JP5305206B2 - Cemented carbide and carbide tools - Google Patents
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本発明は、超硬合金及び超硬工具に関する。 The present invention relates to a cemented carbide and a cemented carbide tool.
従来、炭化タングステン（ＷＣ）粒子と結合金属としてのコバルト（Ｃｏ）とを適切な割合で混合し、焼結させた超硬合金が知られている（特許文献１）。ＷＣ粒子とＣｏを混合し焼結させた超硬合金は、高硬度かつ高強度であることなどから、切削工具や金型などの超硬工具を製造するための材料として使用されている。 Conventionally, a cemented carbide is known in which tungsten carbide (WC) particles and cobalt (Co) as a binding metal are mixed at an appropriate ratio and sintered (Patent Document 1). A cemented carbide obtained by mixing and sintering WC particles and Co is used as a material for manufacturing a cemented carbide tool such as a cutting tool or a mold because it has high hardness and high strength.
他方、耐酸化性を高める目的で、アルミニウム（Ａｌ）を結合金属に含めた超硬合金が提案されている（特許文献２）。しかしながら、Ａｌを結合金属に含めた超硬合金は、その抗折強度が２．０ＧＰａに達せず、超硬工具を製造するための材料としては使用できなかった。ここで、超硬工具とは、超硬合金を用いた切削工具、金型、耐摩工具、鉱山土木工具などである。 On the other hand, a cemented carbide containing aluminum (Al) as a binding metal has been proposed for the purpose of improving oxidation resistance (Patent Document 2). However, the cemented carbide containing Al in the bonding metal does not reach the bending strength of 2.0 GPa and cannot be used as a material for producing a cemented carbide tool. Here, the cemented carbide tool is a cutting tool using a cemented carbide, a die, a wear-resistant tool, a mining civil engineering tool, or the like.
昨今、前記結合金属として使用されているコバルト（Ｃｏ）は希少資源であるが、その工業用途が拡大していることなどから資源枯渇の問題を有しており、価格が高騰し価格変動も大きいため、Ｃｏの供給が不安視されている。 Recently, cobalt (Co), which is used as the binding metal, is a scarce resource, but it has a problem of resource depletion due to the expansion of its industrial use. For this reason, the supply of Co is considered uneasy.
しかしながら、従来、コバルト（Ｃｏ）を使用しない超硬合金は、その抗折強度が低く、超硬工具を製造するための材料としては使用できなかった（特許文献２等）。 However, conventionally, a cemented carbide which does not use cobalt (Co) has a low bending strength, and cannot be used as a material for manufacturing a cemented carbide tool (Patent Document 2, etc.).
このような実情に鑑みて、本発明の目的は、コバルト（Ｃｏ）を使用しない超硬合金において、従来よりも抗折強度を高めた超硬合金及び超硬工具を提供するものである。 In view of such circumstances, an object of the present invention is to provide a cemented carbide and a cemented carbide tool that have higher bending strength than conventional cemented carbides that do not use cobalt (Co).
本発明の超硬合金は、金属元素の化合物からなるセラミックス粒子を分散させ、結合相が鉄（Ｆｅ）、アルミニウム（Ａｌ）、ホウ素（Ｂ）、及び不可避不純物からなる超硬合金であって、
前記金属元素の化合物からなるセラミックス粒子が、炭化タングステン（ＷＣ）粒子を含み、かつ、前記結合相中のＢの含有量が０．０７質量％以上かつ０．２８質量％以下であることを特徴とする。
Cemented carbide of the present invention, the ceramic particles comprising a compound of a metal element is dispersed, binder phase of iron (Fe), aluminum (Al), boron (B), and a Ru cemented carbide name from unavoidable impurities ,
The ceramic particles composed of the compound of the metal element include tungsten carbide (WC) particles , and the B content in the binder phase is 0.07% by mass or more and 0.28% by mass or less. And
本発明によれば、結合相としてのＦｅとＡｌとで構成される合金若しくは金属間化合物に適量のＢを添加することで、抗折強度が高められる。特に前記結合相中のＢの含有量を０．０７質量％以上かつ０．２８質量％以下とすることで、抗折強度に加えて破壊靱性などの機械的特性が向上し、ＷＣとこの結合相とで構成される超硬合金の機械的特性が改善される。前記結合相中のＢの含有量が少ないと機械的特性の改善効果が見られず、前記結合相中のＢの含有量が多いとＷやＦｅ等と結合してホウ化タングステンやホウ化鉄等のホウ化物が形成され、抗折強度の低下を招くこととなることから、前記結合相中のＢの含有量を０．０７質量％以上かつ０．２８質量％以下と規定している。 According to the present invention, the bending strength can be increased by adding an appropriate amount of B to an alloy or intermetallic compound composed of Fe and Al as a binder phase. In particular, when the content of B in the binder phase is 0.07 mass% or more and 0.28 mass% or less, mechanical properties such as fracture toughness in addition to bending strength are improved, and WC and this bond The mechanical properties of the cemented carbide composed of phases are improved. When the content of B in the binder phase is small, no improvement effect on mechanical properties is observed, and when the content of B in the binder phase is large, it binds to W, Fe or the like and becomes tungsten boride or iron boride. Therefore, the content of B in the binder phase is specified to be 0.07% by mass or more and 0.28% by mass or less.
本発明は、前記結合相中のＡｌの含有量が１０質量％以上かつ３３質量％以下であることを特徴とする。 The present invention is characterized in that the Al content in the binder phase is 10 mass% or more and 33 mass% or less.
本発明によれば、前記結合相中のＡｌの含有量を１０質量％以上かつ３３質量％以下と規定することで、好適な合金相となり、さらに好ましい割合は、前記結合相中のＡｌの含有量が１３質量％以上かつ２４質量％以下である。 According to the present invention, by defining the content of Al in the binder phase as 10 mass% or more and 33 mass% or less, a suitable alloy phase is obtained, and a more preferable ratio is the content of Al in the binder phase. The amount is 13% by mass or more and 24% by mass or less.
本発明は、前記ＷＣの含有量が４０体積％以上かつ９０体積％以下であることを特徴とする。 The present invention is characterized in that the content of WC is 40% by volume or more and 90% by volume or less.
前記ＷＣと結合相との割合は、超硬合金の使用目的により適宜調節される。この割合の値は、一般に体積％で表現されており、これは、前記結合相の密度が変化することによって前記ＷＣと結合相との重量比が変化した場合でも、前記ＷＣの含有量を体積％で表すことによって、前記ＷＣと結合相との割合を一定の値とし、超硬合金の硬さを決定付けられるからである。
本発明では、硬さを優先する用途の場合には前記ＷＣの含有量を増大させ、抗折強度や破壊靱性を優先する用途の場合には前記ＷＣの含有量を減少させる。前記ＷＣの含有量が少ないと必要な硬さが極端に低下し、前記ＷＣの含有量が多いと焼結が不十分となり空孔が多くなることで必要な抗折強度が得られないことから、前記ＷＣの含有量を４０体積％以上かつ９０体積％以下と規定している。
The ratio between the WC and the binder phase is appropriately adjusted depending on the purpose of use of the cemented carbide. The value of this ratio is generally expressed in volume%, which means that even if the weight ratio of the WC and the binder phase is changed by changing the density of the binder phase, the content of the WC is expressed by volume. This is because the hardness of the cemented carbide can be determined by setting the ratio of the WC and the binder phase to a constant value.
In the present invention, the content of the WC is increased in the case of an application giving priority to hardness, and the content of the WC is reduced in the case of an application giving priority to bending strength and fracture toughness. If the content of the WC is small, the required hardness is extremely reduced, and if the content of the WC is large, the necessary bending strength cannot be obtained because the sintering is insufficient and the number of pores increases. The content of the WC is specified to be 40% by volume or more and 90% by volume or less.
これら本発明の超硬合金から既知の製造方法によって本発明の超硬工具が得られる。 The cemented carbide tool of the present invention can be obtained from these cemented carbides of the present invention by a known production method.
本発明は、前記金属元素セラミックス粒子が、ホウ化タングステン（ＷＢ）、炭化チタン（ＴｉＣ）、炭窒化チタン（ＴｉＣＮ）、窒化チタン（ＴｉＮ）、炭化モリブデン（Ｍｏ２Ｃ）、炭化クロム（Ｃｒ３Ｃ２）、炭化バナジウム（ＶＣ）、炭化タンタル（ＴａＣ）のうちいずれか１種以上を含有することを特徴とする。 In the present invention, the metal element ceramic particles include tungsten boride (WB), titanium carbide (TiC), titanium carbonitride (TiCN), titanium nitride (TiN), molybdenum carbide (Mo 2 C), chromium carbide (Cr 3 One or more of C 2 ), vanadium carbide (VC), and tantalum carbide (TaC) are contained.
本発明によれば、前記金属元素セラミックス粒子として、ホウ化タングステン（ＷＢ）、炭化チタン（ＴｉＣ）、炭窒化チタン（ＴｉＣＮ）、窒化チタン（ＴｉＮ）、炭化モリブデン（Ｍｏ２Ｃ）、炭化クロム（Ｃｒ３Ｃ２）、炭化バナジウム（ＶＣ）、炭化タンタル（ＴａＣ）のうちいずれか１種以上を含有させることで、硬さ、抗折強度、被加工材料との相性などを最適化した良好な加工性を有する超硬工具とすることができる。 According to the present invention, the metal element ceramic particles include tungsten boride (WB), titanium carbide (TiC), titanium carbonitride (TiCN), titanium nitride (TiN), molybdenum carbide (Mo 2 C), chromium carbide ( Cr 3 C 2 ), vanadium carbide (VC), and tantalum carbide (TaC) containing one or more of them, the hardness, bending strength, compatibility with the work material, etc. are optimized It can be a cemented carbide tool having workability.
本発明に使用される原料としてのＷＣ、Ｆｅ、Ａｌ、及びＢは粉末にて供給される。それぞれの原料には、不可避不純物が含有される。不可避不純物の多くは構成元素の酸化物として含有され、最終形態の構造材においても微量の酸素が存在する。この酸素を除くために本発明の超硬合金の製造過程では適量の炭素（Ｃ）を混合させており、最終形態の構造材においても微量のＣが存在する場合がある。 WC, Fe, Al, and B as raw materials used in the present invention are supplied in powder form. Each raw material contains inevitable impurities. Most of the inevitable impurities are contained as constituent element oxides, and a trace amount of oxygen is also present in the final structural material. In order to remove this oxygen, an appropriate amount of carbon (C) is mixed in the manufacturing process of the cemented carbide of the present invention, and a trace amount of C may exist even in the final structural material.
本発明に係る超硬合金の製造方法としては、粉末冶金法が最も適切である。粉末冶金法では、例えば、ＷＣ、Ｆｅ、Ａｌ、及びＢの各粉末を予め適量混合し、その混合粉末をプレス成型した後、真空中で適温に加熱し焼結させ焼結体とする。または、プレス成型と真空加熱を同時に行う手法、例えば、通電焼結法を採用してもよい。さらには、前記焼結体に熱間等方加圧焼結処理（ＨＩＰ処理）を施してもよい。 As a method for producing a cemented carbide according to the present invention, powder metallurgy is most suitable. In the powder metallurgy method, for example, WC, Fe, Al, and B powders are mixed in an appropriate amount in advance, and the mixed powder is press-molded, and then heated to an appropriate temperature in a vacuum and sintered to obtain a sintered body. Or you may employ | adopt the method of performing press molding and vacuum heating simultaneously, for example, an electric current sintering method. Furthermore, you may perform a hot isostatic pressing sintering process (HIP process) to the said sintered compact.
本発明によれば、結合相としてのＦｅとＡｌとで構成される合金若しくは金属間化合物に適量のＢを添加することで、抗折強度が高められ、特に前記結合相中のＢの含有量を０．０７質量％以上かつ０．３質量％以下とすることで、抗折強度に加えて破壊靱性などの機械的特性が向上し、ＷＣと前記結合相とで構成される超硬合金の機械的特性が改善される。前記結合相中のＡｌの含有量を１０質量％以上かつ３３質量％以下と規定することで、好適な合金相となり、さらに好ましい割合は、前記結合相中のＡｌの含有量が１３質量％以上かつ２４質量％以下である。 According to the present invention, the bending strength is increased by adding an appropriate amount of B to an alloy or intermetallic compound composed of Fe and Al as the binder phase, and in particular, the B content in the binder phase. Of 0.07 mass% or more and 0.3 mass% or less improves mechanical properties such as fracture toughness in addition to the bending strength, and the cemented carbide composed of WC and the binder phase. Mechanical properties are improved. By defining the Al content in the binder phase as 10% by mass or more and 33% by mass or less, a suitable alloy phase is obtained, and a more preferable ratio is that the Al content in the binder phase is 13% by mass or more. And it is 24 mass% or less.
本発明では、硬さを優先する用途の場合には前記ＷＣの含有量を増大させ、抗折強度や破壊靱性を優先する用途の場合には前記ＷＣの含有量を減少させる。前記ＷＣの含有量が少ないと必要な硬さが極端に低下し、前記ＷＣの含有量が多いと焼結が不十分となり空孔が多くなることで必要な抗折強度が得られないことから、前記ＷＣの含有量を４０体積％以上かつ９０体積％以下と規定している。さらには、ホウ化タングステン（ＷＢ）、炭化チタン（ＴｉＣ）、炭窒化チタン（ＴｉＣＮ）、窒化チタン（ＴｉＮ）、炭化モリブデン（Ｍｏ２Ｃ）、炭化クロム（Ｃｒ３Ｃ２）、炭化バナジウム（ＶＣ）、炭化タンタル（ＴａＣ）のうちいずれか１種以上を含有させることで、硬さ、抗折強度、被加工材料との相性などを最適化した良好な加工性を有する超硬工具とすることができる。したがって、本発明によって、コバルト（Ｃｏ）を使用しない超硬合金において、従来よりも抗折強度を高めた超硬合金及び超硬工具が実現する。 In the present invention, the content of the WC is increased in the case of an application giving priority to hardness, and the content of the WC is reduced in the case of an application giving priority to bending strength and fracture toughness. If the content of the WC is small, the required hardness is extremely reduced, and if the content of the WC is large , the necessary bending strength cannot be obtained because the sintering is insufficient and the number of pores increases. The content of the WC is specified to be 40% by volume or more and 90% by volume or less. Furthermore , tungsten boride (WB), titanium carbide (TiC), titanium carbonitride (TiCN), titanium nitride (TiN), molybdenum carbide (Mo2C), chromium carbide (Cr3C2), vanadium carbide (VC), tantalum carbide ( By including any one or more of TaC), it is possible to obtain a cemented carbide tool having good workability with optimized hardness, bending strength, compatibility with a material to be processed, and the like. Therefore, according to the present invention, a cemented carbide and a cemented carbide tool having higher bending strength than those of conventional cemented carbides that do not use cobalt (Co) are realized.
以下、本発明を実施するための最良の形態を、実施例に基づいて以下に説明する。なお、本発明は、以下の実施の形態に限定されるものではなく、本発明と実質同一又は均等の範囲内において、既知の変更を加えることが可能である。 Hereinafter, the best mode for carrying out the present invention will be described based on examples. It should be noted that the present invention is not limited to the following embodiments, and known modifications can be made within a range substantially the same as or equivalent to the present invention.
（実施例１）
炭化タングステン（ＷＣ）の含有量を５０体積％とし、Ｆｅ−Ａｌ結合相中のＢの添加量を変化させて焼結体を作製し、抗折強度、硬さ、破壊靱性を測定した。測定結果を表１に示す。
Example 1
Sintered bodies were made by changing the content of tungsten carbide (WC) to 50% by volume and changing the addition amount of B in the Fe—Al binder phase, and the bending strength, hardness, and fracture toughness were measured. The measurement results are shown in Table 1.
表１から、硬さは結合相中のＢ量に依存せず、ＨＲＡ８０程度である。抗折強度は結合相中のＢ量が０．０７質量％から増加し、最大２．９２ＧＰａに達した。さらにＢ量を増加させ０．２８質量％以上となると、結合相中のホウ化物の析出が著しくなることによって、Ｂを添加しない場合と同程度まで抗折強度が低下した。 From Table 1, the hardness does not depend on the amount of B in the binder phase and is about HRA80. The bending strength increased from 0.07% by mass of B in the binder phase and reached a maximum of 2.92 GPa. When the amount of B was further increased to 0.28% by mass or more, the precipitation of boride in the binder phase became significant, and the bending strength was reduced to the same extent as when B was not added.
上記実施例にてＦｅ−Ａｌ結合相中のＢの添加量を０．２１質量％としたときの超硬合金の結合相の組織を、光学顕微鏡にて撮像した画像を図１に示し、走査型電子顕微鏡（ＳＥＭ）にて撮像した画像を図２に示す。図１に示す画像は、白く見える部分が結合相のＦｅ−Ａｌ金属間化合物であり、少し灰色がかって見え、線で囲まれたように見える部分が硬質相のＷＣであり、黒く見える部分がＢの化合物と推察する。図２に示す画像は、灰色の部分が結合相のＦｅ−Ａｌ金属間化合物であり、白く見える部分がＷＣであり、黒く見える部分がＡｌの酸化物と推察する。 FIG. 1 shows an image taken with an optical microscope of the cemented carbide structure of the cemented carbide when the addition amount of B in the Fe—Al binder phase is 0.21% by mass in the above embodiment. An image taken with a scanning electron microscope (SEM) is shown in FIG. In the image shown in FIG. 1, the part that appears white is the Fe—Al intermetallic compound in the binder phase, the part appears grayish, the part that appears to be surrounded by the line is the WC in the hard phase, and the part that appears black Presumed to be a compound of B. In the image shown in FIG. 2, the gray portion is the Fe—Al intermetallic compound in the binder phase, the white portion is WC, and the black portion is an Al oxide.
上記実施例に示す結果から、コバルト（Ｃｏ）を使用しない超硬合金においても、従来よりも抗折強度を高めた超硬合金及び超硬工具となることがわかった。 From the results shown in the above examples, it was found that a cemented carbide and a cemented carbide tool having higher bending strength than those of conventional cemented carbides that do not use cobalt (Co).
（実施例２）
Ｆｅ−Ａｌ結合相中のＢの添加量を０．１４質量％とし、炭化タングステン（ＷＣ）の含有量を変化させて焼結体を作製し、抗折強度、硬さ、破壊靱性を測定した。このときのＦｅ−Ａｌ結合相中のＡｌの含有量は１３．９質量％である。測定結果を表２に示す。
(Example 2)
The amount of B added in the Fe-Al binder phase was 0.14% by mass, the content of tungsten carbide (WC) was changed to produce a sintered body, and the bending strength, hardness, and fracture toughness were measured. . At this time, the content of Al in the Fe—Al bonded phase is 13.9% by mass. The measurement results are shown in Table 2.
表２から、ＷＣ含有量の低下に伴って、硬さが低下し、抗折強度と破壊靭性が上昇することが判明した。 From Table 2, it was found that the hardness decreases and the bending strength and fracture toughness increase as the WC content decreases.
（実施例３）
炭化タングステン（ＷＣ）の含有量を５０体積％とし、Ｆｅ−Ａｌ結合相中のＡｌの添加量を変化させて焼結体を作製し、抗折強度、硬さ、破壊靱性を測定した。このときのＦｅ−Ａｌ結合相中のＢの添加量は０．１４質量％である。測定結果を表３に示す。
(Example 3)
Sintered bodies were prepared by changing the content of tungsten carbide (WC) to 50% by volume and changing the addition amount of Al in the Fe—Al binder phase, and the bending strength, hardness, and fracture toughness were measured. The amount of B added in the Fe—Al bonded phase at this time is 0.14% by mass. Table 3 shows the measurement results.
表３から、Ｆｅ−Ａｌ結合相中のＡｌ含有量の低下に伴って、硬さが低下し、抗折強度と破壊靭性が上昇することが判明した。表３で、Ｆｅ−Ａｌ結合相中のＡｌ含有量が３２．５質量％の焼結体は非磁性体であり、Ｆｅ−Ａｌ結合相中のＡｌ含有量が２４．３質量％の焼結体は非磁性体であり、Ｆｅ−Ａｌ結合相中のＡｌ含有量が１３．９質量％の焼結体は磁性体である。 From Table 3, it became clear that hardness fell and bending strength and fracture toughness raised with the fall of Al content in a Fe-Al binder phase. In Table 3, the sintered body having an Al content of 32.5% by mass in the Fe—Al bonded phase is a non-magnetic material, and the sintered body having an Al content of 24.3% by mass in the Fe—Al bonded phase. The body is a non-magnetic body, and the sintered body having an Al content of 13.9% by mass in the Fe—Al bonded phase is a magnetic body.
（実施例４）
ＷＣ含有量を５０体積％とし、Ｆｅ−Ａｌ結合相中のＡｌの添加量を３３質量％とし、Ｆｅ−Ａｌ結合相中のＢの添加量を０．１４質量％とした場合のＷＣ−ＦｅＡｌ焼結体を本実施例の超硬合金とし、そして、ＷＣ含有量を７０体積％とし、Ｃｏ結合相とした場合のＷＣ−Ｃｏ焼結体を従来の超硬合金として、それぞれの超硬合金の銅に対する反応性を比較した。真空度が１．３Ｘ１０−３の真空中において、各焼結体の上に銅を載置し、常温から１０９４℃の高温まで昇温した。銅の融点は１０８５℃であるので上記昇温中に銅は溶融する。そこで、各焼結体における、溶融した銅と焼結体とのぬれ性を調べることとし、溶融した銅が焼結体の上でドーム状になることから、銅と焼結体のつくる接触角度によって、ぬれ性の良否を判定することとした。調査の結果、本実施例のＷＣ−ＦｅＡｌ焼結体における１０９４℃での銅の接触角度は３７．２°であり、従来例のＷＣ−Ｃｏ焼結体における１０９４℃での銅の接触角度は１１．３°であった。つまり、本実施例の超硬合金のほうが従来例よりも結合相の割合が多いにもかかわらず、本実施例のＷＣ−ＦｅＡｌ焼結体のほうが銅とのぬれ性が悪い結果となった。すなわち、銅に対する反応性はＷＣ−Ｃｏ焼結体（従来例）よりＷＣ−ＦｅＡｌ焼結体（本実施例）のほうが低い結果となった。したがって、銅を含む材料を高温下で加工する際には、従来の材料を用いた超硬工具に比べて、本発明の開発材を用いた超硬工具のほうが好適であるといえるので、優れた切削工具や金型となる。
Example 4
WC-FeAl in the case where the WC content is 50% by volume, the additive amount of Al in the Fe-Al bonded phase is 33% by mass, and the additive amount of B in the Fe-Al bonded phase is 0.14% by mass. The sintered body is the cemented carbide of this example, and the WC-Co sintered body when the WC content is 70 volume% and the Co binder phase is used as the conventional cemented carbide. The reactivity of copper to copper was compared. In a vacuum with a degree of vacuum of 1.3 × 10 −3 , copper was placed on each sintered body, and the temperature was raised from room temperature to a high temperature of 1094 ° C. Since the melting point of copper is 1085 ° C., copper melts during the above temperature rise. Therefore, we investigated the wettability between the molten copper and the sintered body in each sintered body, and since the molten copper becomes a dome shape on the sintered body, the contact angle created by the copper and the sintered body Therefore, it was decided to determine the wettability. As a result of the investigation, the contact angle of copper at 1094 ° C. in the WC-FeAl sintered body of this example is 37.2 °, and the contact angle of copper at 1094 ° C. in the WC-Co sintered body of the conventional example is It was 11.3 °. That is, although the cemented carbide of this example had a higher binder phase ratio than the conventional example, the WC-FeAl sintered body of this example had poorer wettability with copper. That is, the reactivity with respect to copper was lower in the WC-FeAl sintered body (this example) than in the WC-Co sintered body (conventional example). Therefore, when processing a material containing copper at high temperature, it can be said that the cemented carbide tool using the developed material of the present invention is more suitable than the cemented carbide tool using the conventional material. Cutting tools and molds.
Claims (5)
前記金属元素の化合物からなるセラミックス粒子が、炭化タングステン（ＷＣ）粒子を含み、かつ、前記結合相中のＢの含有量が０．０７質量％以上かつ０．２８質量％以下であることを特徴とする超硬合金。 The ceramic particles made of a compound of a metal element is dispersed, binder phase of iron (Fe), aluminum (Al), a boron (B), and Ru cemented carbide name from unavoidable impurities,
The ceramic particles composed of the compound of the metal element include tungsten carbide (WC) particles , and the B content in the binder phase is 0.07% by mass or more and 0.28% by mass or less. Cemented carbide.
A cemented carbide tool comprising the cemented carbide according to any one of claims 1 to 4.
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