WO2017073297A1 - 複合多結晶体 - Google Patents
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- WO2017073297A1 WO2017073297A1 PCT/JP2016/079939 JP2016079939W WO2017073297A1 WO 2017073297 A1 WO2017073297 A1 WO 2017073297A1 JP 2016079939 W JP2016079939 W JP 2016079939W WO 2017073297 A1 WO2017073297 A1 WO 2017073297A1
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- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23B—TURNING; BORING
- B23B27/00—Tools for turning or boring machines; Tools of a similar kind in general; Accessories therefor
- B23B27/14—Cutting tools of which the bits or tips or cutting inserts are of special material
- B23B27/18—Cutting tools of which the bits or tips or cutting inserts are of special material with cutting bits or tips or cutting inserts rigidly mounted, e.g. by brazing
- B23B27/20—Cutting tools of which the bits or tips or cutting inserts are of special material with cutting bits or tips or cutting inserts rigidly mounted, e.g. by brazing with diamond bits or cutting inserts
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Definitions
- the present invention relates to a composite polycrystal.
- This application claims priority based on Japanese Patent Application No. 2015-214038 filed on Oct. 30, 2015, and incorporates all the content described in the Japanese Patent Application. .
- the sintered body or polycrystalline body containing diamond is used as a material for wear-resistant tools, cutting tools and the like.
- Patent Document 1 Japanese Patent Application Laid-Open No. 2003-292397 (Patent Document 1) is a polycrystalline body composed of diamond obtained by converting and sintering a carbon material having a graphite-type layered structure under ultrahigh pressure and high temperature without adding a sintering aid or a catalyst.
- a diamond polycrystal having an average particle diameter of diamond of 100 nm or less and a purity of 99% or more is disclosed.
- a non-diamond carbon material is placed in a pressure cell equipped with a means for indirectly heating, and heating and pressurizing are performed to produce a polycrystalline diamond by direct conversion without the addition of a sintering aid or a catalyst.
- a method is disclosed.
- Patent Document 2 is a polycrystalline diamond obtained by conversion and sintering from non-diamond-type carbon without addition of a sintering aid or a catalyst under ultra-high pressure and high temperature,
- the sintered diamond particles constituting the polycrystalline diamond have an average particle size of more than 50 nm and less than 2500 nm, a purity of 99% or more, and a diamond D90 particle size of (average particle size + average particle size ⁇ 0.9) or less is disclosed.
- Patent Document 3 Japanese Patent Application Laid-Open No. 9-142933 is characterized in that a substance comprising a rare earth element oxide and / or carbonate and / or carbide is contained in an amount of 0.1 to 30% by volume, and the balance is diamond. A diamond polycrystal is disclosed.
- JP-A-2005-239472 is a high-strength, high-abrasion-resistant diamond sintered body comprising sintered diamond particles having an average particle diameter of 2 ⁇ m or less and the remaining binder phase,
- the content of sintered diamond particles in the diamond sintered body is 80% by volume or more and 98% by volume or less, and the content in the binder phase is 0.5% by mass or more and less than 50% by mass, titanium, zirconium, hafnium
- the binder phase comprises at least one element selected from the group consisting of vanadium, niobium, tantalum, chromium, and molybdenum, and cobalt whose content in the binder phase is 50 mass% or more and less than 99.5 mass%.
- a part of or all of the particles are present as carbide particles having an average particle size of 0.8 ⁇ m or less, the structure of the carbide particles is discontinuous, and adjacent sintered diamond particles are bonded to each other. ⁇ Disclose high-abrasion resistant diamond sintered bodies.
- the composite polycrystalline body of the present disclosure includes polycrystalline diamond formed by directly bonding diamond particles to each other, and compressed graphite dispersed in the polycrystalline diamond.
- FIG. 1 is a schematic cross-sectional view of a composite polycrystalline body according to an embodiment of the present invention.
- the diamond polycrystal disclosed in Japanese Patent Application Laid-Open No. 2003-292397 (Patent Document 1) and International Publication No. 2009/099130 (Patent Document 2) causes local wear when applied to a wire drawing die which is a wear-resistant tool. Pulling resistance during wire drawing increases, wire diameter after drawing decreases and wire breakage increases, and when applied to a scribe wheel or excavation bit as a cutting tool, tool life is shortened due to local wear, chipping due to impact, etc. There was a problem.
- the diamond polycrystal or sintered body disclosed in JP-A-9-142933 (Patent Document 3) and JP-A-2005-239472 (Patent Document 4) is applied to a wire drawing die which is a wear-resistant tool. Included when applied to a scribe wheel or excavation bit, which is a cutting tool, because the friction coefficient of the metal oxide and metal contained in the metal increases and the wire drawing resistance increases, the wire diameter after drawing decreases and the wire breakage increases. There is a problem that the cutting coefficient is increased because the friction coefficient is increased by the metal oxide and the metal, and the tool life is shortened due to internal fracture due to thermal expansion of the contained metal.
- the problem that the tool life is shortened is related to wear of the polycrystalline diamond or sintered body. Then, it aims at providing the composite polycrystalline body containing a polycrystalline diamond and non-diamond-like carbon with high abrasion resistance suitably used as materials, such as a wear-resistant tool and a cutting tool.
- a composite polycrystalline body including polycrystalline diamond and non-diamond-like carbon having high wear resistance which is preferably used as a material for wear-resistant tools and cutting tools. Since such a composite polycrystal has high wear resistance, the tool life can be extended in order to prevent the tool life from being shortened due to wear.
- a composite polycrystalline body according to an embodiment of the present invention includes polycrystalline diamond formed by directly bonding diamond particles to each other and compressed graphite dispersed in the polycrystalline diamond. Since the composite polycrystalline body of this embodiment includes compressed graphite dispersed in polycrystalline diamond, it has high wear resistance.
- the phase of polycrystalline diamond is three-dimensionally continuous.
- Such a composite polycrystal has higher wear resistance.
- the average particle diameter of diamond particles forming polycrystalline diamond is 10 nm or more and 1000 nm or less. Such a composite polycrystal has higher wear resistance.
- the average particle diameter of the compressed graphite is preferably 10 nm or more and 2000 nm or less. Such a composite polycrystal has higher wear resistance.
- the ratio of the compressed graphite to the entire composite polycrystal of the present embodiment is the Ig (002) area of the X-ray diffraction peak derived from the (002) plane of the compressed graphite in the X-ray diffraction profile of the composite polycrystal.
- Id (111) the area of the X-ray diffraction peak derived from the (111) plane of polycrystalline diamond is Id (111)
- the value of 100 ⁇ Ig (002) / ⁇ Id (111) + Ig (002) ⁇ is 0. It is preferably 1% or more and 40% or less.
- Such a composite polycrystal has higher wear resistance.
- the composite polycrystal of the present embodiment preferably has a Knoop hardness of 50 GPa or more. Such a composite polycrystal has higher wear resistance.
- the composite polycrystalline body of this embodiment includes polycrystalline diamond formed by directly bonding diamond particles to each other, and compressed graphite dispersed in the polycrystalline diamond, and the phase of the polycrystalline diamond is three-dimensional.
- the average particle size of diamond particles forming the polycrystalline diamond is 10 nm or more and 1000 nm or less, and the average particle size of the compressed graphite is 10 nm or more and 2000 nm or less.
- the proportion of type graphite is derived from the (111) plane of polycrystalline diamond, with the area of the X-ray diffraction peak derived from the (002) plane of compressed graphite as Ig (002) in the X-ray diffraction profile of the composite polycrystal 100 ⁇ Ig (002) / ⁇ where the area of the X-ray diffraction peak to be taken is Id (111)
- the value of d (111) + Ig (002) ⁇ is not more than 40% of 0.1%, it is preferred Knoop hardness of more than 50 GPa. Such a composite polycrystal has higher wear resistance.
- a composite polycrystalline body 10 of the present embodiment includes a polycrystalline diamond 11 formed by directly combining diamond particles with each other, and a compressed graphite 12 dispersed in the polycrystalline diamond. Including. Since the composite polycrystalline body 10 of the present embodiment includes the compressed graphite 12 dispersed in the polycrystalline diamond 11, the composite polycrystalline body 10 has high wear resistance.
- the polycrystalline diamond 11 and the compressed graphite 12 contained in the composite polycrystalline body 10 are observed by SEM (scanning electron microscope) or TEM (transmission electron microscope). In SEM observation or TEM observation, the polycrystalline diamond 11 is confirmed as a bright field, and the compressed graphite 12 is confirmed as a dark field.
- the compression-type graphite 12 contained in the composite polycrystalline body 10 has a shorter crystal plane spacing in the C-axis direction (referred to as d value) than that of normal graphite (d value is about 335 nm) (d value is smaller).
- d value crystal plane spacing in the C-axis direction
- d value is about 335 nm
- d value is smaller.
- (About 310 nm) refers to graphite, and can be identified by the position of the X-ray diffraction peak derived from the (002) plane of graphite in the X-ray diffraction profile.
- the diamond particles being directly bonded to each other means that the diamond particles are bonded so that the diamond particles are in direct contact with each other. This refers to bonding to each other without intervention. It is confirmed by SEM observation or TEM observation that the diamond particles are directly bonded to each other. Moreover, the hydrogen concentration of the composite polycrystalline body 10 is measured by SIMS (secondary ion mass spectrometry).
- the phase of the polycrystalline diamond 11 is preferably three-dimensionally continuous from the viewpoint of higher wear resistance.
- the phrase “the phase of the polycrystalline diamond 11 is three-dimensionally continuous” means that the phase of the polycrystalline diamond 11 is a continuous phase continuously present in a three-dimensional space.
- the average particle diameter of diamond particles forming the polycrystalline diamond 11 is preferably 10 nm or more and 1000 nm or less, and more preferably 100 nm or more and 800 nm or less from the viewpoint of higher wear resistance.
- the average particle size of the compressed graphite is preferably 10 nm or more and 2000 nm or less, and more preferably 30 nm or more and 1500 nm or less from the viewpoint of higher wear resistance.
- the average particle diameter of diamond particles forming the polycrystalline diamond in the composite polycrystalline body 10 and the average particle diameter of the compressed graphite mean a diameter having an area equal to the average cross-sectional area of each particle.
- the ratio of the compressed graphite 12 to the entire composite polycrystalline body 10 of the present embodiment is that the compressed graphite in the X-ray diffraction profile of the composite polycrystalline body 10 from the viewpoint of higher wear resistance of the composite polycrystalline body 10.
- the value of Ig (002) / ⁇ Id (111) + Ig (002) ⁇ is preferably 0.1% or more and 40% or less, and more preferably 0.5% or more and 35% or less.
- the X-ray diffraction profile of the composite polycrystalline body 10 is measured by a 2 ⁇ scan method using a K ⁇ ray of Cu as a radiation source.
- the composite polycrystalline body 10 of the present embodiment has a Knoop hardness of preferably 50 GPa or more, more preferably 70 GPa or more, from the viewpoint of higher wear resistance.
- the composite polycrystalline body of the present embodiment includes polycrystalline diamond formed by bonding diamond particles directly to each other and compressed graphite dispersed in the polycrystalline diamond from the viewpoint of higher wear resistance.
- the phases of the polycrystalline diamond are three-dimensionally continuous, the diamond particles forming the polycrystalline diamond have an average particle size of 10 nm to 1000 nm, and the compressed graphite has an average particle size of 10 nm to 2000 nm.
- the ratio of the compression-type graphite to the whole of the composite polycrystal is such that the area of the X-ray diffraction peak derived from the (002) plane of the compression-type graphite is Ig (002) in the X-ray diffraction profile of the composite polycrystal.
- the method for producing the composite polycrystalline body 10 of the present embodiment is not particularly limited, but non-diamond carbon is prepared as a raw material from the viewpoint of efficiently and inexpensively manufacturing the composite polycrystalline body 10 having high wear resistance. It is preferable to include a raw material preparation step for performing the composite polycrystal body forming step for forming the composite polycrystal body 10 by sintering the raw material under conditions of temperature and pressure at which the diamond phase is formed.
- the raw material non-diamond carbon prepared in the raw material preparation step may be a powder or a molded body.
- the average particle size of the powder or the average particle size of the particles forming the compact is preferably 10 nm or more, more preferably 5000 nm or less, and even more preferably 2000 nm or less.
- the raw material non-diamond carbon is not particularly limited, but is preferably graphite from the viewpoint of forming a high-quality and high-purity composite polycrystal, and the purity of graphite is preferably 99% by mass or more. More preferably 5% by mass or more.
- the sintering conditions are not particularly limited as long as the conditions of the temperature and pressure at which the diamond phase is formed, but the proportion of the compression-type phrafite phase that efficiently forms the diamond phase.
- a temperature of 1800 ° C. to 2500 ° C. and a pressure of 8 GPa to 15 GPa are preferable.
- 9 GPa is preferably 2000 ° C. or more and 2500 ° C. or less
- 12 GPa is 1900 ° C. or more and 2400 ° C. or less
- 16 GPa is 1800 ° C. or more and 2000 ° C. or less.
- the high-temperature and high-pressure generator for generating such high temperature and high pressure is not particularly limited, and examples thereof include a belt type, a cubic type, and a split sphere type.
- Examples 1 to 5 The composite polycrystals related to Examples 1 to 5 were produced by the following method. First, as a starting material, a graphite molded body having a density of 1.85 g / cm 3 and a purity of 99.95% by mass or more was prepared by baking and solidifying graphite particles having an average particle size of 300 to 3000 nm (raw material). Preparation step). Next, the graphite molded body prepared above is put in a capsule made of a refractory metal, and is held for 20 minutes at the temperature and pressure described in Table 1 (“Synthesis conditions” column) using a high-pressure generator. The graphite compact was converted into diamond and sintered (composite polycrystalline body forming step). This obtained the composite polycrystal of each Example.
- Table 1 Synthesis conditions
- Comparative Example 1 A composite polycrystal related to Comparative Example 1 was produced by the following method. First, as a starting material, a graphite molded body having a density of 1.85 g / cm 3 and a purity of 99.95% by mass formed by molding graphite particles having an average particle diameter of 300 nm was prepared (raw material preparation step). Next, the graphite molded body prepared above is put in a capsule made of a refractory metal, and is held for 20 minutes at the temperature and pressure described in Table 1 (“Synthesis conditions” column) using a high-pressure generator. The graphite compact was converted into diamond and sintered (composite polycrystalline body forming step). This obtained the composite polycrystal of each comparative example.
- a composite polycrystal related to Comparative Examples 2 and 3 was produced by the following method. First, a graphite powder having a density of 1.80 g / cm 3 and a purity of 99.5% by mass was prepared as a starting material by extruding a graphite powder finely pulverized with a planetary ball mill to an average particle size of less than 10 nm. (Raw material preparation process). Next, the graphite molded body prepared above is put in a capsule made of a refractory metal, and is held for 20 minutes at the temperature and pressure described in Table 1 (“Synthesis conditions” column) using a high-pressure generator. The graphite compact was converted into diamond and sintered (composite polycrystalline body forming step). This obtained the composite polycrystal of each comparative example.
- the non-diamond-like carbon in Examples 1 to 5 was compression-type graphite
- the non-diamond-like carbon in Comparative Example 3 was graphite
- the non-diamond-like carbon in Comparative Example 2 was amorphous carbon Was identified by the expression position and half width of the X-ray diffraction peak in the X-ray diffraction profile described later.
- diamond particles are directly bonded to each other in the polycrystalline diamond phase in the composite polycrystal, and the polycrystalline diamond phase is tertiary. It was confirmed that it was originally continuous.
- the X-ray diffraction profiles of the composite polycrystals of Examples 1 to 5 and Comparative Examples 1 to 3 were measured by a 2 ⁇ scan method using an X-ray having a K ⁇ ray of Cu as a radiation source, and compressed graphite. 12.
- the area of the X-ray diffraction peak derived from the (111) plane of the polycrystalline diamond 11 is defined as Ig (002) where the area of the X-ray diffraction peak derived from the (002) plane of non-diamond carbon of graphite or amorphous carbon
- Knoop hardness of the composite polycrystals of Examples 1 to 5 and Comparative Examples 1 to 3 was measured with a microhardness meter using a diamond Knoop type indenter at a load of 4.9 N.
- a composite polycrystal sample is processed to have a diameter ⁇ 2 mm ⁇ height 2 mm, joined to the sample holder with an active brazing material, processed into a conical shape with a tip angle of 120 °, and the tip of the cone is
- a flat sample surface having a diameter ⁇ of 0.3 ⁇ 0.005 mm serving as a test surface was formed by skiff polishing to prepare a truncated cone-shaped diamond sample piece.
- this sample piece is attached to the main spindle of the machining center as a tool, and an air cylinder is used to apply a constant load to the sample piece at an air pressure of 0.3 MPa, and an alumina (Al 2 O 3 ) sintered body plate : Several microns, purity: 99.9%).
- the size of the Al 2 O 3 sintered body plate was 100 mm ⁇ 100 mm ⁇ 0.1 mm, and the trajectory of the tool was set so that the sample piece had a spiral pattern.
- the moving speed of the tool was 5 m / min, the sliding distance was 10 km, and the sliding time was 2000 min.
- the amount of wear was calculated by measuring the spread of the tip diameter after the sliding test. The results are summarized in Table 1.
- a composite polycrystalline body including polycrystalline diamond formed by direct bonding of diamond particles and compressed graphite dispersed in polycrystalline diamond Increased wear resistance.
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Abstract
Description
特開2003-292397号公報(特許文献1)および国際公開第2009/099130号(特許文献2)に開示されるダイヤモンド多結晶体は、耐摩耗工具である伸線ダイスに適用すると、局所摩耗により伸線時の引抜抵抗が増大し伸後の線径が小さくなり断線が多くなり、切削工具であるスクライブホイールや掘削用ビットに適用すると、局所摩耗、衝撃による欠けなどにより工具寿命が短くなるという問題点があった。
[本開示の効果]
本開示によれば、耐摩耗工具、切削工具などの材料として好適に用いられる、耐摩耗性の高い、多結晶ダイヤモンドと非ダイヤモンド状炭素とを含む複合多結晶体を提供できる。かかる複合多結晶体は、耐摩耗性が高いことから、摩耗により工具寿命が短くなるのを防ぐため、工具寿命を延ばすことができる。
本発明のある実施形態である複合多結晶体は、ダイヤモンド粒子が互いに直接結合して形成される多結晶ダイヤモンドと、多結晶ダイヤモンド中に分散される圧縮型グラファイトと、を含む。本実施形態の複合多結晶体は、多結晶ダイヤモンド中に分散される圧縮型グラファイトを含むため、耐摩耗性が高い。
図1を参照して、本実施形態の複合多結晶体10は、ダイヤモンド粒子が互いに直接結合して形成される多結晶ダイヤモンド11と、多結晶ダイヤモンド中に分散される圧縮型グラファイト12と、を含む。本実施形態の複合多結晶体10は、多結晶ダイヤモンド11中に分散される圧縮型グラファイト12を含むため、耐摩耗性が高い。
本実施形態の複合多結晶体10の製造方法は、特に制限はないが、耐摩耗性の高い複合多結晶体10を効率よくかつ低コストで製造する観点から、原料として非ダイヤモンド状炭素を準備する原料準備工程と、上記原料をダイヤモンド相が形成される温度および圧力の条件で焼結することにより複合多結晶体10を形成する複合多結晶体形成工程と、を含むことが好ましい。
実施例1~5に関わる複合多結晶体を以下の方法で作製した。まず、出発物質として、平均粒径が300~3000nmのグラファイト粒子を焼き固めて型押し成形された、密度1.85g/cm3、純度99.95質量%以上のグラファイト成形体を準備した(原料準備工程)。次いで、上記で準備したグラファイト成形体を高融点金属からなるカプセルに入れ、高圧発生装置を用いて、表1(「合成条件」の欄)に記載した温度および圧力において20分間保持することにより、グラファイト成形体をダイヤモンドに変換させ、かつ焼結させた(複合多結晶体形成工程)。これにより各実施例の複合多結晶体を得た。
比較例1に関わる複合多結晶体を以下の方法で作製した。まず、出発物質として、平均粒径300nmのグラファイト粒子を型押し成形された、密度1.85g/cm3、純度99.95質量%のグラファイト成形体を準備した(原料準備工程)。次いで、上記で準備したグラファイト成形体を高融点金属からなるカプセルに入れ、高圧発生装置を用いて、表1(「合成条件」の欄)に記載した温度および圧力において20分間保持することにより、グラファイト成形体をダイヤモンドに変換させ、かつ焼結させた(複合多結晶体形成工程)。これにより各比較例の複合多結晶体を得た。
比較例2および3に関わる複合多結晶体を以下の方法で作製した。まず、出発物質として、グラファイト粉末を、遊星ボールミルで平均粒径10nm未満に微粉砕したもの型押し成形して、密度1.80g/cm3、純度99.5質量%のグラファイト成形体を準備した(原料準備工程)。次いで、上記で準備したグラファイト成形体を高融点金属からなるカプセルに入れ、高圧発生装置を用いて、表1(「合成条件」の欄)に記載した温度および圧力において20分間保持することにより、グラファイト成形体をダイヤモンドに変換させ、かつ焼結させた(複合多結晶体形成工程)。これにより各比較例の複合多結晶体を得た。
Claims (7)
- ダイヤモンド粒子が互いに直接結合して形成される多結晶ダイヤモンドと、前記多結晶ダイヤモンド中に分散される圧縮型グラファイトと、を含む複合多結晶体。
- 前記多結晶ダイヤモンドの相が三次元的に連続している請求項1に記載の複合多結晶体。
- 前記多結晶ダイヤモンドを形成する前記ダイヤモンド粒子の平均粒径が10nm以上1000nm以下である請求項1または請求項2に記載の複合多結晶体。
- 前記圧縮型グラファイトの平均粒径が10nm以上2000nm以下である請求項1から請求項3のいずれか1項に記載の複合多結晶体。
- 前記複合多結晶体の全体に対する前記圧縮型グラファイトの占める割合は、前記複合多結晶体のX線回折プロファイルにおいて前記圧縮型グラファイトの(002)面に由来するX線回折ピークの面積をIg(002)とし前記多結晶ダイヤモンドの(111)面に由来するX線回折ピークの面積をId(111)とするときの100×Ig(002)/{Id(111)+Ig(002)}の値が、0.1%以上40%以下である請求項1から請求項4のいずれか1項に記載の複合多結晶体。
- ヌープ硬度が50GPa以上である請求項1から請求項5のいずれか1項に記載の複合多結晶体。
- ダイヤモンド粒子が互いに直接結合して形成される多結晶ダイヤモンドと、前記多結晶ダイヤモンド中に分散される圧縮型グラファイトと、を含み、
前記多結晶ダイヤモンドの相が三次元的に連続しており、
前記多結晶ダイヤモンドを形成する前記ダイヤモンド粒子の平均粒径が10nm以上1000nm以下であり、
前記圧縮型グラファイトの平均粒径が10nm以上2000nm以下であり、
前記複合多結晶体の全体に対する前記圧縮型グラファイトの占める割合は、前記複合多結晶体のX線回折プロファイルにおいて前記圧縮型グラファイトの(002)面に由来するX線回折ピークの面積をIg(002)とし前記多結晶ダイヤモンドの(111)面に由来するX線回折ピークの面積をId(111)とするときの100×Ig(002)/{Id(111)+Ig(002)}の値が、0.1%以上40%以下であり、
ヌープ硬度が50GPa以上である複合多結晶体。
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JP7180052B1 (ja) * | 2021-06-11 | 2022-11-30 | 住友電工ハードメタル株式会社 | 複合多結晶体、及び複合多結晶体を備える工具 |
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