JP2016513177A

JP2016513177A - Cemented carbide material and method for producing the same

Info

Publication number: JP2016513177A
Application number: JP2015556525A
Authority: JP
Inventors: イゴールユリエヴィチコンヤシン; ベルントハインリッヒリース; フランクフリードリッヒラヒマン
Original assignee: Element Six GmbH
Current assignee: Element Six GmbH
Priority date: 2013-02-11
Filing date: 2014-02-10
Publication date: 2016-05-12
Anticipated expiration: 2034-02-10
Also published as: US20150376744A1; EP2954082A2; CN105074029A; WO2014122306A2; GB2512983A; GB201302345D0; WO2014122306A3; GB201402248D0; EP2954082B1; CN105074029B; JP6275750B2; US20210222273A1; US20190368011A1; GB2512983B

Abstract

超硬合金材料は、ＷＣ、約３〜約１０質量％の間のＣｏおよび約０．５〜約８質量％の間のＲｅを含む。ＷＣに対する超硬合金材料の全炭素当量（ＥＴＣ）含有率は、約６．３質量％〜約６．９質量％の間であり、超硬合金材料は、η相および遊離炭素を実質的に含まない。また、そのような材料を生成する方法およびそのような材料の使用が開示される。The cemented carbide material includes WC, between about 3 and about 10% by weight Co and between about 0.5 and about 8% by weight Re. The total carbon equivalent (ETC) content of the cemented carbide material relative to the WC is between about 6.3 wt% and about 6.9 wt%, and the cemented carbide material substantially contains η phase and free carbon. Not included. Also disclosed are methods of producing such materials and uses of such materials.

Description

本開示は、例えばダイヤモンドもしくはｃ−ＢＮの合成、または多結晶のダイヤモンドもしくはｃ−ＢＮの製造のための高圧構成要素における使用のための超硬合金材料、およびそれを作製する方法に関する。 The present disclosure relates to cemented carbide materials for use in high pressure components, for example for the synthesis of diamond or c-BN, or for the production of polycrystalline diamond or c-BN, and methods of making the same.

ダイヤモンド合成および多結晶ダイヤモンド（ＰＣＤ）の製造に使用され、アンビルおよびダイを含む高圧高温（ＨＰＨＴ）構成要素に採用される超硬合金が、高い圧力、温度および負荷を受けることは周知である。そのような好ましくない条件はそれらの変形をもたらし、変形がある特定のレベルを超えると、ＨＰＨＴ構成要素は破損する。この点において、高圧での変形を低減し、結果としてＨＰＨＴ構成要素の変形抵抗および寿命を改善するために、高レベルのヤング率を有する超硬合金材料を有することが非常に重要である。 It is well known that cemented carbides used in diamond synthesis and polycrystalline diamond (PCD) production and employed in high pressure high temperature (HPHT) components, including anvils and dies, are subject to high pressures, temperatures and loads. Such unfavorable conditions result in their deformation, and if the deformation exceeds a certain level, the HPHT component breaks. In this regard, it is very important to have a cemented carbide material with a high level of Young's modulus in order to reduce deformation at high pressure and consequently improve the deformation resistance and life of the HPHT component.

したがって、改善された変形抵抗、ならびに高い破壊靭性および強度を有する高圧高温構成要素の製造における使用のための超硬合金材料が必要とされている。 Accordingly, there is a need for a cemented carbide material for use in the manufacture of high pressure, high temperature components having improved deformation resistance and high fracture toughness and strength.

第１の態様から見ると、ＷＣ、ＣｏおよびＲｅを含む超硬合金材料であって、
超硬合金材料は、約３〜約１０質量％の間のＣｏおよび約０．５〜約８質量％の間のＲｅを含み、
ＷＣに対する超硬合金材料の全炭素当量（ＥＴＣ）含有率は、約６．３質量％〜約６．９質量％の間であり、
超硬合金材料は、η相および遊離炭素を実質的に含まない、超硬合金材料が提供される。
第２の態様から見ると、
上で定義された超硬合金材料を含む基材と、
界面に沿って基材に結合された多結晶性超硬質材料の物体
とを備える、多結晶性超硬質構造物が提供される。
第３の態様から見ると、地面穿孔用の回転ドリルビットに適合された多結晶性超硬質材料の物体に結合された、上で定義された超硬合金材料を含む基材を備えるカッターが提供される。
第４の態様から見ると、地面穿孔用の回転せん断ビット、パーカッション用ドリルビットまたは採鉱もしくはアスファルト分解用のピックのＰＣＤ要素であって、上で定義されたような超硬合金材料の物体に結合された超硬質多結晶性材料の物体を備えるカッター要素を備えるＰＣＤ要素が提供される。
第５の態様から見ると、上で定義されたようなＰＣＤ要素を備える、地面穿孔用のドリルビットまたはドリルビットの構成要素が提供される。
第６の態様から見ると、上で定義された超硬合金材料を生成する方法であって、
ＷＣおよび炭素と共に、Ｒｅ、Ｃｏ、Ｎｉおよび／またはＦｅを含有し、Ｖ、Ｃｒ、Ｔａ、Ｔｉ、Ｍｏ、Ｚｒ、ＮｂおよびＨｆの１種もしくは複数種、またはそれらの炭化物を含む粒子成長阻害剤を含有してもよい超硬合金混合物を粉砕するステップと、
混合物から超硬合金物品をプレスするステップと、
真空中約１〜１０分の間の期間、およびＡｒの圧力下（ＨＩＰ）で約５〜１２０分の期間、約１４５０℃超の温度で物品を焼結するステップと、
焼結温度から摂氏約１３００度（℃）まで物品を冷却するステップと
を含む方法が提供される。
第７の態様から見ると、上で定義された超硬合金材料をリサイクルする方法であって、炭化物材料を保護雰囲気中で液体Ｚｎと共に溶融するステップと、Ｚｎを蒸発させて最終生成物を形成するステップと、最終生成物を粉砕して生成物からＲｅを回収するステップとを含む方法が提供される。 Viewed from the first aspect, a cemented carbide material containing WC, Co and Re,
The cemented carbide material comprises between about 3 to about 10% by weight Co and between about 0.5 to about 8% by weight Re;
The total carbon equivalent (ETC) content of the cemented carbide material relative to WC is between about 6.3 wt% and about 6.9 wt%,
A cemented carbide material is provided that is substantially free of η phase and free carbon.
From the second aspect,
A substrate comprising a cemented carbide material as defined above;
A polycrystalline superhard structure is provided comprising an object of polycrystalline superhard material bonded to a substrate along an interface.
Viewed from a third aspect, there is provided a cutter comprising a substrate comprising a cemented carbide material as defined above bonded to an object of polycrystalline cemented carbide material adapted to a rotating drill bit for ground drilling Is done.
Viewed from a fourth aspect, a rotary shear bit for ground drilling, a percussion drill bit or a PCD element for picking for mining or asphalt decomposition, bonded to an object of cemented carbide material as defined above There is provided a PCD element comprising a cutter element comprising an object of a fabricated ultra-hard polycrystalline material.
Viewed from a fifth aspect, there is provided a drill bit for drilling ground or a component of a drill bit comprising a PCD element as defined above.
Viewed from a sixth aspect, a method of producing a cemented carbide material as defined above, comprising:
Particle growth inhibitor containing Re, Co, Ni and / or Fe together with WC and carbon, and containing one or more of V, Cr, Ta, Ti, Mo, Zr, Nb and Hf, or carbides thereof Crushing a cemented carbide mixture that may contain:
Pressing a cemented carbide article from the mixture;
Sintering the article at a temperature greater than about 1450 ° C. for a period of between about 1-10 minutes in a vacuum and under a pressure of Ar (HIP) for about 5-120 minutes;
Cooling the article from a sintering temperature to about 1300 degrees Celsius (° C.).
Viewed from a seventh aspect, a method of recycling a cemented carbide material as defined above, comprising melting a carbide material with liquid Zn in a protective atmosphere and evaporating Zn to form a final product And a step of grinding the final product to recover Re from the product.

第８の態様から見ると、上で定義された超硬合金材料をリサイクルする方法であって、超硬合金材料を酸浸出混合物に供し、超硬合金材料から結合剤相を除去するステップと、除去された結合剤相からＣｏおよびＲｅを化学的に回収するステップとを含む方法が提供される。
第９の態様から見ると、上で定義された超硬合金材料をリサイクルする方法であって、超硬合金材料を酸化して炭化物、ＲｅおよびＣｏを溶解するステップと、Ｒｅを回収するステップとを含む方法が提供される。
第１０の態様から見ると、５ＧＰａ超の圧力および１１００℃超の温度で行われる、ダイヤモンドもしくはｃ−ＢＮの合成のための、または多結晶のダイヤモンドもしくはｃ−ＢＮの製造における、高圧構成要素中での超硬合金材料の使用であって、超硬合金材料が、
第二炭化物相の形態をした、または材料中の結合剤相に固溶した１種または複数種の金属の炭化物であって、１種または複数種の前記金属が、Ｔｉ、Ｖ、Ｃｒ、Ｍｎ、Ｚｒ、Ｎｂ、Ｍｏ、Ｈｆおよび／またはＴａを含む、炭化物と、
約０．５〜約８質量％の間のＲｅおよび約３〜約１０質量％の間のＣｏとを含み、
ＷＣに対する超硬合金材料の全炭素当量（ＥＴＣ）含有率が、約６．３質量％〜約６．９質量％の間であり、
超硬合金材料が、η相および遊離炭素を実質的に含まない、超硬合金材料の使用が提供される。
ここで、例示として、および添付の図面を参照して実施形態を説明する。 Viewed from an eighth aspect, a method of recycling a cemented carbide material as defined above, comprising subjecting the cemented carbide material to an acid leaching mixture to remove the binder phase from the cemented carbide material; Chemically recovering Co and Re from the removed binder phase.
Viewed from a ninth aspect, a method of recycling a cemented carbide material as defined above, comprising: oxidizing a cemented carbide material to dissolve carbides, Re and Co; and collecting Re Is provided.
Viewed from the tenth aspect, in a high pressure component for the synthesis of diamond or c-BN or in the production of polycrystalline diamond or c-BN, carried out at a pressure of more than 5 GPa and a temperature of more than 1100 ° C. Use of cemented carbide material in which the cemented carbide material is
A carbide of one or more metals in the form of a second carbide phase or dissolved in a binder phase in the material, wherein the one or more metals are Ti, V, Cr, Mn Carbides containing Zr, Nb, Mo, Hf and / or Ta,
Between about 0.5 and about 8% by weight of Re and between about 3 and about 10% by weight of Co;
The total carbon equivalent (ETC) content of the cemented carbide material relative to WC is between about 6.3 wt% and about 6.9 wt%,
There is provided the use of a cemented carbide material, wherein the cemented carbide material is substantially free of η phase and free carbon.
Embodiments will now be described by way of example and with reference to the accompanying drawings.

第１の例による、ＷＣ−Ｃｏ−Ｒｅを含む超硬合金材料のＳＥＭ画像である。It is a SEM image of the cemented carbide material containing WC-Co-Re by the 1st example. 図１のＷＣ−Ｃｏ−Ｒｅ超硬合金材料のＥＢＳＤ画像である。It is an EBSD image of the WC-Co-Re cemented carbide material of FIG. 従来のＷＣ−Ｃｏ超硬合金材料の微細構造を示すＥＢＳＤ画像である。It is an EBSD image which shows the microstructure of the conventional WC-Co cemented carbide material.

従来のＷＣ−Ｃｏ材料のＷＣに対する全炭素当量（ＥＴＣ）含有率は、約６．０〜６．３質量％の間であることは周知である。［例えば、「Exner H., Gurland J. A review of parameters influencing some mechanical properties of tungsten carbide-cobalt alloy. Powder Met., 13 (1970) 13-31」；およびI. Konyashin, S. Hlawatschek, B. Ries, F. Lachmann, T. Weirich, F. Dorn, A. Sologubenko on the 「Mechanism of WC Coarsening in WC-Co Hardmetals with Various Carbon Contents」, International Journal of Refractory Metals and Hard Materials, 27 (2009) 234-243を参照されたい。］炭素含量がこの範囲の炭素含量より低い、または高い場合、炭化物微細構造中に追加的な相（例えばη相または遊離炭素）が出現し、ＷＣ−Ｃｏ材料の機械的特性、例えば圧縮強度、抗折力、および破壊靭性の大幅な低下をもたらす。
ここで、驚くべきことに、ＷＣ−Ｃｏ−Ｒｅ超硬合金が、６．３質量％〜６．９質量％の間のＷＣに対する全炭素当量（ＥＴＣ）含有率に対応する著しく増加した炭素含量を有する場合、その機械的特性、例えば圧縮強度、抗折力、硬度、破壊靭性および高温硬度が劇的に改善され得ることが認識された。 It is well known that the total carbon equivalent (ETC) content of WC-Co material to WC is between about 6.0 and 6.3 wt%. [For example, “Exner H., Gurland J. A review of parameters influencing some mechanical properties of tungsten carbide-cobalt alloy. Powder Met., 13 (1970) 13-31”; and I. Konyashin, S. Hlawatschek, B. Ries, F. Lachmann, T. Weirich, F. Dorn, A. Sologubenko on the `` Mechanism of WC Coarsening in WC-Co Hardmetals with Various Carbon Contents '', International Journal of Refractory Metals and Hard Materials, 27 (2009) 234- See 243. When the carbon content is lower or higher than this range, additional phases (eg, η phase or free carbon) appear in the carbide microstructure and mechanical properties of the WC-Co material, such as compressive strength, This results in a significant decrease in bending strength and fracture toughness.
Here, surprisingly, the WC—Co—Re cemented carbide has a significantly increased carbon content corresponding to a total carbon equivalent (ETC) content of WC between 6.3 wt% and 6.9 wt%. It has been recognized that its mechanical properties such as compressive strength, bending strength, hardness, fracture toughness and high temperature hardness can be dramatically improved.

理論に束縛されることを望まないが、その考えられる理由は、そのような材料中のＷＣ−Ｃｏ−Ｒｅ超硬合金の結合剤相における残留圧縮応力の存在であり得る。ＷＣ−Ｃｏ超硬合金における残留応力に関する多くの出版物によれば、ＷＣ−Ｃｏ中の結合剤相は常に高い残留引張応力下にあり、従来のＷＣ−Ｃｏ材料の硬度および破壊靭性の組合せの低下をもたらす［例えば、Mari D、Clausen B、Bourke M A M、Buss Kによる出版物、「Measurement of residual thermal stress in WC-Co by neutron diffraction」, Int. J. Refractory Met. Hard Mater., 2009; 27: 282-287、Krawitz A D、Venter A M、Drake E F、Luyckx S B、Clausen Bによる出版物、「Phase response in WC-Ni to cyclic compressive loading and its relation to roughness」, Int. J. Refractory Met. Hard Mater., 2009; 27: 313-316、およびCoats D I、Krawitz A Dによる出版物、「Effect of particle size on thermal residual stress in WC-Co composites」, Mater. Sci. Engin., 2003; A359:338-342を参照されたい］。 Without wishing to be bound by theory, the possible reason may be the presence of residual compressive stress in the binder phase of the WC-Co-Re cemented carbide in such materials. According to many publications on residual stresses in WC-Co cemented carbides, the binder phase in WC-Co is always under high residual tensile stress, a combination of the hardness and fracture toughness of conventional WC-Co materials. [For example, publication by Mari D, Clausen B, Bourke MAM, Buss K, “Measurement of residual thermal stress in WC-Co by neutron diffraction”, Int. J. Refractory Met. Hard Mater., 2009; 27 : 282-287, Krawitz AD, Venter AM, Drake EF, Luyckx SB, Clausen B publication, "Phase response in WC-Ni to cyclic compressive loading and its relation to roughness", Int. J. Refractory Met. Hard Mater 27, 313-316, and publication by Coats DI, Krawitz AD, “Effect of particle size on thermal residual stress in WC-Co composites”, Mater. Sci. Engin., 2003; A359: 338-342 Please refer to].

本明細書において使用される場合、「超硬質材料」は、少なくとも約２５ＧＰａのビッカース硬度を有する材料である。ダイヤモンドおよび立方晶窒化ホウ素（ｃＢＮ）材料が、超硬質材料の例である。
本明細書において使用される場合、「超硬質構造物」は、多結晶性超硬質材料もしくは超硬質複合材料を含む構造物、または、超硬合金基材に結合された多結晶性超硬質材料および超硬質複合材料を含む構造物を意味する。
本明細書において使用される場合、多結晶ダイヤモンド（ＰＣＤ）は、その実質的な部分が互いに直接相互結合しているダイヤモンド粒塊を含むＰＣＳ材料であり、ダイヤモンドの含量は、材料の少なくとも約８０体積パーセントである。ＰＣＤ材料の一実施形態において、ダイヤモンド粒間の隙間は、ダイヤモンドの触媒を含む結合剤材料で少なくとも部分的に充填されていてもよい。本明細書において使用される場合、「隙間」または「隙間領域」は、ＰＣＤ材料のダイヤモンド粒間の領域である。ＰＣＤ材料の実施形態において、隙間または隙間領域は、ダイヤモンド以外の材料で実質的にもしくは部分的に充填されていてもよく、または実質的に空であってもよい。ＰＣＤ材料の実施形態は、少なくとも、触媒材料が隙間から除去され、ダイヤモンド粒間に空隙が残された領域を含んでもよい。 As used herein, an “ultrahard material” is a material having a Vickers hardness of at least about 25 GPa. Diamond and cubic boron nitride (cBN) materials are examples of ultra-hard materials.
As used herein, “superhard structure” refers to a structure comprising a polycrystalline superhard material or a superhard composite material, or a polycrystalline superhard material bonded to a cemented carbide substrate. And a structure including an ultra-hard composite material.
As used herein, polycrystalline diamond (PCD) is a PCS material that includes diamond agglomerates whose substantial portions are directly interconnected with each other, and the diamond content is at least about 80% of the material. Volume percent. In one embodiment of the PCD material, the gaps between the diamond grains may be at least partially filled with a binder material comprising a diamond catalyst. As used herein, “gap” or “gap region” is a region between diamond grains of PCD material. In embodiments of the PCD material, the gap or gap area may be substantially or partially filled with a material other than diamond, or may be substantially empty. Embodiments of the PCD material may include at least a region where the catalyst material is removed from the gaps and voids are left between the diamond grains.

本明細書において使用される場合、多結晶立方晶窒化ホウ素（ＰＣＢＮ）材料は、セラミックもしくは金属材料、またはその両方を含んでもよい耐摩耗性マトリックス内に分散したｃＢＮ粒塊を含むＰＣＳ材料であり、ｃＢＮの含量は、材料の少なくとも約５０体積パーセントである。ＰＣＢＮ材料のいくつかの実施形態において、ｃＢＮ粒の含量は、少なくとも約６０体積パーセント、少なくとも約７０体積パーセント、または少なくとも約８０体積パーセントである。超硬質材料の実施形態は、硬質マトリックス内に分散した超硬質材料の粒を含んでもよく、硬質マトリックスは、好ましくは、主要成分としてセラミック材料を含み、セラミック材料は、好ましくは炭化ケイ素、窒化チタンおよび炭窒化チタンから選択される。
図１および図２を参照すると、超硬合金材料は、炭化物相を含む硬質材料の粒塊と、結合剤相を構成する結合剤材料で充填された硬質粒間の隙間とを含む。図１に示される実施形態において、炭化物相は、ＷＣであり、結合剤相は、ＣｏおよびＲｅの合金、ならびにそれに固溶した一部のＷおよびＣを含む。 As used herein, a polycrystalline cubic boron nitride (PCBN) material is a PCS material comprising cBN agglomerates dispersed within a wear resistant matrix that may comprise a ceramic or metallic material, or both. , CBN content is at least about 50 volume percent of the material. In some embodiments of the PCBN material, the content of cBN grains is at least about 60 volume percent, at least about 70 volume percent, or at least about 80 volume percent. Embodiments of the superhard material may include grains of superhard material dispersed within the hard matrix, the hard matrix preferably including a ceramic material as a major component, the ceramic material preferably being silicon carbide, titanium nitride. And selected from titanium carbonitride.
Referring to FIGS. 1 and 2, the cemented carbide material includes hard material agglomerates including a carbide phase and gaps between hard particles filled with the binder material that constitutes the binder phase. In the embodiment shown in FIG. 1, the carbide phase is WC, and the binder phase includes an alloy of Co and Re, and some W and C dissolved therein.

図３は、比較のために、炭化物相としてＷＣを、および結合剤相としてＣｏを含む従来の超硬合金材料を示す。
いくつかの実施形態において、超硬合金材料は、第二炭化物相の形態の、または結合剤相に固溶した１種または複数種の金属の炭化物をさらに含み、１種または複数種の金属は、Ｔｉ、Ｖ、Ｃｒ、Ｍｎ、Ｚｒ、Ｎｂ、Ｍｏ、Ｈｆおよび／またはＴａを含む。超硬合金材料は、η相および遊離炭素を実質的に含まない。
いくつかの実施形態において、超硬合金材料は、約０．５〜約８質量％の間のＲｅを含む。 FIG. 3 shows, for comparison, a conventional cemented carbide material containing WC as the carbide phase and Co as the binder phase.
In some embodiments, the cemented carbide material further comprises a carbide of one or more metals in the form of a second carbide phase or dissolved in the binder phase, wherein the one or more metals are , Ti, V, Cr, Mn, Zr, Nb, Mo, Hf and / or Ta. The cemented carbide material is substantially free of η phase and free carbon.
In some embodiments, the cemented carbide material comprises between about 0.5 and about 8% by weight of Re.

いくつかの実施形態において、超硬合金材料は、約３〜約１０質量％の間のＣｏを含む。
他の実施形態において、超硬合金材料は、約０．５〜約６質量％の間のＲｅを含む。
超硬合金材料中のＷＣは、例えば、約０．６μｍ未満の平均粒径を有してもよい。
さらに、いくつかの実施形態において、ＷＣに対する全炭素当量（ＥＴＣ）含有率は、約６．３質量％〜約６．９質量％の間である。 In some embodiments, the cemented carbide material comprises between about 3 to about 10% by weight Co.
In other embodiments, the cemented carbide material comprises between about 0.5 and about 6 weight percent Re.
The WC in the cemented carbide material may have an average particle size of less than about 0.6 μm, for example.
Further, in some embodiments, the total carbon equivalent (ETC) content relative to WC is between about 6.3 wt% and about 6.9 wt%.

超硬合金材料の磁気特性は、重要な構造および組成特性に関連し得、超硬合金材料中の炭素含量の指標として理解される。超硬合金中の炭素含量を測定するための最も一般的な技法は、炭素含量が間接的に比例する結合剤に固溶したタングステンの濃度を測定することによる、間接的なものである。結合剤に固溶した炭素の含量が高い程、結合剤に固溶したタングステンの濃度は低い。超硬炭化タングステンがその一例である硬質金属の磁気飽和４πσまたは磁気モーメントσは、単位質量当たりの磁気モーメントまたは磁気飽和として定義される。純Ｃｏの磁気モーメントσは、１６．１マイクロテスラ×立方メートル毎キログラム（μＴ．ｍ³／ｋｇ）であり、純Ｃｏの磁気飽和４πσとも呼ばれる飽和の誘導は、２０１．９μＴ．ｍ³／ｋｇである。結合剤中のタングステン含量は、磁気モーメントσまたは磁気飽和Ｍ_s＝４πσの測定から決定され得るが、これらの値は、タングステン含量と反比例関係にある（Roebuck (1996), 「Magnetic moment (saturation) measurements on cemented carbide materials」, Int. J. Refractory Met., Vol. 14, pp. 419-424.）。以下の式は、磁気飽和Ｍｓを、結合剤中のＷおよびＣの濃度と関連付けるために使用され得る。
Ｍ_s∝［Ｃ］／［Ｗ］×Ｃｏの質量％×２０１．９（μＴ．ｍ³／ｋｇの単位） The magnetic properties of a cemented carbide material can be related to important structural and compositional properties and are understood as an indicator of the carbon content in the cemented carbide material. The most common technique for measuring the carbon content in cemented carbide is indirect, by measuring the concentration of tungsten dissolved in a binder whose carbon content is indirectly proportional. The higher the content of carbon dissolved in the binder, the lower the concentration of tungsten dissolved in the binder. The magnetic saturation 4πσ or magnetic moment σ of a hard metal, for example, tungsten carbide is defined as the magnetic moment or magnetic saturation per unit mass. The magnetic moment σ of pure Co is 16.1 microtesla × cubic meter per kilogram (μT.m ³ / kg), and the induction of saturation, also called magnetic saturation 4πσ of pure Co, is 201.9 μT. m ³ / kg. The tungsten content in the binder can be determined from measurements of magnetic moment σ or magnetic saturation M _s = 4πσ, but these values are inversely related to tungsten content (Roebuck (1996), “Magnetic moment (saturation) measurements on cemented carbide materials ", Int. J. Refractory Met., Vol. 14, pp. 419-424.). The following equation can be used to relate the magnetic saturation Ms to the concentration of W and C in the binder.
M _s ∝ [C] / [W] × mass% of Co × 201.9 (unit of μT.m ³ / kg)

超硬合金材料のいくつかの実施形態は、名目上純粋なＣｏの磁気飽和の少なくとも約４０パーセント〜約８０パーセントの関連磁気飽和を有する。
ＷＣ粒等の炭化物粒の平均粒径は、例えば平均直線切片（ｍｅａｎｌｉｎｅａｒｉｎｔｅｒｃｅｐｔ）技法を適用して、超硬合金材料体の冶金学的に調製された断面の走査型電子顕微鏡（ＳＥＭ）または光学顕微鏡画像を使用して得られた顕微鏡写真の検査により決定され得る。代替として、ＷＣ粒の平均径は、粒の間に介在するＣｏの平均自由行程を示す超硬合金材料の保磁力を測定することにより間接的に推定することができ、その保磁力から、当該技術分野において周知の単純な式を使用して、ＷＣ粒径を計算することができる。この式は、Ｃｏ超硬ＷＣ超硬合金材料の保磁力とＣｏ平均自由行程との間の反比例関係を数値化し、結果として平均ＷＣ粒径を数値化する。保磁力は、ＭＦＰと反比例関係を有する。 Some embodiments of the cemented carbide material have an associated magnetic saturation of at least about 40 percent to about 80 percent of the magnetic saturation of nominally pure Co.
The average particle size of carbide grains, such as WC grains, can be determined by scanning electron microscopy (SEM) of a metallurgically prepared cross-section of a cemented carbide material body, for example, by applying a mean linear intercept technique. It can be determined by examination of micrographs obtained using optical microscope images. Alternatively, the average diameter of the WC grains can be estimated indirectly by measuring the coercivity of the cemented carbide material showing the mean free path of Co intervening between the grains, and from the coercivity, WC particle size can be calculated using simple formulas well known in the art. This equation quantifies the inverse relationship between the coercivity of the Co cemented carbide WC cemented carbide material and the Co mean free path, resulting in a quantification of the average WC grain size. The coercive force has an inversely proportional relationship with the MFP.

本明細書において使用される場合、超硬合金等の複合材料の「平均自由行程」（ＭＦＰ）は、結合剤材料内の超硬凝集炭化物粒間の平均距離の尺度である。超硬合金材料の平均自由行程特性は、材料の研磨断面の顕微鏡写真を使用して測定され得る。例えば、顕微鏡写真は、約１５００倍の倍率を有し得る。ＭＦＰは、均一グリッド上で線および粒界の各交点の間の距離を測定することにより決定され得る。マトリックスの線分Ｌｍが合計され、粒の線分Ｌｇが合計される。両方の軸を使用した平均マトリックス線分長さが、「平均自由行程」である。炭化タングステン粒子経の複数の分布の混合は、同じマトリックス含量に対して広いＭＦＰ値の分布をもたらし得る。
本明細書において使用される場合、粒径は、ＩＳＯＦＤＩＳ１３０６７標準に従う円相当径（ＥＣＤ）の点で表現される。ＥＣＤは、研磨表面に露出した各粒の面積Ａを測定し、式ＥＣＤ＝（４Ａ／π）^1/2に従い同じ面積Ａを有する円の直径を計算することにより得られる（ISO FDIS 13067のセクション3.3.2「Microbeam analysis - Electron Backscatter Diffraction - Measurement of average grain size.」, International Standards Organisation Geneva, Switzerland, 2011を参照されたい）。 As used herein, the “mean free path” (MFP) of a composite material such as cemented carbide is a measure of the average distance between cemented carbide grains within the binder material. The mean free path characteristics of a cemented carbide material can be measured using a photomicrograph of a polished cross section of the material. For example, the micrograph may have a magnification of about 1500 times. The MFP can be determined by measuring the distance between each intersection of lines and grain boundaries on a uniform grid. The line segments Lm of the matrix are summed, and the line segments Lg of the grains are summed. The average matrix segment length using both axes is the “average free path”. Mixing multiple distributions of tungsten carbide particles may result in a broad distribution of MFP values for the same matrix content.
As used herein, particle size is expressed in terms of equivalent circle diameter (ECD) according to the ISO FDIS 13067 standard. The ECD is obtained by measuring the area A of each grain exposed on the polished surface and calculating the diameter of a circle with the same area A according to the formula ECD = (4A / π) ^1/2 (section of ISO FDIS 13067 See 3.3.2 “Microbeam analysis-Electron Backscatter Diffraction-Measurement of average grain size”, International Standards Organization Geneva, Switzerland, 2011).

いくつかの実施形態において、超硬合金材料の炭化物相は、少なくとも約０．１μｍ〜最大約１０μｍの平均粒径を有する炭化物粒で形成され、超硬合金材料は、約２ｋＡ／ｍ〜約７０ｋＡ／ｍで変動する関連保磁力を有してもよい。
いくつかの実施形態において、炭化物相は、ＷＣを含み、超硬合金材料は、炭化物微細構造のＥＢＳＤ画像に基づき決定されるμｍ単位のＷＣ平均粒径Ｄ_wcの関数として、以下の式により与えられる値以下のｋＡ／ｍ単位の保磁力Ｈｃを有する。
Ｈｃ＝１０×Ｄ_wc ^-0.62 In some embodiments, the carbide phase of the cemented carbide material is formed of carbide grains having an average particle size of at least about 0.1 μm to up to about 10 μm, and the cemented carbide material is about 2 kA / m to about 70 kA. It may have an associated coercivity that varies at / m.
In some embodiments, the carbide phase comprises WC and the cemented carbide material is given by the following equation as a function of the WC average particle size D _{wc in} μm determined based on the EBSD image of the carbide microstructure: It has a coercive force Hc of kA / m unit or less.
Hc = 10 × D _wc ^-0.62

いくつかの実施形態において、炭化物相は、ＷＣを含み、結合剤相は、ＣｏおよびＲｅを含む。
超硬合金材料の結合剤相は、例えば、Ｒｅ、炭素およびＷ、ならびにＦｅ、ＣｏおよびＮｉの１種または複数種の固溶体であってもよい。いくつかの実施形態において、結合剤相は、固溶体として、および／または炭化物化合物の形態で少なくとも約０．１質量パーセント〜最大約５質量パーセントのＶ、Ｃｒ、Ｔａ、Ｔｉ、Ｍｏ、Ｚｒ、ＮｂおよびＨｆの１種または複数種を含む。いくつかの他の実施形態において、材料は、少なくとも約０．０１質量パーセントおよび最大約２質量パーセントのＲｕ、Ｒｈ、Ｐｄ、Ｏｓ、ＩｒおよびＰｔの１種または複数種を含む。 In some embodiments, the carbide phase includes WC and the binder phase includes Co and Re.
The binder phase of the cemented carbide material may be, for example, Re, carbon and W, and one or more solid solutions of Fe, Co and Ni. In some embodiments, the binder phase is at least about 0.1 weight percent up to about 5 weight percent V, Cr, Ta, Ti, Mo, Zr, Nb as a solid solution and / or in the form of a carbide compound. And one or more of Hf. In some other embodiments, the material comprises at least about 0.01 weight percent and up to about 2 weight percent of one or more of Ru, Rh, Pd, Os, Ir, and Pt.

超硬合金は、関連硬度を有し、いくつかの実施形態において、３００℃における硬度低下は、最大２０％であり、またはいくつかの他の実施形態において、最大１７％である。硬度測定は、ＤＩＮＩＳＯ３８７８に従い、Ａｒ雰囲気中、室温ならびに３００℃、５００℃および８００℃で、３０ｋｇｆの負荷で金属断面に対し行われた。高温に達した後、断面を１０分間アニールし、その後３０ｋｇｆの負荷下でビッカース押込みを行い、負荷を１５秒間印加した。Ｃｏ結合剤を含有する従来の超硬合金材料、およびＣｏ−Ｒｅ結合剤を含有する超硬合金材料の実施形態の両方の硬度値を測定し、従来の材料および実施形態の材料の両方に対して、室温における硬度低下と比較した高温における硬度低下を計算した。 Cemented carbide has an associated hardness, and in some embodiments, the hardness drop at 300 ° C. is up to 20%, or in some other embodiments, up to 17%. Hardness measurements were performed on metal cross sections according to DIN ISO 3878, in an Ar atmosphere at room temperature and at 300 ° C., 500 ° C. and 800 ° C. with a load of 30 kgf. After reaching high temperature, the cross section was annealed for 10 minutes, and then Vickers indentation was performed under a load of 30 kgf, and the load was applied for 15 seconds. The hardness values of both the conventional cemented carbide material containing the Co binder and the embodiment of the cemented carbide material containing the Co-Re binder are measured and for both the conventional material and the material of the embodiment Thus, the decrease in hardness at high temperature compared to the decrease in hardness at room temperature was calculated.

超硬合金材料は、例えば、５００℃において最大３０％、またはいくつかの他の実施形態において最大２７％の硬度低下を有してもよい。
ＧＰａ単位のビッカース硬度およびＭＰａｍ^1/2単位の押込み破壊靭性を乗じることにより、硬度−靭性係数を計算してもよく、いくつかの実施形態において、これは１５０超である。いくつかの実施形態において、超硬合金材料は、ビッカース硬度を有する。
いくつかの実施形態において、超硬合金材料の結合剤相は、１つまたは複数の残留圧縮応力を有し、これらは、例えば、約−５ＭＰａ〜約１００ＭＰａの間であってもよい。
超硬合金材料の実施形態は、炭化物と共に、Ｒｅ、Ｃｏ、Ｎｉおよび／またはＦｅを含有し、Ｖ、Ｃｒ、Ｔａ、Ｔｉ、Ｍｏ、Ｚｒ、ＮｂおよびＨｆまたはそれらの炭化物を含む粒子成長阻害剤を含有してもよい超硬合金混合物を粉砕するステップと、次いで混合物から超硬合金物品をプレスするステップとを含む方法により作製されてもよい。物品は、次いで、真空中１〜１０分間、およびその後Ａｒの圧力下（ＨＩＰ）で５〜１２０分間、１４５０℃超の温度で焼結される。物品は、次いで、不活性ガス、窒素、水素もしくはそれらの混合物を含む雰囲気中で、または真空中で、１分当たり約０．２〜２度の冷却速度で焼結温度から摂氏約１３００度（℃）まで冷却される。
ここで、限定を意図しない以下に続く例を参照しながら、いくつかの実施形態をより詳細に説明する。 The cemented carbide material may have a hardness reduction of, for example, up to 30% at 500 ° C., or up to 27% in some other embodiments.
The hardness-toughness coefficient may be calculated by multiplying the Vickers hardness in GPa units and the indentation fracture toughness in MPa m ^1/2 units, and in some embodiments this is greater than 150. In some embodiments, the cemented carbide material has a Vickers hardness.
In some embodiments, the binder phase of the cemented carbide material has one or more residual compressive stresses, which may be, for example, between about −5 MPa and about 100 MPa.
Embodiments of cemented carbide materials include particle growth inhibitors containing Re, Co, Ni and / or Fe with carbides, including V, Cr, Ta, Ti, Mo, Zr, Nb and Hf or carbides thereof May be made by a method comprising crushing a cemented carbide mixture that may contain, and then pressing a cemented carbide article from the mixture. The article is then sintered at a temperature above 1450 ° C. in a vacuum for 1 to 10 minutes and then under Ar pressure (HIP) for 5 to 120 minutes. The article is then cooled to about 1300 degrees Celsius from the sintering temperature at a cooling rate of about 0.2 to 2 degrees per minute in an atmosphere containing an inert gas, nitrogen, hydrogen or mixtures thereof, or in a vacuum. ℃).
Several embodiments will now be described in more detail with reference to the following examples that are not intended to be limiting.

ＷＣ粒が約０．６μｍの平均粒径を有し、炭素含量が６．１３質量％である炭化タングステン粉末を、５．５％のＲｅ粉末および３．７％のＣｏ粉末と共に粉砕した。Ｃｏ粒は、約１μｍの平均粒径を有していた。ボールミルを使用して、２質量％のパラフィンワックスと共にヘキサンを含む粉砕媒体中、１：６の粉末対ボール比を用いて粉末を一緒に２４時間粉砕することにより、粉末混合物を生成した。粉砕後、０．３５質量％のカーボンブラックを添加し、さらなる粉砕を１時間行うと、混合物のＷＣに対する全炭素当量（ＥＴＣ）含有率が、６．５１質量％と等しいことが事実となった。混合物を乾燥させた後、素地を１５４０℃で６０分間プレスおよび焼結した（３０分間真空＋３０分間５０バールの圧力のＡｒ中でのＨＩＰ）。１５４０℃で焼結した後、焼結体を１分当たり０．５度の速度で１３００℃まで冷却し、その後は非制御速度で室温まで冷却した。ＬＥＣＯＷＣ６００機器を用いて、焼結試料を手作業で粉砕した後にその炭素含量を測定すると、５．８５質量％に等しいと決定され、ＷＣに対する全炭素当量（ＥＴＣ）含有率が６．４４質量％に等しいことが証明された。 Tungsten carbide powder with WC grains having an average particle size of about 0.6 μm and a carbon content of 6.13% by mass was pulverized with 5.5% Re powder and 3.7% Co powder. The Co grains had an average particle size of about 1 μm. A powder mixture was produced using a ball mill by grinding the powder together for 24 hours in a grinding media containing hexane with 2% by weight paraffin wax using a powder to ball ratio of 1: 6. After pulverization, 0.35% by mass of carbon black was added and further pulverization was performed for 1 hour, and it became a fact that the total carbon equivalent (ETC) content with respect to WC of the mixture was equal to 6.51% by mass . After the mixture had dried, the substrate was pressed and sintered at 1540 ° C. for 60 minutes (30 minutes vacuum + 30 minutes HIP in Ar at 50 bar pressure). After sintering at 1540 ° C., the sintered body was cooled to 1300 ° C. at a rate of 0.5 degrees per minute and then cooled to room temperature at an uncontrolled rate. Using a LECO WC600 instrument to measure the carbon content after manually grinding the sintered sample, it was determined to be equal to 5.85% by weight, and the total carbon equivalent (ETC) content relative to WC was 6.44%. Proven to be equal to%.

Ｒｅを含まない従来のＷＣ−Ｃｏ超硬合金の対照バッチを、同じＷＣ粉末バッチおよび６質量％のＣｏから作製したが、これは、カーボンブラックを添加しないＷＣ−Ｃｏ−Ｒｅ材料の場合と同じ結合剤の体積パーセントに相当する。バッチを、ＷＣ−Ｃｏ−Ｒｅ炭化物と同じ様式で粉砕し、１４４０℃で、３０の真空焼結および３０分の圧力下（ＨＩＰ）焼結を含む１時間の焼結を行った。ＷＣ−Ｃｏ−Ｒｅ超硬合金の場合と同じ様式で焼結試料の炭素含量を測定すると、５．７７質量％に等しいことが判明し、ＷＣに対する全炭素当量（ＥＴＣ）含有率が６．１３質量％に等しいことが証明された。
ＷＣ−Ｃｏ−ＲｅおよびＷＣ−Ｃｏ超硬合金の金属断面を作製し、光学顕微鏡およびＳＥＭにより検査した。焼結体の硬度（ＨＶ２０）、押込み破壊靭性（Ｋ_1C）、抗折力（ＴＲＳ）、圧縮強度およびヤング率、ならびに保磁力および磁気モーメント（飽和）を調査した。 A control batch of conventional WC-Co cemented carbide without Re was made from the same WC powder batch and 6 wt% Co, which is the same as for the WC-Co-Re material without the addition of carbon black Corresponds to the volume percent of binder. The batch was ground in the same manner as the WC—Co—Re carbide and sintered at 1440 ° C. for 1 hour including 30 vacuum sinterings and 30 minutes of pressure (HIP) sintering. Measuring the carbon content of the sintered sample in the same manner as for the WC-Co-Re cemented carbide, it was found to be equal to 5.77 wt% and the total carbon equivalent (ETC) content relative to WC was 6.13. Equal to mass%.
Metal cross sections of WC-Co-Re and WC-Co cemented carbide were prepared and examined with an optical microscope and SEM. The sintered body was examined for hardness (HV20), indentation fracture toughness (K _1C ), bending strength (TRS), compressive strength and Young's modulus, and coercive force and magnetic moment (saturation).

ＷＣ平均粒径は、K.P. Mingard, B. Roebuck a, E.G. Bennett, M.G. Gee, H. Nordenstrom, G. Sweetman, P. Chan. Comparison of EBSD and conventional methods of grain size measurement of hard metals. Int. Journal of Refractory Metals & Hard Materials 27 (2009) 213-223に記載の手順に従い、断面のＥＢＳＤ画像に基づいて測定した。
図１および２は、それぞれ、実施例１に従い形成されたＷＣ−Ｃｏ−Ｒｅ超硬合金のＳＥＭおよびＥＢＳＤ画像を示し、図３は、Ｒｅを含まず、６．１３質量％のＷＣに対する等価全炭素含量を有する従来のＷＣ−Ｃｏ超硬合金の微細構造を示す。図１および図２に示されるＷＣ−Ｃｏ−Ｒｅ炭化物は、０．４４μｍのＷＣ平均粒径を有する。図１および２に示される両方の炭化物材料の微細構造には、η相も遊離炭素も細孔も存在しないことが観察される。表１は、図１および図２に示されるＷＣ−Ｃｏ−Ｒｅ超硬合金の微細構造における粒径分布を示す。 WC average particle size is measured by KP Mingard, B. Roebuck a, EG Bennett, MG Gee, H. Nordenstrom, G. Sweetman, P. Chan. Comparison of EBSD and conventional methods of grain size measurement of hard metals. Int. Journal of According to the procedure described in Refractory Metals & Hard Materials 27 (2009) 213-223, the measurement was performed based on the EBSD image of the cross section.
FIGS. 1 and 2 show SEM and EBSD images of a WC—Co—Re cemented carbide formed according to Example 1, respectively, and FIG. 3 shows the equivalent total for 6.13 wt% WC without Re. 1 shows the microstructure of a conventional WC-Co cemented carbide having a carbon content. The WC—Co—Re carbide shown in FIGS. 1 and 2 has a WC average particle size of 0.44 μm. It is observed that neither the η phase, free carbon nor pores are present in the microstructure of both carbide materials shown in FIGS. Table 1 shows the particle size distribution in the microstructure of the WC—Co—Re cemented carbide shown in FIGS. 1 and 2.

図１および図２のＷＣ−Ｃｏ−Ｒｅ炭化物材料の磁気モーメントは、４．７Ｇｃｍ³／ｇに等しく、これは、３．７％の名目上純粋なＣｏを有する超硬合金に対する理論値の６４％であり、パーセント単位のその固有磁気飽和（ＳＭＳ）を証明している。ＷＣ−Ｃｏ−Ｒｅ材料の保磁力は、２８４Ｏｅと決定された。その機械的特性は、ＨＶ２０＝１８６０または１８．６ＧＰａ、Ｋ_1C＝１０．５ＭＰａｍ^1/2、およびＴＲＳ＝３７００ＭＰａと決定された。したがって、ＧＰａ単位のビッカース硬度およびＭＰａｍ^1/2単位の破壊靭性を乗じることにより計算される硬度−靭性係数は、１９５に等しかった。ＷＣ−Ｃｏ−Ｒｅ超硬合金の圧縮強度は、６０２０ＭＰａと決定され、そのヤングモジュールは、７１２ＧＰａに等しいと決定された。その高温硬度は、３００℃で１６．９ＧＰａおよび５００℃で１４．９ＧＰａに等しいことが判明し、高温における硬度低下は、それに対応して約９．１％および１９．８％であることが証明された。温度を室温から３００℃および５００℃に上昇させても、圧縮強度はほとんど変化しなかった。 The magnetic moment of the WC—Co—Re carbide material of FIGS. 1 and 2 is equal to 4.7 Gcm ³ / g, which is the theoretical value of 64 for a cemented carbide with 3.7% nominally pure Co. %, Demonstrating its intrinsic magnetic saturation (SMS) in percent. The coercivity of the WC—Co—Re material was determined to be 284 Oe. Its mechanical properties were determined as HV20 = 1860 or 18.6 GPa, K _1C = 10.5 MPa m ^1/2 , and TRS = 3700 MPa. Therefore, the hardness-toughness coefficient calculated by multiplying the Vickers hardness in GPa and the fracture toughness in MPa m ^1/2 was equal to 195. The compressive strength of the WC-Co-Re cemented carbide was determined to be 6020 MPa, and its Young module was determined to be equal to 712 GPa. Its high temperature hardness was found to be equal to 16.9 GPa at 300 ° C. and 14.9 GPa at 500 ° C., and the decrease in hardness at high temperatures was correspondingly about 9.1% and 19.8%. It was done. Even when the temperature was increased from room temperature to 300 ° C. and 500 ° C., the compressive strength hardly changed.

ＷＣ−Ｃｏ−Ｒｅ超硬合金のＣｏ−Ｒｅ結合剤相内の残留応力を、Ｃｕ−Ｋα放射線を用いたＢｒｕｋｅｒＤ８Ｄｉｓｃｏｖｅｒ回折計を使用して測定した。このＸ線の波長は、典型的には約５μｍの深さからの回折情報を得た。０．０１０５９°のビンサイズでＢｒａｕｎＰｏｓｉｔｉｏｎＳｅｎｓｉｖｉｔｅＤｅｔｅｃｔｏｒを使用して回折ビームを収集した。残留応力測定は、０．０１０５９°のステップ幅、およびステップ当たり１０秒の計数時間を使用して、１４６．６°の角度のＣｏ（２１１）ピークを用いることにより行った。残留応力測定は、参考文献「Fitzpatrick M, Fry T, Holdway P, et al. NPL Good Practice Guide No. 52: Determination of Residual Stresses by X-ray Diffraction - Issue 2. September 2005」に従い、標準的並傾ｓｉｎ²ψ技法を使用して行った。 Residual stress in the Co-Re binder phase of the WC-Co-Re cemented carbide was measured using a Bruker D8 Discover diffractometer with Cu-Ka radiation. This X-ray wavelength typically obtained diffraction information from a depth of about 5 μm. The diffracted beam was collected using a Braun Position Sensitive Detector with a 0.01059 ° bin size. Residual stress measurements were made by using a Co (211) peak at an angle of 146.6 ° using a step width of 0.01059 ° and a counting time of 10 seconds per step. Residual stress measurement is performed in accordance with the reference `` Fitzpatrick M, Fry T, Holdway P, et al. NPL Good Practice Guide No. 52: Determination of Residual Stresses by X-ray Diffraction-Issue 2. September 2005 ''. This was done using the sin ² ψ technique.

ＷＣ−Ｃｏ−Ｒｅ超硬合金の２回の測定を行ったが、これは、第１の測定において、圧縮応力がφ＝０の方向で−１１ＭＰａ、およびφ＝９０の方向で−８ＭＰａであり、第２の測定において、φ＝０の方向で−９ＭＰａ、およびφ＝９０の方向で−３１ＭＰａであるデータを提供した。したがって、すべての場合において、ＷＣ−Ｃｏ−Ｒｅ材料の結合剤相は、残留圧縮応力下であった。
ＷＣ−Ｃｏ−Ｒｅ超硬合金と同じ体積割合の結合剤相を有する従来のＷＣ−６％Ｃｏ炭化物材料の磁気モーメントは、９．２Ｇｃｍ³／ｇに等しいことが判明し、これは、６％の名目上純粋なＣｏを有する超硬合金に対する理論値の９５．２％であり、保磁力は２７０Ｏｅ、ＨＶ２０＝１６１０または１６．１ＧＰａ、Ｋ_1C＝９．５ＭＰａｍ^1/2、ＴＲＳ＝２９００ＭＰａ、圧縮強度は５２００ＧＰａ、およびヤング率は６４０ＧＰａであった。そのＷＣ平均粒径は、０．５９μｍに等しいと決定された。その高温硬度は、３００℃で１２．１ＧＰａおよび５００℃で８．１ＧＰａに等しいことが判明し、硬度低下は、それに対応して約２５％および４９％であることが証明された。 Two measurements of the WC-Co-Re cemented carbide were performed. In the first measurement, the compressive stress was -11 MPa in the direction of φ = 0, and -8 MPa in the direction of φ = 90. In the second measurement, data was provided that was −9 MPa in the direction of φ = 0 and −31 MPa in the direction of φ = 90. Therefore, in all cases, the binder phase of the WC-Co-Re material was under residual compressive stress.
The magnetic moment of a conventional WC-6% Co carbide material with the same volume fraction binder phase as the WC-Co-Re cemented carbide was found to be equal to 9.2 Gcm ³ / g, which is 6% 95.2% of the theoretical value for a cemented carbide with nominally pure Co, the coercivity being 270 Oe, HV20 = 1610 or 16.1 GPa, K _1C = 9.5 MPa m ^1/2 , TRS = 2900 MPa, The compressive strength was 5200 GPa and the Young's modulus was 640 GPa. The WC average particle size was determined to be equal to 0.59 μm. Its high temperature hardness was found to be equal to 12.1 GPa at 300 ° C. and 8.1 GPa at 500 ° C., and the hardness reduction proved to be correspondingly about 25% and 49%.

ヤング率は弾性係数の１種であり、材料が弾性挙動を示す応力範囲内の一軸応力に対する一軸歪みの尺度である。ヤング率Ｅを測定する方法は、超音波を使用して材料を通る音の速さの横成分および縦成分を測定することによるものである。具体的には、ヤング率Ｅを測定する好ましい方法は、式Ｅ＝２ρ．Ｃ_T ²（１＋ν）（式中、ν＝（１−２（Ｃ_T／Ｃ_L）²）／（２−２（Ｃ_T／Ｃ_L）²）であり、Ｃ_LおよびＣ_Tは、それぞれ、それを通る音の測定された縦方向および横方向速度であり、ρは、材料の密度である）に従い、材料を通る音の速さの横成分および縦成分を測定することによるものである。音の縦方向および横方向速度は、当該技術分野において周知のように、超音波を使用して測定され得る。材料が異なる材料の複合物である場合、平均ヤング率は、３つの式、すなわち以下のような調和、幾何学的、および複合則の式の１つを使用して推定され得る：Ｅ＝１／（ｆ₁／Ｅ₁＋ｆ₂／Ｅ₂））；Ｅ＝Ｅ₁ ^f1＋Ｅ₁ ^f2；およびＥ＝ｆ₁Ｅ₁＋ｆ₂Ｅ₂。ここで、異なる材料は、合計が１となる各体積分率ｆ₁およびｆ₂を有する２つの部分に分割される。 Young's modulus is a type of elastic modulus and is a measure of uniaxial strain relative to uniaxial stress within the stress range in which the material exhibits elastic behavior. The method of measuring the Young's modulus E is by measuring the transverse and longitudinal components of the speed of sound through the material using ultrasound. Specifically, a preferred method for measuring the Young's modulus E is the formula E = 2ρ. C _T ² (1 + ν) (where ν = (1-2 (C _T / C _L ) ² ) / (2-2 (C _T / C _L ) ² ), where C _L and C _T are respectively , Is the measured longitudinal and transverse velocities of the sound through it, and ρ is the density of the material), according to measuring the transverse and longitudinal components of the speed of sound through the material . The longitudinal and lateral velocities of the sound can be measured using ultrasound, as is well known in the art. If the material is a composite of different materials, the average Young's modulus can be estimated using one of three equations: the harmonic, geometric, and compound law equations as follows: E = 1 / (F ₁ / E ₁ + f ₂ / E ₂ )); E = E ₁ ^f1 + E ₁ ^f2 ; and E = f ₁ E ₁ + f ₂ E ₂ . Here, the different material is divided into two parts having respective volume fractions f ₁ and f ₂ which add up to one.

１つまたは複数の実施形態の超硬合金材料は、５ＧＰａ超の圧力および１１００℃超の温度で行われる、ダイヤモンドもしくはｃ−ＢＮの合成のための、または多結晶ダイヤモンドもしくはｃ−ＢＮの製造における高圧構成要素における使用の特定の用途を見出すことができる。
そのような用途において、ＰＣＤ複合材圧密要素は、上述の金属炭化物および結合剤材料の粒子を含む超硬合金基材の実施形態に界面に沿って結合したＰＣＤ構造を備えてもよい。 The cemented carbide material of one or more embodiments is for the synthesis of diamond or c-BN, or in the production of polycrystalline diamond or c-BN, carried out at pressures greater than 5 GPa and temperatures greater than 1100 ° C. Specific applications for use in high pressure components can be found.
In such applications, the PCD composite consolidation element may comprise a PCD structure bonded along the interface to an embodiment of a cemented carbide substrate comprising particles of the metal carbide and binder material described above.

ＰＣＤ複合材圧密要素の実施形態は、超硬合金基材を提供するステップと、凝集した実質的に結合していないダイヤモンド粒子塊を基材の表面に接触させ、焼結前アセンブリを形成するステップと、焼結前アセンブリを超高圧炉用のカプセル内に封入して、焼結前アセンブリを少なくとも約５．５ＧＰａの圧力および少なくとも摂氏約１，２５０度の温度に供するステップと、ダイヤモンド粒子を焼結して、超硬合金基材上に一体形成され接合されたＰＣＤ構造を備えるＰＣＤ複合材圧密要素を形成するステップとを含む方法により作製され得る。本発明のいくつかの実施形態において、焼結前アセンブリは、少なくとも約６ＧＰａ、少なくとも約６．５ＧＰａ、少なくとも約７ＧＰａ、またはさらに少なくとも約７．５ＧＰａの圧力を受けてもよい。 Embodiments of a PCD composite consolidation element include providing a cemented carbide substrate and contacting an agglomerated substantially unbonded diamond particle mass with the surface of the substrate to form a pre-sinter assembly. Encapsulating the pre-sinter assembly in a capsule for an ultra-high pressure furnace, subjecting the pre-sinter assembly to a pressure of at least about 5.5 GPa and a temperature of at least about 1,250 degrees Celsius; And forming a PCD composite consolidation element comprising a PCD structure integrally formed and bonded onto a cemented carbide substrate. In some embodiments of the invention, the pre-sinter assembly may be subjected to a pressure of at least about 6 GPa, at least about 6.5 GPa, at least about 7 GPa, or even at least about 7.5 GPa.

超硬炭化タングステン基材の硬度は、基材を超高圧および高温に、特にダイヤモンドが熱力学的に安定である圧力および温度に供することにより向上され得る。硬度の向上の程度は、圧力および温度条件に依存し得る。特に、硬度向上は、圧力が高い程増加し得る。特定の理論に束縛されることを望まないが、これは、硬度増加の度合いが基材内のＣｏ含量の低下に直接依存するため、プレス焼結の間の基材からＰＣＤ内へのＣｏの移動に関連すると考えられる。
いくつかの実施形態において、上述のように、基材を形成する超硬合金材料は、約２〜約９質量％の間のＲｅ、および約３〜約９質量％の間のＣｏを含んでもよく、残りはＷＣであってもよい。
高圧構成要素の表面上の作用温度は、少なくとも約２００℃および最大約８００℃であってもよい。 The hardness of a cemented tungsten carbide substrate can be improved by subjecting the substrate to ultra-high pressures and temperatures, particularly pressures and temperatures at which diamond is thermodynamically stable. The degree of hardness improvement can depend on pressure and temperature conditions. In particular, the hardness improvement can increase as the pressure increases. While not wishing to be bound by any particular theory, this is because the degree of hardness increase is directly dependent on the decrease in Co content in the substrate, so that the amount of Co into the PCD from the substrate during press sintering. It is thought to be related to movement.
In some embodiments, as described above, the cemented carbide material forming the substrate may comprise between about 2 and about 9 wt% Re and between about 3 and about 9 wt% Co. Well, the rest may be WC.
The working temperature on the surface of the high pressure component may be at least about 200 ° C and up to about 800 ° C.

本発明に関連して、ここで、驚くべきことに、超硬合金がコバルト（Ｃｏ）およびレニウム（Ｒｅ）を含有し、ＲｅおよびＣｏの割合がある特定範囲内にある場合、超硬合金材料のヤング率を大幅に改善することが可能となり得ることが発見された。同時に、飛躍的にも、８００℃までの温度での超硬合金の高温硬度を改善することも可能となり得る。その結果、ＨＰＨＴ構成要素としてＷＣ−Ｃｏ−Ｒｅ超硬合金材料の実施形態を使用することが可能となり得る。
さらに、超硬合金材料の使用済みの実施形態をリサイクルすることが可能となり得る。これは、明確な環境的および経済的利益を有する。リサイクル手順は、超硬合金材料を保護雰囲気中で液体Ｚｎと共に溶融し、その結果Ｚｎを混合物から蒸発させることと、最終生成物を粉砕することとを含んでもよい。 In the context of the present invention, here, surprisingly, when the cemented carbide contains cobalt (Co) and rhenium (Re) and the ratio of Re and Co is within a certain range, the cemented carbide material. It has been discovered that it may be possible to significantly improve the Young's modulus. At the same time, it may be possible to dramatically improve the high temperature hardness of the cemented carbide at temperatures up to 800 ° C. As a result, it may be possible to use embodiments of the WC-Co-Re cemented carbide material as HPHT components.
Furthermore, it may be possible to recycle used embodiments of cemented carbide material. This has clear environmental and economic benefits. The recycling procedure may include melting the cemented carbide material with liquid Zn in a protective atmosphere so that the Zn is evaporated from the mixture and the final product is comminuted.

代替として、超硬合金材料を酸浸出処理に供して、超硬合金物品の結合剤相を除去し、ＣｏおよびＲｅを化学的に回収してもよい。
超硬合金材料をリサイクルするさらなる方法は、超硬合金物品の酸化、またその結果としての炭化物、ＲｅおよびＣｏの溶解、ならびにそれらの回収を含んでもよい。
例を参照しながら様々な実施形態を説明したが、様々な変更が行われてもよく、また均等物がその要素と置換されてもよいこと、およびこれらの例が開示される具体的実施形態を限定することを意図しないことが、当業者に理解される。 Alternatively, the cemented carbide material may be subjected to an acid leaching process to remove the binder phase of the cemented carbide article and chemically recover Co and Re.
Further methods of recycling the cemented carbide material may include oxidation of the cemented carbide article and the resulting dissolution of carbides, Re and Co, and their recovery.
While various embodiments have been described with reference to examples, various modifications may be made and equivalents may be substituted for the elements and the specific embodiments in which these examples are disclosed It will be understood by those skilled in the art that this is not intended to be limiting.

代替として、超硬合金材料を酸浸出処理に供して、超硬合金物品の結合剤相を除去し、ＣｏおよびＲｅを化学的に回収してもよい。
超硬合金材料をリサイクルするさらなる方法は、超硬合金物品の酸化、またその結果としての炭化物、ＲｅおよびＣｏの溶解、ならびにそれらの回収を含んでもよい。
例を参照しながら様々な実施形態を説明したが、様々な変更が行われてもよく、また均等物がその要素と置換されてもよいこと、およびこれらの例が開示される具体的実施形態を限定することを意図しないことが、当業者に理解される。
本発明のまた別の態様は、以下のとおりであってもよい。
〔１〕ＷＣ、ＣｏおよびＲｅを含む超硬合金材料であって、
超硬合金材料は、約３〜約１０質量％の間のＣｏおよび約０．５〜約８質量％の間のＲｅを含み、
ＷＣに対する超硬合金材料の全炭素当量（ＥＴＣ）含有率は、約６．３質量％〜約６．９質量％の間であり、
超硬合金材料は、η相および遊離炭素を実質的に含まない、超硬合金材料。
〔２〕約０．５〜約６質量％の間のＲｅを含む、前記〔１〕に記載の超硬合金材料。
〔３〕材料中のＷＣが、約０．６μｍ未満の平均粒径を有する、前記〔１〕または〔２〕に記載の超硬合金材料。
〔４〕名目上純粋なＣｏの磁気飽和の少なくとも約４０パーセント〜約８０パーセントの磁気飽和を有する、前記〔１〕から〔３〕までのいずれか１項に記載の超硬合金材料。
〔５〕炭化物相が、少なくとも約０．１μｍ〜最大約１０μｍの平均粒径を有する炭化物粒で形成される、前記〔１〕から〔４〕までのいずれか１項に記載の超硬合金材料。
〔６〕約２ｋＡ／ｍ〜約７０ｋＡ／ｍで変動する関連保磁力を有する、前記〔１〕から〔５〕までのいずれか１項に記載の超硬合金材料。
〔７〕第二炭化物相の形態の、または材料中の結合剤相に固溶した１種または複数種の金属の炭化物をさらに含み、前記１種または複数種の金属は、Ｔｉ、Ｖ、Ｃｒ、Ｍｎ、Ｚｒ、Ｎｂ、Ｍｏ、Ｈｆおよび／またはＴａを含む、前記〔１〕から〔６〕までのいずれか１項に記載の超硬合金材料。
〔８〕１つまたは複数の残留圧縮応力を有する結合剤相を含む、前記〔１〕から〔７〕までのいずれか１項に記載の超硬合金材料。
〔９〕結合剤相が、約−５ＭＰａ〜約１００ＭＰａの間の１つまたは複数の残留圧縮応力を有する、前記〔８〕に記載の超硬合金材料。
〔１０〕結合剤相が、Ｃｏ、Ｒｅ、ＷおよびＣを含む結合剤材料を含む、前記〔８〕または〔９〕に記載の超硬合金材料。
〔１１〕結合剤相が、結合剤材料を含み、結合剤材料が、Ｒｅ、炭素およびＷ、ならびにＦｅ、Ｃｏ、およびＮｉの１種または複数種の固溶体を含む、前記〔８〕または〔９〕に記載の超硬合金材料。
〔１２〕炭化物相が、ＷＣを含み；超硬合金材料が、炭化物微細構造のＥＢＳＤ画像に基づき決定されるμｍ単位のＷＣ平均粒径Ｄ _wc の関数として、以下の式により与えられる値以下のｋＡ／ｍ単位の保磁力Ｈｃを有する、前記〔１〕から〔１１〕までのいずれか１項に記載の超硬合金材料。
Ｈｃ＝１０×Ｄ _wc ^-0.62
〔１３〕室温および約５００℃までの高温で約５５００ＭＰａ超の圧縮強度を有する、前記〔１〕から〔１２〕までのいずれか１項に記載の超硬合金材料。
〔１４〕前記材料が、ビッカース硬度を有し、３００℃における硬度低下が、最大約１２％である、前記〔１３〕に記載の超硬合金材料。
〔１５〕前記材料が、ビッカース硬度を有し、５００℃における硬度低下が、最大約２１％である、前記〔１〕から〔１４〕までのいずれか１項に記載の超硬合金材料。
〔１６〕前記材料のヤング率が、約７００ＧＰａ超である、前記〔１〕から〔１５〕までのいずれか１項に記載の超硬合金材料。
〔１７〕ＧＰａ単位のビッカース硬度およびＭＰａｍ ^1/2 単位の破壊靭性を乗じることにより計算される硬度−靭性係数が、約１９０超である、前記〔１〕から〔１６〕までのいずれか１項に記載の超硬合金材料。
〔１８〕固溶体として、および／または炭化物化合物の形態で少なくとも約０．１質量パーセントから最大約５質量パーセントのＶ、Ｃｒ、Ｔａ、Ｔｉ、Ｍｏ、Ｚｒ、ＮｂおよびＨｆの１種または複数種を含む結合剤材料を有する結合剤相を含む、前記〔１〕から〔１７〕までのいずれか１項に記載の超硬合金材料。
〔１９〕少なくとも約０．０１質量パーセントおよび最大約２質量パーセントのＲｕ、Ｒｈ、Ｐｄ、Ｏｓ、ＩｒおよびＰｔの１種または複数種を含む、前記〔１〕から〔１８〕までのいずれか１項に記載の超硬合金材料。
〔２０〕前記〔１〕から〔１９〕までのいずれか１項に記載の超硬合金材料を含む基材と、
界面に沿って基材に結合された多結晶性超硬質材料の物体と
を備える、多結晶性超硬質構造物。
〔２１〕多結晶性超硬質材料の物体が、多結晶ダイヤモンド（ＰＣＤ）材料を含む、前記〔２０〕に記載の多結晶性超硬質構造物。
〔２２〕多結晶性超硬質材料の物体が、ＰＣＢＮを含む、前記〔２０〕に記載の多結晶性超硬質構造物。
〔２３〕地面穿孔用の回転ドリルビットに適合された多結晶性超硬質材料の物体に結合された、前記〔１〕から〔１９〕までのいずれか１項に記載の超硬合金材料を含む基材を備えるカッター。
〔２４〕地面穿孔用の回転せん断ビット、パーカッション用ドリルビットまたは採鉱もしくはアスファルト分解用のピックのＰＣＤ要素であって、前記〔１〕から〔１９〕までのいずれか１項に記載の超硬合金材料の物体に結合された超硬質多結晶性材料の物体を備えるカッター要素を備えるＰＣＤ要素。
〔２５〕前記〔２４〕に記載のＰＣＤ要素を備える、地面穿孔用のドリルビットまたはドリルビットの構成要素。
〔２６〕前記〔１〕から〔１９〕までのいずれか１項に記載の超硬合金材料を生成する方法であって、
− ＷＣおよび炭素と共に、Ｒｅ、Ｃｏ、Ｎｉおよび／またはＦｅを含有し、Ｖ、Ｃｒ、Ｔａ、Ｔｉ、Ｍｏ、Ｚｒ、ＮｂおよびＨｆまたはそれらの炭化物の１種または複数種を含む粒子成長阻害剤を含有してもよい超硬合金混合物を粉砕するステップと、
− 混合物から超硬合金物品をプレスするステップと、
− 真空中約１〜１０分の間の期間、およびＡｒの圧力下（ＨＩＰ）で約５〜１２０分の期間、約１４５０℃超の温度で物品を焼結するステップと、
− 焼結温度から摂氏約１３００度（℃）まで物品を冷却するステップと
を含む方法。
〔２７〕物品を冷却するステップが、不活性ガス、窒素、水素またはそれらの混合物の１つまたは複数を含む雰囲気中で、１分当たり約０．２〜２度の冷却速度で物品を冷却するステップを含む、前記〔２６〕に記載の方法。
〔２８〕物品を冷却するステップが、真空中で、１分当たり約０．２〜２度の冷却速度で物品を冷却するステップを含む、前記〔２６〕に記載の方法。
〔２９〕超硬合金混合物を粉砕するステップが、１種または複数種の炭化物を約０．５〜約８質量％の間のＲｅと共に粉砕して、約０．５〜約８質量％の間のＲｅを含む超硬合金材料を形成するステップを含む、前記〔２６〕から〔２８〕までのいずれか１項に記載の方法。
〔３０〕前記〔１〕から〔１９〕までのいずれか１項に記載の超硬合金材料をリサイクルする方法であって、炭化物材料を保護雰囲気中で液体Ｚｎと共に溶融するステップと、Ｚｎを蒸発させて最終生成物を形成するステップと、最終生成物を粉砕して生成物からＲｅを回収するステップとを含む方法。
〔３１〕前記〔１〕から〔１９〕までのいずれか１項に記載の超硬合金材料をリサイクルする方法であって、超硬合金材料を酸浸出混合物に供し、超硬合金材料から結合剤相を除去するステップと、除去された結合剤相からＣｏおよびＲｅを化学的に回収するステップとを含む方法。
〔３２〕前記〔１〕から〔１９〕までのいずれか１項に記載の超硬合金材料をリサイクルする方法であって、超硬合金材料を酸化して炭化物、ＲｅおよびＣｏを溶解するステップと、Ｒｅを回収するステップとを含む方法。
〔３３〕５ＧＰａ超の圧力および１１００℃超の温度で行われる、ダイヤモンドもしくはｃ−ＢＮの合成のための、または多結晶ダイヤモンドもしくはｃ−ＢＮの製造における高圧構成要素における、超硬合金材料の使用であって、超硬合金材料は、
第二炭化物相の形態の、または材料中の結合剤相に固溶した１種または複数種の金属の炭化物であって、前記１種または複数種の金属は、Ｔｉ、Ｖ、Ｃｒ、Ｍｎ、Ｚｒ、Ｎｂ、Ｍｏ、Ｈｆおよび／またはＴａを含む、炭化物と、
約０．５〜約８質量％の間のＲｅおよび約３〜約１０質量％の間のＣｏとを含み、
ＷＣに対する超硬合金材料の全炭素当量（ＥＴＣ）含有率は、約６．３質量％〜約６．９質量％の間であり、
超硬合金材料は、η相および遊離炭素を実質的に含まない、超硬合金材料の使用。
〔３４〕超硬合金材料が、約０．５〜約６質量％の間のＲｅを含む、前記〔３３〕に記載の超硬合金材料の使用。
〔３５〕材料中のＷＣが、約０．６μｍ未満の平均粒径を有する、前記〔３３〕または〔３４〕に記載の超硬合金材料の使用。
〔３６〕超硬合金材料が、名目上純粋なＣｏの磁気飽和の少なくとも約４０パーセント〜約８０パーセントの磁気飽和を有する、前記〔３３〕から〔３５〕までのいずれか１項に記載の超硬合金材料の使用。
〔３７〕炭化物相が、少なくとも約０．１μｍ〜最大約１０μｍの平均粒径を有する炭化物粒で形成される、前記〔３３〕から〔３６〕までのいずれか１項に記載の超硬合金材料の使用。
〔３８〕超硬合金材料が、約２ｋＡ／ｍ〜約７０ｋＡ／ｍで変動する関連保磁力を有する、前記〔３３〕から〔３７〕までのいずれか１項に記載の超硬合金材料の使用。
〔３９〕炭化物相がＷＣを含む、前記〔３３〕から〔３８〕までのいずれか１項に記載の超硬合金材料の使用。
〔４０〕超硬合金材料が、Ｃｏ、Ｒｅ、ＷおよびＣを含む結合剤材料を有する結合剤相を含む、前記〔３３〕から〔３９〕までのいずれか１項に記載の超硬合金材料の使用。
〔４１〕超硬合金材料が、結合剤材料を有する結合剤相を含み、結合剤材料が、Ｒｅ、炭素およびＷ、ならびにＦｅ、Ｃｏ、およびＮｉの１種または複数種の固溶体を含む、前記〔３３〕から〔３９〕までのいずれか１項に記載の超硬合金材料の使用。
〔４２〕炭化物相が、ＷＣを含み；超硬合金材料が、炭化物微細構造のＥＢＳＤ画像に基づき決定されるμｍ単位のＷＣ平均粒径Ｄ _wc の関数として、以下の式により与えられる値以下のｋＡ／ｍ単位の保磁力Ｈｃを有する、前記〔３３〕から〔４１〕までのいずれか１項に記載の超硬合金材料の使用。
Ｈｃ＝１０×Ｄ _wc ^-0.62
〔４３〕材料が、ビッカース硬度を有し、室温における硬度低下と比較して、３００℃における硬度低下が、最大２０％である、前記〔３３〕から〔４２〕までのいずれか１項に記載の超硬合金材料の使用。
〔４４〕３００℃における硬度低下が、最大１７％である、前記〔４３〕に記載の超硬合金材料の使用。
〔４５〕材料が、ビッカース硬度を有し、５００℃における硬度低下が、最大３０％である、前記〔３３〕から〔４４〕までのいずれか１項に記載の超硬合金材料の使用。
〔４６〕５００℃における硬度低下が、最大２７％である、前記〔４５〕に記載の超硬合金材料の使用。
〔４７〕ＧＰａ単位のビッカース硬度およびＭＰａｍ ^1/2 単位の破壊靭性を乗じることにより計算される硬度−靭性係数が、１５０超である、前記〔３３〕から〔４６〕までのいずれか１項に記載の超硬合金材料の使用。
〔４８〕材料が、固溶体として、および／または炭化物化合物の形態で少なくとも約０．１質量パーセント〜最大約５質量パーセントのＶ、Ｃｒ、Ｔａ、Ｔｉ、Ｍｏ、Ｚｒ、ＮｂおよびＨｆの１種または複数種を含む結合剤材料を有する結合剤相を含む、前記〔３３〕から〔４７〕までのいずれか１項に記載の超硬合金材料の使用。
〔４９〕材料が、少なくとも約０．０１質量パーセントおよび最大約２質量パーセントのＲｕ、Ｒｈ、Ｐｄ、Ｏｓ、ＩｒおよびＰｔの１種または複数種を含む、前記〔３３〕から〔４８〕までのいずれか１項に記載の超硬合金材料の使用。
〔５０〕任意の１つの実施形態を参照して実質的に上述され、その実施形態は添付の図面に示されている、超硬合金材料。
〔５１〕任意の１つの実施形態を参照して実質的に上述され、その実施形態は添付の図面に示されている、超硬合金材料を生成する方法。 Alternatively, the cemented carbide material may be subjected to an acid leaching process to remove the binder phase of the cemented carbide article and chemically recover Co and Re.
Further methods of recycling the cemented carbide material may include oxidation of the cemented carbide article and the resulting dissolution of carbides, Re and Co, and their recovery.
While various embodiments have been described with reference to examples, various modifications may be made and equivalents may be substituted for the elements and the specific embodiments in which these examples are disclosed It will be understood by those skilled in the art that this is not intended to be limiting.
Another aspect of the present invention may be as follows.
[1] A cemented carbide material containing WC, Co and Re,
The cemented carbide material comprises between about 3 to about 10% by weight Co and between about 0.5 to about 8% by weight Re;
The total carbon equivalent (ETC) content of the cemented carbide material relative to WC is between about 6.3 wt% and about 6.9 wt%,
The cemented carbide material is a cemented carbide material substantially free of η phase and free carbon.
[2] The cemented carbide material according to the above [1], which contains Re of about 0.5 to about 6 mass%.
[3] The cemented carbide material according to [1] or [2], wherein the WC in the material has an average particle size of less than about 0.6 μm.
[4] The cemented carbide material according to any one of [1] to [3], having a magnetic saturation of at least about 40 percent to about 80 percent of the magnetic saturation of nominally pure Co.
[5] The cemented carbide material according to any one of [1] to [4], wherein the carbide phase is formed of carbide grains having an average grain size of at least about 0.1 μm to a maximum of about 10 μm. .
[6] The cemented carbide material according to any one of [1] to [5], which has an associated coercive force that varies between about 2 kA / m and about 70 kA / m.
[7] It further includes one or more metal carbides in the form of a second carbide phase or dissolved in a binder phase in the material, wherein the one or more metals are Ti, V, Cr The cemented carbide material according to any one of [1] to [6], including Mn, Zr, Nb, Mo, Hf and / or Ta.
[8] The cemented carbide material according to any one of [1] to [7], including a binder phase having one or more residual compressive stresses.
[9] The cemented carbide material according to [8], wherein the binder phase has one or more residual compressive stresses between about −5 MPa and about 100 MPa.
[10] The cemented carbide material according to [8] or [9], wherein the binder phase includes a binder material containing Co, Re, W, and C.
[11] The above [8] or [9], wherein the binder phase contains a binder material, and the binder material contains Re, carbon and W, and one or more solid solutions of Fe, Co, and Ni. ] The cemented carbide material described in the above.
[12] The carbide phase contains WC; the cemented carbide material is less than or equal to the value given by the following equation as a function of the WC average particle size D _{wc in} μm determined based on the EBSD image of the carbide microstructure : The cemented carbide material according to any one of [1] to [11], which has a coercive force Hc of kA / m.
Hc = 10 × D _wc ^-0.62
[13] The cemented carbide material according to any one of [1] to [12], which has a compressive strength of more than about 5500 MPa at room temperature and a high temperature up to about 500 ° C.
[14] The cemented carbide material according to [13], wherein the material has Vickers hardness, and the maximum decrease in hardness at 300 ° C. is about 12%.
[15] The cemented carbide material according to any one of [1] to [14], wherein the material has Vickers hardness, and the maximum decrease in hardness at 500 ° C. is about 21%.
[16] The cemented carbide material according to any one of [1] to [15], wherein a Young's modulus of the material is greater than about 700 GPa.
[17] Any one of [1] to [16] above, wherein the hardness-toughness coefficient calculated by multiplying the Vickers hardness in GPa unit and the fracture toughness in MPa m ^1/2 unit is about 190 or more. The cemented carbide material according to item.
[18] At least about 0.1 weight percent up to about 5 weight percent of one or more of V, Cr, Ta, Ti, Mo, Zr, Nb and Hf as a solid solution and / or in the form of a carbide compound The cemented carbide material according to any one of [1] to [17], including a binder phase having a binder material.
[19] Any one of [1] to [18] above, comprising at least about 0.01 weight percent and at most about 2 weight percent of one or more of Ru, Rh, Pd, Os, Ir and Pt The cemented carbide material according to item.
[20] A substrate containing the cemented carbide material according to any one of [1] to [19],
An object of polycrystalline superhard material bonded to the substrate along the interface; and
A polycrystalline super-hard structure comprising:
[21] The polycrystalline superhard structure according to [20], wherein the object of the polycrystalline superhard material includes a polycrystalline diamond (PCD) material.
[22] The polycrystalline superhard structure according to [20] above, wherein the object of the polycrystalline superhard material includes PCBN.
[23] The cemented carbide material according to any one of [1] to [19], which is bonded to an object of polycrystalline superhard material adapted to a rotary drill bit for ground drilling. A cutter provided with a base material.
[24] A rotational shear bit for drilling the ground, a drill bit for percussion, or a PCD element for picking for mining or asphalt decomposition, the cemented carbide according to any one of [1] to [19] A PCD element comprising a cutter element comprising an object of ultra-hard polycrystalline material bonded to an object of material.
[25] A drill bit for drilling a ground or a component of a drill bit, comprising the PCD element according to [24].
[26] A method of producing the cemented carbide material according to any one of [1] to [19],
A particle growth inhibitor containing Re, Co, Ni and / or Fe, together with WC and carbon, comprising one or more of V, Cr, Ta, Ti, Mo, Zr, Nb and Hf or their carbides Crushing a cemented carbide mixture that may contain:
-Pressing the cemented carbide article from the mixture;
Sintering the article at a temperature above about 1450 ° C. for a period of between about 1-10 minutes in a vacuum and under a pressure of Ar (HIP) for about 5-120 minutes;
Cooling the article from the sintering temperature to about 1300 degrees Celsius (° C.);
Including methods.
[27] The step of cooling the article cools the article at a cooling rate of about 0.2 to 2 degrees per minute in an atmosphere containing one or more of an inert gas, nitrogen, hydrogen, or a mixture thereof. The method according to [26] above, comprising a step.
[28] The method according to [26], wherein the step of cooling the article includes the step of cooling the article in a vacuum at a cooling rate of about 0.2 to 2 degrees per minute.
[29] crushing the cemented carbide mixture comprising crushing one or more carbides with between about 0.5 and about 8 wt% Re, between about 0.5 and about 8 wt% The method according to any one of [26] to [28], comprising the step of forming a cemented carbide material containing Re.
[30] A method for recycling the cemented carbide material according to any one of [1] to [19], wherein the carbide material is melted together with liquid Zn in a protective atmosphere, and Zn is evaporated. Forming a final product, and crushing the final product to recover Re from the product.
[31] A method for recycling the cemented carbide material according to any one of [1] to [19], wherein the cemented carbide material is subjected to an acid leaching mixture, and the cemented carbide material is used as a binder. Removing the phase and chemically recovering Co and Re from the removed binder phase.
[32] A method for recycling the cemented carbide material according to any one of [1] to [19], wherein the cemented carbide material is oxidized to dissolve carbides, Re, and Co; Recovering Re.
[33] Use of cemented carbide materials for the synthesis of diamond or c-BN, or in high pressure components in the production of polycrystalline diamond or c-BN, carried out at pressures above 5 GPa and temperatures above 1100 ° C. And the cemented carbide material is
A carbide of one or more metals in the form of a second carbide phase or dissolved in a binder phase in the material, wherein the one or more metals are Ti, V, Cr, Mn, Carbides including Zr, Nb, Mo, Hf and / or Ta;
Between about 0.5 and about 8% by weight of Re and between about 3 and about 10% by weight of Co;
The total carbon equivalent (ETC) content of the cemented carbide material relative to WC is between about 6.3 wt% and about 6.9 wt%,
Use of cemented carbide material that is substantially free of η phase and free carbon.
[34] Use of the cemented carbide material according to the above [33], wherein the cemented carbide material contains between about 0.5 and about 6 mass% of Re.
[35] Use of the cemented carbide material according to the above [33] or [34], wherein the WC in the material has an average particle size of less than about 0.6 μm.
[36] The superhard according to any one of [33] to [35], wherein the cemented carbide material has a magnetic saturation of at least about 40 percent to about 80 percent of the magnetic saturation of nominally pure Co. Use of hard alloy material.
[37] The cemented carbide material according to any one of [33] to [36], wherein the carbide phase is formed of carbide grains having an average grain size of at least about 0.1 μm to a maximum of about 10 μm. Use of.
[38] Use of the cemented carbide material according to any one of [33] to [37], wherein the cemented carbide material has an associated coercive force that varies between about 2 kA / m and about 70 kA / m. .
[39] Use of the cemented carbide material according to any one of [33] to [38], wherein the carbide phase includes WC.
[40] The cemented carbide material according to any one of [33] to [39], wherein the cemented carbide material includes a binder phase having a binder material containing Co, Re, W, and C. Use of.
[41] The cemented carbide material includes a binder phase having a binder material, and the binder material includes one or more solid solutions of Re, carbon and W, and Fe, Co, and Ni. Use of the cemented carbide material according to any one of [33] to [39].
[42] The carbide phase contains WC; the cemented carbide material is less than or equal to the value given by the following equation as a function of the WC average particle size D _{wc in} μm determined based on the EBSD image of the carbide microstructure : Use of the cemented carbide material according to any one of [33] to [41], which has a coercive force Hc of kA / m unit.
Hc = 10 × D _wc ^-0.62
[43] The material according to any one of [33] to [42], wherein the material has Vickers hardness, and the hardness decrease at 300 ° C. is 20% at maximum compared to the hardness decrease at room temperature. Use of cemented carbide material.
[44] Use of the cemented carbide material according to [43], wherein the hardness decrease at 300 ° C. is 17% at maximum.
[45] Use of the cemented carbide material according to any one of [33] to [44], wherein the material has Vickers hardness, and the maximum decrease in hardness at 500 ° C is 30%.
[46] Use of the cemented carbide material according to the above [45], wherein the hardness decrease at 500 ° C. is a maximum of 27%.
[47] Any one of [33] to [46], wherein the hardness-toughness coefficient calculated by multiplying the Vickers hardness in GPa unit and the fracture toughness in MPa m1 ^{/ 2} unit is over 150. Use of the cemented carbide material described in 1.
[48] The material is at least about 0.1 weight percent up to about 5 weight percent of one of V, Cr, Ta, Ti, Mo, Zr, Nb and Hf as a solid solution and / or in the form of a carbide compound or Use of the cemented carbide material according to any one of [33] to [47], including a binder phase having a binder material containing a plurality of species.
[49] The above [33] to [48], wherein the material comprises at least about 0.01 weight percent and up to about 2 weight percent of one or more of Ru, Rh, Pd, Os, Ir and Pt Use of the cemented carbide material according to any one of the above.
[50] A cemented carbide material substantially as described above with reference to any one embodiment, the embodiment being shown in the accompanying drawings.
[51] A method of producing a cemented carbide material substantially as described above with reference to any one embodiment, which embodiment is illustrated in the accompanying drawings.

Claims

A cemented carbide material containing WC, Co and Re,
The cemented carbide material comprises between about 3 to about 10% by weight Co and between about 0.5 to about 8% by weight Re;
The total carbon equivalent (ETC) content of the cemented carbide material relative to WC is between about 6.3 wt% and about 6.9 wt%,
The cemented carbide material is a cemented carbide material substantially free of η phase and free carbon.

The cemented carbide material according to claim 1, comprising between about 0.5 and about 6 mass% Re.

The cemented carbide material according to claim 1 or 2, wherein the WC in the material has an average particle size of less than about 0.6 m.

The cemented carbide material according to any one of claims 1 to 3, having a magnetic saturation of at least about 40 percent to about 80 percent of the magnetic saturation of nominally pure Co.

The cemented carbide material according to any one of claims 1 to 4, wherein the carbide phase is formed of carbide grains having an average grain size of at least about 0.1 µm to a maximum of about 10 µm.

The cemented carbide material according to any one of claims 1 to 5, having an associated coercivity that varies from about 2 kA / m to about 70 kA / m.

And further comprising a carbide of one or more metals in the form of a second carbide phase or dissolved in a binder phase in the material, wherein the one or more metals are Ti, V, Cr, Mn, The cemented carbide material according to any one of claims 1 to 6, comprising Zr, Nb, Mo, Hf and / or Ta.

Cemented carbide material according to any one of the preceding claims, comprising a binder phase having one or more residual compressive stresses.

The cemented carbide material according to claim 8, wherein the binder phase has one or more residual compressive stresses between about −5 MPa and about 100 MPa.

The cemented carbide material according to claim 8 or 9, wherein the binder phase comprises a binder material comprising Co, Re, W and C.

The cemented carbide according to claim 8 or 9, wherein the binder phase comprises a binder material, the binder material comprising Re, carbon and W, and one or more solid solutions of Fe, Co, and Ni. Alloy material.

The carbide phase contains WC; the cemented carbide material is kA / m below the value given by the following equation as a function of the WC average particle size D _{wc in} μm determined based on the EBSD image of the carbide microstructure: The cemented carbide material according to any one of claims 1 to 11, which has a coercive force Hc of a unit.
Hc = 10 × D _wc ^-0.62

The cemented carbide material according to any one of claims 1 to 12, having a compressive strength of greater than about 5500 MPa at room temperature and at elevated temperatures up to about 500 ° C.

14. The cemented carbide material according to claim 13, wherein the material has a Vickers hardness and the hardness reduction at 300 ° C is up to about 12%.

The cemented carbide material according to any one of claims 1 to 14, wherein the material has a Vickers hardness and the hardness decrease at 500 ° C is a maximum of about 21%.

The cemented carbide material according to any one of claims 1-15, wherein the Young's modulus of the material is greater than about 700 GPa.

17. The cemented carbide according to claim 1, wherein the hardness-toughness coefficient calculated by multiplying the Vickers hardness in GPa and the fracture toughness in MPa m ^1/2 is greater than about 190. Alloy material.

Binder comprising at least about 0.1 weight percent up to about 5 weight percent of one or more of V, Cr, Ta, Ti, Mo, Zr, Nb and Hf as a solid solution and / or in the form of a carbide compound 18. The cemented carbide material according to any one of claims 1 to 17, comprising a binder phase with the material.

The cemented carbide according to any one of the preceding claims, comprising at least about 0.01 weight percent and up to about 2 weight percent of one or more of Ru, Rh, Pd, Os, Ir and Pt. Alloy material.

A substrate comprising the cemented carbide material according to any one of claims 1 to 19,
A polycrystalline superhard structure comprising an object of polycrystalline superhard material bonded to a substrate along an interface.

21. The polycrystalline superhard structure of claim 20, wherein the body of polycrystalline superhard material comprises a polycrystalline diamond (PCD) material.

21. The polycrystalline superhard structure of claim 20, wherein the body of polycrystalline superhard material comprises PCBN.

A cutter comprising a substrate comprising a cemented carbide material according to any one of claims 1 to 19, bonded to an object of polycrystalline superhard material adapted to a rotating drill bit for ground drilling.

20. A rotary shear bit for ground drilling, a drill bit for percussion or a PCD element for picking for mining or asphalt decomposition, which is bonded to an object of cemented carbide material according to any one of claims 1-19. PCD element comprising a cutter element comprising an object of a very hard polycrystalline material.

A drill bit for drilling ground or a component of a drill bit comprising the PCD element according to claim 24.

A method for producing a cemented carbide material according to any one of claims 1 to 19, comprising:
A particle growth inhibitor containing Re, Co, Ni and / or Fe, together with WC and carbon, comprising one or more of V, Cr, Ta, Ti, Mo, Zr, Nb and Hf or their carbides Crushing a cemented carbide mixture that may contain:
-Pressing the cemented carbide article from the mixture;
Sintering the article at a temperature above about 1450 ° C. for a period of between about 1-10 minutes in a vacuum and under a pressure of Ar (HIP) for about 5-120 minutes;
Cooling the article from a sintering temperature to about 1300 degrees Celsius (° C.).

Cooling the article includes cooling the article at a cooling rate of about 0.2 to 2 degrees per minute in an atmosphere containing one or more of an inert gas, nitrogen, hydrogen, or a mixture thereof. 27. The method of claim 26.

27. The method of claim 26, wherein cooling the article comprises cooling the article in a vacuum at a cooling rate of about 0.2 to 2 degrees per minute.

The step of grinding the cemented carbide mixture comprises grinding one or more carbides with between about 0.5 and about 8% by weight of Re to obtain between about 0.5 and about 8% by weight of Re. 29. A method according to any one of claims 26 to 28, comprising forming a cemented carbide material comprising.

A method for recycling the cemented carbide material according to any one of claims 1 to 19, wherein the carbide material is melted together with liquid Zn in a protective atmosphere, and the final product is obtained by evaporating Zn. A method comprising the steps of forming and grinding the final product to recover Re from the product.

20. A method of recycling the cemented carbide material according to any one of claims 1 to 19, wherein the cemented carbide material is subjected to an acid leaching mixture to remove the binder phase from the cemented carbide material; Chemically recovering Co and Re from the removed binder phase.

A method for recycling the cemented carbide material according to any one of claims 1 to 19, wherein the cemented carbide material is oxidized to dissolve carbides, Re and Co, and Re is recovered. And a method comprising.

Use of cemented carbide material for the synthesis of diamond or c-BN or in the production of polycrystalline diamond or c-BN in a high pressure component, carried out at a pressure above 5 GPa and a temperature above 1100 ° C. Cemented carbide materials are
A carbide of one or more metals in the form of a second carbide phase or dissolved in a binder phase in the material, wherein the one or more metals are Ti, V, Cr, Mn, Carbides including Zr, Nb, Mo, Hf and / or Ta;
Between about 0.5 and about 8% by weight of Re and between about 3 and about 10% by weight of Co;
The total carbon equivalent (ETC) content of the cemented carbide material relative to WC is between about 6.3 wt% and about 6.9 wt%,
Use of cemented carbide material that is substantially free of η phase and free carbon.

34. Use of the cemented carbide material according to claim 33, wherein the cemented carbide material comprises between about 0.5 and about 6 wt% Re.

35. Use of a cemented carbide material according to claim 33 or 34, wherein the WC in the material has an average particle size of less than about 0.6 [mu] m.

36. Use of the cemented carbide material according to any one of claims 33 to 35, wherein the cemented carbide material has a magnetic saturation of at least about 40 percent to about 80 percent of the magnetic saturation of nominally pure Co.

37. Use of the cemented carbide material according to any one of claims 33 to 36, wherein the carbide phase is formed of carbide grains having an average grain size of at least about 0.1 [mu] m up to about 10 [mu] m.

38. Use of a cemented carbide material according to any one of claims 33 to 37, wherein the cemented carbide material has an associated coercivity that varies from about 2 kA / m to about 70 kA / m.

Use of the cemented carbide material according to any one of claims 33 to 38, wherein the carbide phase comprises WC.

40. Use of a cemented carbide material according to any one of claims 33 to 39, wherein the cemented carbide material comprises a binder phase having a binder material comprising Co, Re, W and C.

The cemented carbide material comprises a binder phase having a binder material, and the binder material comprises Re, carbon and W, and one or more solid solutions of Fe, Co, and Ni. Use of the cemented carbide material according to any one of up to 39.

The carbide phase contains WC; the cemented carbide material is kA / m below the value given by the following equation as a function of the WC average particle size D _{wc in} μm determined based on the EBSD image of the carbide microstructure: Use of the cemented carbide material according to any one of claims 33 to 41, having a coercivity Hc of units.
Hc = 10 × D _wc ^-0.62

43. The cemented carbide material according to any one of claims 33 to 42, wherein the material has a Vickers hardness and the hardness reduction at 300 ° C is a maximum of 20% compared to the hardness reduction at room temperature. use.

44. Use of the cemented carbide material according to claim 43, wherein the decrease in hardness at 300 <0> C is a maximum of 17%.

45. Use of a cemented carbide material according to any one of claims 33 to 44, wherein the material has a Vickers hardness and the hardness reduction at 500 ° C is a maximum of 30%.

The use of the cemented carbide material according to claim 45, wherein the decrease in hardness at 500 ° C is a maximum of 27%.

The cemented carbide according to any one of claims 33 to 46, wherein the hardness-toughness coefficient calculated by multiplying the Vickers hardness in GPa by the fracture toughness in MPa m1 ^{/ 2} is greater than 150. Use of materials.

The material comprises at least about 0.1 weight percent up to about 5 weight percent of one or more of V, Cr, Ta, Ti, Mo, Zr, Nb and Hf as a solid solution and / or in the form of a carbide compound. 48. Use of a cemented carbide material according to any one of claims 33 to 47, comprising a binder phase with a binder material comprising.

49. A material according to any one of claims 33 to 48, wherein the material comprises at least about 0.01 weight percent and up to about 2 weight percent of one or more of Ru, Rh, Pd, Os, Ir and Pt. Use of cemented carbide material.

A cemented carbide material substantially as described above with reference to any one embodiment, the embodiment shown in the accompanying drawings.

A method of producing a cemented carbide material substantially as described above with reference to any one embodiment, which embodiment is shown in the accompanying drawings.