201042054 六、發明說明： 【發明所屬之技術領域】 本發明係關於一種適於切削工具之構成材料之金屬陶 瓷、及以該金屬陶瓷為基材之被覆金屬陶瓷工具。尤其， 本發明係關於一種可獲得耐缺損性優異、並且能夠進行被 切削材之加工面之品質優異之切削加工之切削工具的金屬 陶瓷。 【先前技術】 自先前以來，作為切削工具之基材材料，利用以碳化鈦 (TiC)或碳氮化鈦（Ti(c、N))為主要硬質相且藉由鈷（c〇)、 鎳（Ni)之類之鐵族元素鍵結而成之金屬陶瓷。於專利文獻】 中，揭示有以單相結構之粒子及芯部由周邊部覆蓋之有芯 結構之粒子為硬質相的金屬陶瓷。於專利文獻2、3中，揭 示有以包含芯部及覆蓋芯部之周邊部之有芯結構之粒子為 硬質相的金屬陶瓷。 先前技術文獻 專利文獻 專利文獻1 :日本專利特開平〇2_ 19043 8號公報 專利文獻2 :日本專利特開2004-292842號公報 專利文獻3 :曰本專利特開2006-13 1975號公報 【發明内容】 發明所欲解決之問題 以金屬陶瓷為基材之金屬陶瓷工具與包含以碳化鶴 (WC)為主要硬質相之超硬合金之工具相比，通常耐磨損性 147241.doc 201042054 優異 '被切削材之加工面（精加工面）漂亮，但韌性較低且 耐缺損性較差。因此，容易產生突發性缺損，工具壽命不 穩定。近年來’業界要求進—步提高切削加工中之被切削 材之加工面之品質，並且提高作為金屬陶瓷工具之弱點之 耐缺損性而使工具壽命穩定化。 於硬質相包含不具有周邊部之單相結構之粒子之先前的 金屬陶瓷中，與鍵結相之潤濕性較差且耐缺損性較差。 ，於硬負相包含有芯結構之粒子之先前的金屬陶瓷中，龜 裂容易經由芯部與周邊部之邊界而進展，由於該龜裂而導 致耐缺彳貝性下降。尤其，若芯部微細，則難以抑制龜裂之 進展，從而難以提高耐缺損性。 因此，本發明之目的之一在於提供—種金屬陶究，其係 適於耐缺損性優異、並且可進行加卫面之品f優異之切削 加工之切削工具之構成材料。又，本發明之其他目的在於 提供-種被覆金屬陶竟工具，其係包括包含上述金屬陶竞 之基材者。 解決問題之技術手段 本發明者等人獲得以下之知識見解：於金屬陶瓷中在特 疋範圍内存在硬質相、且存在組成或形態相異之四種粒子 作為構成該硬質相之粒子之情形時，具有高耐磨損性，並 且有望顯著提高耐缺損性及㈣接性。又，藉由提高财溶 接性等，Φ可提高被切削#之面α口口質。I發明係、基於上述 知識見解而規定硬質相之含量及四種硬質相。 本發明之金屬陶瓷係硬質相藉由鍵結相鍵結而成者該 147241.doc 201042054 硬質相係包含選自由週期表4、5、6族金屬之碳化物、氮 化物、碳氮化物及該等之固溶體所組成之群之丨種以上之 化合物，該鍵結相係以鐵族金屬為主成分。該金屬陶瓷含 有70質量％以上且97質量％以下之上述硬質相，剩餘部分 貫質上係由鍵結相構成。又，該金屬陶瓷包含以下之第i 硬質相、第2硬質相、第3硬質相及第4硬質相作為上述硬 質相。 〇 第1硬質相：其係硬質相，其僅由碳氮化鈦（Ti(c、N))之 單相構成，或Ti(C、N)之周圍之一部分由鈦（Ti)與選自週 期表4、5、6族金屬（其中Ti除外）之1種以上之金屬的複合 碳氮化物固溶體覆蓋。 第2硬質相：其係包含芯部及覆蓋該芯部整個周圍之周 邊部之有芯結構之硬質相。上述芯部包含Ti(c、N)，上述 周邊部包含Ti與選自週期表4、5、6族金屬（其中Ti除外）之 1種以上之金屬的複合碳氮化物固溶體。 〇 第3硬質相：其係包含芯部及覆蓋該芯部整個周圍之周 邊部之有芯結構之硬質相。上述芯部及上述周邊部包含相 同元素，並包含至少含有丁丨與界之複合碳氮化物固溶體。 又’上述芯部之w濃度大於上述周邊部之w濃度。 第4硬質相：其係單相結構之硬質相’其包含Ti與選自 週期表4、5、6族金屬（其中Ti除外種以上之金屬的複 合碳氮化物固溶體。 本發明金屬陶瓷係含有特定量之硬質相，並且作為該硬 質相而共存有上述第1硬質相、第2硬質相、第3硬質相及 147241.doc 201042054 更貝相，藉此可兼具第1硬質相〜第4硬質相之各自所發 揮之功能。具體而言，本發明金屬陶瓷係存在高硬度之硬 質相，藉此耐磨損性優異，並且存在與鍵結相之潤濕性優 ”之硬貝相，藉此可維持與鍵結相之良好之潤濕性，或者 可形成鍵結相均勻存在之組織，可有望藉由該組織之均勻 化而提高耐磨損性及耐缺損性。i ’本發明金屬陶瓷係存 在熱特性優異之硬質相，藉此可提高導熱性，亦可有望抑 制熱龜裂或提高耐熔接性。如上所述，本發明金屬陶瓷係 具有優異之耐磨損性，並且可顯著提高耐缺損性及耐熔接 性。因此，包含本發明金屬陶瓷之切削工具係難以產生磨 損或缺損，故而可實現工具壽命之穩定化或長命化，並且 難以產生溶接’藉此可獲得漂亮之加卫面，有望提高被切 削材之加工面之品質。以下，就本發明加以更詳細說明。 <金屬陶瓷> 《全體組成》 本發明金屬陶瓷包含70質量％以上且97質量％以下之硬 質相及剩餘部分，該剩餘部分包含鍵結相及不可避免之雜 質。不可避免之雜質可列舉包含於原料中或者製造步驟中 所混入之氧或ppm等級之金屬元素。 《硬質相》 [組成] 硬質相包含選自週期表4、5、6族金屬之至少1種金屬元 素與碳（C)及氮（N)之至少1種元素之化合物，亦即，包含 選自上述金屬兀素之碳化物、氮化物、碳氮化物及該等之 147241.doc 201042054 固溶體之至少1種。尤其，本發明金屬陶瓷係至少包含鈦 碳氮化物（Ti(C、N))及含有鈦（Ti)之碳氮化物固溶體之 Ti(C、N)基金屬陶瓷。若硬質相之含量超過97質量。/。，則 . 鍵結相過少，故而耐缺損性顯著下降，若未達70質量％， 則鍵結相過多，故而硬度顯著下降且耐磨損性劣化。硬質 相之含量更好的是80質量％以上且9〇質量％以下。 又’硬質相包含上述第1硬質相、第2硬質相、第3硬質 〇 相及第4硬質相之組成或形態相異之四種硬質相。具體而 言，包含Ti(C、N)系之硬質相及含有Ti之其他組成之硬質 相、及單相結構之硬質相及有芯結構之硬質相。上述四種 硬質相之存在狀態係可根據掃描型電子顯微鏡（SEM， scanning electron microsc〇pe)之顯微鏡照片之濃淡而容易 判別。 (第1硬質相） 構成第1硬質相之粒子係實質上僅由Ti(c、…構成之單 〇 相、'°構之粒子，或者Tl(C、N)之周圍之一部分由Ti與除Ti 以外之選自週期表4、5、6族金屬種以上之金屬的複合 碳氮化物固溶體覆蓋之粒子，亦即係聊、n)之周圍未由 上述複合碳氮化物固溶體完全覆蓋之粒子。第1硬質相與 下«3硬質相及第4硬質相相比而含有較多之^，藉此硬 度南，且與廣泛使用於被切削材之鋼之反應性⑯。因此， 於金屬陶竟中存在第丄硬質相，藉此尤其可達成耐磨損性 及耐炼接性之提高。 (第2硬質相） 147241.doc 201042054 構成第2硬質相之粒子係有芯結構之粒子，其怎部實質 上包含Ti(C、N)(以原子比例計，Ti(C、N)佔芯部全體之 95。/。以上），且覆蓋該芯部整個周圍之周邊部包含丁丨與除^ 以外之選自週期表4、5、6族金屬之至少丨種金屬的複合碳 氮化物固溶體。周邊部之具體組成可列舉例如：（Ti、w、201042054 VI. Description of the Invention: [Technical Field] The present invention relates to a metal ceramic suitable for a constituent material of a cutting tool, and a coated cermet tool based on the cermet. In particular, the present invention relates to a cermet that can obtain a cutting tool which is excellent in defect resistance and capable of performing cutting work having excellent quality of a machined surface of a workpiece. [Prior Art] Since the prior art, as a substrate material for a cutting tool, titanium carbide (TiC) or titanium carbonitride (Ti(c, N)) has been used as the main hard phase and cobalt (c〇), nickel A cermet in which iron-related elements such as (Ni) are bonded. In the patent document, a cermet having a single-phase structure and a core-structured core-coated particle having a core structure as a hard phase is disclosed. Patent Documents 2 and 3 disclose a cermet in which a core portion and particles having a core structure covering a peripheral portion of the core portion are hard phases. CITATION LIST Patent Literature Patent Literature 1: Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. No. Hei. No. 2004-292842. The problem to be solved by the invention is that the cermet tool based on cermet is generally superior to the tool comprising a superhard alloy having a carbonized crane (WC) as the main hard phase, and generally has an abrasion resistance of 147241.doc 201042054 The machined surface (finished surface) of the cutting material is beautiful, but the toughness is low and the defect resistance is poor. Therefore, sudden defects are easily generated and the tool life is not stable. In recent years, the industry has been demanding to improve the quality of the machined surface of the workpiece during cutting and to improve the defect resistance of the cermet tool to stabilize the tool life. In the prior cermet in which the hard phase contains particles having a single-phase structure having no peripheral portion, the wettability with the bonded phase is poor and the defect resistance is poor. In the prior cermet in which the hard-negative phase contains particles having a core structure, the crack easily progresses through the boundary between the core portion and the peripheral portion, and the crack resistance causes a decrease in the resistance to the shellfish. In particular, when the core portion is fine, it is difficult to suppress the progress of the crack, and it is difficult to improve the defect resistance. Accordingly, it is an object of the present invention to provide a metal material which is suitable for a cutting tool which is excellent in defect resistance and which can perform cutting work excellent in the surface of the garnish. Further, another object of the present invention is to provide a coated metal ceramic tool comprising a substrate comprising the above-mentioned metal Tao Jing. Means for Solving the Problems The inventors of the present invention have obtained the knowledge that in a cermet, when a hard phase exists in a characteristic range, and four kinds of particles having different compositions or forms exist as a particle constituting the hard phase, It has high wear resistance and is expected to significantly improve the defect resistance and (four) joint. Further, by improving the solubility and the like, Φ can improve the quality of the alpha port of the surface to be cut #. The Department of Inventions specifies the content of the hard phase and the four hard phases based on the above knowledge. The cermet-based hard phase of the present invention is bonded by a bonding phase. The 147241.doc 201042054 hard phase system comprises carbides, nitrides, carbonitrides selected from the metals of Groups 4, 5, and 6 of the periodic table and A compound of the above group consisting of a solid solution, the bond phase is mainly composed of an iron group metal. The cermet contains 70% by mass or more and 97% by mass or less of the above hard phase, and the remaining portion is composed of a bonded phase. Further, the cermet includes the following i-th hard phase, second hard phase, third hard phase, and fourth hard phase as the hard phase. 〇1st hard phase: it is a hard phase consisting of only a single phase of titanium carbonitride (Ti(c, N)), or a part of the periphery of Ti(C, N) is selected from titanium (Ti) and selected from A composite carbonitride solid solution of one or more metals of Group 4, 5, and 6 metals (excluding Ti) is covered. The second hard phase is a hard phase comprising a core portion and a core structure covering a peripheral portion of the entire periphery of the core portion. The core portion contains Ti (c, N), and the peripheral portion includes a composite carbonitride solid solution of Ti and one or more metals selected from Groups 4, 5, and 6 of the periodic table (excluding Ti). 〇 Third hard phase: This is a hard phase containing a core and a core structure covering the peripheral portion of the entire circumference of the core. The core portion and the peripheral portion include the same element, and include a composite carbonitride solid solution containing at least butadiene and a boundary. Further, the w concentration of the core portion is larger than the w concentration of the peripheral portion. The fourth hard phase: a hard phase of a single-phase structure comprising Ti and a composite carbonitride solid solution selected from the group consisting of metals of Groups 4, 5, and 6 of the periodic table (including metals other than Ti). The cermet of the present invention A specific amount of the hard phase is contained, and the first hard phase, the second hard phase, the third hard phase, and the 147241.doc 201042054 are further contained as the hard phase, whereby the first hard phase can be combined. Specifically, the cermet of the present invention has a hard phase having a high hardness, whereby the wear resistance is excellent, and the wettability with the bonded phase is excellent. The phase can thereby maintain good wettability with the bonding phase, or can form a structure in which the bonding phase is uniformly present, and it is expected that the wear resistance and the defect resistance can be improved by the homogenization of the structure. The cermet according to the present invention has a hard phase excellent in thermal characteristics, thereby improving thermal conductivity, and is also expected to suppress thermal cracking or improve weld resistance. As described above, the cermet of the present invention has excellent wear resistance. And can significantly improve the defect resistance Therefore, the cutting tool including the cermet of the present invention is less likely to be worn or damaged, so that the life of the tool can be stabilized or prolonged, and it is difficult to produce a fusion, thereby obtaining a beautifully reinforced surface, and it is expected The quality of the machined surface of the workpiece is improved. Hereinafter, the present invention will be described in more detail. <Metal Ceramics> <<Complete Composition>> The cermet of the present invention contains 70% by mass or more and 97% by mass or less of the hard phase and the remainder. The remaining portion contains a bonded phase and unavoidable impurities. The unavoidable impurities may be listed as oxygen or ppm metal elements contained in the raw material or in the manufacturing step. "Hard phase" [composition] Hard phase inclusion a compound of at least one metal element of a metal of Groups 4, 5, and 6 and at least one element of carbon (C) and nitrogen (N), that is, a carbide or nitride selected from the above metal halogen. At least one of a carbonitride and the above-mentioned 147241.doc 201042054 solid solution. In particular, the cermet of the present invention contains at least titanium carbonitride (Ti(C, N)) and Ti(C,N)-based cermet of titanium (Ti) carbonitride solid solution. If the content of the hard phase exceeds 97 mass%, the bonding phase is too small, so the defect resistance is remarkably lowered. When the amount is 70% by mass, the bonding phase is too large, so that the hardness is remarkably lowered and the abrasion resistance is deteriorated. The content of the hard phase is more preferably 80% by mass or more and 9% by mass or less. Further, the hard phase includes the above first hard material. The hard phase of the phase, the second hard phase, the third hard enthalpy phase, and the fourth hard phase having different compositions or forms. Specifically, the hard phase containing Ti (C, N) and other compositions containing Ti The hard phase, the hard phase of the single-phase structure, and the hard phase of the core structure. The existence of the above four hard phases is easy according to the brightness of the microscope image of the scanning electron microscope (SEM). Discrimination. (First hard phase) The particles constituting the first hard phase are substantially only composed of Ti (c, ..., a single 〇 phase, a '° structure particle), or a part of T1 (C, N) is surrounded by Ti and A composite carbonitride solid solution coated with a metal other than a metal of Groups 4, 5, and 6 of the periodic table other than Ti, that is, the surrounding of the composite carbonitride solid solution is not completely surrounded by the above-mentioned composite carbonitride solid solution. Covered particles. The first hard phase contains a larger amount than the lower hard metal phase and the fourth hard phase, whereby the hardness is south and the reactivity with the steel widely used for the workpiece is 16 . Therefore, the third hard phase exists in the metal ceramics, whereby in particular, the abrasion resistance and the resistance to refining can be improved. (Second hard phase) 147241.doc 201042054 The particles constituting the second hard phase are particles having a core structure, and the portion thereof substantially contains Ti (C, N) (Ti(C, N) accounts for the core in terms of atomic ratio 95% or more of the entire portion, and the peripheral portion covering the entire periphery of the core portion contains a composite carbonitride solid of at least a metal selected from the group consisting of metals of Groups 4, 5, and 6 of the periodic table except for Solution. Specific examples of the peripheral portion include, for example, (Ti, w,
Mo)(C、N)、（Ti、W、Nb)(C、N)、（Ti、W、M。、Nb) (C、N)、（Ti、W、Mo、Nb、Zr)(c、N)#。第 2硬質相係 與第1硬質相不同而存在遍及芯部整個周圍與鍵結相具有 良好之潤濕性之周邊部，故而可降低金屬陶瓷中產生孔穴 而實現組織之均質化，其結果，可使硬度穩定化。又，藉 由上述組織之均質化，有望進一步提高耐缺損性之類之韌 性。因此，藉由在金屬陶瓷中存在第2硬質相，尤其可使 耐磨損性及耐缺損性之效果穩定。 (第3硬質相） 構成第3硬質相之粒子係芯部及周邊部包含相同元素之 有心結構之粒子’ i包含至少含有了丨與w之複合碳氮化物 固'合體。且，該粒子之芯部之W濃度大於周邊部之W濃 度具體組成可列舉例如：（Ti、W)(C、N)、（Ti、W、 )(C N)、（Tl、w、Nb)(C、N)、（Ti、W、Mo、Nb) I N)等。第3硬質相係與第1硬質相或第2硬質相相比而 有藉此有望於維持高硬度之狀態下，提高導 熱率。因此，可蔣古勒私也 奴间熱強度、耐熱龜裂性、耐缺損性、耐 塑性變形性。 (第4硬質相） 147241.doc 201042054 構成第4硬質相之粒子係單相結構之粒子，纟包含^與 矛、Τι以外之選自週期表4、5、6族金屬之至少1種金屬的複 合碳氮化物固溶體。該粒子係與第3硬質相不同而不具有 芯部與周邊部之明確邊界，粒子全體包含均勾之組成。作 4構成第4硬質相之除加外之金屬，具代表性的是可列 舉W。 第4硬質相之具體組成可列舉例如：（^、w)(c、ν)、 (Τι W、Mo)(C、N)、（Ti、w、Nb)(C、N)、（Ti、W、 Mo Nb)(C、N)。尤其’於第4硬質相含有w之情形時， 並非如第3硬質相般W濃度有較大變化（觀察不到w之分 布），遍及第4硬質相全體均勻地存在贾。因此，藉由在金 屬陶免中存在第4硬·質相，雖然硬度少許降低，但硬度均 勻而使得龜裂難以於硬質相内進展。除此以外，有望提高 導熱率，故而可提高耐熱龜裂性及耐缺損性。 於硬質相實質上僅由第1硬質相及第2硬質相構成之情形 ◎ 時，難以提高耐缺損性。於硬質相實質上僅由第！硬質相 及第3硬質相構成之情形時，與鍵結相之潤濕性變差，故 而容易產生孔穴，耐缺損性差。於硬質相實質上僅由第i 硬質相及第4硬質相構成之情形時，與鍵結相之潤濕性亦 差，故而容易產生孔穴，無法獲得足夠之硬度，並且耐缺 損性差。 於硬質相實質上僅由第2硬質相及第3硬質相構成之情形 時，難以抑制先前以來之問題、即龜裂經由芯部與周邊部 之邊界而進展，從而無法獲得令人期待之耐缺損性。於硬 147241.doc 201042054 質相實質上僅由第2硬質相及第4硬質相構成之情形時，無 法期待耐缺損性之提高。 ·、、、 於硬質相實質上包含第1硬質相、第2硬質相及第3硬質 相且不包含第4硬質相之情形時，含有w之第3硬質相之存 在比例相對性地增加。若存在大量w，則切削中容易與2 切削材（尤其鋼）進行反應，容易產生熔接。因此，導致被 切削材之加工面劣化。亦即，除上述第丨硬質相、第2硬質 相及第3硬質相以外，還存在第4硬質相，藉此被切削材之 加工面之品質（光澤性）優異，並且可穩定保持該優異之。 質。 、口口 於更為相實貝上包含第1硬質相、第2硬質相及第4硬質 相且不包含第3硬質相之情形時，雖然有望提高導熱率、 <會引起硬度下降，從而龜裂容易進展，故而缺損產生率 ^曰冋。亦即，除上述第1硬質相、第2硬質相及第4硬質相 以外，還存在第3硬質相，藉此可進一步提高導熱率，降 低熱龜裂或該龜裂之進展，從而可有效率地提高耐缺損 性。 於硬質相實質上包含第2硬質相、第3硬質相及第4硬質 相且不包3第1硬質相之情形時，難以獲得藉由第^硬質相 之存在而提向所期待之耐磨損性及耐熔接性之效果，尤其 被切削材之加工面之光澤性較差。 於硬質相實質上包含第1硬質相、第3硬質相及第4硬質 相且不包含第2硬質相之情形時，亦即，作為金屬陶究中 之硬為相之主成分之Ti(c、N)系硬質相僅為第1硬質相之 147241.doc •10- 201042054 情形時，如上所述與鍵結相之潤濕性極端惡化而容易產生 孔穴’故而導致機械特性劣化。 本發明金屬陶瓷係除第1硬質相及第2硬質相以外，尤其 同時存在第3硬質相與第4硬質相，藉此既可維持熱強度， 又可抑制與鋼產生反應。因此，以本發明金屬陶瓷為基材 之切削工具將有望提高對熱塑性變形之耐性、耐熱龜裂性 及耐熔接性，故而期待可提高被切削材之加工面之性狀。 [粒徑] 〇 硬質相較好的是混有粗大粒子與微細粒子，尤其混有粒 徑為1 μηι以下之微粒與粒徑超過丨μιη且為3 μιηα下之粗 粒。更好的是相對於硬質相之總面積而為6〇%以上且9〇% 以下之硬質相係包含上述粗粒，硬質相之剩餘部分係包含 上述微粒。又，較好的是上述粗粒係包含上述第丨硬質 相、第2硬質相、第3硬質相及第4硬質相，上述微粒係實 邊上包含第1硬質相及第2硬質相。 〇 於如此之混粒組織中，以填埋形成於粗大粒子間之間隙 之方式存在微細粒子，藉此可實現硬度之提高或破壞韌性 之提尚。粗大粒子之粒徑超過丨μιη且微細粒子之粒徑為i μπι以下，藉此於粗大粒子之間設置有足夠之間隙，可使 微細粒子介在於該間隙中，故而可獲得提高上述硬度或破 壞韌性之效果。又，粗大粒子之粒徑為3 μπι以下，藉此存 在於粒子之間之鍵結相不會過剩，從而可降低因較大之鍵 結相池之存在所造成之硬度之下降或破壞韌性之劣化。微 細粒子之粒徑尤其好的是〇 1 pm以上且〇 8 μιη以下。 147241.doc 201042054 又，上述粗粒之面積率為60%以上，藉此適當地存在粗 粒，故而抑制龜裂進展之效果較大，可提高韌性。又，上 述粗粒之面積率為90%以下’藉此於形成於粗大粒子之間 之間隙内存在充足之微細粒子，從而可抑制硬度之提高或 龜裂之進展。進而’ ϋ由適當地存在微細粒子，可減小金 屬陶竟之最表面之表面粗輪度，從而可獲得優異之切削性 能。上述粗粒之面積率之範圍更好的是7〇%以上且85%以 下。進而，相對於微細粒子之總面積為8〇%以上、較好的 疋90/❶以上、更好的是大致全部包含第丄硬質相及第2硬質❹ 相，藉此存在充足之高硬度且微細之Ti(c、N)，從而可提 高耐磨損性。本發明中規定之粒徑、面積及面積率之計算 方法將於下文47進行敍述。 硬質相粒子之粒徑及面積率之調整係可藉由調整例如原 料粉末之大小或添加量、製造條件（粉碎時間或煅燒條件 等）而進行。若延長粉碎時間，則存在金屬陶瓷中之硬質 相粒子變微細之傾向，若煅燒溫度高，則存在金屬陶瓷中 之硬質相粒子變粗大之傾向。又，即便延長粉碎時間而使 〇 粉末變微細，若提高煅燒溫度，則亦存在如下情形，即， 粒子成長而存在粗大之硬質相粒子。 相對於硬質相之總面積，將粒徑超過1 μιη且為3 μιη以下 (粗粒）之第1硬質相之面積率設為S1，並將粒徑超過1 μιη · 且為3 μιη以下（粗粒）之第2硬質相之面積率設為S2時， (S1 + S2)較好的是滿足0.1以上且ο·5以下。若（S1+S2)為0.1Mo) (C, N), (Ti, W, Nb) (C, N), (Ti, W, M, Nb) (C, N), (Ti, W, Mo, Nb, Zr) (c , N)#. The second hard phase is different from the first hard phase, and has a peripheral portion having good wettability with the bonding phase over the entire periphery of the core. Therefore, it is possible to reduce the generation of voids in the cermet and achieve homogenization of the structure. As a result, The hardness can be stabilized. Moreover, with the homogenization of the above organizations, it is expected to further improve the toughness such as defect tolerance. Therefore, by the presence of the second hard phase in the cermet, the effect of abrasion resistance and defect resistance can be stabilized. (3rd hard phase) The particle core portion and the peripheral portion of the particle-shaped core portion and the peripheral portion constituting the third hard phase include a composite carbonitride solid-solid body containing at least yttrium and w. Further, the W concentration of the core portion of the particle is larger than the W concentration of the peripheral portion, and examples thereof include (Ti, W) (C, N), (Ti, W, ) (CN), (Tl, w, Nb). (C, N), (Ti, W, Mo, Nb) IN) and the like. The third hard phase system is more likely to have a higher heat resistance than the first hard phase or the second hard phase. Therefore, Jiang Gul's private slaves also have thermal strength, heat crack resistance, defect resistance, and plastic deformation resistance. (4th hard phase) 147241.doc 201042054 The particles constituting the fourth hard phase are particles of a single-phase structure, and the ruthenium contains at least one metal selected from the group consisting of metals of Groups 4, 5, and 6 of the periodic table other than spear and Τι. Composite carbonitride solid solution. This particle system is different from the third hard phase and does not have a clear boundary between the core portion and the peripheral portion, and the entire particle contains a uniform composition. The metal which constitutes the fourth hard phase except for the addition is representative W. Specific examples of the fourth hard phase include (^, w) (c, ν), (Τι W, Mo) (C, N), (Ti, w, Nb) (C, N), (Ti, W, Mo Nb) (C, N). In particular, when the fourth hard phase contains w, the W concentration does not largely change as in the third hard phase (the distribution of w is not observed), and Jia is uniformly present throughout the fourth hard phase. Therefore, by the presence of the fourth hard phase in the metal pottery, although the hardness is slightly lowered, the hardness is uniform and the crack is difficult to progress in the hard phase. In addition to this, it is expected to improve the thermal conductivity, so that the heat crack resistance and the defect resistance can be improved. In the case where the hard phase consists essentially only of the first hard phase and the second hard phase ◎, it is difficult to improve the defect resistance. In the hard phase is essentially only by the first! In the case where the hard phase and the third hard phase are formed, the wettability with the bonded phase is deteriorated, so that voids are likely to occur and the defect resistance is poor. When the hard phase consists essentially of only the i-th hard phase and the fourth hard phase, the wettability with the bonded phase is also poor, so that voids are likely to occur, sufficient hardness cannot be obtained, and defect resistance is poor. When the hard phase is substantially composed of only the second hard phase and the third hard phase, it is difficult to suppress the problem that the crack has progressed through the boundary between the core portion and the peripheral portion, and the desired resistance cannot be obtained. Defective. In the case where the quality phase consists essentially only of the second hard phase and the fourth hard phase, it is not expected to improve the defect resistance. When the hard phase substantially includes the first hard phase, the second hard phase, and the third hard phase and does not include the fourth hard phase, the ratio of the third hard phase containing w relatively increases. If a large amount of w is present, it is easy to react with 2 cutting materials (especially steel) during cutting, and welding is likely to occur. Therefore, the processed surface of the workpiece is deteriorated. In other words, in addition to the above-described second hard phase, the second hard phase, and the third hard phase, the fourth hard phase is present, whereby the quality of the processed surface of the workpiece (glossiness) is excellent, and the excellent quality can be stably maintained. It. quality. In the case where the mouth contains the first hard phase, the second hard phase, and the fourth hard phase, and does not include the third hard phase, the thermal conductivity may be increased, and the hardness may be lowered. Cracks are easy to progress, so the rate of defect production is ^曰冋. In other words, in addition to the first hard phase, the second hard phase, and the fourth hard phase, the third hard phase is present, whereby the thermal conductivity can be further improved, and the thermal cracking or the progress of the crack can be reduced. Improve defect resistance efficiently. When the hard phase substantially includes the second hard phase, the third hard phase, and the fourth hard phase, and the third hard phase is not included, it is difficult to obtain the desired wear resistance by the presence of the second hard phase. The effect of damage and weld resistance, especially the gloss of the machined surface of the workpiece is poor. When the hard phase substantially includes the first hard phase, the third hard phase, and the fourth hard phase, and does not include the second hard phase, that is, Ti (c) which is a hard component of the metal ceramics. In the case where the hard phase is only the first hard phase, 147241.doc •10-201042054 In the case where the wettability with the bonded phase is extremely deteriorated as described above, the pores are easily generated, and the mechanical properties are deteriorated. In the cermet according to the present invention, in addition to the first hard phase and the second hard phase, in particular, the third hard phase and the fourth hard phase are present, whereby the heat strength can be maintained and the reaction with steel can be suppressed. Therefore, the cutting tool having the cermet as the base material of the present invention is expected to have improved resistance to thermoplastic deformation, heat crack resistance and weld resistance, and therefore it is expected to improve the properties of the machined surface of the workpiece. [Particle size] 〇 The hard phase is preferably a mixture of coarse particles and fine particles, in particular, fine particles having a particle diameter of 1 μm or less and coarse particles having a particle diameter of more than 丨μηη and 3 μηηα. More preferably, the hard phase of 6 % by mass or more and 9% by mass or less based on the total area of the hard phase contains the above coarse particles, and the remainder of the hard phase contains the fine particles. Further, it is preferable that the coarse particles include the first hard phase, the second hard phase, the third hard phase, and the fourth hard phase, and the first hard phase and the second hard phase are included on the solid side. In such a mixed structure, fine particles are present in such a manner that a gap is formed between the coarse particles by landfill, whereby improvement in hardness or deterioration of toughness can be achieved. When the particle size of the coarse particles exceeds 丨μιη and the particle diameter of the fine particles is i μπι or less, a sufficient gap is provided between the coarse particles, so that the fine particles can be interposed in the gap, so that the hardness or the damage can be improved. The effect of resilience. Further, the particle size of the coarse particles is 3 μm or less, whereby the bonding phase existing between the particles is not excessive, thereby reducing the decrease in hardness or the deterioration of the fracture toughness due to the presence of a large bonded phase cell. . The particle size of the fine particles is particularly preferably 〇 1 pm or more and 〇 8 μηη or less. Further, since the area ratio of the coarse particles is 60% or more, the coarse particles are appropriately formed, so that the effect of suppressing the progress of the crack is large, and the toughness can be improved. Further, the area ratio of the coarse particles is 90% or less. Thus, sufficient fine particles are present in the gap formed between the coarse particles, whereby the improvement in hardness or the progress of cracking can be suppressed. Further, by appropriately presenting fine particles, the surface roughness of the outermost surface of the metal ceramic can be reduced, and excellent cutting performance can be obtained. The range of the area ratio of the above coarse particles is more preferably 7% by weight or more and 85% or less. Further, the total area of the fine particles is 8 % by mass or more, preferably 疋 90 / ❶ or more, and more preferably substantially all of the second hard phase and the second hard ❹ phase, whereby there is sufficient high hardness and Fine Ti (c, N), which can improve wear resistance. The method of calculating the particle size, area and area ratio specified in the present invention will be described in 47 below. The adjustment of the particle size and the area ratio of the hard phase particles can be carried out by adjusting, for example, the size or amount of the raw material powder, the production conditions (pulverization time, calcination conditions, etc.). When the pulverization time is prolonged, the hard phase particles in the cermet tend to be fine, and if the calcination temperature is high, the hard phase particles in the cermet tend to become coarse. Further, even if the pulverization time is prolonged and the cerium powder is made fine, if the firing temperature is increased, there is a case where the particles grow and coarse solid phase particles are present. With respect to the total area of the hard phase, the area ratio of the first hard phase having a particle diameter of more than 1 μm and being 3 μm or less (coarse grain) is S1, and the particle diameter is more than 1 μm· and is 3 μm or less (thickness). When the area ratio of the second hard phase of the particles is S2, (S1 + S2) preferably satisfies 0.1 or more and ο. 5 or less. If (S1+S2) is 0.1
I 上’則難以與被切削材熔接，降低於被切削材之表面上 147241.doc 12. 201042054 產生微小之缺損，可提高被切削材之加工面之性狀，除此 以外，藉由耐熔接性之提高而降低熔接所造成之磨損，可 提高工具之耐磨損性。又，藉由使（81+82)為〇 5以下，可 抑制高硬度化所造成之韌性之下降，從而難以引起缺口或 碎屑。（S1 + S2)之範圍更好的是〇·3以上且〇_5以下。 又，將粒徑超過1 μπι且為3 μηι以下（粗粒）之第3硬質相 之面積率設為S3，並將粒徑超過1 μπι且為3 μιη以下（粗粒） 之第4硬質相之面積率設為84時，若S1/(S1 + S2)滿足〇」以 上且0.4以下及S3/(S3 + S4)滿足0_4以上且0.9以下，則可進 一步兼顧耐磨損性與耐缺損性，並且可進一步提高被切削 材之表面光澤。此時，S1/(S1 + S2)之範圍更好的是〇.3以上 且0.4以下’ S3/(S3 + S4)之範圍更好的是0.7以上且0.9以 下。 將粒徑為1 μηι以下（微粒）之第1硬質相之面積設為SS1， 並將粒徑為1 μιη以下（微粒）之第2硬質相之面積設為SS2 時，SS1/(SS1+SS2)較好的是〇.5以上且0.9以下。若SS1/ (SS1 + SS2)為0.5以上，則與第2硬質相相比，存在較多之 微小的第1硬質相，藉此有望顯著提高耐磨損性。又，若 SS1/(SS1+SS2)為0.9以下，則於微細硬質相中第1硬質相所 佔之比例不會過剩，可抑制因微細之第1硬質相之過剩存 在所造成之潤濕性之下降、及伴隨該潤濕性之下降之微小 孔穴之產生而引起硬度劣化的可能性。SS1/(SS1 + SS2)之 範圍更好的是0.55以上且0.7以下。 相對於金屬陶瓷之總面積（硬質相+鍵結相）’第3硬質相 147241.doc -13- 201042054 面積與第4硬質相之面積《總計面積率較好的是大於 。於該清形時，熱特性穩定，故而可提高对熱龜裂 性’進而可提高耐缺損性。尤其，該等第3硬質相及第4硬 質相較好的是如上所述大體上為粗粒。 《鍵結相》 鍵、，。相係以選自鈷、鐵、鎳⑺丨）之類之鐵族金 屬之至少1種金屬為主成分。所謂「主成分」，係指鍵結相 實貝上僅由選自上述鐵族金屬中之i種以上之金屬構成之 情形，或者於選自上述鐵族金屬令之i種以上之金屬中以 相對於鍵結相之總質量為G.lf量％以上錢質量％以下固 溶有上述硬質相之構成元素而成的合金，亦即鍵結相之⑼ 質量％以上包含鐵族金屬之情形。於鍵結相固溶有硬質相 之構成元素之情形時’存在如下傾向，即藉由固溶強化 而可提高㈣’從而可提高㈣損性。又，若鍵結相之主 成分（鍵結相之總質量之80質量％以上）為〇〇及州之至少一 者，則與硬質相之潤濕性高，並且耐腐錄優異，故而成 為更適於切削工具之構成材料之金屬陶瓷。 於鍵結相中包含Ni及C。之雙方之情料，尤其將鍵結相 中之N々C。之存在質量比（Nif量相對於㈣量之比）設為 Ni/C〇時，Ni/Co較好的是〇.7以上幻5以下。職〇滿足 0.7以上且Μ以下，藉此可降低潤濕性之下降而維持高動 性，並且可降低硬度之下降而維持高強度。Ni/Co尤直好 的是0.8以上且L2以下。Ni/Co之調整係可藉由調整例如原 料中使用之Co粉末或Ni粉末之添加量而進行。 147241.doc -14- 201042054 [其他含有元素] 本發明金屬陶兗亦可含有顧（Mo)。於含有m〇之情形 時，尤其存在容易形成第2硬質相之傾向。因此，可提^ ⑨質相與鍵結相之潤濕性，故而鍵結相可充分存在於構: 硬質相之粒子周圍，可提高動性。M。含量較好的是0.01質 里％以上且2.0質量％以下。若胸含量為〇 〇1質量％以上， 則如上所述作為金屬陶瓷全體提高潤濕性，可提高硬度或 0 韌性，藉由設為2·0質量％以下’可抑制難以形成第1硬質 相而第2硬質相、第3硬質相相對性地增多之情形。因此， 可抑制先前以來之問題、即龜裂經由硬質相之芯部與周邊 部之邊界而進展，從而可獲得令人期待之耐缺損性。 含量更好的是0.5質量％以上且^質量％以下。亦可不含有 Mo 〇 <金屬陶瓷工具> 《基材》 ◎ 具有上述構成之本發明金屬陶瓷係如上所述包括四種硬 質相，藉此不僅耐磨損性優異，耐缺損性及耐熔接性亦優 異，故而可較佳用於期望良好之精加工面之切削工具（金 屬陶瓷工具）之基材材料。 《硬質膜》 上述基材亦可包含至少被覆於其表面之一部分之硬質 膜。硬質膜較好的是至少包含於刀尖及其附近，亦可遍及 整個基材表面而包含該硬質膜。硬質膜可為丨層亦可為多 層，總計厚度較好的是卜20 μηι ^硬質膜之形成方法亦可 147241.doc •15- 201042054 利用熱CVD(ChemicaI Vapor Deposition，化學氣相沈積）法 之化學蒸鍍法（CVD法）、電弧離子電鍍法之物理蒸鍍法 (PVD(Physical Vapor Deposition，物理氣相沈積）法）之任 一者。 硬質膜之組成可列舉選自由如下化合物、立方晶氮化硼 (cBN，cubic boron nitride)、鑽石及類鑽石碳（DLC， diamond-like carbon)所組成之群中之丨種以上，該化合物 係選自由週期表4、5、6族金屬 '鋁（A1)及矽（si)所組成之 群中之1種以上之元素、與選自由碳（c)、氮（N)'氧（〇)及 硼（B)所組成之群中之丨種以上之元素的化合物，亦即包含 上述金屬等元素之碳化物、氮化物、氧化物、硼化物及該 等之固溶體之化合物。具體之膜質可列舉：Ti(c、n)、 ai2o3、（Ti、A1)N、TiN、Tic、⑷、Cr)N 等。 <金屬陶瓷之製造方法> 金屬陶瓷係通常藉由原料之準備_原料之粉碎及混合-成 形-煅燒之步驟而製造。本發明金屬陶瓷係可藉由使用下 述原料粉末且調整粉碎及混合時間或煅燒條件而製造。 《原料之準備》 席料使用包含選 屬、與碳(C)及氮(Ν)之至少i種元素之化合物的化合物 末及構成鍵結相之粉末，具代表性的是鐵族金屬粉末 藉由使用微細粉末與相對粗大之粉末作為該等粉末，可 易獲得如上所述之具有混合著粗粒與微粒之硬質相之金 陶免。粉末之大小係考慮硬質相之粒子大小而適當地選 14724l.doc 16 201042054 即可。 為生成第1硬質相及第2硬質相，例如使 Ο 末。就Ti(C、N)粉末而言，先前有生成海韓Ti作為起始材 料者，但尤其若使用生成有Ti〇2作為起始材料之聊、N) 粉末’則存在容易形成微粒之第i硬質相之傾向。又，如 上所述若一併使用含有Mo之化合物粉末，則存在容易形 成第2硬質相之傾向。為生成第3硬質相而使用含有W之粉 末，例如wc粉末。為生成第4硬質相而使用含有Ti與除ή 以外之週期表4、5、6族金屬之化合物粉末，例如使用 (L、W)(C、N)粉末。藉由使用此種化合物粉末，可容易 獲仔第4硬質相之粒子’亦即，可容易獲得均勾地固溶有 Ή與除Τί以外之週期表4、5、6族金屬之單相結構之粒 子0 《粉碎及混合》 ^延長粉碎時間，料❹末變得微細，存在金屬陶竟 〇 中谷易生成微細之硬質相粒子之傾向。但若粉碎時間過 長，則存在再凝聚或者變得過於微細而難以形成成為核之 化合物之顧慮。粉碎及混合時間較好的是12小時以上且％ 小時以下。 《煅燒》 若過度提高級燒溫度，則存在如下顧慮，即，構成硬質 /粒子成長而於金屬陶瓷中容易存在較多之粗大粒子， 5尤y、難以形成第4硬質相之粒子。因此，烺燒溫度較 好的是140(TC以上且16〇〇t：以下。又於锻燒步驟中於 H7241.doc •17- 201042054 將以規定時間保持煅燒溫度來進行加熱之成形體進行冷卻 時，較好的是於真空或氬（Ar)之惰性氣體環境中進行冷 卻。於為惰性氣體環境之情形時，尤其好的是設為665 pa 以上且6650 Pa以下之相對低壓。又，若加快冷卻速度， 具體而言設為1〇。〇/min以上，則存在容易生成第4硬質相 之傾向。 發明之效果 本發明被覆金屬陶瓷工具之耐磨損性及耐缺損性優異， 而且可進行被切削材之加工面之品質優異之切削加工。本 發明金屬陶瓷可較佳地用於此種工具之構成材料。 【實施方式】 <測試例> 製作包含金屬陶竟之切削工具，並對金屬陶竟之組成、 組織及切削工具之切削性能進行調查。 切削工具係以如下方式劍你 r万式I作。百先，作為原料粉末而準 備以下者。 (1) 平均粒徑為0.7 μιη之粉末 該Ti(C、N)粉末係生成有Ti〇2作為起始原料之粉末， C/N 比為 1/1。 (2) 平均粒徑為 〇·8 Tirr .. . „ μηι之i1(C、Ν)粉末及平均粒徑為3.0 μπι之 Ti(C、Ν)粉末 。亥等Ti(C N)&末之任—者均係生成有海綿了丨作為起始 原料之⑧末’ C/Ν比為。於表丨中，將該等哪、ν)粉 末記作「s-TiCN」。 巧 147241.doc -18· 201042054 (3) 平均粒徑為2 8 μπι之（Ti、W)(C、Ν)粉末 該（Τι、W)(C、Ν)粉末係預先使w固溶於Ti(C、Ν)粉末 中之粉末，C/N比為m。 (4) 平均粒徑為〇 5〜3〇 _之\\7(：粉末、NbC粉末、TaC粉 末M〇2C粉末、州粉末、c〇粉末 該等粉末之任一者均係市售之粉末。 以達到表1所示之調配比例（質量％)之方式秤取.調配所 ΟI is difficult to weld to the material to be cut, and it is lowered on the surface of the workpiece. 147241.doc 12. 201042054 A slight defect is generated, which improves the properties of the machined surface of the workpiece, and is resistant to fusion. The improvement and the reduction of the wear caused by the welding can improve the wear resistance of the tool. Further, by setting (81 + 82) to 〇 5 or less, it is possible to suppress a decrease in the toughness due to the increase in hardness, and it is difficult to cause a chipping or chipping. The range of (S1 + S2) is more preferably 〇·3 or more and 〇_5 or less. Further, the area ratio of the third hard phase having a particle diameter of more than 1 μm and being 3 μm or less (coarse grains) is S3, and the fourth hard phase having a particle diameter of more than 1 μm and being 3 μm or less (coarse grain) is used. When the area ratio is 84, when S1/(S1 + S2) satisfies 〇" or more and 0.4 or less and S3/(S3 + S4) satisfies 0_4 or more and 0.9 or less, wear resistance and defect resistance can be further achieved. And can further improve the surface gloss of the workpiece. In this case, the range of S1/(S1 + S2) is more preferably 〇.3 or more and 0.4 or less. The range of S3/(S3 + S4) is more preferably 0.7 or more and 0.9 or less. When the area of the first hard phase having a particle diameter of 1 μm or less (fine particles) is SS1, and the area of the second hard phase having a particle diameter of 1 μm or less (fine particles) is SS2, SS1/(SS1+SS2) It is preferably 5.5 or more and 0.9 or less. When SS1/(SS1 + SS2) is 0.5 or more, a large number of minute first hard phases are present as compared with the second hard phase, and it is expected that the wear resistance is remarkably improved. In addition, when SS1/(SS1+SS2) is 0.9 or less, the proportion of the first hard phase in the fine hard phase is not excessive, and the wettability due to the excessive presence of the fine first hard phase can be suppressed. The decrease in hardness and the possibility of deterioration of hardness due to the occurrence of minute voids due to the decrease in wettability. The range of SS1/(SS1 + SS2) is more preferably 0.55 or more and 0.7 or less. Relative to the total area of the cermet (hard phase + bonded phase) '3rd hard phase 147241.doc -13- 201042054 Area and the area of the 4th hard phase "The total area ratio is preferably greater than. At the time of the clearing, the thermal characteristics are stabilized, so that the thermal cracking resistance can be improved, and the defect resistance can be improved. In particular, the third hard phase and the fourth hard phase are preferably substantially coarse particles as described above. "Key phase" key, ,. The phase is mainly composed of at least one metal selected from the group consisting of cobalt, iron, and nickel (7) ruthenium. The term "main component" means a case where only a metal selected from the group consisting of the above iron group metals is formed on the bonded phase shell, or in a metal selected from the group consisting of the above iron group metals. The alloy in which the total mass of the bonded phase is G.lf% by mass or more and the mass% by mass or less of the hard phase is solid-solved, that is, the (9) mass% or more of the bonded phase contains the iron group metal. In the case where the bonding phase solid-dissolves the constituent elements of the hard phase, there is a tendency that the (four)' can be improved by solid solution strengthening to improve the (four) loss. In addition, when the main component of the bonded phase (80% by mass or more of the total mass of the bonded phase) is at least one of 〇〇 and the state, the wettability with the hard phase is high, and the corrosion resistance is excellent, so that it becomes A cermet that is more suitable for the constituent materials of the cutting tool. Ni and C are contained in the bonded phase. The situation of both parties, especially the N々C in the bonded phase. When the existence mass ratio (ratio of the amount of Nif to the amount of (iv)) is Ni/C, Ni/Co is preferably 〇.7 or more and 5 or less. The job satisfies 0.7 or more and Μ or less, whereby the decrease in wettability can be reduced to maintain high mobility, and the decrease in hardness can be reduced to maintain high strength. Ni/Co is particularly preferably 0.8 or more and L2 or less. The adjustment of Ni/Co can be carried out by adjusting, for example, the addition amount of Co powder or Ni powder used in the raw material. 147241.doc -14- 201042054 [Other elements included] The metal pottery of the present invention may also contain Gu (Mo). In the case where m〇 is contained, there is a tendency that the second hard phase is easily formed. Therefore, the wettability of the phase and the bonding phase can be improved, so that the bonding phase can be sufficiently present around the particles of the hard phase to improve the mobility. M. The content is preferably 0.01% by mass or more and 2.0% by mass or less. When the thoracic content is 〇〇1% by mass or more, the wettability is improved as a whole of the cermet, and the hardness or the 0 toughness can be improved as described above, and it is possible to suppress the formation of the first hard phase by being made 2% by mass or less. On the other hand, the second hard phase and the third hard phase are relatively increased. Therefore, it is possible to suppress the problem that the crack has progressed through the boundary between the core portion and the peripheral portion of the hard phase, and the desired defect resistance can be obtained. The content is more preferably 0.5% by mass or more and 5% by mass or less. The cermet of the present invention having the above-described configuration may include four kinds of hard phases as described above, thereby not only excellent wear resistance, but also resistance to breakage and fusion resistance. It is also excellent in properties, and therefore can be preferably used for a substrate material of a cutting tool (cermet tool) which is desired to have a good finished surface. "Hard film" The above substrate may also comprise a hard film covering at least a part of its surface. The hard film is preferably contained at least in the vicinity of the blade edge, and may be contained throughout the surface of the substrate. The hard film may be a layer of ruthenium or a plurality of layers. The total thickness of the film is preferably 20 μηι ^ hard film formation method 147241.doc •15- 201042054 using thermal CVD (ChemicaI Vapor Deposition, chemical vapor deposition) method Any of a chemical vapor deposition method (CVD method) and a physical vapor deposition method (PVD (Physical Vapor Deposition) method). The composition of the hard film may be selected from the group consisting of the following compounds, cubic boron nitride (cBN), diamonds, and diamond-like carbon (DLC). Selecting one or more elements selected from the group consisting of Groups 4, 5, and 6 metals 'aluminum (A1) and bismuth (si), and selected from the group consisting of carbon (c) and nitrogen (N) 'oxygen (〇) And a compound of the above-mentioned elements of the group consisting of boron (B), that is, a compound containing a carbide, a nitride, an oxide, a boride, and a solid solution of the above-mentioned metal. Specific examples of the film quality include Ti(c, n), ai2o3, (Ti, A1)N, TiN, Tic, (4), Cr)N and the like. <Manufacturing Method of Cermet> The cermet is usually produced by the steps of preparation of raw materials, pulverization of raw materials, and mixing-forming-calcination. The cermet of the present invention can be produced by using the raw material powder described below and adjusting the pulverization and mixing time or the calcination conditions. "Preparation of raw materials" The use of a compound containing a compound selected from at least one element of carbon (C) and nitrogen (Ν) and a powder constituting a bonded phase are representative of an iron group metal powder. By using a fine powder and a relatively coarse powder as the powders, it is easy to obtain a gold saponin having a hard phase in which coarse particles and fine particles are mixed as described above. The size of the powder is appropriately selected from 14724l.doc 16 201042054 in consideration of the particle size of the hard phase. In order to generate the first hard phase and the second hard phase, for example, the end is made. In the case of Ti(C, N) powder, there has been a formation of Haihan Ti as a starting material, but especially if a powder containing Ti〇2 as a starting material is used, N) powder is present. The tendency of i hard phase. Further, when a compound powder containing Mo is used in combination as described above, there is a tendency that the second hard phase is easily formed. A powder containing W, such as wc powder, is used to form the third hard phase. For the formation of the fourth hard phase, a compound powder containing Ti and a metal of Groups 4, 5, and 6 of the periodic table other than ruthenium is used, and for example, (L, W) (C, N) powder is used. By using such a compound powder, the particles of the fourth hard phase can be easily obtained, that is, a single-phase structure of the metals of Groups 4, 5, and 6 of the periodic table other than the solid solution and the enthalpy can be easily obtained. Particles 0 "Crushing and mixing" ^The pulverization time is prolonged, and the end of the mash is made fine. There is a tendency that the metal terracotta is easy to form fine hard phase particles. However, if the pulverization time is too long, there is a concern that it re-agglomerates or becomes too fine to form a compound which becomes a nucleus. The pulverization and mixing time is preferably 12 hours or more and less than 1 hour. "Calcination" If the temperature of the calcination is excessively increased, there is a concern that the hard particles are grown and the coarse particles are likely to be present in the cermet, and it is difficult to form the particles of the fourth hard phase. Therefore, the calcining temperature is preferably 140 (TC or more and 16 〇〇t: or less. In the calcining step, H7241.doc • 17-201042054, the shaped body which is heated at a predetermined time for the calcination temperature is cooled. In the case of an inert gas atmosphere, it is preferred to set it to a relatively low pressure of 665 Pa or more and 6650 Pa or less. When the cooling rate is increased to be 1 〇.min or more, the fourth hard phase tends to be formed. Advantageous Effects of the Invention The coated cermet tool of the present invention is excellent in abrasion resistance and defect resistance, and The cutting process of the machined surface of the workpiece is excellent in quality. The cermet of the present invention can be preferably used as a constituent material of such a tool. [Embodiment] <Test Example> A cutting tool including a metal pottery is produced. In addition, the cutting performance of the composition, organization and cutting tools of the metal pottery is investigated. The cutting tool is designed as follows: 1. First, prepare the following as the raw material powder. 1) Powder having an average particle diameter of 0.7 μη The Ti(C, N) powder is a powder having Ti〇2 as a starting material, and the C/N ratio is 1/1. (2) The average particle diameter is 〇·8 Tirr .. . „ μηι i1 (C, Ν) powder and Ti (C, Ν) powder with an average particle size of 3.0 μπι. Ti (CN) & The final 'C/Ν ratio of the starting material was 8. In the table, the ν) powder was referred to as "s-TiCN". Qiao 147241.doc -18· 201042054 (3) (Ti, W) (C, Ν) powder with an average particle size of 2 8 μπι (该, W) (C, Ν) powder is pre-solved w in Ti (C, Ν) powder in the powder, the C/N ratio is m. (4) \\7 (average particle size 〇5~3〇_) (: powder, NbC powder, TaC powder M〇2C powder, state powder, c〇 powder, any of these powders are commercially available powders Weighing and arranging in the manner of achieving the blending ratio (% by mass) shown in Table 1.
準備之上述原料粉末，準備粉末No. 1〜12。 [表1] 原料粉末之調配比例（質量％)The above raw material powder was prepared, and powder Nos. 1 to 12 were prepared. [Table 1] Preparation ratio of raw material powder (% by mass)
做 6c ~~~^~~ 1 〇 1 ίο 1 〇 I 1 1 7 17 將所準備之各粉末蛊 /、丙酿1溶劑及超硬合金製球珠一併裝 入不鏽鋼製坩堝内，進 衣 製作各樣品時传用夕//7碎及混合（濕式）。於表2中表示 時）。向&#月 原料粉末編號、粉碎.混合時間（小 才’向粉碎及混合後 運仃乾燥所獲得之混合粉末中添加 147241.doc -19· 201042054 少量石蠟之後，使用模具以98 MPa之壓力進行壓製成型， 從而製作CNMG120408形狀之成形體。 [表2] 樣品 No. 粉末 No. 粉碎·混合時間 (小時） 煅燒條件 Ni/Co Mo含量 (質量％) 1 6 36 B 0.73 0.94 2 6 24 B 0.72 0.94 3 2 12 A 1.31 0.93 4 2 12 C 1.29 0.93 5 1 24 A 0.96 0.94 6 3 24 A 0.96 0.95 7 4 36 A 1.34 0.93 8 8 24 C 0.96 0.92 9 3 36 C 0.96 0 94 10 5 36 A 0.97 0.93 11 4 36 _ C 1.29 0.93 12 4 36 B 1.29 〇 〇3 13 5 24 A 0.96 〇 〇4 14 2 36 A 1 29 Λ QA 15 —-—_ 16 —5 36 C 0.96 yj.y^ 0.93 2 24 B 0.97 η _ 17— 18 — 19 —6 12 C 0.74 0 93 36 A 0.72 0.95 9 36 B 0.93 100 —-一， 7 12 c — 0.96 0.93 101 9 36 A 0.92 102 ----- 103 — 104 』 36 ——Λ B 0.97 Π Q飞 12 -A 0.96 0.93 12 ------ 10 36 ----— 36 Δ___ A __〇96__ -Ml _—— 0.94 於 …/姐刀π加熟至45CTC而去除石蠟後 '工中自至溫升溫至1250。(^為μ廿於矣1 υ'-馮止’並於表3所示之條 147241.doc •20- 201042054 下進行其後之锻燒（亦包括冷卻步驟），從而獲得锻燒體。 [表3] 煅燒條件 條件 環境氣體 壓力 煅燒溫度 (Pa) (°C) A n2 133 1500 B n2 1330 1420 C n2 399 15506c ~~~^~~ 1 〇1 ίο 1 〇I 1 1 7 17 The prepared powder 蛊/, propylene 1 solvent and super hard alloy beads are placed in a stainless steel crucible and fed. When each sample was prepared, it was transferred to _/7 mash and mixed (wet). Shown in Table 2). Adding 147241.doc -19· 201042054 a small amount of paraffin to the mixed powder obtained by pulverizing and mixing and mixing and drying, and using a mold at a pressure of 98 MPa. Press molding was carried out to prepare a molded body of the shape of CNMG120408. [Table 2] Sample No. Powder No. Pulverization/mixing time (hour) Calcination condition Ni/Co Mo content (% by mass) 1 6 36 B 0.73 0.94 2 6 24 B 0.72 0.94 3 2 12 A 1.31 0.93 4 2 12 C 1.29 0.93 5 1 24 A 0.96 0.94 6 3 24 A 0.96 0.95 7 4 36 A 1.34 0.93 8 8 24 C 0.96 0.92 9 3 36 C 0.96 0 94 10 5 36 A 0.97 0.93 11 4 36 _ C 1.29 0.93 12 4 36 B 1.29 〇〇3 13 5 24 A 0.96 〇〇4 14 2 36 A 1 29 Λ QA 15 —-—_ 16 —5 36 C 0.96 yj.y^ 0.93 2 24 B 0.97 η _ 17— 18 — 19 — 6 12 C 0.74 0 93 36 A 0.72 0.95 9 36 B 0.93 100 —- one, 7 12 c — 0.96 0.93 101 9 36 A 0.92 102 ----- 103 — 104 』 36 ——Λ B 0.97 Π Q fly 12 -A 0.96 0.93 12 ------ 10 36 ----— 36 Δ___ A __〇96__ -Ml _—— 0.9 4 After the ... / sister knife π plus cooked to 45 CTC and remove the paraffin after the 'work from the temperature to 1250. (^ is μ廿 in 矣 1 υ '- Feng Zhi' and shown in Table 3 147241.doc • 20- 201042054 Subsequent calcination (including cooling step) to obtain a calcined body [Table 3] Calcination conditions Conditions Ambient gas pressure Calcination temperature (Pa) (°C) A n2 133 1500 B n2 1330 1420 C n2 399 1550
〇 〇 對所獲得之各锻燒體分別取任意之剖面，藉由掃描型電 子顯微鏡（SEM)放大至5000倍觀察該剖面。其結果，於各 煅燒體之觀察視野中，分別確認出如下粒子之°至少【種粒 子：黑色粒子、黑色粒子周圍之-部分被灰色區域覆蓋之 粒子（以下，將該等兩種粒子一併稱作黑色單粒子）；黑色 粒子之整個周圍被灰色區域覆蓋之粒子（以下，將該=子 稱作黑芯雙重粒子）；自色粒子之整個周圍被灰色區域覆 蓋之粒子（以下，將該粒子稱作白芯雙重粒子广及灰色粒 子（以下，將該粒子稱作灰色粒子）。於樣品n〇卜19之煅 燒體中，如B1所示觀察到黑色單粒子（第i硬質相”、黑芯 雙重粒子（第2硬質相2)、白纪雙重粒子（第3硬質相3)及灰 色粒子（第4硬質相4)之四種粒子。觀察到^硬質相【具有 僅由黑色粒子構成者及黑色粒子之—部分被灰色區域（周 邊部ib)覆蓋者，第2硬f相2之芯部2a為黑色、周邊料 為灰色，冑3硬質相3之芯部3a為白色、周邊部⑽灰色。 於粒子之間存在鍵結相1〇。另一方面，於樣品N〇. ι〇〇〜！〇5之锻燒體中，觀察不到黑色單粒子u雙重粒 147241.doc 201042054 子、白芯雙重粒子及灰色粒子中之至少一者。 藉由 TEM-EDX(transmission electron microscope-energy dispersive X-ray spectrometer，穿透式電子顯微鏡-能量色 散X射線光譜儀）分析對上述各粒子之組成進行調查’結果 得知黑色單粒子包含Ti(C、N);黑芯雙重粒子之芯部包含 Ti(C、N)，且覆蓋芯部之周邊部包含含有Ti與W、Nb、Ta 及Mo之1種以上之金屬的複合碳氮化物固溶體；白芯雙重 粒子包含含有Ti與W、Nb、Ta及Mo之1種以上之金屬的複 合碳氮化物固溶體，且芯部之W濃度高於覆蓋該芯部之周 邊部者；灰色粒子包含含有Ti與W、Nb、Ta及Mo之1種以 上之金屬的複合碳氮化物固溶體。又，灰色粒子係觀察不 到芯部與周邊部之明確邊界。另外，硬質相之成分分析， 除TEM-EDX分析以外，還可使用EPMA(electron probe micro analyser，電子探針微量分析器）、螢光χ射線、1〇卩-AES(Inductively Coupled Plasm Atomic Emission Spectroscopy 5 感應耦合電漿原子發射光譜分析儀）等進行分析。 於上述粒子之間存在鍵結相，藉由TEM-EDX分析進行 調查’結果得知鍵結相實質上包含Co及Ni。於樣品中，有 於鍵結相中固溶著數質量％左右之硬質相之構成元素者。 又’進行分析之結果存在如下傾向，即，煅燒體中之Co含 量與原料之Co粉末之添加量大致相同，烺燒體中之Ni含量 與原料之Ni粉末之添加量相比減少〇.2〜0.3%左右。根據該 情形，可認為各樣品（煅燒體）中之硬質相之含量係與減去 原料中使用之Co粉末及Ni粉末之添加量所得之量（86質量 147241.doc -22- 201042054 %左右）大致相等。進而，求得存在於鍵結相中之㈣co 之存在質量比Ni/C〇e將其結果示於表2。χ，藉由icp分 析，對各樣品（锻燒體）之編含量（質量％)進行調查。亦將 其結果不於表2。 ' 使用上述SEM之剖面觀察圖像（5〇〇〇倍），求得各樣品（炮 燒體）之觀察視野中所存在之所有粒子之粒徑。粒徑設為 Martin(馬丁）直徑（自固定方向將粒子投影於平面時之粒子 之投影面積二等分之線段之長度）。具體而言，利用觀察 煅燒體之剖面之顯微鏡照片，將該顯微鏡照片中所存在之 粒子之面積進行二等分之線段之長度設為粒徑。有芯結構 之粒子係於包括周邊部之狀態下求得粒徑。其結果任一 樣品中幾乎觀察不到粒徑超過3 μιη之粒子，故而硬質相實 質上包含粒徑為3 μιη以下之粒子。 利用就剖面觀察圖像（5000倍）所獲得之粒徑（上述Manin 直控）’分別求得各粒子之面積。又，就第1硬質相、第2 〇 硬質相、第3硬質相及第4硬質相，分別求得粒徑超過i μηι 且為3 μιη以下之粒子之總計面積（以下，將該等之總計面 積分別稱作粗粒面積（1)、粗粒面積（2)、粗粒面積（3)、粗 粒面積（4)) ’針對第1硬質相求得粒徑為1 以下之粒子之 總計面積（以下’將該總計面積稱作微粒面積，針對第 2硬質相s十箅粒彳坐為1 μπι以下之粒子之總計面積（以下，將 該總計面積稱作微粒面積（2))。針對粗粒面積（丨）、粗粒面 積（2)、粗粒面積（3)、粗粒面積（4)、微粒面積（1)及微粒面 積（2)之總計設為硬質相之總面積，並將粗粒面積（1)〜(4)相 147241.doc -23· 201042054 對於硬質相之總面積之總計比例’亦即粗粒面積率「粒 粒/硬質相全體」（％)示於表4。又，將粗粒面積（1)、粗粒 面積（2)、粗粒面積（3)、粗粒面積（4)、微粒面積（1)及微粒 面積（2)相對於硬質相之總面積之各個面積率（％)示於表4。 將粗粒面積（1)相同對於硬質相之總面積之面積率設為 《 S1 ’將粗粒面積（2)相對於硬質相之總面積之面積率設為 S2，將粗粒面積（3)相對於硬質相之總面積之面積率設為 S3 ’將粗粒面積（4)相對於硬質相之總面積之面積率設為 S4，求得此時之（S1+S2)、S1/(S1+S2)、s3/(S3 + S4)。將其 結果示於表4。進而，於將微粒面積（1)設為SS1、 面積（2)設為SS2時：求得SS1/(SS1 + SS2)，求得第3硬質相 之面積與第4硬質相之面積之總計面積相對於金屬陶竟全 陶瓷全〇 取 Each of the obtained calcined bodies was subjected to an arbitrary cross section, and the cross section was observed by scanning electron microscopy (SEM) to a magnification of 5000 times. As a result, in the observation field of each of the calcined bodies, it was confirmed that at least the following particles (the particles: black particles, and the portions around the black particles are partially covered by the gray regions) (hereinafter, the two kinds of particles are collectively combined a black single particle); a particle surrounded by a gray area around the black particle (hereinafter, this = sub is called a black core double particle); a particle surrounded by a gray area around the entire color particle (hereinafter, The particles are referred to as white core double particles and gray particles (hereinafter, the particles are referred to as gray particles). In the calcined body of sample n〇19, black single particles (i-th hard phase) were observed as indicated by B1, Four kinds of particles of black core double particles (second hard phase 2), white matter double particles (third hard phase 3), and gray particles (fourth hard phase 4). Observed ^ hard phase [having only black particles The part of the black particle and the black particle are covered by the gray area (the peripheral portion ib), the core portion 2a of the second hard f phase 2 is black, the peripheral material is gray, and the core portion 3a of the hard phase 3 of the crucible 3 is white and the peripheral portion. (10) Gray. In the particle There is a bonding phase between the two. On the other hand, in the calcined body of the sample N〇. ι〇〇~!〇5, no black single particle u double particle 147241.doc 201042054 sub-white core double particle was observed. And at least one of the gray particles. The TEM-EDX (transmission electron microscope-energy dispersive X-ray spectrometer) is used to analyze the composition of each of the above particles. It is understood that the black single particles include Ti (C, N); the core portion of the black core double particles contains Ti (C, N), and the peripheral portion covering the core portion contains one or more of Ti, W, Nb, Ta, and Mo. a composite carbonitride solid solution of metal; the white core double particle contains a composite carbonitride solid solution containing one or more metals of Ti, W, Nb, Ta, and Mo, and the W concentration of the core is higher than the coverage The peripheral portion of the core; the gray particles include a composite carbonitride solid solution containing one or more metals of Ti, W, Nb, Ta, and Mo. Further, the gray particles are not clearly defined in the core portion and the peripheral portion. Boundary. In addition, component analysis of the hard phase, except TEM-EDX In addition to the analysis, an EPMA (electron probe micro analyser), a fluorescent X-ray, an Inductively Coupled Plasm Atomic Emission Spectroscopy (Inductively Coupled Plasma Atomic Emission Spectrometer), or the like can be used. The analysis was carried out. A bonded phase was present between the above particles, and investigation was carried out by TEM-EDX analysis. As a result, it was found that the bonded phase substantially contained Co and Ni. In the sample, a constituent element of a hard phase in which about several mass% of solid phase is dissolved in the bonded phase is present. Further, as a result of the analysis, there is a tendency that the Co content in the calcined body is substantially the same as the addition amount of the Co powder in the raw material, and the Ni content in the calcined body is reduced as compared with the addition amount of the Ni powder of the raw material. ~0.3% or so. According to this case, the content of the hard phase in each sample (calcined body) is determined by subtracting the amount of addition of Co powder and Ni powder used in the raw material (86 mass 147241.doc -22- 201042054% or so) Almost equal. Further, the existence mass ratio Ni/C〇e of (4) co present in the bonded phase was determined, and the results are shown in Table 2. Then, the content (% by mass) of each sample (calcined body) was investigated by icp analysis. The results are also not shown in Table 2. Using the cross-sectional observation image (5 〇〇〇) of the above SEM, the particle diameters of all the particles present in the observation field of each sample (artifact) were determined. The particle size is set to the Martin diameter (the length of the line segment in which the projected area of the particles when the particles are projected onto the plane from the fixed direction is halved). Specifically, the length of the line segment in which the area of the particles present in the microscope photograph is halved is defined by the micrograph of the cross section of the observed calcined body. The particle having the core structure is obtained by measuring the particle diameter in a state including the peripheral portion. As a result, almost no particles having a particle diameter of more than 3 μη were observed in any of the samples, and thus the hard phase substantially contained particles having a particle diameter of 3 μm or less. The area of each particle was determined by the particle diameter obtained by observing the cross-sectional observation image (5000 times) (Manin direct control described above). Further, in the first hard phase, the second hard phase, the third hard phase, and the fourth hard phase, the total area of the particles having a particle diameter exceeding i μηι and being 3 μm or less is determined (hereinafter, the total of these is equal to The area is referred to as the coarse grain area (1), the coarse grain area (2), the coarse grain area (3), and the coarse grain area (4). 'The total area of the particles having a particle diameter of 1 or less is determined for the first hard phase. (Hereinafter, the total area is referred to as the particle area, and the total area of the particles of 1 μπι or less for the second hard phase s 箅 箅 ( (hereinafter, the total area is referred to as the particle area (2)). The total area of the hard phase (设为), the coarse grain area (2), the coarse grain area (3), the coarse grain area (4), the particle area (1), and the particle area (2) are set to the total area of the hard phase, and Coarse grain area (1) to (4) phase 147241.doc -23· 201042054 The total ratio of the total area of the hard phase, that is, the coarse grain area ratio "granule/hard phase total" (%) is shown in Table 4. Further, the coarse particle area (1), the coarse particle area (2), the coarse particle area (3), the coarse particle area (4), the particle area (1), and the fine particles The area ratio (%) of the area (2) with respect to the total area of the hard phase is shown in Table 4. The area ratio of the coarse grain area (1) is the same as the area ratio of the total area of the hard phase, and the area of the coarse grain is set to "S1' ( 2) The area ratio with respect to the total area of the hard phase is set to S2, and the area ratio of the coarse grain area (3) to the total area of the hard phase is set to S3 'the total area of the coarse grain (4) relative to the hard phase The area ratio of the area is set to S4, and (S1+S2), S1/(S1+S2), and s3/(S3 + S4) are obtained at this time. The results are shown in Table 4. Further, the area of the particles is 1) When SS1 and area (2) are set to SS2: SS1/(SS1 + SS2) is obtained, and the total area of the area of the third hard phase and the area of the fourth hard phase is determined with respect to the metal ceramics. all
粒子或第4硬質相之粒子。 [表4] t粒子之粒徑大部分均 μιη以下之第3硬質相 〇 I4724J.doc • 24 - 201042054 οο (第3+第4)金屬 陶瓷全體 in 5 5 Μ 9 cc CO \η m ri yn m m 9 SS1/(SS1+SS2) 00 ο s o o s o 妄 O 5： o 〇 s o v〇 00 o cn ON ο S ο S ο *η ο ο Ο ο ίο ο s ο Os <N 〇 o o o g P o r^t 'sO 〇 o o ο S3/(S3+S4) d o o o o o o o o o o o o o ο ο § ο m Os Ο OS Ό ο 艺 ο ΟΝ ο 00 ο 00 «η Ο 00 o 00 00 d o P o o o 〇 o o ο S1/(S1+S2) m VsO 〇 ?: o s o oo m o 荔 o 其 o 艺 o o 艺 o 芝 ο ο 芝 Ο ο ζΐ ο g ο ro m ο m cn d o o o o o o 00 m o Ό (N <0 o o ο S1+S2 g d m o m CN 〇 芝 o CN m O (N m· 〇 (N m 〇 r4 m O (N m o <Ν ο Ρ； ο <Ν m ο 穿 ο fn »Τί Ο ΓΟ ο ΓΛ ΓΛ ο m d CN <N o 〇 (N o ΓΟ o as <N 〇 rn o ON fS o (Ν Ο 粗粒面積 率(％) 粗粒/硬質 相全體 § <N fN cn fN rJ cs (N <N fN (Ν (Ν ΟΟ § § »n ON V) (N VO On <D 04 o o CN 00 S 面積率(％) 第4硬質相 1~3 μπι 粗粒(4) 00 CM cn CS cs CN <S iS (Ν 卜 m OS 卜 OS cn Si 00 v〇 CS Ό 寸 o *ri ο 第3硬質相 1 〜3 μπι 粗粒(3) 艺 00 CN 00 OO (N 00 rj 00 00 CN 00 (N 00 (Ν 00 (Ν S 00 ΟΟ 00 m •ri m »〇 m o O' CO 〇 S 第2硬質相 1 〜3 μπι 粗粒(2) is 口 ΟΝ <Ν 沄 (Ν fM S (N fS 〇 fS Cn| 〇 00 m OS CN ο II VI寒 卜 o 〇 〇 »〇 ·«·· m o o 对 (Ν ο ο Ο Ο Γ〇 «Λ» (N Ό (N o m 〇 00 »— 00 ο 第1硬質相 1~3 μπα 粗粒(1) r- ΓΊ ，㈣ 二 二 二 二 二 Ό w-m 8 ΓΛ (Ν (Ν 二 〇 〇 m 〇 m 二 00 o <1 μΐΏ 微粒(1) CN 00 oo 00 CO oo oo Ό (Ν ΟΟ 00 fS »« Ο 卜 o 00 cs o 00 CN (N <N σ·\ o ΟΝ 樣品 1 — CN 寸 Ό 卜 00 a\ Ο 二 (Ν 寸 卜 00 o 〇 S m 〇 S 147241.doc -25- 201042054 對所獲付之各锻燒體之表面分別貫施平面研磨處理及刀 尖處理，製作CNMG120408形狀之附破碎件之切削刀片（切 削工具）。使用所獲得之各切削刀片，分別於以下表5所示 之條件下進行切削測試（任一者均進行旋轉切削加工），對 而寸磨損性、财缺損性、加工面之表面粗糙度進行調杳。將 其結果示於表6。表面粗糙度Ra係依據Jis b 〇6〇1(2〇〇ι)進 行測定。 [表5] 耐磨損測試 耐缺損性測試 —~~-— 加工面之表面粗縫度測試 被切削材：SCM415 被切削材·· SCM435 附4條狹槽 被切削材：SCM415 切削速度：300m/min 切削速度：250m/min 切削速度：lOOm/min 切口 ： 1.0mm 切口 ： 1·5 mm 切口 ： 1.0 mm 輸送：0.15 mm/rev. 輪送：0.15 mm/rev. 輸送：0.15 mm/rev· 切削油：使用 切削油：使用 切削油：使用 切削時間：30min 評價：直至產生缺損為 止之次數(次;） 切削時間：30 min 評價：切削時間後之刀腹 面Vb磨損量(mm) 評價：表面粗縫度Ra [表6] 樣品 No. 耐磨損測試 (mm) 耐缺損性測試 (次） 表面粗糙度測試 Ra(pm) 1 0.16 7694 1.3 2 0.14 6982 1.2 3 0.13 8352 1.1 4 0.12 8006 1.1 5 0.105 8350 0.8 6 0.09 9860 0.9 7 0.08 9003 0.8 8 0.09 8344 0.9 147241.doc -26- 201042054 9 0.08 10312 0.7 10 0.11 8634 0.8 11 0.13 7983 1.2 12 0.12 8693 1.3 13 0.12 8560 1.2 14 0.11 5970 1.1 15 0.15 7543 0.9 16 0.13 5880 0.75 17 0.16 7330 1.2 18 0.17 6580 1.4 19 0.14 6230 1.3 100 0.31 4005 2.1 101 0.23 3653 1.5 102 0.19 4210 1.2 103 0.32 4998 2 104 0.15 3991 1.3 105 0.28 2980 1.9Particles or particles of the fourth hard phase. [Table 4] The third hard phase of the particle size of the t particle is mostly the same as the third hard phase 〇 I4724J.doc • 24 - 201042054 οο (3rd + 4th) cermet all in 5 5 Μ 9 cc CO \η m ri yn Mm 9 SS1/(SS1+SS2) 00 ο sooso 妄O 5: o 〇sov〇00 o cn ON ο S ο S ο *η ο ο Ο ο ίο ο s ο Os <N 〇ooog P or^t ' sO 〇oo ο S3/(S3+S4) dooooooooooooo ο ο § ο m Os Ο OS Ό ο Art ο ο 00 00 00 «η Ο 00 o 00 00 do P ooo 〇oo ο S1/(S1+S2) m VsO 〇?: oso oo mo 荔o its o oo art o 芝 ο ο Ο Ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο m O (N m· 〇(N m 〇r4 m O (N mo <Ν ο Ρ; ο <Ν m ο wearο fn »Τί Ο ΓΟ ο ΓΛ ΓΛ ο md CN <N o 〇(N o ΓΟ o as <N 〇rn o ON fS o (Ν 粗 coarse area ratio (%) coarse/hard phase § <N fN cn fN rJ cs (N <N fN (Ν (Ν ΟΟ § § »n ON V) (N VO On <D 04 oo CN 00 S Area ratio (%) 4th质 phase 1~3 μπι coarse grain (4) 00 CM cn CS cs CN <S iS (Ν m m OS 卜 OS cn Si 00 v〇CS Ό inch o *ri ο 3rd hard phase 1 ~ 3 μπι coarse grain (3) Art 00 CN 00 OO (N 00 rj 00 00 CN 00 (N 00 (Ν 00 (Ν S 00 ΟΟ 00 m • ri m » 〇mo O' CO 〇S 2nd hard phase 1 ~ 3 μπι coarse grain (2) is ΟΝ ΟΝ <Ν 沄 (Ν fM S (N fS 〇fS Cn| 〇00 m OS CN ο II VI 卜 o 〇〇 〇 〇 « « mo mo mo mo mo mo mo mo mo mo mo mo mo mo mo mo mo mo «Λ» (N om (N om 〇00 »— 00 ο 1st hard phase 1~3 μπα coarse grain (1) r- ΓΊ , (4) 2222 Ό wm 8 ΓΛ (Ν (Ν 2〇〇m 〇m 00 o <1 μΐΏ particles (1) CN 00 oo 00 CO oo oo Ό (Ν 00 00 fS »« Ο 卜 o 00 cs o 00 CN (N <N σ·\ o ΟΝ Sample 1 - CN寸Ό 00 00 a Ο Ο Ν Ν 00 00 00 147 147 147 147 147 147 147 147 147 147 147 147 147 147 147 147 147 147 147 147 147 147 147 147 147 147 147 147 147 147 147 147 147 147 147 147 147 147 147 147 147 147 147 147 147 147 147 147 147 147 147 147 A cutting insert (cutting tool) with a broken piece of shape. Using each of the obtained cutting inserts, the cutting test was performed under the conditions shown in Table 5 below (any of which was subjected to the rotary cutting process), and the wear resistance, the defect, and the surface roughness of the machined surface were adjusted. dark and quiet. The results are shown in Table 6. The surface roughness Ra was measured in accordance with Jis b 〇6〇1 (2〇〇ι). [Table 5] Abrasion resistance test Defect resistance test—~~-— Surface roughness test of machined surface: SCM415 Cutting material · SCM435 Attached to 4 slots: SCM415 Cutting speed: 300m /min Cutting speed: 250m/min Cutting speed: lOOm/min Incision: 1.0mm Incision: 1·5 mm Incision: 1.0 mm Delivery: 0.15 mm/rev. Round: 0.15 mm/rev. Delivery: 0.15 mm/rev· Cutting oil: using cutting oil: using cutting oil: cutting time: 30min Evaluation: the number of times until the defect is produced (times;) Cutting time: 30 min Evaluation: Vb wear amount (mm) of the flank face after cutting time Evaluation: Surface Roughness Ra [Table 6] Sample No. Abrasion resistance test (mm) Defect resistance test (times) Surface roughness test Ra(pm) 1 0.16 7694 1.3 2 0.14 6982 1.2 3 0.13 8352 1.1 4 0.12 8006 1.1 5 0.105 8350 0.8 6 0.09 9860 0.9 7 0.08 9003 0.8 8 0.09 8344 0.9 147241.doc -26- 201042054 9 0.08 10312 0.7 10 0.11 8634 0.8 11 0.13 7983 1.2 12 0.12 8693 1.3 13 0.12 8560 1.2 14 0.11 5970 1.1 15 0.15 7543 0.9 16 0.13 5880 0. 75 17 0.16 7330 1.2 18 0.17 6580 1.4 19 0.14 6230 1.3 100 0.31 4005 2.1 101 0.23 3653 1.5 102 0.19 4210 1.2 103 0.32 4998 2 104 0.15 3991 1.3 105 0.28 2980 1.9
如表6所示可知，存在有第1硬質相、第2硬質相、第3硬 質相及第4硬質相之全部之樣品N〇. i〜19係與不存在上述 四種相中之某—種之樣品No. 100〜1 〇5相比，财磨損性優 異’並且财缺損性亦優異。且可知，使用該等樣品N〇. 1〜19時’被切削材之加工面之表面粗糙度以較小，且加工 面之面品質較高。 可知’於樣品No. 1〜19中，尤其粗粒粒子之面積率滿足 60%以上且90%以下’則硬度提高或破壞韌性提高，藉此 存在耐磨損性或耐缺損性進一步優異之傾向。又可知，於 樣品No. 1〜19中’尤其（S1 + S2)滿足〇丨以上且〇 5以下之樣 品或S1/(S1 + S2)滿足〇1以上且〇,4以下、及S3/(S3 + S4)滿足 0.4以上且〇.9以下之樣品，存在表面粗糙度Ra變得更小之 147241.doc •27- 201042054 傾向，且面品質優異。可知，於樣品N〇 i〜19中，尤其 SS1/(SS1 + SS2)滿足0.5以上且0.9以下之樣品，存在耐磨損 性更優異之傾向。又可知，於樣品No. 1〜19中，尤其（第3 + 第4)/(金屬陶瓷全體）超過40%之樣品之韌性優異。 於樣品No. 1〜19之切削刀片之表面上，形成有藉由電弧 離子電鍍法形成（Ti、A1)N膜（厚度為4 μιη)之被覆刀片，並 於表5所不之測試條件下進行耐磨損性測試。其結果任 一樣品均與不存在硬質膜之情形相比，耐磨損性更優異。 另外上述實施形悲可於不脫離本發明主旨之範圍内進 行適當變更，並不限定於上述構成。例如，可適當變更原 料粉末之組成或平均粒徑、硬質相之各粒子之存在狀態、 硬質膜之組成或厚度。 產業上之可利用性 本發明金屬陶瓷係可較佳地用於切削工具之原材料。本 电明被覆金屬陶兗工具係可較佳地用於旋轉切削加工、研 磨切削加工，尤其可較佳地用於鋼之切削。 【圖式簡單說明】 圖1係不意性地表示本發明金屬陶瓷中所存在之四種硬 質相之說明圖。 【主要元件符號說明】 1 第1硬質相 lb 周邊部 2 第2硬質相 2a ' 3a 芯部 147241.doc 201042054 2b ' 3b 周邊部 3 第3硬質相 4 第4硬質相 10 鍵結相 Ο ❹ 147241.doc -29-As shown in Table 6, it can be seen that there are samples of the first hard phase, the second hard phase, the third hard phase, and the fourth hard phase, N〇. i~19 and some of the above four phases are not present. Compared with the sample No. 100 to 1 〇5, the product has excellent wear resistance and excellent financial defects. It is also known that when the samples are used N〇. 1 to 19, the surface roughness of the machined surface of the workpiece is small, and the surface quality of the machined surface is high. In the sample Nos. 1 to 19, in particular, when the area ratio of the coarse particles is 60% or more and 90% or less, the hardness is improved or the fracture toughness is improved, whereby the wear resistance or the defect resistance is further improved. . In the sample Nos. 1 to 19, it is found that the sample (S1 + S2) which satisfies 〇丨 or more and 〇 5 or less or S1/(S1 + S2) satisfies 〇1 or more and 〇, 4 or less, and S3/( S3 + S4) A sample satisfying 0.4 or more and 〇.9 or less has a tendency to have a smaller surface roughness Ra, 147241.doc • 27- 201042054, and has excellent surface quality. In the samples N〇 i to 19, in particular, the sample having SS1/(SS1 + SS2) satisfying 0.5 or more and 0.9 or less has a tendency to be more excellent in abrasion resistance. Further, in Sample Nos. 1 to 19, in particular, the toughness of the sample of more than 40% of (3 + 4th) / (the entire cermet) was excellent. On the surface of the cutting insert of Sample Nos. 1 to 19, a coated blade formed of a (Ti, A1)N film (thickness of 4 μm) by arc ion plating was formed, and under the test conditions of Table 5 Wear resistance test. As a result, any of the samples was superior in abrasion resistance as compared with the case where no hard film was present. Further, the above-described embodiments can be appropriately modified without departing from the spirit and scope of the invention, and are not limited to the above configuration. For example, the composition or average particle diameter of the raw material powder, the existence state of each particle of the hard phase, and the composition or thickness of the hard film can be appropriately changed. Industrial Applicability The cermet of the present invention can be preferably used as a raw material for a cutting tool. The electric capping metal ceramic tool system can be preferably used for rotary cutting, grinding and cutting, and particularly for steel cutting. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is an explanatory view showing, in an unintentional manner, four hard phases present in a cermet of the present invention. [Description of main component symbols] 1 First hard phase lb Peripheral part 2 Second hard phase 2a ' 3a Core 147241.doc 201042054 2b ' 3b Peripheral part 3 Third hard phase 4 Fourth hard phase 10 Bond phase Ο 147241 .doc -29-