JPH09324236A - Diamond sintered body and method for manufacturing the same - Google Patents
Diamond sintered body and method for manufacturing the sameInfo
- Publication number
- JPH09324236A JPH09324236A JP8143994A JP14399496A JPH09324236A JP H09324236 A JPH09324236 A JP H09324236A JP 8143994 A JP8143994 A JP 8143994A JP 14399496 A JP14399496 A JP 14399496A JP H09324236 A JPH09324236 A JP H09324236A
- Authority
- JP
- Japan
- Prior art keywords
- diamond
- sintered body
- powder
- iron
- cobalt
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000010432 diamond Substances 0.000 title claims abstract description 104
- 229910003460 diamond Inorganic materials 0.000 title claims abstract description 103
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 19
- 238000000034 method Methods 0.000 title claims description 13
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 75
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 52
- 238000005245 sintering Methods 0.000 claims abstract description 39
- 229910052751 metal Inorganic materials 0.000 claims abstract description 33
- 239000002184 metal Substances 0.000 claims abstract description 33
- 239000000843 powder Substances 0.000 claims abstract description 29
- 239000010941 cobalt Substances 0.000 claims abstract description 28
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 28
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910052742 iron Inorganic materials 0.000 claims abstract description 28
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 25
- 239000011572 manganese Substances 0.000 claims abstract description 18
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 15
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims abstract description 15
- 150000001875 compounds Chemical class 0.000 claims abstract description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 9
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims abstract description 9
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 9
- 239000001301 oxygen Substances 0.000 claims abstract description 9
- 239000010703 silicon Substances 0.000 claims abstract description 9
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 9
- 239000000126 substance Substances 0.000 claims abstract description 8
- 239000011812 mixed powder Substances 0.000 claims abstract description 6
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 5
- 150000002739 metals Chemical class 0.000 claims abstract description 4
- 239000000203 mixture Substances 0.000 claims description 21
- 239000002245 particle Substances 0.000 claims description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 7
- 239000002253 acid Substances 0.000 abstract description 5
- 229910004283 SiO 4 Inorganic materials 0.000 description 22
- 239000002994 raw material Substances 0.000 description 13
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 8
- 239000011230 binding agent Substances 0.000 description 6
- 238000005520 cutting process Methods 0.000 description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 4
- 238000010306 acid treatment Methods 0.000 description 4
- 239000002775 capsule Substances 0.000 description 4
- 230000006866 deterioration Effects 0.000 description 4
- 229910002804 graphite Inorganic materials 0.000 description 4
- 239000010439 graphite Substances 0.000 description 4
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 3
- 239000011362 coarse particle Substances 0.000 description 3
- 229910000428 cobalt oxide Inorganic materials 0.000 description 3
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000007373 indentation Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- -1 ferrous metals Chemical class 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L manganese oxide Inorganic materials [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 230000002159 abnormal effect Effects 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000005587 carbonate group Chemical group 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- 238000005087 graphitization Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052914 metal silicate Inorganic materials 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
Landscapes
- Cutting Tools, Boring Holders, And Turrets (AREA)
Abstract
(57)【要約】
【課題】 耐欠損性、耐熱性、耐酸性を有するダイヤモ
ンド焼結体とその製造方法を提供すること。
【解決手段】 鉄、コバルト、ニッケル及びマンガンか
ら選ばれる一種以上の金属と、ケイ素及び酸素を含有す
る化合物からなる物質を０．１〜３０体積％含み残部が
ダイヤモンドであるダイヤモンド焼結体及びこのダイヤ
モンド焼結体の製造方法として、焼結助剤として鉄、コ
バルト、ニッケル及びマンガンから選ばれる金属のケイ
酸塩を用い、この粉末と、ダイヤモンド粉末または非ダ
イヤモンド炭素粉末またはダイヤモンドと非ダイヤモン
ド炭素の混合粉末とを混合し、これをダイヤモンドの熱
力学的安定領域の圧力、温度条件で保持し、焼結するこ
とを特徴とする。(57) Abstract: To provide a diamond sintered body having fracture resistance, heat resistance and acid resistance, and a method for producing the same. A diamond sintered body having 0.1 to 30% by volume of a substance composed of a compound containing one or more metals selected from iron, cobalt, nickel and manganese, and a compound containing silicon and oxygen, and the balance being diamond, and As a method for producing a diamond sintered body, a silicate of a metal selected from iron, cobalt, nickel and manganese is used as a sintering aid, and this powder, a diamond powder or a non-diamond carbon powder, or a diamond and a non-diamond carbon. It is characterized in that it is mixed with a mixed powder, and this is held under the pressure and temperature conditions of the thermodynamically stable region of diamond and sintered.
Description
【０００１】[0001]
【発明の属する技術分野】本発明はダイヤモンド焼結体
およびその製造方法に関するものである。本発明のダイ
ヤモンド焼結体は非鉄金属やセラミックス等の切削、切
削工具用素材や掘削用ビット素材などに有効に使用でき
るものである。The present invention relates to a diamond sintered body and a method for producing the same. INDUSTRIAL APPLICABILITY The diamond sintered body of the present invention can be effectively used for cutting non-ferrous metals and ceramics, cutting tool materials, drill bit materials, and the like.
【０００２】[0002]
【従来の技術】従来のダイヤモンド焼結体としては、焼
結助材あるいは結合材としてＣｏ、Ｎｉ、Ｆｅなどの鉄
族金属を用いたものや、ＳｉＣなどのセラミックスを用
いたものが知られており、非鉄金属の切削工具や掘削ビ
ットなどに工業的に利用されている。また、焼結助材と
して炭酸塩を用いたものが知られている（特開平４−７
４７６６号、特開平４−１１４９６６号各公報）。その
他、天然のダイヤモンド焼結体（カーボナード）がある
が、材質のバラツキが大きく、また産出量も極少である
ため、ほとんど工業的には使用されていない。2. Description of the Related Art As a conventional diamond sintered body, one using an iron group metal such as Co, Ni, or Fe as a sintering aid or a binder, and one using a ceramic such as SiC is known. And is industrially used for non-ferrous metal cutting tools and drill bits. Further, a material using a carbonate as a sintering aid is known (Japanese Patent Laid-Open No. 4-7).
4766, JP-A-4-114966). In addition, there is a natural diamond sintered body (carbonate), but it is rarely used industrially because of the large variation in the material and the minimal production.
【０００３】Ｃｏなどの鉄族金属を焼結助材としたダイ
ヤモンド焼結体は、Ｃｏなどの非鉄金属がダイヤモンド
の黒鉛化を促す触媒として作用するため耐熱性に劣る。
すなわち、不活性ガス雰囲気中で、７００℃程度で黒鉛
化してしまう。また、ダイヤモンド粒の粒界にＣｏなど
の金属が連続相として存在するため焼結体の強度はあま
り高くなく、欠損しやすい。そして、この金属とダイヤ
モンドの熱膨張差のため熱劣化が起こり易くなるという
問題もある。耐熱性を上げるために上記の粒界の金属を
酸処理により除去されたものも知られている（特開昭５
３−１１４５８９号公報）。これにより耐熱温度は約１
２００℃と向上するが、焼結体が多孔質となるため強度
がさらに大幅（３０％程度）に低下する。ＳｉＣを結合
材としたダイヤモンド焼結体は耐熱性には優れるが、ダ
イヤモンド粒同士は結合がないため、強度は低い（米国
特許第４１２４４０１号明細書）。一方上記のように、
焼結助材として炭酸塩を用いたダイヤモンド焼結体は、
Ｃｏバインダーによる焼結体に比べると耐熱性に優れる
が、１０００℃程度より炭酸塩の分解がはじまり焼結体
の強度が低下する。また、炭酸塩は酸に溶けるため、掘
削ビットなどの用途で使用できない。A diamond sintered body using an iron group metal such as Co as a sintering aid is inferior in heat resistance because a non-ferrous metal such as Co acts as a catalyst for promoting graphitization of diamond.
That is, it is graphitized at about 700 ° C. in an inert gas atmosphere. In addition, since a metal such as Co exists as a continuous phase in the grain boundary of the diamond grain, the strength of the sintered body is not so high and the sintered body is easily broken. There is also a problem that thermal deterioration easily occurs due to the difference in thermal expansion between the metal and diamond. It is also known that the metal of the above grain boundary is removed by acid treatment in order to improve heat resistance (Japanese Patent Laid-Open No. Sho 5).
3-114589). As a result, the heat resistant temperature is about 1
Although the temperature is improved to 200 ° C., the strength becomes much lower (about 30%) because the sintered body becomes porous. A diamond sintered body using SiC as a binder has excellent heat resistance, but since diamond grains do not bond to each other, the strength is low (US Pat. No. 4,124,401). On the other hand, as mentioned above,
The diamond sintered body using carbonate as a sintering aid,
Although it has more excellent heat resistance than a sintered body using a Co binder, decomposition of carbonate starts at about 1000 ° C. and the strength of the sintered body decreases. In addition, since carbonate dissolves in acid, it cannot be used in applications such as drill bits.
【０００４】[0004]
【発明が解決しようとする課題】本発明は上記のような
課題を解決することを目的として開発されたものであ
り、耐欠損性、耐熱性及び耐酸性を有するダイヤモンド
焼結体とその製造方法を提供することを意図したもので
ある。The present invention was developed for the purpose of solving the above-mentioned problems, and has a diamond sintered body having fracture resistance, heat resistance and acid resistance, and a method for producing the same. Is intended to provide.
【０００５】[0005]
【課題を解決するための手段】上記の課題を解決するた
めの手段として、本発明は、鉄、コバルト、ニッケル及
びマンガンから選ばれる一種以上の金属と、ケイ素及び
酸素を含有する化合物からなる物質を０．１〜３０体積
％含み残部がダイヤモンドであるダイヤモンド焼結体を
提供する。また、鉄、コバルト、ニッケル及びマンガン
から選ばれる一種以上の金属と、ケイ素及び酸素を含有
する化合物が、鉄、コバルト、ニッケル及びマンガンか
ら選ばれる金属のケイ酸塩であるダイヤモンド焼結体を
提供する。また、上記、鉄、コバルト、ニッケル及びマ
ンガンから選ばれる一種以上の金属と、ケイ素及び酸素
を含有する化合物が、鉄、コバルト、ニッケル及びマン
ガンから選ばれる金属の酸化物と酸化ケイ素からなる化
合物であるダイヤモンド焼結体を提供する。Means for Solving the Problems As a means for solving the above problems, the present invention provides a substance comprising a compound containing at least one metal selected from iron, cobalt, nickel and manganese, and silicon and oxygen. The present invention provides a diamond sintered body containing 0.1 to 30% by volume and the balance being diamond. Also provided is a diamond sintered body, wherein the compound containing one or more metals selected from iron, cobalt, nickel and manganese, and a compound containing silicon and oxygen is a silicate of a metal selected from iron, cobalt, nickel and manganese. To do. Further, the compound containing one or more metals selected from iron, cobalt, nickel and manganese, and silicon and oxygen is a compound consisting of an oxide of a metal selected from iron, cobalt, nickel and manganese and silicon oxide. A diamond sintered body is provided.
【０００６】また、このダイヤモンド焼結体の製造方法
として、焼結助剤として鉄、コバルト、ニッケル及びマ
ンガンから選ばれる金属のケイ酸塩を用い、この粉末
と、ダイヤモンド粉末または非ダイヤモンド炭素粉末ま
たはダイヤモンドと非ダイヤモンド炭素の混合粉末とを
混合し、これをダイヤモンドの熱力学的安定領域の圧
力、温度条件で保持し、焼結する方法を提供する。この
ダイヤモンド焼結体の別の製造方法として、焼結助剤と
して鉄、コバルト、ニッケル及びマンガンから選ばれる
金属のケイ酸塩を用い、この粉末の成形体と、ダイヤモ
ンド粉末の成形体または非ダイヤモンド炭素粉末の成形
体またはダイヤモンドと非ダイヤモンド炭素の混合粉末
の成形体とを積層し、これをダイヤモンドの熱力学的安
定領域の圧力、温度条件で保持し、焼結する方法を提供
する。 また、このダイヤモンド焼結体の製造のための
別の焼結助剤としてケイ酸塩の代わりに、鉄、コバル
ト、ニッケル及びマンガンから選ばれる金属の酸化物と
酸化ケイ素の混合物を用いる方法を提供する。また上記
のダイヤモンド焼結体の製造方法において、ダイヤモン
ド粉末の粒径が０．０１〜２００μｍの範囲にある方法
を提供する。As a method for producing this diamond sintered body, a silicate of a metal selected from iron, cobalt, nickel and manganese is used as a sintering aid, and this powder and diamond powder or non-diamond carbon powder or Provided is a method of mixing diamond and a non-diamond carbon mixed powder, holding the mixture under pressure and temperature conditions in the thermodynamically stable region of diamond, and sintering the mixture. As another method for producing this diamond sintered body, a silicate of a metal selected from iron, cobalt, nickel and manganese is used as a sintering aid, and this powder molded body and a diamond powder molded body or non-diamond are used. Provided is a method of laminating a molded body of carbon powder or a molded body of a mixed powder of diamond and non-diamond carbon, holding the laminated body under pressure and temperature conditions in a thermodynamically stable region of diamond, and sintering the laminated body. Also provided is a method of using a mixture of an oxide of a metal selected from iron, cobalt, nickel and manganese and silicon oxide instead of silicate as another sintering aid for the production of this diamond sintered body. To do. Further, it provides a method for producing a diamond sintered body, wherein the diamond powder has a particle size in the range of 0.01 to 200 μm.
【０００７】[0007]
【発明の実施の形態】従来、鉄、コバルト、ニッケル及
びマンガンから選ばれる金属のケイ酸塩や、鉄、コバル
ト、ニッケル及びマンガンから選ばれる金属の酸化ケイ
素の混合物がダイヤモンド焼結体の有効な焼結助剤とし
て用いられた例はない。今回、本発明者らにより、これ
らの物質を焼結助剤とすることで、従来にない高強度
で、かつ耐欠損性、耐熱性、耐食性に優れたダイヤモン
ド焼結体が得られることが見いだされ、本発明に至っ
た。本発明の特徴は、ダイヤモンド焼結体の焼結助剤と
して鉄、コバルト、ニッケル及びマンガンから選ばれる
金属のケイ酸塩あるいは、鉄、コバルト、ニッケル及び
マンガンから選ばれる金属の酸化物と酸化ケイ素の混合
物を用いた点にある。該金属の酸化物と酸化ケイ素の混
合物を用いるときは、混合モル比は０．５〜２の範囲と
するのが好ましい。鉄、コバルト、ニッケル及びマンガ
ンから選ばれる金属のケイ酸塩としては、例えば、Ｆｅ
2 ＳｉＯ4 、Ｃｏ2 ＳｉＯ4 、Ｎｉ2 ＳｉＯ4 、Ｍｎ2
ＳｉＯ4 などが挙げられる。これらは、ダイヤモンドに
対し、強い触媒作用を示し、これらを焼結助剤とすると
ダイヤモンド粒子が極めて強固に結合したマトリックス
形成される。また、異常粒成長が起こり難く、均質な組
織の焼結体が得られる。その結果、従来にない高強度で
耐欠損性や耐摩耗性に優れたダイヤモンド焼結体が得ら
れる。BEST MODE FOR CARRYING OUT THE INVENTION Conventionally, a mixture of a silicate of a metal selected from iron, cobalt, nickel and manganese and a silicon oxide of a metal selected from iron, cobalt, nickel and manganese is effective for a diamond sintered body. It has not been used as a sintering aid. This time, the present inventors have found that by using these substances as a sintering aid, a diamond sintered body having unprecedented high strength and excellent in fracture resistance, heat resistance, and corrosion resistance can be obtained. This led to the present invention. A feature of the present invention is that a silicate of a metal selected from iron, cobalt, nickel and manganese, or an oxide and a silicon oxide of a metal selected from iron, cobalt, nickel and manganese as a sintering aid of a diamond sintered body. The point of using a mixture of. When using a mixture of the metal oxide and silicon oxide, the mixing molar ratio is preferably in the range of 0.5 to 2. Examples of metal silicates selected from iron, cobalt, nickel and manganese include Fe.
2 SiO 4 , Co 2 SiO 4 , Ni 2 SiO 4 , Mn 2
Examples thereof include SiO 4 . These have a strong catalytic action on diamond, and when these are used as a sintering aid, a matrix is formed in which diamond particles are extremely strongly bonded. Further, abnormal grain growth is unlikely to occur, and a sintered body having a uniform structure can be obtained. As a result, it is possible to obtain a diamond sintered body having a high strength, which is unprecedented, and excellent in fracture resistance and abrasion resistance.
【０００８】こうして得られるダイヤモンド焼結体は、
鉄やコバルトなどの金属とケイ素および酸素を含有する
化合物からなる物質を含むのが特徴で、このような物質
としては、上記のような鉄やコバルトなどのケイ酸塩、
あるいは酸化鉄や酸化コバルトなどの金属酸化物と酸化
ケイ素の複合体もしくは固溶体が挙げられる。これらの
物質は１０００℃を越える高温下でも安定で、また、酸
やアルカリに対しても安定である。このため、本発明の
ダイヤモンド焼結体は耐熱性や耐食性にも非常に優れた
特性を示す。本発明のダイヤモンド焼結体において、
鉄、コバルト、ニッケル及びマンガンから選ばれる金属
とケイ素および酸素を含有する化合物からなる物質の含
有量は０．１〜３０体積％が好ましいが、この理由は
０．１体積％未満ではダイヤモンド粒子間の結合性、す
なわち焼結性が低下し、３０体積％を越えると過剰のケ
イ酸塩の影響で、強度、耐摩耗性が低下するからであ
る。The diamond sintered body thus obtained is
It is characterized by containing a substance consisting of a compound containing a metal such as iron or cobalt and silicon and oxygen.As such a substance, a silicate such as iron or cobalt as described above,
Alternatively, a complex or solid solution of a metal oxide such as iron oxide or cobalt oxide and silicon oxide can be used. These substances are stable even at a high temperature exceeding 1000 ° C., and are also stable against acids and alkalis. Therefore, the diamond sintered body of the present invention has excellent heat resistance and corrosion resistance. In the diamond sintered body of the present invention,
The content of the substance consisting of a metal selected from iron, cobalt, nickel and manganese and a compound containing silicon and oxygen is preferably 0.1 to 30% by volume, because the reason is less than 0.1% by volume between diamond particles. This is because the binding property, that is, the sinterability, is deteriorated, and when it exceeds 30% by volume, the strength and the wear resistance are deteriorated due to the influence of the excess silicate.
【０００９】原料としては合成ダイヤモンド粉末、天然
ダイヤモンド粉末、多結晶ダイヤモンド粉末などを用い
ることができる。粉末の粒径は０．０１〜２００μｍ
で、用途によって微粒または粗粒に粒径を揃えたもの、
もしくは微粒、粗粒の混合物を用いる。粒径が０．０１
μｍ未満であると焼結体の硬度、靱性が低下し、また２
００μｍを超えると均質な焼結性を有する焼結体の作製
が困難となるので０．０１〜２００μｍのものを用いる
のが好ましい。粒径が異なる範囲にあるもの、例えば粒
径（１〜４０μｍ）と粗粒（７０〜１００μｍ）の混合
物を用いると均質で高硬度、高靱性な焼結体が得られよ
り好ましい。また、これらのダイヤモンドに代えて黒鉛
やグラッシーカーボン、熱分解黒鉛などの非ダイヤモン
ドも原料とすることができる。また、ダイヤモンドとこ
れら非ダイヤモンド黒鉛の混合物を用いることもでき
る。本発明のダイヤモンド焼結体の製造方法としては、
ダイヤモンド粉末や非ダイヤモンド粉末と、鉄やコバル
トのケイ酸塩あるいは酸化鉄や酸化コバルトと酸化ケイ
素の混合物とを、ダイヤモンドが熱力学的に安定な圧
力、温度条件下で保持する方法と、ダイヤモンド粉末や
非ダイヤモンド黒鉛の成形体と、鉄やコバルトのケイ酸
塩あるいは酸化鉄や酸化コバルトと酸化ケイ素の混合物
の成形体を積層したものを原料として、上記の圧力、温
度条件下で保持する方法がある。焼結の際の条件は一般
に圧力５〜１０ＧＰａ、温度１４００〜２５００℃とす
るのが好ましい。As raw materials, synthetic diamond powder, natural diamond powder, polycrystalline diamond powder and the like can be used. The particle size of the powder is 0.01 to 200 μm
With a fine or coarse particle size, depending on the application,
Alternatively, a mixture of fine particles and coarse particles is used. Particle size is 0.01
If it is less than μm, the hardness and toughness of the sintered body are lowered, and 2
If it exceeds 00 μm, it becomes difficult to produce a sintered body having a uniform sinterability, so that it is preferable to use a sintered body of 0.01 to 200 μm. It is more preferable to use a mixture having different particle diameters, for example, a mixture of particle diameters (1 to 40 μm) and coarse particles (70 to 100 μm) because a homogeneous, high hardness and high toughness sintered body can be obtained. Further, instead of these diamonds, non-diamond such as graphite, glassy carbon, and pyrolytic graphite can be used as a raw material. Also, a mixture of diamond and these non-diamond graphites can be used. The method for producing a diamond sintered body of the present invention,
Method for holding diamond powder or non-diamond powder and iron or cobalt silicate or mixture of iron oxide or cobalt oxide and silicon oxide under thermodynamically stable pressure and temperature conditions, and diamond powder A method of holding a molded body of non-diamond graphite and a molded body of a silicate of iron or cobalt or a mixture of iron oxide or cobalt oxide and silicon oxide as a raw material and holding it under the above pressure and temperature conditions is used. is there. Generally, the conditions for sintering are preferably a pressure of 5 to 10 GPa and a temperature of 1400 to 2500 ° C.
【００１０】原料と焼結助剤を混合する方法において
は、原料と焼結助剤を、機械的に乾式または湿式混合し
た粉末を圧縮成形したもの、もしくはＭｏ等のカプセル
に充填したものを高圧高温焼結する。原料粉末が微粒で
も焼結助剤を均一に分散でき、また、厚い形状のダイヤ
モンド焼結体の製造が可能である。例えば、良好な仕上
げ面が必要な切削工具（微粒焼結体）の製造や、ダイス
などの厚い形状を必要とする焼結体の製造に適する。た
だし、粗粒の原料を用いた場合、均一に焼結助剤を混合
するのに困難を要す。一方、原料と焼結助剤を積層配置
する方法は、原料と焼結助剤の板状の成形体をそれぞれ
作製し、これらを積層して接触させ、高圧高温処理す
る。このとき、焼結助剤が原料層に拡散含浸し、ダイヤ
モンド粒子が焼結する。この方法は、粗粒の原料を用い
ても焼結助剤を均一に添加できるため、より高強度で耐
摩耗性のあるダイヤモンド焼結体を安定して得ることが
でき、耐摩耗工具やドリルビットなどの焼結体の製造に
適する。In the method of mixing the raw material and the sintering aid, the raw material and the sintering aid are mechanically dry- or wet-mixed powder, compression-molded, or filled in a capsule such as Mo under high pressure. Sinter at high temperature. Even if the raw material powder is fine, the sintering aid can be uniformly dispersed, and a thick diamond sintered body can be manufactured. For example, it is suitable for manufacturing a cutting tool (fine-grained sintered body) that requires a good finished surface and a sintered body that requires a thick shape such as a die. However, when a coarse-grain raw material is used, it is difficult to uniformly mix the sintering aid. On the other hand, in the method of stacking and placing the raw material and the sintering aid, plate-shaped compacts of the raw material and the sintering aid are prepared, and these are stacked and brought into contact with each other, and subjected to high-pressure and high-temperature treatment. At this time, the raw material layer is diffused and impregnated with the sintering aid, and the diamond particles are sintered. With this method, even if a coarse-grained raw material is used, the sintering aid can be added uniformly, so that a diamond sintered body with higher strength and wear resistance can be stably obtained. Suitable for manufacturing sintered bodies such as bits.
【００１１】[0011]
【実施例】本発明を以下の実施例により具体的に説明す
るがこれに限定されるものではない。 （実施例１）焼結助剤としてＦｅ2 ＳｉＯ4 を用いた。
平均粒径３．５μｍの合成ダイヤモンド粉末と、Ｆｅ2
ＳｉＯ4 の粉末をそれぞれ９５体積％、５体積％の割合
で十分に混合し、この混合物をＭｏカプセルに入れ、ベ
ルト型の超高圧高温発生装置を用いて、７．５ＧＰａ、
２０００℃の圧力温度条件で１５分間保持し、焼結させ
た。得られたダイヤモンド焼結体について、Ｘ線回折に
より組成を同定したところ、ダイヤモンドの他、約５体
積％のＦｅ2 ＳｉＯ4 が検出された。この焼結体の硬度
をヌープ圧子により評価したところ８１００ｋｇ／ｍｍ
2 と高硬度であった。また、破壊靱性をインデンテーシ
ョン法により従来の市販のＣｏバインダー焼結体に対し
相対比較したとたろ、従来焼結体の約１．４倍の相対靱
性であった。また、得られた焼結体を真空中で１２００
℃に加熱処理した後、硬度、靱性を測定したが、処理前
とほとんど変化がなかった。また、酸処理による焼結体
の劣化は認められなかった。EXAMPLES The present invention will be specifically described by the following examples, but the invention is not limited thereto. With Fe 2 SiO 4 (Example 1) sintering aid.
Fe 2 with synthetic diamond powder having an average particle size of 3.5 μm
The SiO 4 powders were thoroughly mixed at a ratio of 95% by volume and 5% by volume, respectively, and the mixture was put in a Mo capsule, and 7.5 GPa, using a belt type ultrahigh pressure and high temperature generator.
The pressure and temperature conditions of 2000 ° C. were maintained for 15 minutes for sintering. When the composition of the obtained diamond sintered body was identified by X-ray diffraction, about 5% by volume of Fe 2 SiO 4 was detected in addition to diamond. When the hardness of this sintered body was evaluated by a Knoop indenter, it was 8100 kg / mm.
The hardness was 2 and high. Further, when the fracture toughness was compared with the conventional commercially available Co binder sintered body by the indentation method, the relative toughness was about 1.4 times that of the conventional sintered body. In addition, the obtained sintered body is 1200
After heat treatment at ℃, the hardness and toughness were measured, but there was almost no change from before treatment. No deterioration of the sintered body due to the acid treatment was observed.
【００１２】（実施例２）焼結助剤として、５体積％の
Ｃｏ2 ＳｉＯ4 を用いた他は、実施例１と同様にしてダ
イヤモンド焼結体を作製した。得られた焼結体にはＣｏ
2 ＳｉＯ4 が含まれており、硬度、靱性、耐熱性とも実
施例１と同様であった。Example 2 A diamond sintered body was produced in the same manner as in Example 1 except that 5% by volume of Co 2 SiO 4 was used as a sintering aid. Co was added to the obtained sintered body.
2 SiO 4 are included, was similar hardness, toughness, and also heat resistance Example 1.
【００１３】（実施例３）焼結助剤として、５体積％の
Ｎｉ2 ＳｉＯ4 を用いた他は、実施例１と同様にしてダ
イヤモンド焼結体を作製した。得られた焼結体にはＮｉ
2 ＳｉＯ4 が含まれており、硬度、靱性、耐熱性とも実
施例１と同様であった。Example 3 A diamond sintered body was produced in the same manner as in Example 1 except that 5% by volume of Ni 2 SiO 4 was used as a sintering aid. Ni was added to the obtained sintered body.
2 SiO 4 are included, was similar hardness, toughness, and also heat resistance Example 1.
【００１４】（実施例４）焼結助剤として、５体積％の
Ｍｎ2 ＳｉＯ4 を用いた他は、実施例１と同様にしてダ
イヤモンド焼結体を作製した。得られた焼結体にはＭｎ
2 ＳｉＯ4 が含まれており、硬度、靱性、耐熱性とも実
施例１と同様であった。Example 4 A diamond sintered body was produced in the same manner as in Example 1 except that 5% by volume of Mn 2 SiO 4 was used as a sintering aid. The obtained sintered body contains Mn
2 SiO 4 are included, was similar hardness, toughness, and also heat resistance Example 1.
【００１５】（実施例５）焼結剤として、ＦｅＯとＳｉ
Ｏ2 の２：１（モル比）の混合物を用い、実施例１と同
様にしてダイヤモンド焼結体を作製した。得られた焼結
体にはＦｅ2 ＳｉＯ4 が含まれており、硬度、靱性、耐
熱性とも実施例１と同様であった。(Example 5) FeO and Si as sintering agents
A diamond sintered body was produced in the same manner as in Example 1 using a 2: 1 (molar ratio) mixture of O 2 . The obtained sintered body contained Fe 2 SiO 4 and had the same hardness, toughness, and heat resistance as in Example 1.
【００１６】（実施例６）焼結助剤として、ＣｏＯとＳ
ｉＯ2 の２：１（モル比）の混合物を用い、実施例１と
同様にしてダイヤモンド焼結体を作製した。得られた焼
結体にはＣｏ2 ＳｉＯ4 が含まれており、硬度、靱性、
耐熱性とも実施例１と同様であった。(Example 6) CoO and S as sintering aids
A diamond sintered body was produced in the same manner as in Example 1, using a mixture of iO 2 at a ratio of 2: 1 (molar ratio). The obtained sintered body contains Co 2 SiO 4 , and the hardness, toughness,
The heat resistance was the same as in Example 1.
【００１７】（実施例７）焼結助剤としてＦｅ2 ＳｉＯ
4 を用いた。平均粒径１５μｍの合成ダイヤモンド粉末
とＦｅ2 ＳｉＯ4 粉末をそれぞれ厚み２ｍｍ、１ｍｍに
成形したものを交互に積層してＭｏカプセルに入れ、ベ
ルト型の超高圧高温発生装置を用いて、７．５ＧＰａ、
２０００℃の圧力温度条件で１５分間保持し焼結した。
得られたダイヤモンド焼結体について、Ｘ線回折により
組成を同定したところ、ダイヤモンドの他、約２体積％
のＦｅ2 ＳｉＯ4 が検出された。この焼結体の硬度をヌ
ープ圧子により評価したところ約８３００Ｋｇ／ｍｍ2
と高硬度であった。また、破壊靱性をインデンテーショ
ン法により従来の市販のＣｏバインダー焼結体に対し相
対比較したところ、従来焼結体の約１．４倍の相対靱性
であった。また、得られた焼結体を真空中で１２００℃
に加熱処理した後、硬度、靱性を測定したが、処理前と
ほとんど変化がなかった。また、酸処理による焼結体の
劣化は認められなかった。Example 7 Fe 2 SiO as a sintering aid
4 was used. Synthetic diamond powder having an average particle size of 15 μm and Fe 2 SiO 4 powder each having a thickness of 2 mm and 1 mm were alternately laminated and placed in a Mo capsule, using a belt-type ultrahigh pressure and high temperature generator to generate 7.5 GPa. ,
The pressure and temperature conditions of 2000 ° C. were maintained for 15 minutes for sintering.
The composition of the obtained diamond sintered body was identified by X-ray diffraction.
Fe 2 SiO 4 was detected. When the hardness of this sintered body was evaluated by a Knoop indenter, it was about 8300 Kg / mm 2.
And high hardness. Further, when the fracture toughness was compared with the conventional commercially available Co binder sintered body by the indentation method, the relative toughness was about 1.4 times that of the conventional sintered body. In addition, the obtained sintered body is vacuumed at 1200 ° C.
After the heat treatment, the hardness and toughness were measured, but there was almost no change from that before the treatment. No deterioration of the sintered body due to the acid treatment was observed.
【００１８】（実施例８）焼結助剤としてＦｅ2 ＳｉＯ
4 を用いた。平均粒径３μｍの高純度等方性黒鉛の厚み
２ｍｍの板状焼結体と、Ｆｅ2 ＳｉＯ4 の粉末を厚み１
ｍｍに型押し成形したものを交互に積層してＭｏカプセ
ルに入れ、ガードル型の超高圧高温発生装置を用いて、
７．５ＧＰａ、２０００℃の圧力温度条件で１５分間保
持し、焼結させた。得られたダイヤモンド焼結体につい
て、Ｘ線回折により組成を同定したところ、ダイヤモン
ドの他、約３体積％のＦｅ2 ＳｉＯ4 が検出された。こ
の焼結体の硬度をヌープ圧子により評価したところ約７
８００Ｋｇ／ｍｍ2 と高硬度であった。また、破壊靱性
をインデンテーション法により従来の市販のＣｏバイン
ダー焼結体に対し相対比較したところ、従来焼結体の約
１．３倍の相対靱性であった。また、得られた焼結体を
真空中で１２００℃に加熱処理した後、硬度、靱性を測
定したが、処理前とほとんど変化がなかった。また、酸
処理による焼結体の劣化は認められなかった。Example 8 Fe 2 SiO as a sintering aid
4 was used. A high-purity isotropic graphite having an average particle diameter of 3 μm and a plate-shaped sintered body having a thickness of 2 mm and a powder of Fe 2 SiO 4 having a thickness of 1
mm, which are embossed and molded, are alternately laminated and placed in a Mo capsule, and a girdle type ultra high pressure and high temperature generator is used.
It was held under pressure and temperature conditions of 7.5 GPa and 2000 ° C. for 15 minutes for sintering. When the composition of the obtained diamond sintered body was identified by X-ray diffraction, about 3% by volume of Fe 2 SiO 4 was detected in addition to diamond. The hardness of this sintered body was evaluated by a Knoop indenter to be about 7
The hardness was as high as 800 Kg / mm 2 . Further, when the fracture toughness was compared with the conventional commercially available Co binder sintered body by the indentation method, the relative toughness was about 1.3 times that of the conventional sintered body. Further, the obtained sintered body was heat-treated at 1200 ° C. in vacuum and then the hardness and toughness were measured, but there was almost no change from that before the treatment. No deterioration of the sintered body due to the acid treatment was observed.
【００１９】（実施例９）Ｆｅ2 ＳｉＯ4 の添加量と２
０体積％とした他は、実施例１と同様にしてダイヤ焼結
体を製造した。得られた焼結体は硬度７６００ｋｇ／ｍ
ｍ2 と高硬度で、靱性も従来焼結体の１．３倍と高かっ
た。また耐熱性、耐酸性とも実施例１と同様であった。(Example 9) Amount of Fe 2 SiO 4 added and 2
A diamond sintered body was manufactured in the same manner as in Example 1 except that 0% by volume was used. The obtained sintered body has a hardness of 7600 kg / m
The hardness was as high as m 2, and the toughness was 1.3 times as high as that of the conventional sintered body. The heat resistance and acid resistance were the same as in Example 1.
【００２０】（比較例１）焼結助剤としてＦｅ2 ＳｉＯ
4 を用いた。平均粒径３．５μｍの合成ダイヤモンド粉
末に微量のＦｅ2 ＳｉＯ4 の粉末（約０．０５体積％）
添加し、十分に混合したものを原料にした他は、実施例
１と同様にダイヤモンド焼結体の製造を試みた。しか
し、得られた焼結体には、未焼結部が多く残留してい
た。(Comparative Example 1) Fe 2 SiO as a sintering aid
4 was used. A small amount of Fe 2 SiO 4 powder (about 0.05% by volume) in synthetic diamond powder with an average particle size of 3.5 μm.
An attempt was made to manufacture a diamond sintered body in the same manner as in Example 1, except that the raw material was added and sufficiently mixed. However, many unsintered parts remained in the obtained sintered body.
【００２１】（比較例２）焼結助剤としてＦｅ2 ＳｉＯ
4 を用いた。平均粒径３．５μｍの合成ダイヤモンド粉
末６０体積％と、Ｆｅ2 ＳｉＯ4 の粉末４０体積％を添
加し、十分に混合したものを原料にした他は、実施例１
と同様にダイヤモンド焼結体の製造を試みた。しかし、
得られた焼結体は、粒子同士の結合が十分でなく、硬度
は３５００ｋｇ／ｍｍ2 程度と低かった。Comparative Example 2 Fe 2 SiO as a sintering aid
4 was used. Example 1 except that 60% by volume of synthetic diamond powder having an average particle diameter of 3.5 μm and 40% by volume of Fe 2 SiO 4 powder were added and sufficiently mixed were used as a raw material.
Production of a diamond sintered body was attempted in the same manner as described above. But,
In the obtained sintered body, the particles were not sufficiently bonded to each other, and the hardness was as low as about 3500 kg / mm 2 .
【００２２】[0022]
【発明の効果】以上説明したように、本発明のダイヤモ
ンド焼結体は、従来にない高強度で、耐熱性、耐欠損
性、耐食性を有するので、非鉄金属やセラミックス等の
切削、研削工具用素材の他、掘削用途等のドリルビット
の刃先素材として有効に使用できる。As described above, since the diamond sintered body of the present invention has unprecedented high strength, heat resistance, fracture resistance and corrosion resistance, it can be used for cutting and grinding tools such as non-ferrous metals and ceramics. In addition to the material, it can be effectively used as a cutting edge material for drill bits for drilling applications.
Claims (7)
ら選ばれる一種以上の金属と、ケイ素及び酸素を含有す
る化合物からなる物質を０．１〜３０体積％含み残部が
ダイヤモンドであることを特徴とするダイヤモンド焼結
体。1. A material comprising 0.1 to 30% by volume of a substance consisting of one or more metals selected from iron, cobalt, nickel and manganese, and a compound containing silicon and oxygen, and the balance being diamond. Diamond sintered body.
ら選ばれる一種以上の金属と、ケイ素及び酸素を含有す
る化合物が、鉄、コバルト、ニッケル及びマンガンから
選ばれる金属のケイ酸塩であることを特徴とする請求項
１に記載のダイヤモンド焼結体。2. A compound containing at least one metal selected from iron, cobalt, nickel and manganese, and a compound containing silicon and oxygen is a silicate of a metal selected from iron, cobalt, nickel and manganese. The diamond sintered body according to claim 1.
ら選ばれる一種以上の金属と、ケイ素及び酸素を含有す
る化合物が、鉄、コバルト、ニッケル及びマンガンから
選ばれる金属の酸化物と酸化ケイ素からなる化合物であ
ることを特徴とする請求項１に記載のダイヤモンド焼結
体。3. A compound containing at least one metal selected from iron, cobalt, nickel and manganese, and a compound containing silicon and oxygen, wherein the compound is an oxide of a metal selected from iron, cobalt, nickel and manganese, and silicon oxide. The diamond sintered body according to claim 1, wherein
及びマンガンから選ばれる金属のケイ酸塩を用い、この
粉末と、ダイヤモンド粉末または非ダイヤモンド炭素粉
末またはダイヤモンドと非ダイヤモンド炭素の混合粉末
と混合し、これをダイヤモンドの熱力学的安定領域の圧
力、温度条件で保持し、焼結することを特徴とする請求
項１〜３のいずれかに記載のダイヤモンド焼結体の製造
方法。4. A silicate of a metal selected from iron, cobalt, nickel and manganese is used as a sintering aid, and this powder is mixed with diamond powder or non-diamond carbon powder or a mixed powder of diamond and non-diamond carbon. The method for producing a diamond sintered body according to any one of claims 1 to 3, wherein the diamond sintered body is held under pressure and temperature conditions in a thermodynamically stable region of diamond and sintered.
及びマンガンから選ばれる金属のケイ酸塩を用い、この
粉末の成形体と、ダイヤモンド粉末の成形体または非ダ
イヤモンド炭素粉末の成形体またはダイヤモンドと非ダ
イヤモンド炭素の混合粉末の成形体とを積層し、これを
ダイヤモンドの熱力学的安定領域の圧力、温度条件で保
持し、焼結することを特徴とする請求項１〜３のいずれ
かに記載のダイヤモンド焼結体の製造方法。5. A silicate of a metal selected from iron, cobalt, nickel and manganese is used as a sintering aid, and a compact of this powder and a compact of diamond powder or a compact of non-diamond carbon powder or diamond. 4. A non-diamond carbon mixed powder compact is laminated, and the mixture is held under pressure and temperature conditions in the thermodynamically stable region of diamond, and sintered. A method for manufacturing a diamond sintered body according to the description.
コバルト、ニッケル及びマンガンから選ばれる金属の酸
化物と酸化ケイ素の混合物を用いることを特徴とする請
求項４又は５に記載のダイヤモンド焼結体の製造方法。6. Iron instead of silicate as a sintering aid,
The method for producing a diamond sintered body according to claim 4 or 5, wherein a mixture of silicon oxide and an oxide of a metal selected from cobalt, nickel and manganese is used.
００μｍの範囲にあることを特徴とする請求項４又は５
に記載のダイヤモンド焼結体の製造方法。7. The particle size of diamond powder is 0.01-2.
It is in the range of 00 μm.
The method for producing a diamond sintered body according to 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8143994A JPH09324236A (en) | 1996-06-06 | 1996-06-06 | Diamond sintered body and method for manufacturing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8143994A JPH09324236A (en) | 1996-06-06 | 1996-06-06 | Diamond sintered body and method for manufacturing the same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH09324236A true JPH09324236A (en) | 1997-12-16 |
Family
ID=15351846
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8143994A Pending JPH09324236A (en) | 1996-06-06 | 1996-06-06 | Diamond sintered body and method for manufacturing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH09324236A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012030293A (en) * | 2010-07-28 | 2012-02-16 | Kyocera Corp | Cutting tool and manufacturing method therefor |
-
1996
- 1996-06-06 JP JP8143994A patent/JPH09324236A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012030293A (en) * | 2010-07-28 | 2012-02-16 | Kyocera Corp | Cutting tool and manufacturing method therefor |
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