相を構成するＮｉが１０〜２５重
量％、金属の硼化物が０．２〜５．０重量％の範囲で含
有されると共に、Ｃｒの炭化物が結合相を構成する上記
のＮｉに対して５０〜１５０重量％の範囲で含有されて
なることを特徴とする超硬合金。1. A cemented carbide comprising WC as a main component,
In this cemented carbide, Ni constituting the binder phase is contained in the range of 10 to 25% by weight, metal boride is contained in the range of 0.2 to 5.0% by weight, and carbide of Cr constitutes the binder phase. A cemented carbide comprising 50 to 150% by weight with respect to Ni.
を構成する上記のＮｉの４０％以下がＣｏで置換されて
なることを特徴とする超硬合金。2. A cemented carbide according to claim 1, wherein 40% or less of said Ni constituting the binder phase contained in the cemented carbide is replaced by Co.
いて、この超硬合金における合金炭素量が、遊離炭素が
出現し始める合金炭素量の９０％以上、１００％未満の
範囲であることを特徴とする超硬合金。3. The cemented carbide according to claim 1, wherein the amount of alloyed carbon in the cemented carbide is in the range of 90% or more and less than 100% of the amount of alloyed carbon at which free carbon begins to appear. A hard metal characterized by the following.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000116105A JP2001294969A (en) | 2000-04-18 | 2000-04-18 | Cemented carbide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000116105A JP2001294969A (en) | 2000-04-18 | 2000-04-18 | Cemented carbide |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2001294969A true JP2001294969A (en) | 2001-10-26 |
Family
ID=18627609
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2000116105A Pending JP2001294969A (en) | 2000-04-18 | 2000-04-18 | Cemented carbide |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2001294969A (en) |
-
2000
- 2000-04-18 JP JP2000116105A patent/JP2001294969A/en active Pending
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