JP3064722B2 - Nitrogen-containing sintered hard alloy - Google Patents
Nitrogen-containing sintered hard alloyInfo
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- JP3064722B2 JP3064722B2 JP5018283A JP1828393A JP3064722B2 JP 3064722 B2 JP3064722 B2 JP 3064722B2 JP 5018283 A JP5018283 A JP 5018283A JP 1828393 A JP1828393 A JP 1828393A JP 3064722 B2 JP3064722 B2 JP 3064722B2
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Description
【０００１】[0001]
【産業上の利用分野】本発明は、切削加工用工具の材質
として極めて強度に富む高品質な窒素含有焼結硬質合金
に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a high quality nitrogen-containing sintered hard alloy having extremely high strength as a material for a cutting tool.
【０００２】[0002]
【従来の技術】Ｔｉを主成分とする炭窒化物などを硬質
層とし、これをＮｉとＣｏからなる金属で結合した窒素
を含有する焼結硬質合金が切削工具としてすでに実用化
されている。この窒素含有焼結硬質合金は、従来の窒素
を含有しない焼結硬質合金に比べ硬質相が著しく微粒に
なるため耐高温クリープ特性が大幅に改善されるためＷ
Ｃを主成分としたいわゆる超硬合金と並んで切削工具と
して広く使用されてきている。2. Description of the Related Art A sintered hard alloy containing nitrogen in which a carbon nitride or the like containing Ti as a main component is used as a hard layer and bonded with a metal composed of Ni and Co has already been put into practical use as a cutting tool. This nitrogen-containing sintered hard alloy has a remarkably fine hard phase compared to a conventional sintered hard alloy not containing nitrogen.
It has been widely used as a cutting tool along with a so-called cemented carbide containing C as a main component.
【０００３】しかしながら、この窒素含有焼結硬質合金
は、主成分であるＴｉの炭窒化物の熱伝導度が超硬合
金の主成分であるＷＣのそれに比べ著しく小さいことに
より、合金としての熱伝導度は約１／２である、熱膨
張係数も、同様に主成分の特性値に依存して窒素含有焼
結硬質合金のそれは超硬合金に比べ１．３倍になる、な
どの理由により熱衝撃に対する抵抗が低くなる。このた
め、特に熱衝撃の厳しくなる条件下での切削、例えばフ
ライス切削や角材の旋盤による切削加工、また、切込み
の大きく変動する湿式での倣い切削などには、充分な信
頼性をもって使用されてはいないのが現状だった。However, in this nitrogen-containing sintered hard alloy, the thermal conductivity of the carbonitride of Ti, which is the main component, is significantly smaller than that of WC, which is the main component of the cemented carbide. The degree of thermal expansion is about 1/2, and the coefficient of thermal expansion is 1.3 times higher than that of cemented carbide, which is similar to that of sintered hard alloy containing nitrogen, depending on the characteristic value of the main component. Low resistance to impact. For this reason, it is used with sufficient reliability especially for cutting under severe thermal shock conditions, such as milling and cutting of square bars with a lathe, and wet cutting where the depth of cut fluctuates greatly. There was no current situation.
【０００４】[0004]
【発明が解決しようとする問題点】発明者らは、種々の
切削における工具内での温度分布や応力分布などの切削
現象の解析と、工具内の材料成分の配置との詳細な研究
をしてきた結果、以下の知見を得た。超硬合金は熱伝導
度が高いため切削中に工具表面に発生する高熱が工具内
部を通って速やかに拡散し、このため表面が高温になり
にくく、かつ、急に切削空転したり水溶性切削油がかか
るところに急にこの高温部が露出し急冷されたとして
も、熱膨張係数が小さいことも影響し、表層部に引っ張
り応力が発生、残留しにくい。Problems to be Solved by the Invention The inventors have been conducting detailed studies on the analysis of cutting phenomena such as temperature distribution and stress distribution in a tool in various types of cutting and the arrangement of material components in the tool. As a result, the following findings were obtained. Due to the high thermal conductivity of cemented carbide, high heat generated on the tool surface during cutting is quickly diffused through the inside of the tool, so that the surface does not easily become hot, and the cutting slips suddenly or water-soluble cutting Even if the high-temperature portion is suddenly exposed to the location where the oil is applied and is rapidly cooled, the small thermal expansion coefficient also has an effect, and a tensile stress is generated on the surface layer portion and hardly remains.
【０００５】ところが、Ｔｉを主成分とする窒素含有焼
結硬質合金は、熱伝導度が低いため最も高温となる刃先
先端やすくい面の切り粉の当たる部位から熱が拡散しに
くく、表面は高温でありながら内部は急激に温度が低く
なるといった、急な温度勾配を有する状態になってい
る。従って、一度亀裂が入ってしまったら内部の温度が
低いこの合金は著しく欠損し易くなる。さらにこのよう
な材料の場合、切削油がかかり急冷されたりすると、極
表面のみ冷やされその直下は高温になったままというい
わゆる温度勾配の逆転現象が発生し、熱膨張係数が大き
いことも影響し表層部に引っ張り応力が発生し、熱亀裂
が非常に発生し易くなる状況にある。即ち、窒素含有焼
結硬質合金において、切削仕上げ面を良好にするのに必
要なＴｉを含有したままこの熱伝導度と熱膨張係数の改
善を図ることはおのずと限界があった。そこで発明者ら
は、この問題を解決するために種々の研究を行った結
果、本発明に到達した。However, since a nitrogen-containing sintered hard alloy containing Ti as a main component has a low thermal conductivity, heat hardly diffuses from a portion where the cutting edge on the surface of the cutting edge, which is the hottest, tends to reach the highest temperature, and the surface has a high temperature. However, the inside has a steep temperature gradient such that the temperature drops rapidly. Therefore, once a crack has been formed, the alloy having a low internal temperature tends to be remarkably chipped. Furthermore, in the case of such a material, when the cutting oil is applied and it is rapidly cooled, a so-called temperature gradient reversal phenomenon occurs in which only the pole surface is cooled and the area immediately below the pole is kept at a high temperature, which also has a large thermal expansion coefficient. A tensile stress is generated in the surface layer, and thermal cracks are very likely to occur. That is, in a nitrogen-containing sintered hard alloy, it is naturally limited to improve the thermal conductivity and the thermal expansion coefficient while containing Ti necessary for improving the cut surface. Therefore, the inventors have conducted various studies in order to solve this problem, and as a result, have reached the present invention.
【０００６】[0006]
【問題点を解決するための手段】即ち、本発明の窒素含
有焼結硬質合金は、工具の切削仕上げ面の性状を決定す
る極表層部分にＴｉ成分を多く配置し、その直下から特
定の距離の厚みに靱性の高いＮｉやＣｏなどの結合金属
を多く配置し刃先直下の強度を高める。このＮｉ／Ｃｏ
富化層は熱膨張係数が高いので焼結後の冷却時や切削工
具離脱時に表層部に圧縮応力を発生し得るという効果も
持つ。加えて、硬質層の必須成分であるＷを表面から内
部にかけて富化する。これは窒素含有焼結硬質合金の主
たる熱伝導媒体は結合相と考えられるが硬質相もＷを富
化させることにより特に内部での熱伝導に寄与させるの
である。この結合相富化層の内部で、結合相を減少させ
硬質相を増加させるのは、この熱伝導向上効果をより効
果的に発揮させるためである。Means for Solving the Problems That is, the nitrogen-containing sintered hard alloy of the present invention arranges a large amount of Ti component in an extremely surface layer portion which determines the properties of a cutting surface of a tool, and a specific distance from immediately below. A large number of bonding metals such as Ni and Co with high toughness are arranged in the thickness of the steel sheet to increase the strength immediately below the cutting edge. This Ni / Co
Since the enriched layer has a high coefficient of thermal expansion, it also has the effect of generating a compressive stress in the surface layer when cooling after sintering or when the cutting tool is detached. In addition, W, which is an essential component of the hard layer, is enriched from the surface to the inside. This is because the main heat conduction medium of the nitrogen-containing sintered hard alloy is considered to be the binder phase, but the hard phase also contributes to the internal heat conduction by enriching W. The reason why the binder phase is reduced and the hard phase is increased inside the binder phase-enriched layer is to more effectively exhibit the heat conduction improving effect.
【０００７】このために、該窒素含有焼結硬質合金は、
結合金属相量が表面から３μｍ以上５００μｍ以下の深
さ範囲に結合相量の最高部が存在しその値が合金平均結
合相量の１．１倍以上４倍以下で、深さ８００μｍまで
に合金全体の平均結合相量に戻り、かつ、表面部の結合
相量が結合相量最高部に対し０．９倍以下とする。深さ
８００μｍとするのは、熱伝導率の低下防止と切削時の
工具の耐塑性変形向上のためである。硬質相について
は、Ｔｉ及びこれと同様の鋼切削に対する耐摩耗性向上
効果を有するＴａ，Ｎｂ，Ｚｒを表面部に富化させ、か
わりにその効果の少ないＷ及びＭｏを減らし特に表面に
はＷをＷＣ粒子としては存在しないかまたは存在しても
０．１体積％以下であればよいことを見いだした。For this reason, the nitrogen-containing sintered hard alloy is
The highest part of the amount of the binder phase exists in the depth range of 3 μm to 500 μm from the surface where the amount of the binder metal phase is 1.1 to 4 times the average amount of the average binder phase, and the value of the alloy reaches a depth of 800 μm or less. The amount is returned to the average amount of the entire bonded phase, and the amount of the bonded phase on the surface is set to 0.9 times or less of the highest amount of the bonded phase. The depth of 800 μm is to prevent a decrease in thermal conductivity and to improve the plastic deformation resistance of the tool during cutting. As for the hard phase, Ti and Ta, Nb, and Zr, which have the same effect of improving wear resistance to steel cutting, are enriched in the surface portion. Was not present as WC particles, or even if present, it was found that the content was not more than 0.1% by volume.
【０００８】以下、本発明における制限理由などについ
て詳細に述べる。 結合相量の最高部の存在深さ範囲とその結合相量 結合相富化領域は工具強度を高めるためと、焼結後の冷
却時や切削工具離脱時に表層部に圧縮応力を発生し得る
という効果も持つために必要で、その最高部の深さが３
μｍ未満では工具としての耐摩耗性が劣り、５００μｍ
を越えると表面への圧縮応力印加の作用が十分発揮され
ない。その最高部の結合相量の平均結合相量に対する比
は１．１倍以下では所望の強度向上効果が得られず、４
倍を越えると切削時に塑性変形をするか内部が余りに硬
質になり強度が不足してしまうので好ましくない。Hereinafter, the reasons for limitation in the present invention will be described in detail. The existence depth range of the highest part of the amount of the binder phase and the amount of the binder phase The binder phase enriched region can generate compressive stress on the surface layer when cooling after sintering or when the cutting tool comes off to increase tool strength. It is necessary to have an effect, and the maximum depth is 3
If it is less than μm, the wear resistance as a tool is inferior and 500 μm
If it exceeds, the effect of applying compressive stress to the surface is not sufficiently exhibited. If the ratio of the highest binder phase amount to the average binder phase amount is 1.1 times or less, the desired strength improving effect cannot be obtained, and
Exceeding the number of times is not preferable because plastic deformation occurs during cutting or the inside becomes too hard and the strength becomes insufficient.
【０００９】表面部結合相量 表面部は耐摩耗性を有しかつ内部より熱膨張係数が小さ
くなることによる圧縮応力を受けている必要があり、従
って最高結合相量比０．９倍を越えてしまうとこれらの
所望の効果が得られない。 表面部での硬質相中のＴｉ及びＴａ，Ｎｂ，Ｚｒ量 表面は高い耐摩耗性を有する必要がありＴｉ及びこれと
同様の耐摩耗性向上効果を有するＴａ，Ｎｂ，Ｚｒを表
面部に富化させる必要があるが、合金としての平均比
１．０１倍未満では所望の耐摩耗性が得られない。特に
Ｔａ，Ｎｂは高温耐酸化性も高くし得るため好ましい。
さらにこの富化により切削仕上げ面の性状も極めて優れ
るという効果がある。 表面部での硬質相中のＷ及びＭｏ量The amount of the binder phase at the surface The surface must have abrasion resistance and undergo compressive stress due to a smaller thermal expansion coefficient than the interior, so that the maximum binder phase ratio exceeds 0.9. If they do, these desired effects cannot be obtained. Amount of Ti and Ta, Nb, and Zr in Hard Phase on Surface Surface must have high wear resistance, and Ti and Ta, Nb, and Zr, which have the same effect of improving wear resistance, are rich in the surface. However, if the average ratio of the alloy is less than 1.01, the desired wear resistance cannot be obtained. Particularly, Ta and Nb are preferable because they can also enhance high-temperature oxidation resistance.
Further, this enrichment has an effect that the properties of the cut surface are also extremely excellent. W and Mo contents in the hard phase at the surface
【００１０】硬質相中のＷおよびＭｏ量は、(ＴｉxＷy
Ｍc)および(ＴｉxＷyＭｏbＭc)で表したとき、ｙおよび
ｂで表示される。表面部には耐摩耗性に劣るＷＣおよび
またはＭｏ2Ｃを減らし、結果的に内部にかけて硬質相
中のＷおよびまたはＭｏを富化させる。この量を合金と
しての平均比０．１未満は実質的に作成が不可能であ
り、０．９を越えると耐摩耗性に劣り好ましくない。Ｍ
ｏは、硬質相中ではＷＣとほぼ同様の挙動を示す。The amounts of W and Mo in the hard phase are (Ti x W y
When expressed in M c) and (Ti x W y Mo b M c), it is displayed in y and b. The surface portion reduces WC and / or Mo 2 C, which are inferior in wear resistance, and consequently enriches W and / or Mo in the hard phase toward the inside. If the average ratio of the alloy is less than 0.1, it is practically impossible to prepare the alloy, and if it exceeds 0.9, the wear resistance is poor, which is not preferable. M
o shows almost the same behavior as WC in the hard phase.
【００１１】ここでＷＣのみについて説明する。合金の
表面から内部にかけての硬質相中のＷ富化の形態は、Ｗ
Ｃ粒子として存在しているのも良いし、複合炭窒化物固
溶体の周辺組織がＷーrich になっていても良い。また、
硬質相の存在形態としてＷ-richの固溶体が部分的に存
在し出してきたり、表面組織より多くなっていても良
く、走査型電子顕微鏡において中心が白く周辺が濃く観
察される硬質粒子（白芯粒子と呼ぶ。白いところがＴｉ
-rich部分で灰色のところがＷーrich部分）の比率が増え
ても、所望の熱伝導特性向上と強度向上の効果が得られ
る。尚、0.5＜ｘ≦0.95， 0.05＜ｙ≦0.5 の範囲とす
るのは、耐摩耗性と耐熱性を維持するためである。これ
らの範囲を逸脱すると耐摩耗性と耐熱性が低下するので
本願発明の目的が達成できない。以下、実施例にて詳し
く説明する。Here, only WC will be described. The form of W enrichment in the hard phase from the surface to the interior of the alloy is W
It may be present as C particles or the structure around the composite carbonitride solid solution may be W-rich. Also,
Hard particles (white core) whose center is white and whose periphery is densely observed in a scanning electron microscope may be a W-rich solid solution partially existing as a form of the hard phase or may be larger than the surface texture. The white area is Ti
Even if the ratio of the gray portion in the -rich portion is a W-rich portion), the desired effect of improving the heat conduction characteristics and the strength can be obtained. Note that the ranges of 0.5 <x ≦ 0.95 and 0.05 <y ≦ 0.5 are set to maintain wear resistance and heat resistance. If the content is outside these ranges, the wear resistance and heat resistance decrease, so that the object of the present invention cannot be achieved. Hereinafter, the embodiment will be described in detail.
【００１２】[0012]
（実施例１） 原料粉末として、平均粒径２μｍの（Ｔ
ｉ0.8Ｗ0.2)(Ｃ0.7Ｎ0.3）粉末を４８重量％、同１．５
μｍの（ＴａＮｂ）Ｃ粉末（ＴａＣ：ＮｂＣ＝２：１
(重量比)）を２４重量％、同４μｍのＷＣ粉末を１９重
量％、同１．５μｍのＮｉ粉末とＣｏ粉末をそれぞれ３
重量％、６重量％を湿式混合後、型押し成形し、１０-2
Torrの真空中で１２００℃で脱ガス後、窒素ガス分圧５
Torr、水素ガス分圧０．５Torrで１４００℃に昇温、一
度１０-2Torrの真空とした後再びガス雰囲気を戻し１時
間焼結した。窒素で急冷の後１３３０℃からＣＯ2を１
００Torr流しながら２℃／分で徐冷し、試料１を作成し
た。この試料の構造を第１表に示す。(Example 1) As a raw material powder, (T
i 0.8 W 0.2 ) (C 0.7 N 0.3 ) powder was 48% by weight,
μm (TaNb) C powder (TaC: NbC = 2: 1)
(Weight ratio)) was 24% by weight, the 4 μm WC powder was 19% by weight, and the 1.5 μm Ni powder and Co powder were 3% each.
Wt%, after the wet mixing 6 wt%, embossing molding, 10-2
After degassing at 1200 ° C in vacuum of Torr, nitrogen gas partial pressure 5
The temperature was raised to 1400 ° C. at a hydrogen pressure of 0.5 Torr and a partial pressure of hydrogen gas of 0.5 Torr, the pressure was once reduced to 10 −2 Torr, the gas atmosphere was returned again, and sintering was performed for 1 hour. CO 2 from 1330 ° C. After quenching with nitrogen 1
The sample was slowly cooled at 2 ° C./min while flowing at 00 Torr to prepare Sample 1. Table 1 shows the structure of this sample.
【００１３】[0013]
【表１】 [Table 1]
【００１４】比較のために、いくつかの従来の製法によ
るサンプルとして、同一の型押し成形体を窒素分圧５To
rrで１４００℃で焼結した試料２と、試料２と同一の焼
結後ＣＯ分圧２００Torrで冷却した試料３、試料２と同
一の焼結後窒素分圧１８０Torrで冷却した試料４を作成
した。これらの構造を第２表に示す。[0014] For comparison, the same embossed body was subjected to a nitrogen partial pressure of 5
Sample 2 was sintered at 1400 ° C. at rr, sample 3 was sintered at the same pressure as sample 2 and cooled at a CO partial pressure of 200 Torr, and sample 4 was sintered at the same temperature as sample 2 and cooled at a nitrogen partial pressure of 180 Torr. . Table 2 shows these structures.
【００１５】[0015]
【表２】 [Table 2]
【００１６】各試料１〜４の窒素含有焼結硬質合金を第
３表の切削条件１〜３で実施し併記した判定による結果
を第４表に示す。The nitrogen-containing sintered hard alloys of Samples 1 to 4 were subjected to cutting conditions 1 to 3 shown in Table 3 and the results of the judgments shown in Table 4 are shown in Table 4.
【００１７】[0017]
【表３】 [Table 3]
【００１８】[0018]
【表４】 [Table 4]
【００１９】（実施例２） 原料粉末として、平均粒径
２μｍの（Ｔｉ0.8Ｗ0.2)(Ｃ0.7Ｎ0.3）粉末を５１重量
％、同１．２μｍの（ＴａＮｂ）Ｃ粉末（ＴａＣ：Ｎｂ
Ｃ＝２：１(重量比)）を２７重量％、同５μｍのＷＣ粉
末を１１重量％、同１．５μｍのＮｉ粉末とＣｏ粉末を
それぞれ３重量％、８重量％を湿式混合後、型押し成形
し、１０-2Torrの真空中で１２００℃で脱ガス後、窒素
ガス分圧１０Torrで１４５０℃にて１時間焼結後、１０
-5Torrの高真空下で冷却し試料５を，ＣＯ2冷却し試料
６を作成した。比較のために同一の成形体から第５表に
示す構造の試料７，８も作成した。これらを第６表の切
削条件で評価しその結果を第７表に記した。Example 2 As raw material powder, 51 wt% of (Ti 0.8 W 0.2 ) (C 0.7 N 0.3 ) powder having an average particle size of 2 μm, and 1.2 μm of (TaNb) C powder (TaC: Nb)
C = 2: 1 (weight ratio)), 27% by weight, 11% by weight of 5 μm WC powder, 3% by weight of Ni powder and 1.5% by weight of Co powder, and 8% by weight of 8% by weight after wet mixing. After demolding at 1200 ° C. in a vacuum of 10 −2 Torr, sintering at 1450 ° C. for 1 hour at a partial pressure of nitrogen gas of 10 Torr,
Sample 5 was cooled by cooling under a high vacuum of -5 Torr, and Sample 6 was cooled by CO 2 . For comparison, samples 7 and 8 having the structure shown in Table 5 were prepared from the same molded body. These were evaluated under the cutting conditions in Table 6 and the results are shown in Table 7.
【００２０】[0020]
【表５】 [Table 5]
【００２１】[0021]
【表６】 [Table 6]
【００２２】[0022]
【表７】 [Table 7]
【００２３】（実施例３） 原料粉末として、平均粒径
２．５μｍの（Ｔｉ0.8Ｗ0.2)(Ｃ0.7Ｎ0.3）粉末を４２
重量％、同１．５μｍの（ＴａＮｂ）Ｃ粉末（ＴａＣ：
ＮｂＣ＝２：１(重量比)）を２３重量％、同４μｍのＷ
Ｃ粉末を２５重量％、同１．５μｍのＮｉ粉末とＣｏ粉
末をそれぞれ２．５重量％、６．５重量％を湿式混合
後、型押し成形し、窒素ガス分圧１５Torrで１４３０℃
にて１時間焼結後、ＣＯ2冷却し試料９を、露点−４０
℃の水素ガスで冷却し試料１０を作成した。比較のため
に同一原料粉末から第８表の結合相平均量と内部の硬質
相組成（Ｔｉ＋Ｎｂ、Ｗ）になるように配合した試料１
１〜１３も作成した。試料１４〜１９は試料９、１０と
同一の成形体を使用した比較用の別構造合金である。第
９表にこれらの切削試験の条件とその結果を併記した。Example 3 As a raw material powder, (Ti 0.8 W 0.2 ) (C 0.7 N 0.3 ) powder having an average particle diameter of 2.5 μm was used.
1.5% by weight (TaNb) C powder (TaC:
NbC = 2: 1 (weight ratio): 23% by weight, 4 μm W
25 wt% of C powder, 2.5 wt% and 6.5 wt% of Ni powder and Co powder of 1.5 μm, respectively, were wet-mixed, and then subjected to embossing, and 1430 ° C. at a nitrogen gas partial pressure of 15 Torr.
After sintering for 1 hour at room temperature, CO 2 was cooled and sample 9 was cooled to a dew point of -40.
A sample 10 was prepared by cooling with a hydrogen gas at a temperature of ° C. For comparison, Sample 1 was blended from the same raw material powder so that the average amount of the binder phase and the internal hard phase composition (Ti + Nb, W) shown in Table 8 were obtained.
1 to 13 were also prepared. Samples 14 to 19 are comparative alloys of different structures using the same compacts as Samples 9 and 10. Table 9 also shows the conditions of these cutting tests and the results.
【００２４】[0024]
【表８】 [Table 8]
【００２５】[0025]
【表９】 [Table 9]
【００２６】（実施例４） 平均粒径２μｍで、有芯構
造の外郭部分が反射電子顕微鏡像で白に、芯部分が黒に
見える（Ｔｉ0.75Ｔａ0.04Ｎｂ0.04Ｗ0.17)(Ｃ0.56Ｎ
0.44）粉末と、同１．５μｍのＮｉ粉末とＣｏ粉末をそ
れぞれ８５重量％、８重量％、７重量％を湿式混合後、
型押し成形し、１０-2Torrの真空中で１２００℃で脱ガ
ス後、窒素ガス分圧１０Torrで１４５０℃にて１時間焼
結後、ＣＯ2冷却した合金を試料２０、Ｔｉ(ＣＮ)、Ｔ
ａＣ、ＷＣ、ＮｂＣ、Ｃｏ、Ｎｉを試料２０と同一組成
となるように配合、混合し焼結した試料２１を作成し
た。比較のために試料２０と同一の成形体から第１０表
に示す構造の試料２２，２３を、試料２１と同一の成形
体から第１０表に示す構造の試料２４も作成した。第１
１表にこれらの切削テスト条件と評価結果を記した。Example 4 With a mean particle size of 2 μm, the outer part of the cored structure looks white and the core part looks black in a reflection electron microscope image (Ti 0.75 Ta 0.04 Nb 0.04 W 0.17 ) (C 0.56 N)
0.44 ) After wet mixing 85%, 8%, and 7% by weight of the powder and the same 1.5 μm Ni powder and Co powder,
After embossing, degassing at 1200 ° C. in a vacuum of 10 −2 Torr, sintering at 1450 ° C. for 1 hour at a partial pressure of nitrogen gas of 10 Torr, and CO 2 cooled alloy, sample 20, Ti (CN), T
Sample 21 was prepared by mixing, mixing, and sintering aC, WC, NbC, Co, and Ni so as to have the same composition as Sample 20. For comparison, Samples 22 and 23 having the structure shown in Table 10 were prepared from the same compact as Sample 20, and Sample 24 having the structure shown in Table 10 was prepared from the same compact as Sample 21. First
Table 1 shows these cutting test conditions and evaluation results.
【００２７】[0027]
【表１０】 [Table 10]
【００２８】[0028]
【表１１】 [Table 11]
【００２９】（実施例５） 平均粒径２μｍの（Ｔｉ
0.8Ｗ0.2)(Ｃ0.7Ｎ0.3）粉末、同１．５μｍのＴａＣ粉
末、同４μｍのＷＣ粉末、同２μｍのＺｒＣ粉末、同
１．５μｍのＮｉ粉末とＣｏ粉末を用い第１２表の平均
組成及び構造の合金を作成した。第１３表にそれぞれの
合金試料の特性を示す。Example 5 (Ti) having an average particle size of 2 μm
Average composition in Table 12 using 0.8 W 0.2 ) (C 0.7 N 0.3 ) powder, 1.5 μm TaC powder, 4 μm WC powder, 2 μm ZrC powder, 1.5 μm Ni powder and Co powder. And an alloy of the structure was made. Table 13 shows the characteristics of each alloy sample.
【００３０】[0030]
【表１２】 [Table 12]
【００３１】[0031]
【表１３】 [Table 13]
【００３２】（実施例６） 平均粒径２μｍの（Ｔｉ
0.8Ｗ0.2)(Ｃ0.7Ｎ0.3）粉末、同１．５μｍのＴａＣ粉
末、同３μｍのＮｂＣ粉末、同４μｍのＷＣ粉末、同３
μｍのＭｏ2Ｃ粉末、同１．５μｍのＮｉ粉末とＣｏ粉
末を用い第１４表の平均組成及び構造の合金を作成し
た。第１５表にそれぞれの合金試料の特性を示す。Example 6 (Ti) having an average particle size of 2 μm
0.8 W 0.2 ) (C 0.7 N 0.3 ) powder, 1.5 μm TaC powder, 3 μm NbC powder, 4 μm WC powder, 3
An alloy having an average composition and structure shown in Table 14 was prepared using Mo 2 C powder of μm, Ni powder and Co powder of 1.5 μm. Table 15 shows the characteristics of each alloy sample.
【００３３】[0033]
【表１４】 [Table 14]
【００３４】[0034]
【表１５】 [Table 15]
【００３５】[0035]
【発明の効果】上述のように本発明によれば、切削工具
として特に熱衝撃の厳しい条件での切削、例えばフライ
ス切削や角材の旋盤による切削加工、また、切込みの大
きく変動する湿式での倣い切削加工などに対し、極めて
信頼性の高い窒素含有焼結硬質合金を提供できるという
効果を有する。As described above, according to the present invention, as a cutting tool, cutting under particularly severe conditions of thermal shock, for example, milling or cutting of a square bar by a lathe, or wet copying in which the cutting depth greatly varies. This has the effect of providing a highly reliable nitrogen-containing sintered hard alloy for cutting and the like.
第１図から第４図は、実施例１における試料１〜４の表
面からの深さ方向の、組成分布を模式的に示す図であ
る。 〔図面の簡単な説明〕1 to 4 are diagrams schematically showing the composition distribution in the depth direction from the surface of samples 1 to 4 in Example 1. [Brief description of drawings]
【図１】本実施例１における試料１の表面深さの組成分
布図FIG. 1 is a composition distribution diagram of a surface depth of a sample 1 in Example 1.
【図２】本実施例１における試料２の表面深さの組成分
布図FIG. 2 is a composition distribution diagram of a surface depth of a sample 2 in Example 1.
【図３】本実施例１における試料３の表面深さの組成分
布図FIG. 3 is a composition distribution diagram of the surface depth of Sample 3 in Example 1.
【図４】本実施例１における試料４の表面深さの組成分
布図FIG. 4 is a composition distribution diagram of a surface depth of a sample 4 in the first embodiment.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 平４−120274（ＪＰ，Ａ) 特開 平５−9646（ＪＰ，Ａ) 特開 平２−131803（ＪＰ，Ａ) 特開 昭63−169356（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) C22C 29/00 - 29/16 C22C 1/05 B22F 1/00 - 7/08 ──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-4-120274 (JP, A) JP-A-5-9646 (JP, A) JP-A-2-131803 (JP, A) JP-A-63- 169356 (JP, A) (58) Fields investigated (Int. Cl. 7 , DB name) C22C 29/00-29/16 C22C 1/05 B22F 1/00-7/08
Claims (5)
れた少なくとも２種の遷移金属の炭化物、窒化物、炭窒
化物あるいはこれらの複合炭窒化物の少なくとも１種以
上からなる硬質相と、Ｎｉ及びＣｏ並びに不可避不純物
を含む結合相とからなる窒素含有焼結硬質合金におい
て、結合金属相量が表面から３μｍ以上５００μｍ以下
の深さ範囲に結合相量の最高部が存在しその値が合金平
均結合相量の１．１倍以上４倍以下で、深さ８００μｍ
までに合金全体の平均結合相量に戻り、かつ、表面部の
結合相量が結合相量最高部に対し０．９倍以下であっ
て、かつ、硬質相については、硬質相を形成する金属成
分組成を(ＴｉxＷyＭc)（但し、ＭはＴｉ，Ｗ以外の硬
質相形成遷移金属成分で，ｘ，ｙ，ｃは原子比率でｘ＋
ｙ＋ｃ＝１（0.5＜ｘ≦0.95， 0.05＜ｙ≦0.5）を満た
す）と表したとき、表面部のｘが合金平均のｘに対し
１．０１倍以上、ｙが合金平均のｙに対し０．１以上
０．９以下で、深さ８００μｍまでにそれぞれ合金全体
の平均のｘ，ｙに戻り、かつ、表面部にＷＣ粒子が存在
しないかまたは存在しても０．１体積％以下であること
を特徴とする窒素含有焼結硬質合金。1. A hard phase comprising at least one of carbides, nitrides, carbonitrides, or composite carbonitrides of at least two transition metals selected from groups 4a, 5a, and 6a of the periodic table. And a nitrogen-containing sintered hard alloy comprising Ni and Co and a binder phase containing unavoidable impurities, the highest part of the amount of the binder phase exists in a depth range from 3 μm to 500 μm from the surface where the amount of the binder metal phase is Is not less than 1.1 times and not more than 4 times the average amount of the bonded phase, and has a depth of 800 μm.
By the time, the amount of the binder phase returns to the average amount of the entire alloy, and the amount of the binder phase on the surface is 0.9 times or less of the highest amount of the binder phase. the component composition (Ti x W y M c) ( where, M is Ti, a hard phase forming transition metal component other than W, x, y, c is the atomic ratio x +
When y + c = 1 (satisfies 0.5 <x ≦ 0.95, 0.05 <y ≦ 0.5), x in the surface portion is 1.01 times or more of x in the alloy average, and y is 0 in y of the average alloy. 0.1 or more and 0.9 or less, each of which returns to the average x and y of the entire alloy by 800 μm in depth, and WC particles are absent or 0.1% by volume or less even if present on the surface. A sintered hard alloy containing nitrogen, characterized in that:
れた少なくとも２種の遷移金属の炭化物、窒化物、炭窒
化物あるいはこれらの複合炭窒化物の少なくとも１種以
上からなる硬質相と、Ｎｉ及びＣｏ並びに不可避不純物
を含む結合相とからなる窒素含有焼結硬質合金におい
て、結合金属相量が表面から３μｍ以上５００μｍ以下
の深さ範囲に結合相量の最高部が存在しその値が合金平
均結合相量の１．１倍以上４倍以下で、深さ８００μｍ
までに合金全体の平均結合相量に戻り、かつ、表面部の
結合相量が結合相量最高部に対し０．９倍以下であっ
て、かつ、硬質相については、硬質相を形成する金属成
分組成を(ＴｉxＷyＭ'bＭc)（但し、ＭはＴｉ，Ｗ，Ｔ
ａ，Ｎｂ以外の硬質相形成遷移金属成分で、Ｍ'はＴ
ａ，またはＮｂから選ばれてなり、ｘ，ｙ，ｂ，ｃは原
子比率でｘ＋ｙ＋ｂ＋ｃ＝１（0.5＜ｘ≦0.95， 0.05
＜ｙ≦0.5， 0.01＜ｂ≦0.4）を満たす）と表したと
き、表面部のｘ＋ｂが合金平均のｘ＋ｂに対し１．０１
倍以上、ｙが合金平均のｙに対し０．１以上０．９以下
で、深さ８００μｍまでにそれぞれ合金全体の平均のｘ
＋ｂ，ｙに戻り、かつ、表面部にＷＣ粒子が存在しない
かまたは存在しても０．１体積％以下であることを特徴
とする窒素含有焼結硬質合金。2. A hard phase comprising at least one of carbides, nitrides, carbonitrides or composite carbonitrides of at least two transition metals selected from groups 4a, 5a and 6a of the periodic table. And a nitrogen-containing sintered hard alloy comprising Ni and Co and a binder phase containing unavoidable impurities, the highest part of the amount of the binder phase exists in a depth range from 3 μm to 500 μm from the surface where the amount of the binder metal phase is Is not less than 1.1 times and not more than 4 times the average amount of the bonded phase, and has a depth of 800 μm.
By the time, the amount of the binder phase returns to the average amount of the entire alloy, and the amount of the binder phase on the surface is 0.9 times or less of the highest amount of the binder phase. the component composition (Ti x W y M 'b M c) ( where, M is Ti, W, T
a, Nb is a transition metal component forming a hard phase other than Nb.
a, or Nb, where x, y, b, and c are atomic ratios of x + y + b + c = 1 (0.5 <x ≦ 0.95, 0.05
<Y ≦ 0.5, 0.01 <b ≦ 0.4), the ratio of x + b on the surface to the alloy average x + b is 1.01.
X or more, y is 0.1 or more and 0.9 or less with respect to the average y of the alloy, and the average x of the entire alloy is increased up to a depth of 800 μm.
A nitrogen-containing sintered hard alloy which returns to + b, y and has no or no WC particles on its surface at 0.1% by volume or less.
れた少なくとも２種の遷移金属の炭化物、窒化物、炭窒
化物あるいはこれらの複合炭窒化物の少なくとも１種以
上からなる硬質相と、Ｎｉ及びＣｏ並びに不可避不純物
を含む結合相とからなる窒素含有焼結硬質合金におい
て、結合金属相量が表面から３μｍ以上５００μｍ以下
の深さ範囲に結合相量の最高部が存在しその値が合金平
均結合相量の１．１倍以上４倍以下で、深さ８００μｍ
までに合金全体の平均結合相量に戻り、かつ、表面部の
結合相量が結合相量最高部に対し０．９倍以下であっ
て、かつ、硬質相については、硬質相を形成する金属成
分組成を(ＴｉxＷyＴａaＮｂbＭc)（但し、ＭはＴｉ，
Ｗ，Ｔａ，Ｎｂ以外の硬質相形成遷移金属成分で、ｘ，
ｙ，ａ，ｂ，ｃは原子比率でｘ＋ｙ＋ａ＋ｂ＋ｃ＝１
（0.5＜ｘ≦0.95， 0.05＜ｙ≦0.5， 0.01＜ａ≦0.
4， 0.01＜ｂ≦0.4）を満たす）と表したとき、表面部
のｘ＋ａ＋ｂが合金平均のｘ＋ａ＋ｂに対し１．０１倍
以上、ｙが合金平均のｙに対し０．１以上０．９以下
で、深さ８００μｍまでにそれぞれ合金全体の平均のｘ
＋ａ＋ｂ，ｙに戻り、かつ、表面部にＷＣ粒子が存在し
ないかまたは存在しても０．１体積％以下であることを
特徴とする窒素含有焼結硬質合金。3. A hard phase comprising at least one of carbides, nitrides, carbonitrides, or composite carbonitrides of at least two transition metals selected from groups 4a, 5a, and 6a of the periodic table. And a nitrogen-containing sintered hard alloy comprising Ni and Co and a binder phase containing unavoidable impurities, the highest part of the amount of the binder phase exists in a depth range from 3 μm to 500 μm from the surface where the amount of the binder metal phase is Is not less than 1.1 times and not more than 4 times the average amount of the bonded phase, and has a depth of 800 μm.
By the time, the amount of the binder phase returns to the average amount of the entire alloy, and the amount of the binder phase on the surface is 0.9 times or less of the highest amount of the binder phase. the component composition (Ti x W y Ta a Nb b M c) ( where, M is Ti,
Hard phase forming transition metal components other than W, Ta, Nb, x,
y, a, b, c are atomic ratios x + y + a + b + c = 1
(0.5 <x ≦ 0.95, 0.05 <y ≦ 0.5, 0.01 <a ≦ 0.
4, 0.01 <b ≦ 0.4) when x + a + b of the surface portion is 1.01 times or more of x + a + b of the alloy average, and y is 0.1 or more and 0.9 or less of y of the alloy average. , The average x of the entire alloy up to a depth of 800 μm
+ A + b, y, and no or no WC particles are present on the surface at 0.1% by volume or less.
れた少なくとも２種の遷移金属の炭化物、窒化物、炭窒
化物あるいはこれらの複合炭窒化物の少なくとも１種以
上からなる硬質相と、Ｎｉ及びＣｏ並びに不可避不純物
を含む結合相とからなる窒素含有焼結硬質合金におい
て、結合金属相量が表面から３μｍ以上５００μｍ以下
の深さ範囲に結合相量の最高部が存在しその値が合金平
均結合相量の１．１倍以上４倍以下で、深さ８００μｍ
までに合金全体の平均結合相量に戻り、かつ、表面部の
結合相量が結合相量最高部に対し０．９倍以下であっ
て、かつ、硬質相については、硬質相を形成する金属成
分組成を(ＴｉxＷyＺｒbＭc)（但し、ＭはＴｉ，Ｗ，Ｚ
ｒ以外の硬質相形成遷移金属成分で、ｘ，ｙ，ｂ，ｃは
原子比率でｘ＋ｙ＋ｂ＋ｃ＝１（0.5＜ｘ≦0.95， 0.0
5＜ｙ≦0.5， 0.01＜ｂ≦0.4）を満たす）と表したと
き、表面部のｘ＋ｂが合金平均のｘ＋ｂに対し１．０１
倍以上、ｙが合金平均のｙに対し０．１以上０．９以下
で、深さ８００μｍまでにそれぞれ合金全体の平均のｘ
＋ｂ，ｙに戻り、かつ、表面部にＷＣ粒子が存在しない
かまたは存在しても０．１体積％以下であることを特徴
とする窒素含有焼結硬質合金。4. A hard phase comprising at least one of carbides, nitrides, carbonitrides, or composite carbonitrides of at least two transition metals selected from groups 4a, 5a, and 6a of the periodic table. And a nitrogen-containing sintered hard alloy comprising Ni and Co and a binder phase containing unavoidable impurities, the highest part of the amount of the binder phase exists in a depth range from 3 μm to 500 μm from the surface where the amount of the binder metal phase is Is not less than 1.1 times and not more than 4 times the average amount of the bonded phase, and has a depth of 800 μm.
By the time, the amount of the binder phase returns to the average amount of the entire alloy, and the amount of the binder phase on the surface is 0.9 times or less of the highest amount of the binder phase. the component composition (Ti x W y Zr b M c) ( where, M is Ti, W, Z
x, y, b, c are atomic ratios of x + y + b + c = 1 (0.5 <x ≦ 0.95, 0.0).
5 <y ≦ 0.5, 0.01 <b ≦ 0.4), the ratio of x + b on the surface to the alloy average x + b is 1.01.
X or more, y is 0.1 or more and 0.9 or less with respect to the average y of the alloy, and the average x of the entire alloy is increased up to a depth of 800 μm.
A nitrogen-containing sintered hard alloy which returns to + b, y and has no or no WC particles on its surface at 0.1% by volume or less.
れた少なくとも２種の遷移金属の炭化物、窒化物、炭窒
化物あるいはこれらの複合炭窒化物の少なくとも１種以
上からなる硬質相と、Ｎｉ及びＣｏ並びに不可避不純物
を含む結合相とからなる窒素含有焼結硬質合金におい
て、結合金属相量が表面から３μｍ以上５００μｍ以下
の深さ範囲に結合相量の最高部が存在しその値が合金平
均結合相量の１．１倍以上４倍以下で、深さ８００μｍ
までに合金全体の平均結合相量に戻り、かつ、表面部の
結合相量が結合相量最高部に対し０．９倍以下であっ
て、かつ、硬質相については、硬質相を形成する金属成
分組成を(ＴｉxＷyＭｏbＭc)（但し、ＭはＴｉ，Ｗ，Ｍ
ｏ以外の硬質相形成遷移金属成分で、ｘ，ｙ，ｂ，ｃは
原子比率でｘ＋ｙ＋ｂ＋ｃ＝１（0.5＜ｘ≦0.95， 0.0
5＜ｙ≦0.5， 0.01＜ｂ≦0.4）を満たす）と表したと
き、表面部のｘが合金平均のｘに対し１．０１倍以上、
ｙ＋ｂが合金平均のｙ＋ｂに対し０．１以上０．９以下
で、深さ８００μｍまでにそれぞれ合金全体の平均の
ｘ，ｙ＋ｂに戻り、かつ、表面部にＷＣ粒子が存在しな
いかまたは存在しても０．１体積％以下であることを特
徴とする窒素含有焼結硬質合金。5. A hard phase comprising at least one of carbides, nitrides, carbonitrides, or composite carbonitrides of at least two transition metals selected from groups 4a, 5a, and 6a of the periodic table. And a nitrogen-containing sintered hard alloy comprising Ni and Co and a binder phase containing unavoidable impurities, the highest part of the amount of the binder phase exists in a depth range from 3 μm to 500 μm from the surface where the amount of the binder metal phase is Is not less than 1.1 times and not more than 4 times the average amount of the bonded phase, and has a depth of 800 μm.
By the time, the amount of the binder phase returns to the average amount of the entire alloy, and the amount of the binder phase on the surface is 0.9 times or less of the highest amount of the binder phase. the component composition (Ti x W y Mo b M c) ( where, M is Ti, W, M
x, y, b, and c are atomic ratios of x + y + b + c = 1 (0.5 <x ≦ 0.95, 0.0).
5 <y ≦ 0.5, 0.01 <b ≦ 0.4) when the surface portion x is at least 1.01 times the alloy average x,
y + b is not less than 0.1 and not more than 0.9 with respect to the average y + b of the alloy, and returns to the average x, y + b of the whole alloy by 800 μm in depth, and WC particles do not exist or exist on the surface. Is 0.1% by volume or less.
Priority Applications (9)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5018283A JP3064722B2 (en) | 1993-02-05 | 1993-02-05 | Nitrogen-containing sintered hard alloy |
| US08/313,222 US5577424A (en) | 1993-02-05 | 1994-02-03 | Nitrogen-containing sintered hard alloy |
| DE69433214T DE69433214T2 (en) | 1993-02-05 | 1994-02-03 | Hard sintered alloy containing nitrogen |
| PCT/JP1994/000158 WO1994018351A1 (en) | 1993-02-05 | 1994-02-03 | Nitrogen-containing hard sintered alloy |
| EP98102547A EP0864661B1 (en) | 1993-02-05 | 1994-02-03 | Nitrogen-containing sintered hard alloy |
| EP94905840A EP0635580A4 (en) | 1993-02-05 | 1994-02-03 | Nitrogen-containing hard sintered alloy. |
| KR1019940703517A KR0143508B1 (en) | 1993-02-05 | 1994-02-03 | Nitrogen containing sintered hard alloy |
| TW083101466A TW291499B (en) | 1993-02-05 | 1994-02-19 | |
| KR1019940703517A KR950701006A (en) | 1993-02-05 | 1994-10-05 | NITROGEN-CONTAINING HARD SINTERED ALLOY |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5018283A JP3064722B2 (en) | 1993-02-05 | 1993-02-05 | Nitrogen-containing sintered hard alloy |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06228702A JPH06228702A (en) | 1994-08-16 |
| JP3064722B2 true JP3064722B2 (en) | 2000-07-12 |
Family
ID=11967311
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5018283A Expired - Fee Related JP3064722B2 (en) | 1993-02-05 | 1993-02-05 | Nitrogen-containing sintered hard alloy |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3064722B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6278232B2 (en) * | 2013-11-01 | 2018-02-14 | 住友電気工業株式会社 | cermet |
-
1993
- 1993-02-05 JP JP5018283A patent/JP3064722B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH06228702A (en) | 1994-08-16 |
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