JPH05850A - Composite hard ceramic particles - Google Patents
Composite hard ceramic particlesInfo
- Publication number
- JPH05850A JPH05850A JP3177536A JP17753691A JPH05850A JP H05850 A JPH05850 A JP H05850A JP 3177536 A JP3177536 A JP 3177536A JP 17753691 A JP17753691 A JP 17753691A JP H05850 A JPH05850 A JP H05850A
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- Prior art keywords
- phase
- group
- dispersed
- hard
- particles
- Prior art date
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Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は切削工具として利用され
る焼結硬質合金の硬質相原料に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a hard phase raw material for a sintered hard alloy used as a cutting tool.
【０００２】[0002]
【従来の技術】切削工具用に使われる焼結硬質合金とし
て超硬合金やサーメットが知られている。超硬合金はＷ
Ｃ、ＴｉＣ、ＴａＣ、ＮｂＣ等の硬質炭化物をＣｏ、Ｎ
ｉ等の鉄族金属で焼結した合金であり、サーメットは硬
質相の主成分をＴｉ系（ＴｉＣ、ＴｉＮ、ＴｉＣＮ）と
した合金である。2. Description of the Related Art Cemented carbide and cermet are known as sintered hard alloys used for cutting tools. Cemented carbide is W
Hard carbides such as C, TiC, TaC and NbC are replaced with Co and N
Cermet is an alloy sintered with an iron group metal such as i, and cermet is an alloy in which the main component of the hard phase is Ti-based (TiC, TiN, TiCN).
【０００３】これら焼結硬質合金の硬質相原料としては
単体のＷＣ、ＴｉＣ、ＴａＣ、ＮｂＣ、ＴｉＮ、Ｍｏ2
Ｃ等のセラミック粉末、又はこれらを予め高温で固溶処
理した複合炭化物、複合炭窒化物粉末がある。As a hard phase raw material for these sintered hard alloys, WC, TiC, TaC, NbC, TiN and Mo 2 are used as a simple substance.
There are ceramic powders such as C, and composite carbide and composite carbonitride powders obtained by subjecting these to solid solution treatment at high temperature in advance.
【０００４】[0004]
【発明が解決しようとする課題】焼結硬質合金について
最も重要なことは、耐摩耗性と靱性のバランスをとるこ
とである。一般に耐摩耗性を上げるには硬質相を増やす
ことが効果的である。しかし、硬質相となる上記セラミ
ックス粉末は靱性が低く、多すぎると断続切削等の厳し
い条件では使えなくなるという問題があった。The most important thing for sintered hard alloys is to balance wear resistance and toughness. In general, it is effective to increase the hard phase in order to improve wear resistance. However, there is a problem that the above-mentioned ceramic powder which becomes a hard phase has low toughness, and if it is too much, it cannot be used under severe conditions such as intermittent cutting.
【０００５】[0005]
【課題を解決するための手段】本発明は、上記の課題を
解決するためになされたものであって、２種以上の相を
有する複合セラミックス粒子において、第１相が１ｎｍ
以上５００ｎｍ以下の平均粒径で、平均粒径０．５μｍ
以上１０μｍ以下の第２相の基地中に少なくとも２個以
上分散した組織を有し、第１相の占める割合が体積換算
で１０％以上７０％以下、第１相と第２相の熱膨張係数
の差が５×１０-7以上で第１相の方が大きく、第１相、
第２相ともビッカース硬さで１５００以上を有する複合
硬質セラミックス粒子を提供するものである。The present invention has been made to solve the above-mentioned problems, and in a composite ceramic particle having two or more kinds of phases, the first phase is 1 nm.
0.5 μm or more in average particle diameter of 500 nm or more
It has a structure in which at least two or more are dispersed in the second-phase matrix of 10 μm or less, and the proportion of the first phase is 10% or more and 70% or less in terms of volume, and the thermal expansion coefficient of the first phase and the second phase. Difference of 5 × 10 -7 or more, the first phase is larger, the first phase,
The second phase also provides composite hard ceramic particles having a Vickers hardness of 1500 or more.
【０００６】又、前記複合硬質セラミックス粒子におい
て第１相として、ＴｉＣ、ＴｉＮ、ＴｉＣＮ、（Ｔｉ
1-u Ｍu ）（Ｃ1-v Ｎv ）（ここで前記ＭはＴｉを除く
ＩＶａ族、Ｖａ族、ＶＩａ族の元素、原子占有率は０．
０５≦ｕ≦０．３、０≦ｖ≦１）から選ばれた１種又は
２種以上を分散し、第２相として、ＷＣ、Ｍｏ2 Ｃ、Ｔ
ａＣ、ＴａＮ、ＮｂＣ、ＮｂＮ及びこれらの固溶体、
（Ｔｉ1-u ′Ｍu ′）（Ｃ1-v ′Ｎv ′）（ここで前記
ＭはＴｉを除くＩＶａ族、Ｖａ族、ＶＩａ族の元素、原
子占有率は０．３≦ｕ′≦０．９５、０≦ｖ′≦１）か
ら選ばれた１種又は２種以上を基地とすることが好まし
い。In the composite hard ceramic particles, TiC, TiN, TiCN, (Ti
1-u M u) (C 1-v N v) (IVa group excluding the M is Ti here, Va group, an element of Group VIa, atomic occupancy 0.
05 ≤ u ≤ 0.3, 0 ≤ v ≤ 1) and one or more of them are dispersed, and WC, Mo 2 C, T is used as the second phase.
aC, TaN, NbC, NbN and solid solutions thereof,
(Ti 1-u ′ M u ′) (C 1-v ′ N v ′) (where M is an element of the IVa group, Va group, or VIa group excluding Ti, and the atomic occupancy is 0.3 ≦ u ′. It is preferable to use one type or two or more types selected from ≦ 0.95 and 0 ≦ v ′ ≦ 1) as a base.
【０００７】[0007]
【作用】本発明による複合硬質セラミックス粒子ではそ
の構造からセラミックス粒子自身の靱性が大幅に向上し
ている。以下その作用について述べる。In the composite hard ceramic particles according to the present invention, the toughness of the ceramic particles themselves is significantly improved due to their structure. The operation will be described below.
【０００８】まず、大きな特徴は硬質セラミックス相が
２相以上に分離し、第２相の基地中に第１相の粒子が分
散した形態をとっている。しかもこの分散粒子は極めて
微細であるため、基地部が分散強化されている。有効な
分散強化を実現するには、第１相の分散粒子の大きさ
が、１ｎｍ以上５００ｎｍ以下であることが望ましく、
更に好ましくは、２０ｎｍ以上２００ｎｍ以下である。
粒子が小さすぎると分散強化にならず、大きすぎると分
散粒子に働く応力が無視できず靱性低下の恐れがある。First, the major feature is that the hard ceramic phase is separated into two or more phases, and the particles of the first phase are dispersed in the matrix of the second phase. Moreover, since the dispersed particles are extremely fine, the matrix portion is dispersion strengthened. In order to realize effective dispersion strengthening, the size of the dispersed particles of the first phase is preferably 1 nm or more and 500 nm or less,
More preferably, it is 20 nm or more and 200 nm or less.
If the particles are too small, the dispersion cannot be strengthened. If the particles are too large, the stress acting on the dispersed particles cannot be ignored and the toughness may decrease.
【０００９】分散する粒子の体積率は１０％以上７０％
以下で、望ましくは２０％以上５０％以下である。少な
いと強化が不十分で、多いと粒径にもよるが分散粒子自
身がつながって分散強化にならない。又、分散する粒子
は２個以上で、望ましくは１０個以上である。The volume ratio of dispersed particles is 10% or more and 70% or more.
Below, it is preferably 20% or more and 50% or less. When the amount is small, the strengthening is insufficient, and when the amount is large, the dispersed particles themselves are connected to each other depending on the particle size, but the dispersion cannot be strengthened. The number of dispersed particles is 2 or more, preferably 10 or more.
【００１０】次に両相の熱膨張係数であるが、分散粒子
（第１相）の方が大きく、基地（第２相）の方が小さ
い。その差が５×１０-7以上であり、より望ましくは１
×１０-6以上である。この熱膨張係数の差によって、冷
却時に基地側に残留圧縮応力を生じ、基地はますます強
化される。Next, regarding the thermal expansion coefficients of both phases, the dispersed particles (first phase) are larger and the matrix (second phase) is smaller. The difference is 5 × 10 −7 or more, more preferably 1
× 10 −6 or more. Due to this difference in thermal expansion coefficient, residual compressive stress is generated on the base side during cooling, and the base is further strengthened.
【００１１】このように強化された複合硬質セラミック
スの好ましい実施形態は、第１相として、ＴｉＣ、Ｔｉ
Ｎ、ＴｉＣＮ、（Ｔｉ1-u Ｍu ）（Ｃ1-v Ｎv ）（ここ
で前記ＭはＴｉを除くＩＶａ族、Ｖａ族、ＶＩａ族の元
素、原子占有率は０．０５≦ｕ≦０．３、０≦ｖ≦１）
から選ばれた１種又は２種以上のセラミックスを分散
し、第２相として、ＷＣ、Ｍｏ2 Ｃ、ＴａＣ、ＴａＮ、
ＮｂＣ、ＮｂＮ及びこれらの固溶体、（Ｔｉ1-u ′Ｍ
u ′）（Ｃ1-v ′Ｎv ′）（ここで前記ＭはＴｉを除く
ＩＶａ族、Ｖａ族、ＶＩａ族の元素、原子占有率は０．
３≦ｕ′≦０．９５、０≦ｖ′≦１）から選ばれた１種
又は２種以上のセラミックスを基地とするような複合硬
質セラミックス粒子である。A preferred embodiment of the composite hard ceramics reinforced in this way has TiC, Ti as the first phase.
N, TiCN, (Ti 1-u Mu ) (C 1-v N v ) (wherein M is an element of IVa group, Va group, VIa group excluding Ti, and atomic occupancy is 0.05 ≦ u ≦ 0.3, 0 ≦ v ≦ 1)
One or more ceramics selected from the following are dispersed, and as the second phase, WC, Mo 2 C, TaC, TaN,
NbC, NbN and their solid solutions, (Ti 1- u'M
u ′) (C 1-v ′ N v ′) (where M is an element of group IVa, Va, or VIa excluding Ti, and the atomic occupancy is 0.
The composite hard ceramic particles are based on one or more ceramics selected from 3 ≦ u ′ ≦ 0.95 and 0 ≦ v ′ ≦ 1).
【００１２】内部に分散するＴｉ系セラミックスは耐摩
耗性に優れ、被削材との反応も少ないので硬質相として
好ましい。又、外側に位置する第２相は硬質セラミック
スの中では比較的靱性に優れる。このような複合効果に
加え、熱膨張係数は内部のＴｉ系セラミックスの方が大
きいので粒子自体に残留圧縮応力が生じ、強化されるこ
とになる。The Ti-based ceramics dispersed in the inside are preferable as a hard phase because they are excellent in wear resistance and have little reaction with the work material. Further, the second phase located on the outer side is relatively excellent in toughness in the hard ceramics. In addition to such a combined effect, the thermal expansion coefficient of the internal Ti-based ceramics is larger, so that residual compressive stress is generated in the particles themselves and they are strengthened.
【００１３】内部のＴｉ系セラミックスは単体のＴｉ
Ｃ、ＴｉＮ、ＴｉＮＣ等が使えるし、複合化の過程で外
側の第２相と固溶することを考慮すると、前記のような
複合セラミックスにすることもできる。ただし、この際
前記効果を維持するためには、Ｔｉを所定量に限定する
必要があり、この制約から０．０５≦ｕ≦０．３とし
た。The Ti-based ceramics inside is Ti alone.
Considering that C, TiN, TiNC, etc. can be used and solid-dissolves with the outer second phase in the process of compounding, the compound ceramics as described above can be used. However, at this time, in order to maintain the above effect, it is necessary to limit Ti to a predetermined amount, and due to this constraint, 0.05 ≦ u ≦ 0.3.
【００１４】一方、第２相としてはＷＣ、Ｍｏ2 Ｃ、Ｔ
ａＣ、ＴａＮ、ＮｂＣ、ＮｂＮ及びこれらの固溶体が好
ましいが、同じく複合化の過程で内側の第１相と固溶す
ることを考慮すると、前記のような複合セラミックスと
することもできる。ただし、この際効果を維持するため
にはＴｉを所定量に限定する必要があり、この制約から
０．３≦ｕ′≦０．９５とした。On the other hand, as the second phase, WC, Mo 2 C, T
Although aC, TaN, NbC, NbN, and solid solutions thereof are preferable, the above-mentioned composite ceramics can be used in consideration of the fact that they also form a solid solution with the inner first phase in the process of compounding. However, in order to maintain the effect at this time, it is necessary to limit Ti to a predetermined amount, and from this constraint, 0.3 ≦ u ′ ≦ 0.95.
【００１５】又、第１相、第２相ともＶは非金属元素中
のＮの割合を表しているが、これは０から１の間の任意
の値をとりうる。しかし、硬質合金の硬質相としての利
用からは第１相で０．２５≦ｖ≦０．９５、第２相で
０．０５≦ｖ′≦０．７５程度とするのが好ましい。Further, in both the first phase and the second phase, V represents the ratio of N in the non-metal element, but it can take any value between 0 and 1. However, it is preferable to use 0.25 ≦ v ≦ 0.95 for the first phase and 0.05 ≦ v ′ ≦ 0.75 for the second phase in order to use the hard alloy as the hard phase.
【００１６】尚、組成には不可避的に混入する不純物は
含めていないが、現実に入ってくるものについてはこれ
を排するものではない。特に酸素及び粉砕時に混入する
Ｆｅ等の金属元素や他のセラミックスはどうしても避け
られないが、これらが存在するからといって、本発明の
効果に変わりはない。又、複合化により２相混合組織を
作るが、この２相は明確に区別できる場合もあるし、連
続的に組成が変化し、境界が判然としない場合もある。
両相の硬さは硬質合金の硬質相として利用するというこ
とを考慮してビッカース硬さで１５００以上とした。The composition does not include impurities that are inevitably mixed in, but those that actually enter are not excluded. In particular, oxygen and metallic elements such as Fe mixed in at the time of pulverization and other ceramics cannot be avoided, but the presence of these elements does not change the effect of the present invention. In addition, although a two-phase mixed structure is created by compounding, the two phases may be clearly distinguished in some cases, or the composition may change continuously, and the boundaries may not be clear.
The hardness of both phases was set to 1500 or more in Vickers hardness in consideration of being used as a hard phase of a hard alloy.
【００１７】[0017]
【実施例】平均粒径１００ｎｍの超微粒ＴｉＮ粉末：
９．４重量％、平均粒径３μｍのＷＯ3 粉末：７５．０
重量％、平均粒径０．１μｍの黒鉛粉末：１５．６重量
％を乾式で２４時間ボールミル混合し、造粒後、窒素雰
囲気で１７００℃にて焼成した。得られた粉末を粉砕し
て平均粒径５μｍとし、その組織を観察したところ、Ｗ
Ｃを主成分とするマトリックス（第２相）中に平均粒径
９５μｍのＴｉＮ（第１相）が均一に分散しており、そ
の占有率は３０％であった。この粒子の残留応力を測定
したところ、約３０Ｋｇ／ｍｍ2 の圧縮応力が働いてい
ることがわかった。本セラミックス粒子の概念図を図１
に示す。尚、ＴｉＮの熱膨張係数は６．３×１０-6（室
温）であり、ＷＣのそれは３．７×１０-6（室温）であ
る。又、ＴｉＮのビッカース硬さは２０５０、ＷＣのそ
れは１７８０である。EXAMPLES Ultrafine TiN powder having an average particle size of 100 nm:
WO 3 powder having 9.4% by weight and an average particle size of 3 μm: 75.0
% By weight and graphite powder having an average particle size of 0.1 μm: 15.6% by weight were dry-milled for 24 hours in a ball mill, granulated, and then fired at 1700 ° C. in a nitrogen atmosphere. The obtained powder was pulverized to an average particle size of 5 μm, and its structure was observed.
TiN (first phase) having an average particle size of 95 μm was uniformly dispersed in the matrix containing C as a main component (second phase), and its occupancy was 30%. When the residual stress of these particles was measured, it was found that a compressive stress of about 30 Kg / mm 2 was working. Figure 1 is a conceptual diagram of the ceramic particles.
Shown in. The thermal expansion coefficient of TiN is 6.3 × 10 −6 (room temperature), and that of WC is 3.7 × 10 −6 (room temperature). The Vickers hardness of TiN is 2050 and that of WC is 1780.
【００１８】[0018]
【発明の効果】以上述べてきたように、本発明によると
硬質合金の硬質相自身を強化できる。従って、同じ結合
相量でもその合金全体の靱性を高くでき、合金設計上の
自由度が大きくなる。As described above, according to the present invention, the hard phase itself of the hard alloy can be strengthened. Therefore, even if the amount of the binder phase is the same, the toughness of the entire alloy can be increased and the degree of freedom in alloy design is increased.
【図１】本発明複合硬質セラミックス粒子の概念図（断
面）である。FIG. 1 is a conceptual diagram (cross section) of a composite hard ceramic particle of the present invention.
１ 分散粒子（第１相） ２ 基地（第２相） 1 dispersed particles (first phase) 2 bases (phase 2)
フロントページの続き (51)Int.Cl.5 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｃ０４Ｂ 35/58 １０１ Ｄ 8821−4Ｇ // Ｃ２２Ｃ 29/00 7217−4Ｋ (72)発明者 野村 俊雄 兵庫県伊丹市昆陽北一丁目１番１号住友電 気工業株式会社伊丹製作所内Continuation of the front page (51) Int.Cl. 5 Identification code Internal reference number FI Technical display location C04B 35/58 101 D 8821-4G // C22C 29/00 7217-4K (72) Inventor Toshio Nomura Itami Hyogo Prefecture 1-1-1 Kunyo-Kita, Sumitomo Electric Industrial Co., Ltd.
Claims (2)
粒子において、第１相が１ｎｍ以上５００ｎｍ以下の平
均粒径で、平均粒径０．５μｍ以上１０μｍ以下の第２
相の基地中に少なくとも２個以上分散した組織を有し、
第１相の占める割合が体積換算で１０％以上７０％以
下、第１相と第２相の熱膨張係数の差が５×１０-7以上
で第１相の方が大きく、第１相、第２相ともビッカース
硬さで１５００以上を有することを特徴とする複合硬質
セラミックス粒子。1. A composite ceramic particle having two or more phases, wherein the first phase has an average particle diameter of 1 nm or more and 500 nm or less and an average particle diameter of 0.5 μm or more and 10 μm or less.
Having a structure in which at least two or more are dispersed in the phase base,
The proportion of the first phase is 10% or more and 70% or less in terms of volume, the difference between the thermal expansion coefficients of the first phase and the second phase is 5 × 10 −7 or more, and the first phase is larger, the first phase, Composite hard ceramic particles characterized in that the second phase also has a Vickers hardness of 1500 or more.
Ｎ、（Ｔｉ1-uＭu）（Ｃ1-v Ｎv ）（ここで前記ＭはＴ
ｉを除くＩＶａ族、Ｖａ族、ＶＩａ族の元素、原子占有
率は０．０５≦ｕ≦０．３、０≦ｖ≦１）から選ばれた
１種又は２種以上を分散し、第２相として、ＷＣ、Ｍｏ
2 Ｃ、ＴａＣ、ＴａＮ、ＮｂＣ、ＮｂＮ及びこれらの固
溶体、（Ｔｉ1-u ′Ｍu ′）（Ｃ1-v ′Ｎv′）（ここ
で前記ＭはＴｉを除くＩＶａ族、Ｖａ族、ＶＩａ族の元
素、原子占有率は０．３≦ｕ′≦０．９５、０≦ｖ′≦
１）から選ばれた１種又は２種以上を基地とした、請求
項１記載の複合硬質セラミックス粒子。2. The first phase of TiC, TiN, TiC
N, (Ti 1-u M u ) (C 1-v N v ) (where M is T
An element of IVa group, Va group, VIa group other than i, and atomic occupancy of 0.05 ≤ u ≤ 0.3, 0 ≤ v ≤ 1) are dispersed, or two or more of them are dispersed. As a phase, WC, Mo
2 C, TaC, TaN, NbC, NbN and solid solutions thereof, (Ti 1-u ′ M u ′) (C 1-v ′ N v ′) (where M is Ti, IVa group, Va group, VIa group element, atomic occupancy is 0.3 ≦ u ′ ≦ 0.95, 0 ≦ v ′ ≦
The composite hard ceramic particles according to claim 1, wherein one or more selected from 1) is used as a base.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP03177536A JP3143647B2 (en) | 1991-06-21 | 1991-06-21 | Composite hard ceramic particles |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP03177536A JP3143647B2 (en) | 1991-06-21 | 1991-06-21 | Composite hard ceramic particles |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH05850A true JPH05850A (en) | 1993-01-08 |
| JP3143647B2 JP3143647B2 (en) | 2001-03-07 |
Family
ID=16032656
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP03177536A Expired - Fee Related JP3143647B2 (en) | 1991-06-21 | 1991-06-21 | Composite hard ceramic particles |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3143647B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0913489A1 (en) * | 1996-12-16 | 1999-05-06 | Sumitomo Electric Industries, Limited | Cemented carbide, process for the production thereof, and cemented carbide tools |
| WO2002070762A1 (en) * | 2001-03-06 | 2002-09-12 | Kiyohito Ishida | Member having separation structure and method for manufacture thereof |
| JP2011132057A (en) * | 2009-12-24 | 2011-07-07 | Kyocera Corp | Sintered compact |
| WO2012147737A1 (en) * | 2011-04-26 | 2012-11-01 | 日本タングステン株式会社 | Tungsten carbide-based sinter and abrasion-resistant members using same |
-
1991
- 1991-06-21 JP JP03177536A patent/JP3143647B2/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0913489A1 (en) * | 1996-12-16 | 1999-05-06 | Sumitomo Electric Industries, Limited | Cemented carbide, process for the production thereof, and cemented carbide tools |
| US6299658B1 (en) | 1996-12-16 | 2001-10-09 | Sumitomo Electric Industries, Ltd. | Cemented carbide, manufacturing method thereof and cemented carbide tool |
| EP0913489A4 (en) * | 1996-12-16 | 2006-05-17 | Sumitomo Electric Industries | Cemented carbide, process for the production thereof, and cemented carbide tools |
| WO2002070762A1 (en) * | 2001-03-06 | 2002-09-12 | Kiyohito Ishida | Member having separation structure and method for manufacture thereof |
| JP2011132057A (en) * | 2009-12-24 | 2011-07-07 | Kyocera Corp | Sintered compact |
| WO2012147737A1 (en) * | 2011-04-26 | 2012-11-01 | 日本タングステン株式会社 | Tungsten carbide-based sinter and abrasion-resistant members using same |
| JP2012229138A (en) * | 2011-04-26 | 2012-11-22 | Nippon Tungsten Co Ltd | Tungsten carbide-based sintered body and abrasion resistant member using the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3143647B2 (en) | 2001-03-07 |
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