JP2003113437A - Hard metal alloy, tool for plastic working, and machining tool - Google Patents
Hard metal alloy, tool for plastic working, and machining toolInfo
- Publication number
- JP2003113437A JP2003113437A JP2001307456A JP2001307456A JP2003113437A JP 2003113437 A JP2003113437 A JP 2003113437A JP 2001307456 A JP2001307456 A JP 2001307456A JP 2001307456 A JP2001307456 A JP 2001307456A JP 2003113437 A JP2003113437 A JP 2003113437A
- Authority
- JP
- Japan
- Prior art keywords
- cemented carbide
- zrc
- tool
- examples
- powder
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000003754 machining Methods 0.000 title abstract 3
- 229910001092 metal group alloy Inorganic materials 0.000 title 1
- 239000002245 particle Substances 0.000 claims abstract description 64
- 238000005520 cutting process Methods 0.000 claims abstract description 24
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 9
- 229910009043 WC-Co Inorganic materials 0.000 claims abstract description 8
- 229910052735 hafnium Inorganic materials 0.000 claims abstract description 7
- 239000011230 binding agent Substances 0.000 claims description 25
- 230000003647 oxidation Effects 0.000 abstract description 30
- 238000007254 oxidation reaction Methods 0.000 abstract description 30
- 239000002184 metal Substances 0.000 abstract 4
- 229910052751 metal Inorganic materials 0.000 abstract 4
- 229910019863 Cr3 C2 Inorganic materials 0.000 abstract 2
- 230000000052 comparative effect Effects 0.000 description 39
- 239000000843 powder Substances 0.000 description 36
- 150000001247 metal acetylides Chemical class 0.000 description 28
- 239000002994 raw material Substances 0.000 description 14
- 238000005242 forging Methods 0.000 description 9
- 238000005452 bending Methods 0.000 description 7
- 230000007423 decrease Effects 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000011324 bead Substances 0.000 description 3
- 229910020630 Co Ni Inorganic materials 0.000 description 2
- 229910002440 Co–Ni Inorganic materials 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 238000001513 hot isostatic pressing Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 101100371219 Pseudomonas putida (strain DOT-T1E) ttgE gene Proteins 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
Landscapes
- Cutting Tools, Boring Holders, And Turrets (AREA)
- Powder Metallurgy (AREA)
Abstract
Description
【0001】[0001]
【発明の属する技術分野】この発明は、高温条件で被加
工物を塑性加工するのに使用する熱間鍛造用金型や温間
鍛造用金型等の塑性加工用工具、ビード削りや高速切削
等を行う場合のように高温で被加工物を切削加工するの
に使用する切削加工用工具及びこれらの工具に使用する
超硬合金に係り、特に、上記のような工具に使用する超
硬合金における高温での強度や耐酸化性等を向上させた
点に特徴を有するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a plastic working tool such as a hot forging die or a warm forging die, which is used for plastically working a work under high temperature conditions, bead shaving or high speed cutting. The present invention relates to a cutting tool used for cutting a work piece at a high temperature such as when performing the above, and a cemented carbide used for these tools, in particular, a cemented carbide used for the above tool. It is characterized in that it has improved strength at high temperature and oxidation resistance.
【0002】[0002]
【従来の技術】従来より、被加工物を塑性加工するのに
使用する鍛造用金型等の塑性加工用工具や、被加工物を
切削加工するのに用いる切削加工用工具に、Coを用い
た結合相を有するWC−Co系の超硬合金が使用されて
いる。2. Description of the Related Art Conventionally, Co has been used for plastic working tools such as forging dies used for plastic working of work pieces and cutting tools used for cutting work pieces. The WC-Co type cemented carbide having the above-mentioned binder phase is used.
【0003】しかし、このように塑性加工用工具や切削
加工用工具をWC−Co系の超硬合金で構成した場合、
これらの工具を高温条件で使用すると、これらの工具に
用いた超硬合金が酸化されたり、その硬度が低下したり
して、これらの工具を長期にわたって安定して使用する
ことができないという問題があった。However, when the plastic working tool and the cutting tool are made of WC-Co type cemented carbide as described above,
When these tools are used under high temperature conditions, the cemented carbide used for these tools may be oxidized or their hardness may be reduced, and these tools may not be used stably for a long period of time. there were.
【0004】そこで、近年においては、これらの工具に
おける高温での強度や耐酸化性等を高めるため、特開平
6−158114号公報に示されるように、CoとCr
とを含む結合相を有するWC−Co−Cr系の超硬合金
を用いた鍛造用金型や、CoとNiとを含む結合相を有
するWC−Co−Ni系の超硬合金を用いた鍛造用工具
が提案されている。Therefore, in recent years, in order to enhance the strength at high temperature and the oxidation resistance of these tools, as shown in Japanese Patent Laid-Open No. 6-158114, Co and Cr are used.
A die for forging using a WC-Co-Cr-based cemented carbide having a binder phase containing and a forging using a WC-Co-Ni cemented carbide having a binder phase containing Co and Ni. Tools have been proposed.
【0005】しかし、これらの公報に示されるように、
WC−Co−Cr系の超硬合金や、WC−Co−Ni系
の超硬合金を用いた場合においても、依然として、上記
のような工具における高温での強度や耐酸化性等の特性
を充分に向上させることができないという問題があっ
た。However, as shown in these publications,
Even when a WC-Co-Cr-based cemented carbide or a WC-Co-Ni-based cemented carbide is used, the above-mentioned tools still have sufficient characteristics such as strength at high temperature and oxidation resistance. There was a problem that it could not be improved.
【0006】[0006]
【発明が解決しようとする課題】この発明は、高温条件
で被加工物を塑性加工するのに用いる熱間鍛造用金型や
温間鍛造用金型等の塑性加工用工具や、ビード削りや高
速切削等を行う場合のように高温で被加工物を切削加工
するのに用いる切削加工用工具において、これらの工具
に使用する超硬合金を改善して、上記のような問題を解
決することを課題とするものである。SUMMARY OF THE INVENTION The present invention is directed to a plastic working tool such as a hot forging die or a warm forging die, which is used for plastically working a work under high temperature conditions, or a bead shaving tool. In a cutting tool used for cutting a work piece at a high temperature such as when performing high-speed cutting, improving the cemented carbide used for these tools to solve the above problems Is an issue.
【0007】すなわち、この発明においては、Coを用
いた結合相を有するWC−Co系又はCoとCr3 C2
とを用いた結合相を有するWC−Co−Cr3 C2 系の
超硬合金を改善して、これらの超硬合金における高温で
の強度や耐酸化性等の特性を充分に向上させ、この超硬
合金を用いた上記の塑性加工用工具や切削加工用工具に
おける高温での強度や耐酸化性等を高め、高温条件にお
いてもこれらの工具を長期にわたって安定して使用でき
るようにすることを課題とするものである。That is, according to the present invention, a WC-Co system having a binder phase using Co or Co and Cr 3 C 2 is used.
To improve the binding phase WC-Co-Cr 3 C 2 system cemented carbide having a using preparative sufficiently improve the strength and characteristics of oxidation resistance, etc. at a high temperature in these cemented carbide, this To improve the strength and oxidation resistance at high temperatures of the above plastic working tools and cutting tools using cemented carbide so that these tools can be used stably for a long period of time even under high temperature conditions. This is an issue.
【0008】[0008]
【課題を解決するための手段】この発明における超硬合
金においては、上記のような課題を解決するために、C
oを用いた結合相を有するWC−Co系又はCoとCr
3 C2 とを用いた結合相を有するWC−Co−Cr3 C
2 系の超硬合金において、WC粒子の平均粒径を0.5
〜6μmの範囲にすると共に、上記の結合相の総量に対
して、ZrC又は(Zr,Hf)Cを2.0〜20重量
%の範囲で含有させるようにしたのである。In the cemented carbide according to the present invention, in order to solve the above problems, C
WC-Co system or Co and Cr having a binder phase using o
WC-Co-Cr 3 C with a bonded phase with a 3 C 2
In the 2 series cemented carbide, the average particle size of WC particles is 0.5
The amount of ZrC or (Zr, Hf) C is contained in the range of 2.0 to 20% by weight with respect to the total amount of the binder phase.
【0009】ここで、この発明における超硬合金におい
て、WC粒子の平均粒径を0.5〜6μmの範囲にした
のは、その平均粒径が0.5μm未満になると、超硬合
金の靱性が低下する一方、WC粒子の平均粒径が6μm
を越えると、超硬合金の硬さが低下して、耐摩耗性等が
悪くなるためである。Here, in the cemented carbide of the present invention, the average particle size of the WC particles is set in the range of 0.5 to 6 μm because the toughness of the cemented carbide is set when the average particle size is less than 0.5 μm. While the average particle size of WC particles is 6 μm
If it exceeds, the hardness of the cemented carbide will decrease and the wear resistance will deteriorate.
【0010】また、この発明における超硬合金におい
て、ZrC又は(Zr,Hf)Cを加えるようにしたの
は、高温での強度を向上させると共に、高温での耐酸化
性を高めるためであり、またその量を、結合相の総量に
対して2.0〜20重量%の範囲にしたのは、その量が
2.0重量%未満であると、高温での強度を充分に向上
させることができない一方、その量が20重量%を越え
ると、焼結性が悪くなり、常温での抗折強度が低下する
ためである。なお、ZrC粉中には通常0.1〜2重量
%程度のHfCが含有されており、またこのように含有
されるHfCの量を多くした場合においても同様の効果
が得られる。Further, in the cemented carbide according to the present invention, ZrC or (Zr, Hf) C is added in order to improve the strength at high temperature and the oxidation resistance at high temperature. Further, the amount is set to be in the range of 2.0 to 20% by weight with respect to the total amount of the binder phase, because when the amount is less than 2.0% by weight, the strength at high temperature can be sufficiently improved. On the other hand, if the amount exceeds 20% by weight, the sinterability deteriorates and the bending strength at room temperature decreases. The ZrC powder usually contains about 0.1 to 2% by weight of HfC, and the same effect can be obtained even when the amount of HfC contained is increased.
【0011】また、上記のようにZrC又は(Zr,H
f)Cを結合相の総量に対して、2.0〜20重量%の
範囲で含有させると、ZrC又は(Zr,Hf)Cの多
くが超硬合金中に粒子の状態で存在するようになる。そ
して、この超硬合金中におけるこれらの粒子の粒径が大
きくなると、得られた超硬合金における強度や破壊靱性
値が低下して、塑性加工用工具や切削加工用工具として
使用した場合に、クラックの発生や破損の原因となるた
め、ZrCや(Zr,Hf)Cの平均粒径を、WC粒子
の平均粒径の1/2以下にすることが好ましい。Further, as described above, ZrC or (Zr, H
f) When C is contained in the range of 2.0 to 20 wt% with respect to the total amount of the binder phase, most of ZrC or (Zr, Hf) C is present in the cemented carbide in the form of particles. Become. Then, when the particle size of these particles in the cemented carbide becomes large, the strength and fracture toughness value in the obtained cemented carbide decreases, when used as a tool for plastic working or a tool for cutting, It is preferable that the average particle diameter of ZrC or (Zr, Hf) C is equal to or less than 1/2 of the average particle diameter of WC particles because it may cause cracks or damage.
【0012】そして、この発明における塑性加工用工具
においては、上記のような超硬合金を用いるようにした
ため、常温での抗折強度や破壊靱性値が低下するという
ことが少なく、高温での強度や耐酸化性等が向上し、高
温条件で被加工物を塑性加工することが長期にわたって
安定して行えるようになる。In the plastic working tool according to the present invention, since the cemented carbide as described above is used, the bending strength and the fracture toughness value at room temperature are less likely to decrease, and the strength at high temperature is small. And the oxidation resistance are improved, and it becomes possible to stably perform plastic working of a work piece under high temperature conditions for a long period of time.
【0013】また、この発明における切削加工用工具に
おいても、上記のような超硬合金を用いるようにしたた
め、常温での抗折強度や破壊靱性値が低下するというこ
とが少なく、高温での強度や耐酸化性等が向上し、高温
の被加工物を切削加工する場合や、高速の切削等によっ
て高温になるような場合においても、長期にわたって安
定した切削加工が行えるようになる。Also, in the cutting tool according to the present invention, since the cemented carbide as described above is used, the bending strength and the fracture toughness value at room temperature are not likely to decrease, and the strength at high temperature is small. Further, the oxidation resistance is improved, and stable cutting can be performed for a long period of time even when cutting a high-temperature workpiece or when the temperature becomes high due to high-speed cutting or the like.
【0014】さらに、この発明における塑性加工用工具
や切削加工用工具においてさらに耐摩耗性を向上させる
ため、CVD法やPVD法により、これらの工具の表面
を硬質物質で被覆させることが好ましい。Further, in order to further improve the wear resistance of the plastic working tool and the cutting tool of the present invention, it is preferable to coat the surface of these tools with a hard substance by the CVD method or the PVD method.
【0015】[0015]
【実施例】以下、この発明に係る超硬合金、塑性加工用
工具及び切削加工用工具について実施例を挙げて具体的
に説明すると共に、この発明の実施例に係る超硬合金,
塑性加工用工具及び切削加工用工具が優れている点を、
比較例を挙げて明らかにする。EXAMPLES Hereinafter, the cemented carbide, the plastic working tool and the cutting tool according to the present invention will be specifically described with reference to Examples, and the cemented carbide according to the embodiment of the present invention,
The advantages of plastic processing tools and cutting tools are
A comparative example will be given to clarify.
【0016】(実施例1〜5及び比較例1,2)超硬合
金の原料として、実施例1〜4及び比較例1,2におい
ては、平均粒径が5.0μmのWC粉末と、平均粒径が
1.1μmのCo粉末と、平均粒径が1.2μmのCr
3 C2 粉末と、平均粒径が1.5μmのZrC粉末とを
用いるようにし、また実施例5では、平均粒径が1.5
μmのZrC粉末に代えて、平均粒径が4.0μmのZ
rC粉末を用いるようにした。Examples 1 to 5 and Comparative Examples 1 and 2 As raw materials for cemented carbide, in Examples 1 to 4 and Comparative Examples 1 and 2, WC powder having an average particle size of 5.0 μm and an average Co powder having a particle size of 1.1 μm and Cr having an average particle size of 1.2 μm
3 C 2 powder and ZrC powder having an average particle size of 1.5 μm were used. In Example 5, the average particle size was 1.5 μm.
Instead of ZrC powder of μm, Z having an average particle size of 4.0 μm
The rC powder was used.
【0017】そして、これらの原料を下記の表1に示す
重量比率(wt%)で混合し、これをプレスして成形し
た後、温度1360℃で60分間焼結し、その後、温度
1300℃、圧力1200気圧で熱間静水圧プレスし、
実施例1〜5及び比較例1,2の各超硬合金を作製し
た。Then, these raw materials were mixed in a weight ratio (wt%) shown in Table 1 below, and the mixture was pressed and molded, and then sintered at a temperature of 1360 ° C. for 60 minutes, and then at a temperature of 1300 ° C. Hot isostatic pressing at a pressure of 1200 atm,
The cemented carbides of Examples 1 to 5 and Comparative Examples 1 and 2 were produced.
【0018】ここで、このように作製した各超硬合金に
おいては、Co中にCrやCが固溶された結合相の中
に、WC粒子やZrC粒子が分散した状態で存在してお
り、このWC粒子やZrC粒子の粒径は、原料に用いた
WC粉末及びZrC粉末とほぼ同じであった。Here, in each of the cemented carbides thus produced, WC particles and ZrC particles are present in a dispersed state in the binder phase in which Cr and C are solid-dissolved in Co, The particle diameters of the WC particles and the ZrC particles were almost the same as those of the WC powder and the ZrC powder used as the raw materials.
【0019】また、上記の各超硬合金において、Coと
Cr3 C2 とで構成された結合相の総量に対するZrC
の重量比率M(wt%)を求め、その結果を下記の表1
に示した。In each of the above-mentioned cemented carbides, ZrC relative to the total amount of the binder phase composed of Co and Cr 3 C 2.
The weight ratio M (wt%) of the is calculated, and the result is shown in Table 1 below.
It was shown to.
【0020】[0020]
【表1】 [Table 1]
【0021】次に、上記のようにして得た実施例1〜5
及び比較例1,2の各超硬合金で構成された3.0×
4.0×40mmの各試験片を用い、900℃の高温
と、25℃程度の室温とにおいて、それぞれJIS−R
1601に準拠し、スパン30mmで抗折力試験を行
い、高温及び室温における抗折力(GPa)を求め、そ
の結果を下記の表2に示すと共に、実施例1〜4及び比
較例1,2の各超硬合金における高温及び室温での抗折
力(GPa)を図1に示した。なお、高温での抗折力試
験においては、各試験片の酸化を防止するため、Arガ
ス中で行った。Next, Examples 1 to 5 obtained as described above
And 3.0 × composed of each cemented carbide of Comparative Examples 1 and 2.
Using each of the 4.0 × 40 mm test pieces, JIS-R was measured at a high temperature of 900 ° C. and a room temperature of about 25 ° C.
According to 1601, a transverse rupture strength test is performed with a span of 30 mm to obtain transverse rupture strength (GPa) at high temperature and room temperature. The results are shown in Table 2 below, and the results are shown in Examples 1 to 4 and Comparative Examples 1 and 2. FIG. 1 shows the transverse rupture strength (GPa) of each of the above cemented carbides at high temperature and room temperature. The transverse rupture strength test at high temperature was performed in Ar gas in order to prevent oxidation of each test piece.
【0022】また、上記の実施例1〜5及び比較例1,
2の各超硬合金における破壊靭性値(MPa・m0.5 )
を、JIS−R1607に準拠してSEPB法により求
めると共に、実施例1〜5及び比較例1,2の各超硬合
金におけるロックウェル硬さHRAを求め、これらの結
果を下記の表2に示した。Further, the above Examples 1 to 5 and Comparative Example 1,
Fracture toughness value (MPa · m 0.5 ) for each cemented carbide of No. 2
Is determined by the SEPB method according to JIS-R1607, and the Rockwell hardness HRA in each of the cemented carbides of Examples 1-5 and Comparative Examples 1 and 2 is determined, and these results are shown in Table 2 below. It was
【0023】さらに、上記の実施例1〜5及び比較例
1,2の各超硬合金からなる4×8×25mmの各試験
片を用い、それぞれ大気中において800℃で30分間
放置して酸化させ、単位面積当たりの酸化増量(mg/
mm2 )を求め、その結果を下記の表2に示すと共に、
実施例1〜4及び比較例1,2の各超硬合金における単
位面積当たりの酸化増量(mg/mm2 )を図2に示し
た。Further, using 4 × 8 × 25 mm test pieces made of the cemented carbides of Examples 1 to 5 and Comparative Examples 1 and 2, the samples were left to stand in the air at 800 ° C. for 30 minutes for oxidation. And increase the amount of oxidation per unit area (mg /
mm 2 ), and the results are shown in Table 2 below.
FIG. 2 shows the amount of increased oxidation (mg / mm 2 ) per unit area in each of the cemented carbides of Examples 1 to 4 and Comparative Examples 1 and 2.
【0024】[0024]
【表2】 [Table 2]
【0025】ここで、上記の表1,表2及び図1,図2
に示す結果から明らかなように、WC−Co−Cr3 C
2 系の超硬合金において、CoとCr3 C2 とを用いた
結合相の総量に対してZrCを2.0〜20重量%の範
囲で含有させた実施例1〜5の各超硬合金は、ZrCを
加えていない比較例1の超硬合金に比べ、高温における
抗折力が高くなると共に、高温の大気中において放置し
た場合における酸化増量も少なくなっており、高温での
強度及び耐酸化性が向上していた。また、CoとCr3
C2 とを用いた結合相の総量に対してZrCを25重量
%含有させた比較例2の超硬合金に比べると、室温にお
ける抗折力及び破壊靭性値が高くなっており、室温での
強度が向上していた。Here, the above Tables 1 and 2 and FIGS.
As it is apparent from the results shown in, WC-Co-Cr 3 C
In the 2 series cemented carbide, each of the cemented carbides of Examples 1 to 5 containing ZrC in the range of 2.0 to 20% by weight based on the total amount of the binder phase using Co and Cr 3 C 2. Is higher than the cemented carbide of Comparative Example 1 in which ZrC is not added, the bending resistance at high temperature is high, and the amount of oxidation increase when left in the high temperature atmosphere is small. The chemical conversion was improved. Also, Co and Cr 3
Compared with the cemented carbide of Comparative Example 2 containing 25% by weight of ZrC with respect to the total amount of the binder phase using C 2 , the transverse rupture strength and the fracture toughness value at room temperature were higher, and The strength was improved.
【0026】また、原料の割合が同じで、使用したZr
C粉末の平均粒径だけが異なる実施例4の超硬合金と実
施例5の超硬合金とを比較すると、平均粒径がWC粉末
の1/2以下になったZrC粉末を使用した実施例4の
超硬合金の方が、高温及び室温における抗折力や破壊靭
性値が高くなっていると共に、高温の大気中において放
置した場合における酸化増量も少なくなっていた。Further, the Zr used in the same ratio of raw materials
Comparing the cemented carbide of Example 4 and the cemented carbide of Example 5 that differ only in the average particle size of the C powder, an example using ZrC powder having an average particle size of 1/2 or less of the WC powder was used. The cemented carbide of No. 4 had higher transverse rupture strength and fracture toughness at high temperature and room temperature, and also had a smaller amount of oxidation increase when left in the high temperature atmosphere.
【0027】(実施例6,7及び比較例3)超硬合金の
原料として、上記の実施例1〜4及び比較例1,2の場
合と同様に、平均粒径が5.0μmのWC粉末と、平均
粒径が1.1μmのCo粉末と、平均粒径が1.5μm
のZrC粉末とを用いるようにする一方、Cr3 C2 粉
末を用いないようにした。(Examples 6 and 7 and Comparative Example 3) As a raw material for cemented carbide, as in the case of Examples 1 to 4 and Comparative Examples 1 and 2, WC powder having an average particle size of 5.0 μm. And Co powder having an average particle size of 1.1 μm, and an average particle size of 1.5 μm
ZrC powder of No. 3 was used, while Cr 3 C 2 powder was not used.
【0028】そして、これらの原料を下記の表3に示す
重量比率(wt%)で混合し、それ以外は、上記の実施
例1〜5及び比較例1,2の場合と同様にして、実施例
6,7及び比較例3の各超硬合金を作製した。Then, these raw materials were mixed in the weight ratio (wt%) shown in Table 3 below, and otherwise the same as in Examples 1 to 5 and Comparative Examples 1 and 2 above. The cemented carbides of Examples 6 and 7 and Comparative Example 3 were produced.
【0029】ここで、このように作製した各超硬合金に
おいては、Coからなる結合相中にWC粒子やZrC粒
子が分散された状態になっており、このWC粒子やZr
C粒子の粒径は、原料に用いたWC粉末及びZrC粉末
とほぼ同じであった。Here, in each of the cemented carbides thus produced, the WC particles and ZrC particles are dispersed in the binder phase made of Co.
The particle size of the C particles was almost the same as the WC powder and the ZrC powder used as the raw materials.
【0030】また、上記の各超硬合金において、Coか
らなる結合相の総量に対するZrCの重量比率M(wt
%)を求め、その結果を下記の表3に示した。Further, in each of the above-mentioned cemented carbides, the weight ratio M (wt) of ZrC to the total amount of the binder phase composed of Co.
%) Was obtained and the results are shown in Table 3 below.
【0031】[0031]
【表3】 [Table 3]
【0032】また、このように作製した実施例6,7及
び比較例3の各超硬合金についても、上記の実施例1〜
5及び比較例1,2の場合と同様にして、高温及び室温
における抗折力(GPa)、破壊靭性値(MPa・m
0.5 )、ロックウェル硬さHRAを求めると共に、大気
中において800℃で30分間放置して酸化させた場合
における、単位面積当たりの酸化増量(mg/mm2 )
を求め、これらの結果を下記の表4に示した。Further, regarding each of the cemented carbides of Examples 6 and 7 and Comparative Example 3 thus produced,
5 and Comparative Examples 1 and 2, bending strength (GPa) and fracture toughness value (MPa · m) at high temperature and room temperature.
0.5 ), the Rockwell hardness HRA was determined, and the amount of increase in oxidation per unit area (mg / mm 2 ) when the sample was left standing in the air at 800 ° C for 30 minutes for oxidation
Was obtained and these results are shown in Table 4 below.
【0033】[0033]
【表4】 [Table 4]
【0034】この結果、WC−Co系の超硬合金におい
て、Coからなる結合相の総量に対してZrCを2.0
〜20重量%の範囲で含有させた実施例6,7の各超硬
合金は、ZrCを加えていない比較例3の超硬合金に比
べ、高温における抗折力が高くなると共に、高温の大気
中において放置した場合における酸化増量も少なくなっ
ており、高温での強度及び耐酸化性が向上していた。As a result, in the WC-Co cemented carbide, ZrC was 2.0 with respect to the total amount of the binder phase composed of Co.
Each of the cemented carbides of Examples 6 and 7 contained in the range of up to 20% by weight has higher transverse rupture strength at high temperature and higher atmospheric temperature than the cemented carbide of Comparative Example 3 in which ZrC is not added. The amount of oxidation increase when left to stand inside was also small, and the strength and oxidation resistance at high temperatures were improved.
【0035】次に、上記の実施例1〜7及び比較例1〜
3の各超硬合金を使用して、それぞれ軸受け用部品の熱
間鍛造加工に用いるダイスとパンチとを作製した。Next, the above Examples 1 to 7 and Comparative Examples 1 to 1
Using each of the cemented carbides of No. 3, a die and a punch used for hot forging of bearing parts were produced.
【0036】そして、約1150℃の軸受け用の鋼材
(SUJ2)を所定長さに切断し、上記の各超硬合金で
作製したダイスとパンチとを用いてそれぞれ鍛造加工を
繰り返して行い、上記のダイスの表面に摩耗やクラック
が発生して、加工後における被加工物の表面に傷が生じ
るまでの加工数を寿命として求め、その結果を下記の表
5に示した。Then, the bearing steel material (SUJ2) at about 1150 ° C. is cut into a predetermined length, and the forging process is repeated using the die and the punch made of each of the above-mentioned cemented carbides. The number of processes until the surface of the die is abraded or cracked and the surface of the workpiece after the process is scratched is determined as the life, and the results are shown in Table 5 below.
【0037】[0037]
【表5】 [Table 5]
【0038】この結果、上記の実施例1〜7の各超硬合
金で作製したダイスとパンチとを用いた場合には、比較
例1〜3の各超硬合金で作製したダイスとパンチとを用
いた場合に比べて、寿命が大きく向上していた。As a result, when the dies and punches made of the cemented carbides of Examples 1 to 7 were used, the dies and punches made of the cemented carbides of Comparative Examples 1 to 3 were used. The life was greatly improved as compared with the case where it was used.
【0039】(実施例8〜10及び比較例4)超硬合金
の原料として、実施例8,9及び比較例4においては、
平均粒径が2.0μmのWC粉末と、平均粒径が1.1
μmのCo粉末と、平均粒径が1.2μmのCr3 C2
粉末と、平均粒径が0.8μmのZrC粉末とを用いる
ようにし、また実施例10では、平均粒径が0.8μm
のZrC粉末に代えて、平均粒径が1.5μmのZrC
粉末を用いるようにした。(Examples 8 to 10 and Comparative Example 4) In Examples 8 and 9 and Comparative Example 4, as raw materials for cemented carbide,
WC powder with an average particle size of 2.0 μm and an average particle size of 1.1
μm Co powder and Cr 3 C 2 with an average particle size of 1.2 μm
The powder and the ZrC powder having an average particle size of 0.8 μm are used, and in Example 10, the average particle size is 0.8 μm.
ZrC powder having an average particle size of 1.5 μm instead of the ZrC powder
A powder was used.
【0040】そして、これらの原料を下記の表6に示す
重量比率(wt%)で混合し、これをプレスして成形し
た後、温度1400℃で60分間焼結し、その後、温度
1300℃、圧力1200気圧で熱間静水圧プレスし
て、実施例8〜10及び比較例4の各超硬合金を作製し
た。Then, these raw materials were mixed in a weight ratio (wt%) shown in Table 6 below, and the mixture was pressed and molded, and then sintered at a temperature of 1400 ° C. for 60 minutes, and then at a temperature of 1300 ° C. Each of the cemented carbides of Examples 8 to 10 and Comparative Example 4 was produced by hot isostatic pressing at a pressure of 1200 atm.
【0041】ここで、このように作製した各超硬合金に
おいては、Co中にCrやCが固溶された結合相の中に
WC粒子やZrC粒子が分散された状態になっており、
このWC粒子やZrC粒子の粒径は、原料に用いたWC
粉末及びZrC粉末とほぼ同じであった。Here, in each of the cemented carbides thus prepared, WC particles and ZrC particles are dispersed in the binder phase in which Cr and C are solid-dissolved in Co,
The particle size of these WC particles and ZrC particles depends on the WC used as the raw material.
It was almost the same as the powder and the ZrC powder.
【0042】また、上記の各超硬合金において、Coと
Cr3 C2 とで構成された結合相の総量に対するZrC
の重量比率M(wt%)を求め、その結果を下記の表6
に示した。Further, in each of the above-mentioned cemented carbides, ZrC with respect to the total amount of the binder phase composed of Co and Cr 3 C 2.
The weight ratio M (wt%) of the is calculated, and the result is shown in Table 6 below.
It was shown to.
【0043】[0043]
【表6】 [Table 6]
【0044】また、このように作製した実施例8〜10
及び比較例4の各超硬合金についても、上記の実施例1
〜5及び比較例1,2の場合と同様にして、高温及び室
温における抗折力(GPa)、破壊靭性値(MPa・m
0.5 )、ロックウェル硬さHRAを求めると共に、大気
中において800℃で30分間放置して酸化させた場合
における、単位面積当たりの酸化増量(mg/mm2 )
を求め、これらの結果を下記の表7に示した。Further, Examples 8 to 10 thus produced
Also for each cemented carbide of Comparative Example 4, the above Example 1
5 and Comparative Examples 1 and 2, the transverse rupture strength (GPa) and the fracture toughness value (MPa · m) at high temperature and room temperature.
0.5 ), the Rockwell hardness HRA was determined, and the amount of increase in oxidation per unit area (mg / mm 2 ) when the sample was left standing in the air at 800 ° C for 30 minutes for oxidation
Was obtained and the results are shown in Table 7 below.
【0045】[0045]
【表7】 [Table 7]
【0046】この結果、上記の実施例1〜5の各超硬合
金の場合と同様に、WC−Co−Cr3 C2 系の超硬合
金において、CoとCr3 C2 とを用いた結合相の総量
に対してZrCを2.0〜20重量%の範囲で含有させ
た実施例8〜10の各超硬合金は、ZrCを加えていな
い比較例4の超硬合金に比べ、高温における抗折力が高
くなると共に、高温の大気中において放置した場合にお
ける酸化増量も少なくなっており、高温での強度及び耐
酸化性が向上していた。[0046] Consequently, as in the case of the cemented carbide of Examples 1 to 5, in the cemented carbide of WC-Co-Cr 3 C 2 system, coupled with the Co and Cr 3 C 2 Each of the cemented carbides of Examples 8 to 10 containing ZrC in the range of 2.0 to 20% by weight with respect to the total amount of phases was at a higher temperature than the cemented carbide of Comparative Example 4 to which ZrC was not added. As the transverse rupture strength increased, the increase in oxidation when left in a high temperature atmosphere also decreased, and the strength and oxidation resistance at high temperatures were improved.
【0047】また、原料の割合が同じで、使用したZr
C粉末の平均粒径だけが異なる実施例7の超硬合金と実
施例8の超硬合金とを比較すると、平均粒径がWC粉末
の1/2以下になったZrC粉末を使用した実施例7の
超硬合金の方が、高温及び室温における抗折力や破壊靭
性値が高くなっていると共に、高温の大気中において放
置した場合における酸化増量も少なくなっていた。Further, the Zr used in the same ratio of raw materials
Comparing the cemented carbide of Example 7 and the cemented carbide of Example 8 that differ only in the average particle size of the C powder, an example using ZrC powder having an average particle size of 1/2 or less of the WC powder was used. The cemented carbide of No. 7 had higher transverse rupture strength and fracture toughness at high temperature and room temperature, and also had a smaller increase in oxidation when left in the high temperature atmosphere.
【0048】(実施例11及び比較例5)超硬合金の原
料として、上記の実施例6,7及び比較例4の場合と同
様に、平均粒径が2.0μmのWC粉末と、平均粒径が
1.1μmのCo粉末と、平均粒径が0.8μmのZr
C粉末とを用いるようにする一方、Cr3 C2 粉末を用
いないようにした。(Example 11 and Comparative Example 5) As raw materials for cemented carbide, as in the case of Examples 6 and 7 and Comparative Example 4 described above, a WC powder having an average particle size of 2.0 μm and an average particle size of 2.0 μm were used. Co powder with a diameter of 1.1 μm and Zr with an average particle diameter of 0.8 μm
C powder was used, while Cr 3 C 2 powder was not used.
【0049】そして、これらの原料を下記の表8に示す
重量比率(wt%)で混合し、それ以外は、上記の実施
例6〜8及び比較例4の場合と同様にして、実施例11
及び比較例5の各超硬合金を作製した。Then, these raw materials were mixed in the weight ratio (wt%) shown in Table 8 below, and otherwise the same as in the case of Examples 6 to 8 and Comparative Example 4 described above.
And each cemented carbide of the comparative example 5 was produced.
【0050】ここで、このように作製した各超硬合金に
おいては、Coからなる結合相中にWC粒子やZrC粒
子が分散された状態になっており、このWC粒子やZr
C粒子の粒径は、原料に用いたWC粉末及びZrC粉末
とほぼ同じであった。Here, in each of the cemented carbides thus produced, the WC particles and ZrC particles are dispersed in the binder phase made of Co. The WC particles and Zr particles are dispersed in the binder phase.
The particle size of the C particles was almost the same as the WC powder and the ZrC powder used as the raw materials.
【0051】また、上記の各超硬合金において、Coか
らなる結合相の総量に対するZrCの重量比率M(wt
%)を求め、その結果を下記の表8に示した。Further, in each of the above-mentioned cemented carbides, the weight ratio M (wt) of ZrC to the total amount of the binder phase composed of Co.
%) And the results are shown in Table 8 below.
【0052】[0052]
【表8】 [Table 8]
【0053】また、このように作製した実施例11及び
比較例5の各超硬合金についても、上記の実施例1〜5
及び比較例1,2の場合と同様にして、高温及び室温に
おける抗折力(GPa)、破壊靭性値(MPa・
m0.5 )、ロックウェル硬さHRAを求めると共に、大
気中において800℃で30分間放置して酸化させた場
合における、単位面積当たりの酸化増量(mg/m
m2 )を求め、これらの結果を下記の表9に示した。Further, regarding each of the cemented carbides of Example 11 and Comparative Example 5 thus produced, the above-mentioned Examples 1 to 5 were also used.
And, as in Comparative Examples 1 and 2, the transverse rupture strength (GPa) and the fracture toughness value (MPa.
m 0.5 ), and Rockwell hardness HRA, and increase in oxidation per unit area (mg / m 2) when left to oxidize at 800 ° C. for 30 minutes in air.
m 2 ) was determined and these results are shown in Table 9 below.
【0054】[0054]
【表9】 [Table 9]
【0055】この結果、上記の実施例6,7及び比較例
3の各超硬合金の場合と同様に、WC−Co系の超硬合
金において、Coからなる結合相の総量に対してZrC
を2.0〜20重量%の範囲で含有させた実施例11の
超硬合金は、ZrCを加えていない比較例5の超硬合金
に比べ、高温における抗折力が高くなると共に、高温の
大気中において放置した場合における酸化増量も少なく
なっており、高温での強度及び耐酸化性が向上してい
た。As a result, as in the case of the cemented carbides of Examples 6 and 7 and Comparative Example 3 described above, in the WC-Co type cemented carbide, ZrC was added with respect to the total amount of the binder phase composed of Co.
In the cemented carbide of Example 11 containing 2.0 to 20% by weight, the bending resistance at high temperature is higher than that of the cemented carbide of Comparative Example 5 in which ZrC is not added, and The amount of oxidation increase when left to stand in the air was small, and the strength and oxidation resistance at high temperatures were improved.
【0056】次に、上記の実施例8〜11及び比較例
4,5の各超硬合金を使用して、それぞれ溶接部におけ
る余肉やビードかすを除去して平滑にするのに用いるト
リマーバイト用のインサートを作製した。Next, using each of the cemented carbides of Examples 8 to 11 and Comparative Examples 4 and 5, the trimmer bite used to remove the surplus wall and the bead residue in the welded portion and smooth it, respectively. Inserts were made.
【0057】そして、上記の各超硬合金で構成されたイ
ンサートを用いた各トリマーバイトにより、800℃前
後の鋼製ホイールにおける約200mmの長さになった
溶接部を、それぞれ切り込み3mm,送り速度200m
m/sで切削する切削加工を繰り返して行い、摩耗や欠
けが生じるまでの加工数を寿命として求め、その結果を
下記の表10に示した。なお、この寿命は、上記の各イ
ンサートにおける1つのコーナーを用いた場合における
結果である。Then, with each trimmer bite using the insert made of each of the above-mentioned cemented carbides, a welded portion having a length of about 200 mm in a steel wheel at about 800 ° C. is cut by 3 mm and a feed rate is set. 200 m
The cutting process for cutting at m / s was repeated, and the number of processes until abrasion or chipping occurred was determined as the life, and the results are shown in Table 10 below. It should be noted that this life is the result when one corner in each of the above inserts is used.
【0058】[0058]
【表10】 [Table 10]
【0059】この結果、上記の実施例8〜11の各超硬
合金で作製したインサートを用いたトリマーバイトは、
比較例4,5の各超硬合金で作製したインサートを用い
たトリマーバイトに比べて、寿命が大きく向上してい
た。As a result, the trimer bites using the inserts made of the cemented carbides of Examples 8 to 11 above were:
Compared to the trimmer bite using the inserts made of each cemented carbide of Comparative Examples 4 and 5, the life was greatly improved.
【0060】[0060]
【発明の効果】以上詳述したように、この発明における
超硬合金においては、Coを用いた結合相を有するWC
−Co系又はCoとCr3 C2 とを用いた結合相を有す
るWC−Co−Cr3 C2 系の超硬合金において、WC
粒子の平均粒径を0.5〜6μmの範囲にすると共に、
上記の結合相の総量に対して、ZrC又は(Zr,H
f)Cを2.0〜20重量%の範囲で含有させるように
したため、室温での強度や靱性が低下することなく、高
温での強度や耐酸化性等が向上した。As described above in detail, in the cemented carbide according to the present invention, WC having a binder phase using Co is used.
In WC-Co-Cr 3 C 2 system cemented carbide having -Co-based or Co and Cr 3 C 2 and bonded phase using, WC
The average particle size of the particles is in the range of 0.5 to 6 μm,
Based on the total amount of the above binder phase, ZrC or (Zr, H
f) Since C is contained in the range of 2.0 to 20% by weight, strength and oxidation resistance at high temperature are improved without lowering strength and toughness at room temperature.
【0061】そして、上記のような超硬合金を塑性加工
用工具や切削工具に使用すると、常温での抗折強度や破
壊靱性値が低下するということが少なく、高温での強度
や耐酸化性等が向上し、高温条件で被加工物を塑性加工
したり、高温条件で被加工物を切削加工することが長期
にわたって安定して行えるようになった。When the cemented carbide as described above is used for a plastic working tool or a cutting tool, the bending strength and fracture toughness value at room temperature are less likely to decrease, and the strength at high temperature and the oxidation resistance are high. As a result, it has become possible to perform plastic working on a work piece under high temperature conditions and to perform cutting work on a work piece under high temperature conditions stably over a long period of time.
【図1】この発明の実施例1〜4及び比較例1,2の各
超硬合金において、CoとCr 3 C2 とで構成された結
合相の総量に対するZrCの重量比率M(wt%)と、
高温及び室温における抗折力(GPa)との関係を示し
た図である。FIG. 1 is each of Examples 1 to 4 and Comparative Examples 1 and 2 of the present invention.
Co and Cr in cemented carbide 3C2Yui composed of
A weight ratio M (wt%) of ZrC to the total amount of the combined phase,
Shows the relationship with the transverse rupture strength (GPa) at high temperature and room temperature
It is a figure.
【図2】この発明の実施例1〜4及び比較例1,2の各
超硬合金において、CoとCr 3 C2 とで構成された結
合相の総量に対するZrCの重量比率M(wt%)と、
大気中において800℃で30分間放置して酸化させた
場合における、単位面積当たりの酸化増量(mg/mm
2 )との関係を示した図である。FIG. 2 is each of Examples 1 to 4 and Comparative Examples 1 and 2 of the present invention.
Co and Cr in cemented carbide 3C2Yui composed of
A weight ratio M (wt%) of ZrC to the total amount of the combined phase,
Oxidized by leaving in air at 800 ° C for 30 minutes
In the case of increasing the amount of oxidation per unit area (mg / mm
2It is the figure which showed the relationship with.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 山本 勉 大阪市平野区加美東2丁目1番18号 ダイ ジ▲ェ▼ット工業株式会社内 Fターム(参考) 3C046 FF32 FF39 FF50 FF57 4K018 AB02 AD06 BB04 BC12 CA00 DA00 EA12 KA15 KA18 ─────────────────────────────────────────────────── ─── Continued front page (72) Inventor Tsutomu Yamamoto 2-1-1 Kamihigashi, Hirano-ku, Osaka Inside Jet Industrial Co., Ltd. F-term (reference) 3C046 FF32 FF39 FF50 FF57 4K018 AB02 AD06 BB04 BC12 CA00 DA00 EA12 KA15 KA18
Claims (4)
系又はCoとCr3C2 とを用いた結合相を有するWC
−Co−Cr3 C2 系の超硬合金であって、WC粒子の
平均粒径が0.5〜6μmの範囲であると共に、上記の
結合相の総量に対して、ZrC又は(Zr,Hf)Cが
2.0〜20重量%の範囲で含有されていることを特徴
とする超硬合金。1. WC-Co having a binder phase using Co
System or WC having bonded phase using Co and Cr 3 C 2
A -Co-Cr 3 C 2 system cemented carbide, with an average particle size of the WC particles is in the range of 0.5~6Myuemu, the total amount of the binder phase, ZrC or (Zr, Hf ) C is contained in the range of 2.0 to 20% by weight, a cemented carbide.
均粒径が、上記のWC粒子の平均粒径の1/2以下であ
ることを特徴とする請求項1に記載の超硬合金。2. The cemented carbide according to claim 1, wherein the average particle diameter of ZrC or (Zr, Hf) C is 1/2 or less of the average particle diameter of the WC particles. .
金を用いたことを特徴とする塑性加工用工具。3. A plastic working tool characterized by using the cemented carbide according to claim 1 or 2.
金を用いたことを特徴とする切削加工用工具。4. A cutting tool using the cemented carbide according to claim 1 or 2.
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2012036037A1 (en) | 2010-09-15 | 2012-03-22 | 三菱マテリアル株式会社 | Surface coating insert made of wc-based cemented carbide |
JP2013032559A (en) * | 2011-08-01 | 2013-02-14 | Mts:Kk | High-strength cemented carbide and coated cemented carbide |
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2001
- 2001-10-03 JP JP2001307456A patent/JP2003113437A/en active Pending
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2012036037A1 (en) | 2010-09-15 | 2012-03-22 | 三菱マテリアル株式会社 | Surface coating insert made of wc-based cemented carbide |
US9023467B2 (en) | 2010-09-15 | 2015-05-05 | Mitsubishi Materials Corporation | Surface-coated WC-based cemented carbide insert |
JP2013032559A (en) * | 2011-08-01 | 2013-02-14 | Mts:Kk | High-strength cemented carbide and coated cemented carbide |
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