TWI457445B - Metal cermet - Google Patents
Metal cermet Download PDFInfo
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- TWI457445B TWI457445B TW099108727A TW99108727A TWI457445B TW I457445 B TWI457445 B TW I457445B TW 099108727 A TW099108727 A TW 099108727A TW 99108727 A TW99108727 A TW 99108727A TW I457445 B TWI457445 B TW I457445B
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
- C22C1/05—Mixtures of metal powder with non-metallic powder
- C22C1/051—Making hard metals based on borides, carbides, nitrides, oxides or silicides; Preparation of the powder mixture used as the starting material therefor
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
- C22C29/02—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides
- C22C29/04—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbonitrides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
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- Cutting Tools, Boring Holders, And Turrets (AREA)
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Description
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。The present invention relates to a cermet 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 that is excellent in defect resistance and capable of performing cutting work with excellent quality of a machined surface of a workpiece.
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(Co)、鎳(Ni)之類之鐵族元素鍵結而成之金屬陶瓷。於專利文獻1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。Since the prior art, as a substrate material for cutting tools, titanium carbide (TiC) or titanium carbonitride (Ti (C, N)) has been used as the main hard phase and by cobalt (Co), nickel (Ni) or the like. A cermet made of iron-based elements. Patent Document 1 discloses a cermet in which particles having a single-phase structure and particles having a core structure in which a core portion is covered by a peripheral portion are hard phases. 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.
專利文獻1：日本專利特開平02-190438號公報Patent Document 1: Japanese Patent Laid-Open No. 02-190438
專利文獻2：日本專利特開2004-292842號公報Patent Document 2: Japanese Patent Laid-Open Publication No. 2004-292842
專利文獻3：日本專利特開2006-131975號公報Patent Document 3: Japanese Patent Laid-Open Publication No. 2006-131975
以金屬陶瓷為基材之金屬陶瓷工具與包含以碳化鎢(WC)為主要硬質相之超硬合金之工具相比，通常耐磨損性優異、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，業界要求進一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。A cermet tool based on cermet is generally superior in wear resistance to a tool containing a superhard alloy containing tungsten carbide (WC) as the main hard phase, and the processed surface (finished surface) of the workpiece is beautiful. However, the toughness is low and the defect resistance is poor. Therefore, sudden defects are easily generated and the tool life is unstable. In recent years, the industry has demanded that the quality of the machined surface of the workpiece in the cutting process be further improved, and the defect resistance as a weak point of the cermet tool is improved to stabilize the tool life.
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。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.
於硬質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損性下降。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。In the prior cermet in which the hard phase contains the particles having the core structure, the crack easily progresses through the boundary between the core portion and the peripheral portion, and the crack resistance is lowered due to the crack. 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.
因此，本發明之目的之一在於提供一種金屬陶瓷，其係適於耐缺損性優異、並且可進行加工面之品質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一種被覆金屬陶瓷工具，其係包括包含上述金屬陶瓷之基材者。Therefore, an object of the present invention is to provide a cermet which is suitable as a constituent material of a cutting tool which is excellent in defect resistance and can be subjected to cutting processing having excellent quality of a machined surface. Still another object of the present invention is to provide a coated cermet tool comprising a substrate comprising the above cermet.
本發明者等人獲得以下之知識見解：於金屬陶瓷中在特定範圍內存在硬質相、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耐熔接性。又，藉由提高耐熔接性等，亦可提高被切削材之面品質。本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。The inventors of the present invention have obtained the following knowledge: when there are four phases in the cermet in a specific range and there are four kinds of particles having different compositions or forms as the particles constituting the hard phase, the wear resistance is high. Sexuality, and is expected to significantly improve the defect resistance and weld resistance. Further, by improving the weld resistance and the like, the surface quality of the workpiece can be improved. The present invention defines the content of the hard phase and the four hard phases based on the above knowledge.
本發明之金屬陶瓷係硬質相藉由鍵結相鍵結而成者，該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1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，剩餘部分實質上係由鍵結相構成。又，該金屬陶瓷包含以下之第1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。The cermet-based hard phase of the present invention is bonded by a bonding phase containing carbides, nitrides, carbonitrides, and solids selected from the metals of Groups 4, 5, and 6 of the periodic table. One or more compounds of the group consisting of a solution, the bonding 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 remainder is substantially composed of a bonded phase. Further, the cermet includes the following first hard phase, second hard phase, third hard phase, and fourth hard phase as the hard phase.
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。The first hard phase: it is a hard phase composed of only a single phase of titanium carbonitride (Ti(C, N)), or a part of Ti (C, N) is surrounded by titanium (Ti) and selected from the cycle A composite carbonitride solid solution of one or more metals of Groups 4, 5, and 6 metals (excluding Ti) is covered.
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。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 the group consisting of metals of Groups 4, 5, and 6 (excluding Ti).
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Ti與W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。The third 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 and the peripheral portion include the same element, and include a composite carbonitride solid solution containing at least Ti and W. Further, the W concentration of the core portion is larger than the W concentration of the peripheral portion.
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)之1種以上之金屬的複合碳氮化物固溶體。The fourth hard phase: a hard phase having a single-phase structure comprising a composite carbonitride solid solution of Ti and one or more metals selected from the group consisting of metals of Groups 4, 5, and 6 (excluding Ti).
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硬質相及第4硬質相，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異之硬質相，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。且，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，並且難以產生熔接，藉此可獲得漂亮之加工面，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。The cermet according to the present invention contains a specific amount of a hard phase, and the first hard phase, the second hard phase, the third hard phase, and the fourth hard phase are coexisted as the hard phase, whereby the first hard phase can be combined ~ The function of each of the 4th hard phases. Specifically, the cermet according to the present invention has a hard phase having a high hardness, thereby being excellent in abrasion resistance and having a hard phase excellent in wettability with a bonding phase, whereby the bonding phase can be maintained well. Wettability, or a structure in which a bonding phase is uniformly formed, is expected to improve wear resistance and defect resistance by homogenization of the structure. Further, the cermet according to the present invention has a hard phase excellent in thermal characteristics, whereby thermal conductivity can be improved, and thermal cracking or welding resistance can be suppressed. As described above, the cermet of the present invention has excellent wear resistance and can significantly improve the defect resistance and the weld 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 welding is difficult to be performed, whereby a beautiful processing surface can be obtained, and it is expected to improve the processing of the workpiece. The quality of the face. Hereinafter, the present invention will be described in more detail.
<金屬陶瓷><cermet>
《全體組成》"All Compositions"
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。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, and the remaining portion contains a bonded phase and unavoidable impurities. The unavoidable impurities include metal elements contained in the raw materials or oxygen or ppm grades mixed in the production steps.
《硬質相》Hard Phase
[組成][composition]
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，包含選自上述金屬元素之碳化物、氮化物、碳氮化物及該等之固溶體之至少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90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 microscope)之顯微鏡照片之濃淡而容易判別。The hard phase comprises a compound selected from at least one metal element of a metal of Groups 4, 5, and 6 of the periodic table and at least one element of carbon (C) and nitrogen (N), that is, a carbide selected from the above metal elements. At least one of a nitride, a carbonitride, and a solid solution thereof. In particular, the cermet of the present invention contains at least titanium carbonitride (Ti(C, N)) and a Ti(C, N)-based cermet containing a carbonitride solid solution of titanium (Ti). When the content of the hard phase is more than 97% by mass, the bonding phase is too small, and the defect resistance is remarkably lowered. If the amount is less than 70% by mass, the bonded 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 90% by mass or less. Further, the hard phase includes four hard phases in which the composition or form of the first hard phase, the second hard phase, the third hard phase, and the fourth hard phase are different. Specifically, it includes a hard phase of a Ti (C, N) system and a hard phase containing another composition of Ti, a hard phase of a single phase structure, and a hard phase having a core structure. The existence state of the above four hard phases can be easily determined based on the shading of a microscope photograph of a scanning electron microscope (SEM).
(第1硬質相)(1st hard phase)
構成第1硬質相之粒子係實質上僅由Ti(C、N)構成之單相結構之粒子，或者Ti(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族金屬之1種以上之金屬的複合碳氮化物固溶體覆蓋之粒子，亦即係Ti(C、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硬質相與下述第3硬質相及第4硬質相相比而含有較多之Ti，藉此硬度高，且與廣泛使用於被切削材之鋼之反應性低。因此，於金屬陶瓷中存在第1硬質相，藉此尤其可達成耐磨損性及耐熔接性之提高。The particles constituting the first hard phase are substantially only particles of a single-phase structure composed of Ti (C, N), or a part of the periphery of Ti (C, N) is selected from the group consisting of Ti and Ti except for Ti. 5. A composite carbonitride solid solution coated with one or more metals of a group 6 metal, that is, particles surrounded by Ti (C, N) which are not completely covered by the above composite carbonitride solid solution. The first hard phase contains a large amount of Ti compared to the third hard phase and the fourth hard phase described below, whereby the hardness is high and the reactivity with steel widely used for the workpiece is low. Therefore, the presence of the first hard phase in the cermet can improve the wear resistance and the weld resistance.
(第2硬質相)(2nd hard phase)
構成第2硬質相之粒子係有芯結構之粒子，其芯部實質上包含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Ti與除Ti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。周邊部之具體組成可列舉例如：(Ti、W、Mo)(C、N)、(Ti、W、Nb)(C、N)、(Ti、W、Mo、Nb)(C、N)、(Ti、W、Mo、Nb、Zr)(C、N)等。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。The particles constituting the second hard phase are particles having a core structure, and the core portion substantially contains Ti (C, N) (Ti (C, N) accounts for 95% or more of the entire core portion in terms of atomic ratio) and covers The peripheral portion of the entire periphery of the core includes a composite carbonitride solid solution of Ti and at least one metal selected from the group consisting of metals of Groups 4, 5, and 6 of the periodic table other than Ti. Specific examples of the peripheral portion include (Ti, W, Mo) (C, N), (Ti, W, Nb) (C, N), (Ti, W, Mo, Nb) (C, N), (Ti, W, Mo, Nb, Zr) (C, N) and the like. 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, by the homogenization of the above-mentioned organization, it is expected to further improve the toughness such as defect resistance. Therefore, by the presence of the second hard phase in the cermet, the effect of abrasion resistance and defect resistance can be stabilized.
(第3硬質相)(3rd hard phase)
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芯結構之粒子，且包含至少含有Ti與W之複合碳氮化物固溶體。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、Mo)(C、N)、(Ti、W、Nb)(C、N)、(Ti、W、Mo、Nb)(C、N)等。第3硬質相係與第1硬質相或第2硬質相相比而含有較多之W，藉此有望於維持高硬度之狀態下，提高導熱率。因此，可提高熱強度、耐熱龜裂性、耐缺損性、耐塑性變形性。The particle-based core portion and the peripheral portion constituting the third hard phase include particles having a core structure of the same element, and a composite carbonitride solid solution containing at least Ti and W. Further, the W concentration of the core portion of the particle is larger than the W concentration of the peripheral portion. Specific examples thereof include (Ti, W) (C, N), (Ti, W, Mo) (C, N), (Ti, W, Nb) (C, N), (Ti, W, Mo, Nb) (C, N) and the like. The third hard phase system contains a large amount of W compared to the first hard phase or the second hard phase, and it is expected that the thermal conductivity is improved while maintaining high hardness. Therefore, heat strength, heat crack resistance, defect resistance, and plastic deformation resistance can be improved.
(第4硬質相)(4th hard phase)
構成第4硬質相之粒子係單相結構之粒子，其包含Ti與除Ti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，粒子全體包含均勻之組成。作為構成第4硬質相之除Ti以外之金屬，具代表性的是可列舉W。The particles constituting the fourth hard phase are particles of a single-phase structure, and include a composite carbonitride solid solution of Ti and at least one metal selected from the group consisting of metals of Groups 4, 5, and 6 of the periodic table other than Ti. 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. As a metal other than Ti which comprises a 4th hard phase, W is mentioned typically.
第4硬質相之具體組成可列舉例如：(Ti、W)(C、N)、(Ti、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W。因此，藉由在金屬陶瓷中存在第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內進展。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。Specific examples of the fourth hard phase include (Ti, W) (C, N), (Ti, 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 (W distribution is not observed), and W is uniformly present throughout the fourth hard phase. Therefore, by the presence of the fourth hard phase in the cermet, although the hardness is slightly lowered, the hardness is uniform and it is difficult for the crack 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.
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1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1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。When the hard phase is substantially composed of only the first hard phase and the second hard phase, it is difficult to improve the defect resistance. When the hard phase is substantially composed of only the first hard phase and the third hard phase, 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 first 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.
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。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. When the hard phase is substantially composed of only the second hard phase and the fourth hard phase, the improvement of the defect resistance cannot be expected.
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，則切削中容易與被切削材(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1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品質。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 presence of the third hard phase containing W relatively increases. If a large amount of W is present, it is easy to react with the workpiece (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 first 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. Quality.
於硬質相實質上包含第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，但會引起硬度下降，從而龜裂容易進展，故而缺損產生率增高。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。When the hard phase substantially includes the first hard phase, the second hard phase, and the fourth hard phase and does not include the third hard phase, although the thermal conductivity is expected to increase, the hardness is lowered and the crack is likely to progress. The rate of defect production increased. 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.
於硬質相實質上包含第2硬質相、第3硬質相及第4硬質相且不包含第1硬質相之情形時，難以獲得藉由第1硬質相之存在而提高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。When the hard phase substantially includes the second hard phase, the third hard phase, and the fourth hard phase and does not include the first hard phase, it is difficult to obtain the desired wear resistance by the presence of the first hard phase. And the effect of the weld resistance, especially the gloss of the machined surface of the workpiece is poor.
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，作為金屬陶瓷中之硬質相之主成分之Ti(C、N)系硬質相僅為第1硬質相之情形時，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。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, N) which is a main component of the hard phase in the cermet When the hard phase is only the first hard phase, as described above, the wettability with the bonded phase is extremely deteriorated, and voids are likely to occur, so that mechanical properties are deteriorated.
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。In addition to the first hard phase and the second hard phase, the cermet of the present invention has a third hard phase and a fourth hard phase in particular, whereby the heat strength can be maintained and the reaction with steel can be suppressed. Therefore, the cutting tool using the cermet according to the present invention as a base material 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.
[粒徑][particle size]
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 μm以下之微粒與粒徑超過1 μm且為3 μm以下之粗粒。更好的是相對於硬質相之總面積而為60%以上且90%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1硬質相、第2硬質相、第3硬質相及第4硬質相，上述微粒係實質上包含第1硬質相及第2硬質相。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 1 μm and not more than 3 μm. More preferably, the hard phase of 60% or more and 90% or less with respect to the total area of the hard phase contains the above coarse particles, and the remainder of the hard phase contains the above 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 fine particles substantially include the first hard phase and the second hard phase.
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高。粗大粒子之粒徑超過1 μm且微細粒子之粒徑為1 μm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 μm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0.1 μm以上且0.8 μm以下。In such a mixed structure, fine particles are present in such a manner that a gap is formed between the coarse particles by filling, whereby an improvement in hardness or an improvement in fracture toughness can be achieved. When the particle size of the coarse particles exceeds 1 μm and the particle diameter of the fine particles is 1 μm or less, a sufficient gap is provided between the coarse particles, and 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, so that the decrease in hardness or the deterioration of fracture toughness due to the existence of a large bonded phase cell can be reduced. . The particle diameter of the fine particles is particularly preferably 0.1 μm or more and 0.8 μm or less.
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內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，藉由適當地存在微細粒子，可減小金屬陶瓷之最表面之表面粗糙度，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70%以上且85%以下。進而，相對於微細粒子之總面積為80%以上、較好的是90%以上、更好的是大致全部包含第1硬質相及第2硬質相，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中進行敍述。Further, since the area ratio of the coarse particles is 60% or more, since coarse particles are appropriately present, the effect of suppressing the progress of cracks is large, and the toughness can be improved. Further, since the area ratio of the coarse particles is 90% or less, sufficient fine particles are present in the gap formed between the coarse particles, and the improvement in hardness or the progress of cracking can be suppressed. Further, by appropriately presenting the fine particles, the surface roughness of the outermost surface of the cermet can be reduced, and excellent cutting performance can be obtained. The range of the area ratio of the above coarse particles is more preferably 70% or more and 85% or less. Further, the total area of the fine particles is 80% or more, preferably 90% or more, and more preferably substantially all of the first hard phase and the second hard phase are contained, whereby there is sufficient high hardness and fine Ti (C, N), thereby improving wear resistance. The calculation method of the particle size, area and area ratio prescribed in the present invention will be described below.
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。The adjustment of the particle diameter and the area ratio of the hard phase particles can be carried out by, for example, adjusting the size or addition 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 to make the powder fine, if the firing temperature is increased, there is a case where the particles grow to have coarse hard phase particles.
相對於硬質相之總面積，將粒徑超過1 μm且為3 μm以下(粗粒)之第1硬質相之面積率設為S1，並將粒徑超過1 μm且為3 μm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0.5以下。若(S1+S2)為0.1以上，則難以與被切削材熔接，降低於被切削材之表面上產生微小之缺損，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(S1+S2)為0.5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0.3以上且0.5以下。The area ratio of the first hard phase having a particle diameter of more than 1 μm and 3 μm or less (coarse grain) is set to S1 with respect to the total area of the hard phase, and the particle diameter exceeds 1 μm and is 3 μm or less (coarse grain) When the area ratio of the second hard phase is S2, (S1+S2) preferably satisfies 0.1 or more and 0.5 or less. When (S1+S2) is 0.1 or more, it is difficult to weld to the workpiece, and it is less likely to cause a slight defect on the surface of the workpiece, thereby improving the properties of the machined surface of the workpiece, and by welding resistance. The increase in properties reduces the wear caused by welding, which improves the wear resistance of the tool. In addition, when (S1+S2) is 0.5 or less, it is possible to suppress a decrease in 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 0.3 or more and 0.5 or less.
又，將粒徑超過1 μm且為3 μm以下(粗粒)之第3硬質相之面積率設為S3，並將粒徑超過1 μm且為3 μm以下(粗粒)之第4硬質相之面積率設為S4時，若S1/(S1+S2)滿足0.1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0.3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。In addition, the area ratio of the third hard phase having a particle diameter of more than 1 μm and 3 μm or less (coarse grain) is S3, and the fourth hard phase having a particle diameter of more than 1 μm and 3 μm or less (coarse grain) is obtained. When the area ratio is S4, if S1/(S1+S2) satisfies 0.1 or more and 0.4 or less, and S3/(S3+S4) satisfies 0.4 or more and 0.9 or less, the wear resistance and the defect resistance can be further improved. Moreover, the surface gloss of the workpiece can be further improved. In this case, the range of S1/(S1+S2) is more preferably 0.3 or more and 0.4 or less, and the range of S3/(S3+S4) is more preferably 0.7 or more and 0.9 or less.
將粒徑為1 μm以下(微粒)之第1硬質相之面積設為SS1，並將粒徑為1 μm以下(微粒)之第2硬質相之面積設為SS2時，SS1/(SS1+SS2)較好的是0.5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。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 0.5 or more and 0.9 or less. When SS1/(SS1+SS2) is 0.5 or more, there are many minute first hard phases 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.
相對於金屬陶瓷之總面積(硬質相+鍵結相)，第3硬質相之面積與第4硬質相之面積之總計面積率較好的是大於40%。於該情形時，熱特性穩定，故而可提高耐熱龜裂性，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。The total area ratio of the area of the third hard phase to the area of the fourth hard phase is preferably more than 40% with respect to the total area of the cermet (hard phase + bonded phase). In this case, since the thermal characteristics are stabilized, the heat crack 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.
《鍵結相》Bond phase
鍵結相係以選自鈷(Co)、鐵(Fe)、鎳(Ni)之類之鐵族金屬之至少1種金屬為主成分。所謂「主成分」，係指鍵結相實質上僅由選自上述鐵族金屬中之1種以上之金屬構成之情形，或者於選自上述鐵族金屬中之1種以上之金屬中以相對於鍵結相之總質量為0.1質量%以上且20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80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韌性，從而可提高耐缺損性。又，若鍵結相之主成分(鍵結相之總質量之80質量%以上)為Co及Ni之至少一者，則與硬質相之潤濕性高，並且耐腐蝕性優異，故而成為更適於切削工具之構成材料之金屬陶瓷。The bonding phase is mainly composed of at least one metal selected from the group consisting of cobalt (Co), iron (Fe), and nickel (Ni). The term "main component" means a case where the bonding phase is substantially composed only of one or more metals selected from the group consisting of the above-mentioned iron group metals, or a metal selected from one or more selected from the group consisting of the above iron group metals. The alloy in which the total mass of the bonded phase is 0.1% by mass or more and 20% by mass or less or less is a constituent element of the hard phase, that is, 80% by mass or more of the bonded phase contains an iron group metal. When the constituent phase of the hard phase is solid-dissolved in the bonded phase, there is a tendency that the toughness can be improved by solid solution strengthening, and the defect resistance can be improved. In addition, when at least one of Co and Ni is a main component of the bonded phase (80% by mass or more of the total mass of the bonded phase), the wettability with the hard phase is high, and the corrosion resistance is excellent, so that it becomes more A cermet suitable for the constituent material of the cutting tool.
於鍵結相中包含Ni及Co之雙方之情形時，尤其將鍵結相中之Ni與Co之存在質量比(Ni質量相對於Co質量之比)設為Ni/Co時，Ni/Co較好的是0.7以上且1.5以下。Ni/Co滿足0.7以上且1.5以下，藉此可降低潤濕性之下降而維持高韌性，並且可降低硬度之下降而維持高強度。Ni/Co尤其好的是0.8以上且1.2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。When the bonding phase includes both Ni and Co, especially when the mass ratio of Ni to Co in the bonded phase (ratio of Ni mass to Co mass) is Ni/Co, Ni/Co is compared. Preferably, it is 0.7 or more and 1.5 or less. Ni/Co satisfies 0.7 or more and 1.5 or less, whereby the decrease in wettability can be reduced, high toughness can be maintained, and the decrease in hardness can be reduced to maintain high strength. Ni/Co is particularly preferably 0.8 or more and 1.2 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.
[其他含有元素][Other elements included]
本發明金屬陶瓷亦可含有鉬(Mo)。於含有Mo之情形時，尤其存在容易形成第2硬質相之傾向。因此，可提高硬質相與鍵結相之潤濕性，故而鍵結相可充分存在於構成硬質相之粒子周圍，可提高韌性。Mo含量較好的是0.01質量%以上且2.0質量%以下。若Mo含量為0.01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。Mo含量更好的是0.5質量%以上且1.5質量%以下。亦可不含有Mo。The cermet of the present invention may also contain molybdenum (Mo). In the case where Mo is contained, there is a tendency that the second hard phase is easily formed. Therefore, the wettability of the hard phase and the bonded phase can be improved, so that the bonded phase can sufficiently exist around the particles constituting the hard phase, and the toughness can be improved. The Mo content is preferably 0.01% by mass or more and 2.0% by mass or less. When the Mo content is 0.01% by mass or more, the wettability is improved as a whole of the cermet, and the hardness and toughness can be improved as described above. When the Mo content is 2.0% by mass or less, it is possible to suppress the formation of the first hard phase and the second hard phase. The third hard phase is 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 it is possible to obtain the desired defect resistance. The Mo content is more preferably 0.5% by mass or more and 1.5% by mass or less. It may or may not contain Mo.
<金屬陶瓷工具><Metal Ceramic Tools>
《基材》Substrate
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。The cermet of the present invention having the above-described configuration includes four hard phases as described above, and is excellent in not only excellent in abrasion resistance but also excellent in defect resistance and weld resistance, so that it can be preferably used for a desired finished surface. The substrate material of the cutting tool (cermet tool).
《硬質膜》Hard Film
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1層亦可為多層，總計厚度較好的是1~20 μm。硬質膜之形成方法亦可利用熱CVD(Chemical 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。The substrate may also comprise a hard film that is at least partially coated on a surface thereof. Preferably, the hard film is contained at least in the vicinity of the blade edge, and may be contained throughout the entire surface of the substrate. The hard film may be one layer or multiple layers, and the total thickness is preferably 1 to 20 μm. The method of forming a hard film may also be a chemical vapor deposition method (CVD method) by thermal CVD (Chemical Vapor Deposition) or a physical vapor deposition method (PVD (Physical Vapor Deposition). Any of the deposition methods).
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1種以上，該化合物係選自由週期表4、5、6族金屬、鋁(Al)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(O)及硼(B)所組成之群中之1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)、Al2 O3 、(Ti、Al)N、TiN、TiC、(Al、Cr)N等。The composition of the hard film may be one or more selected from the group consisting of a compound, cubic boron nitride (cBN), diamond, and diamond-like carbon (DLC). Selecting one or more elements selected from the group consisting of Group 4, 5, and 6 metals, aluminum (Al), and bismuth (Si), and selected from the group consisting of carbon (C), nitrogen (N), and oxygen (O) And a compound of one or more elements selected from 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-described metal. Specific examples of the film quality include Ti (C, N), Al 2 O 3 , (Ti, Al) N, TiN, TiC, (Al, Cr) N and the like.
<金屬陶瓷之製造方法><Method of manufacturing cermet>
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。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 following raw material powder and adjusting the pulverization and mixing time or the calcination conditions.
《原料之準備》Preparation of raw materials
原料使用包含選自週期表4、5、6族金屬之至少1種金屬、與碳(C)及氮(N)之至少1種元素之化合物的化合物粉末，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，可容易獲得如上所述之具有混合著粗粒與微粒之硬質相之金屬陶瓷。粉末之大小係考慮硬質相之粒子大小而適當地選擇即可。As the raw material, a compound powder containing at least one metal selected from the group consisting of metals of Groups 4, 5, and 6 of the periodic table, and a compound of at least one of carbon (C) and nitrogen (N), and a powder constituting the bonded phase are used. Representative of the iron group metal powder. By using a fine powder and a relatively coarse powder as the powder, a cermet having a hard phase in which coarse particles and fine particles are mixed as described above can be easily obtained. The size of the powder may be appropriately selected in consideration of the particle size of the hard phase.
為生成第1硬質相及第2硬質相，例如使用Ti(C、N)粉末。就Ti(C、N)粉末而言，先前有生成海綿Ti作為起始材料者，但尤其若使用生成有TiO2 作為起始材料之Ti(C、N)粉末，則存在容易形成微粒之第1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Ti以外之週期表4、5、6族金屬之化合物粉末，例如使用(Ti、W)(C、N)粉末。藉由使用此種化合物粉末，可容易獲得第4硬質相之粒子，亦即，可容易獲得均勻地固溶有Ti與除Ti以外之週期表4、5、6族金屬之單相結構之粒子。To form the first hard phase and the second hard phase, for example, Ti (C, N) powder is used. In the case of Ti(C, N) powder, there has been previously produced sponge Ti as a starting material, but especially if Ti(C, N) powder having TiO 2 as a starting material is used, there is a possibility that particles are easily formed. 1 tendency of hard phase. Moreover, when the compound powder containing Mo is used together 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. In order to form the fourth hard phase, a compound powder containing Ti and a metal of Groups 4, 5, and 6 of the periodic table other than Ti is used, and for example, (Ti, W) (C, N) powder is used. By using such a compound powder, particles of the fourth hard phase can be easily obtained, that is, particles having a single phase structure in which Ti and a metal other than Ti of the periodic table other than Ti are uniformly dissolved can be easily obtained. .
《粉碎及混合》"Crush and Mix"
若延長粉碎時間，則可使粉末變得微細，存在金屬陶瓷中容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36小時以下。When the pulverization time is prolonged, the powder can be made fine, and there is a tendency that fine hard phase particles are easily formed in the cermet. 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 core. The pulverization and mixing time is preferably from 12 hours to 36 hours.
《煅燒》Calcination
若過度提高煅燒溫度，則存在如下顧慮，即，構成硬質相之粒子成長而於金屬陶瓷中容易存在較多之粗大粒子，或者尤其難以形成第4硬質相之粒子。因此，煅燒溫度較好的是1400℃以上且1600℃以下。又，於煅燒步驟中，於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10℃/min以上，則存在容易生成第4硬質相之傾向。When the calcination temperature is excessively increased, there is a concern that particles constituting the hard phase grow, and a large number of coarse particles are likely to be present in the cermet, or it is particularly difficult to form particles of the fourth hard phase. Therefore, the calcination temperature is preferably 1400 ° C or more and 1600 ° C or less. Further, in the calcination step, when the molded body which is heated while maintaining the calcination temperature for a predetermined period of time is cooled, it is preferably cooled in a vacuum or an inert gas atmosphere of argon (Ar). In the case of an inert gas atmosphere, it is particularly preferable to set a relatively low pressure of 665 Pa or more and 6650 Pa or less. In addition, when the cooling rate is increased, specifically, 10 ° C / min or more, the fourth hard phase tends to be easily formed.
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。The coated cermet tool of the present invention is excellent in abrasion resistance and defect resistance, and can perform cutting processing excellent in the quality of the machined surface of the workpiece. The cermet of the present invention can be preferably used as a constituent material of such a tool.
<測試例><Test example>
製作包含金屬陶瓷之切削工具，並對金屬陶瓷之組成、組織及切削工具之切削性能進行調查。A cutting tool containing cermet is produced, and the composition, organization and cutting performance of the cermet are investigated.
切削工具係以如下方式製作。首先，作為原料粉末而準備以下者。The cutting tool was produced in the following manner. First, the following is prepared as a raw material powder.
(1)平均粒徑為0.7 μm之Ti(C、N)粉末該Ti(C、N)粉末係生成有TiO2 作為起始原料之粉末，C/N比為1/1。(1) Ti (C, N) powder having an average particle diameter of 0.7 μm The Ti (C, N) powder was a powder obtained by using TiO 2 as a starting material, and the C/N ratio was 1/1.
(2)平均粒徑為0.8 μm之Ti(C、N)粉末及平均粒徑為3.0 μm之Ti(C、N)粉末(2) Ti(C, N) powder having an average particle diameter of 0.8 μm and Ti(C, N) powder having an average particle diameter of 3.0 μm
該等Ti(C、N)粉末之任一者均係生成有海綿Ti作為起始原料之粉末，C/N比為1/1。於表1中，將該等Ti(C、N)粉末記作「s-TiCN」。Any of the Ti(C, N) powders was a powder obtained by using sponge Ti as a starting material, and the C/N ratio was 1/1. In Table 1, these Ti(C, N) powders are referred to as "s-TiCN".
(3)平均粒徑為2.8 μm之(Ti、W)(C、N)粉末(3) (Ti, W) (C, N) powder with an average particle diameter of 2.8 μm
該(Ti、W)(C、N)粉末係預先使W固溶於Ti(C、N)粉末中之粉末，C/N比為1/1。The (Ti, W) (C, N) powder was a powder in which W was dissolved in Ti (C, N) powder in advance, and the C/N ratio was 1/1.
(4)平均粒徑為0.5～3.0 μm之WC粉末、NbC粉末、TaC粉末Mo2 C粉末、Ni粉末、Co粉末(4) WC powder, NbC powder, TaC powder Mo 2 C powder, Ni powder, Co powder having an average particle diameter of 0.5 to 3.0 μm
該等粉末之任一者均係市售之粉末。Any of these powders are commercially available powders.
以達到表1所示之調配比例(質量%)之方式秤取‧調配所準備之上述原料粉末，準備粉末No. 1～12。The raw material powder prepared in accordance with the blending ratio (% by mass) shown in Table 1 was prepared, and the powder Nos. 1 to 12 were prepared.
將所準備之各粉末與丙酮溶劑及超硬合金製球珠一併裝入不鏽鋼製坩堝內，進行粉碎及混合(濕式)。於表2中表示製作各樣品時使用之原料粉末編號、粉碎‧混合時間(小時)。向粉碎及混合後進行乾燥所獲得之混合粉末中添加少量石蠟之後，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。Each of the prepared powders was placed in a stainless steel crucible together with an acetone solvent and a cemented carbide bead, and pulverized and mixed (wet). Table 2 shows the raw material powder numbers used for the preparation of each sample, and the pulverization and mixing time (hours). A small amount of paraffin wax was added to the mixed powder obtained by pulverization and mixing, and then subjected to press molding at a pressure of 98 MPa using a mold to prepare a molded body of CNMG120408 shape.
將所獲得之各成形體分別加熱至450℃而去除石蠟後，於真空中自室溫升溫至1250℃為止，並於表3所示之條件下進行其後之煅燒(亦包括冷卻步驟)，從而獲得煅燒體。Each of the obtained molded bodies was heated to 450 ° C to remove paraffin, and then heated from room temperature to 1,250 ° C in a vacuum, and then calcined (including a cooling step) under the conditions shown in Table 3, thereby A calcined body is obtained.
對所獲得之各煅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1種粒子：黑色粒子、黑色粒子周圍之一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，將該粒子稱作黑芯雙重粒子)；白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)；及灰色粒子(以下，將該粒子稱作灰色粒子)。於樣品No. 1~19之煅燒體中，如圖1所示觀察到黑色單粒子(第1硬質相1)、黑芯雙重粒子(第2硬質相2)、白芯雙重粒子(第3硬質相3)及灰色粒子(第4硬質相4)之四種粒子。觀察到第1硬質相1具有僅由黑色粒子構成者及黑色粒子之一部分被灰色區域(周邊部1b)覆蓋者，第2硬質相2之芯部2a為黑色、周邊部2b為灰色，第3硬質相3之芯部3a為白色、周邊部3b為灰色。於粒子之間存在鍵結相10。另一方面，於樣品No. 100~105之煅燒體中，觀察不到黑色單粒子、黑芯雙重粒子、白芯雙重粒子及灰色粒子中之至少一者。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, at least one kind of particles of the following particles were observed in the observation field of each of the calcined bodies: black particles and particles surrounded by a gray region around one of the black particles (hereinafter, these two kinds of particles are collectively referred to as a black single particle); a particle surrounded by a gray region around the black particle (hereinafter, the particle is referred to as a black core double particle); a particle surrounded by a gray region around the white particle (hereinafter, the particle is 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 Nos. 1 to 19, black single particles (first hard phase 1), black core double particles (second hard phase 2), and white core double particles (third hard) were observed as shown in Fig. 1 . Phase 3) and four particles of gray particles (4th hard phase 4). It is observed that the first hard phase 1 is composed of only black particles and one of the black particles is covered by the gray region (peripheral portion 1b), the core portion 2a of the second hard phase 2 is black, and the peripheral portion 2b is gray, and the third portion The core portion 3a of the hard phase 3 is white, and the peripheral portion 3b is gray. There is a bonded phase 10 between the particles. On the other hand, in the calcined body of Sample Nos. 100 to 105, at least one of black single particles, black core double particles, white core double particles, and gray particles was not observed.
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X射線、ICP-AES(Inductively Coupled Plasm Atomic Emission Spectroscopy，感應耦合電漿原子發射光譜分析儀)等進行分析。The composition of each of the above particles was investigated by TEM-EDX (Transmission Electron Microscope-Energy Dispersive X-ray Spectrometer), and it was found that the black single particle contained Ti (C, N); the core portion of the black core double particle contains Ti (C, N), and the peripheral portion covering the core portion contains a composite carbonitride solid solution containing one or more metals of Ti, W, Nb, Ta, and Mo The white core double particle includes 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 periphery of the core; gray particles A composite carbonitride solid solution containing one or more metals of Ti, W, Nb, Ta, and Mo. Moreover, the clear boundary between the core portion and the peripheral portion was not observed in the gray particles. In addition, in the component analysis of the hard phase, in addition to TEM-EDX analysis, EPMA (electron probe micro analyser), fluorescent X-ray, ICP-AES (Inductively Coupled Plasm Atomic Emission Spectroscopy) can be used. A coupled plasma atomic emission spectrometer) was analyzed.
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，煅燒體中之Ni含量與原料之Ni粉末之添加量相比減少0.2~0.3%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%左右)大致相等。進而，求得存在於鍵結相中之Ni與Co之存在質量比Ni/Co。將其結果示於表2。又，藉由ICP分析，對各樣品(煅燒體)之Mo含量(質量%)進行調查。亦將其結果示於表2。A bonded phase exists between the above particles, and investigation by TEM-EDX analysis revealed that the bonded phase substantially contains Co and Ni. In the sample, there is a constituent element of a hard phase in which about several mass% of solid phase is dissolved in the bonded phase. 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 of the raw material, and the Ni content in the calcined body is reduced by 0.2 to 0.3% as compared with the addition amount of the Ni powder of the raw material. about. In this case, it is considered that the content of the hard phase in each sample (calcined body) is substantially equal to the amount obtained by subtracting the addition amount of the Co powder and the Ni powder used in the raw material (about 86% by mass). Further, the existence mass ratio Ni/Co of Ni and Co existing in the bonded phase was determined. The results are shown in Table 2. Further, the Mo content (% by mass) of each sample (calcined body) was investigated by ICP analysis. The results are also shown in Table 2.
使用上述SEM之剖面觀察圖像(5000倍)，求得各樣品(煅燒體)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 μm之粒子，故而硬質相實質上包含粒徑為3 μm以下之粒子。Using the cross-sectional observation image (5000 times) of the above SEM, the particle diameters of all the particles present in the observation field of each sample (calcined body) 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 determining the particle diameter in a state including the peripheral portion. As a result, particles having a particle diameter of more than 3 μm were hardly observed in any of the samples, and thus the hard phase substantially contained particles having a particle diameter of 3 μm or less.
利用就剖面觀察圖像(5000倍)所獲得之粒徑(上述Martin直徑)，分別求得各粒子之面積。又，就第1硬質相、第2硬質相、第3硬質相及第4硬質相，分別求得粒徑超過1 μm且為3 μm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 μm以下之粒子之總計面積(以下，將該總計面積稱作微粒面積(1))，針對第2硬質相計算粒徑為1 μm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(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)之總計設為硬質相之總面積，並將粗粒面積(1)~(4)相對於硬質相之總面積之總計比例，亦即粗粒面積率「粗粒/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、將微粒面積(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瓷全體(硬質相+鍵結相)之面積(於此，觀察圖像之視野面積)之面積率：(第3+第4)/(金屬陶瓷全體)。亦將其結果示於表4。另外，存在第3硬質相或第4硬質相之樣品之任一者中，第3硬質相之粒子或第4硬質相之粒子之粒徑大部分均超過1 μm，幾乎觀察不到粒徑為1 μm以下之第3硬質相之粒子或第4硬質相之粒子。The area of each particle was determined by the particle diameter (the above Martin diameter) obtained by observing the cross-sectional observation image (5000 times). 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 of more than 1 μm and 3 μm or less is obtained (hereinafter, the total area of these is equal to They are called coarse grain area (1), coarse grain area (2), coarse grain area (3), and coarse grain area (4), and the total area of particles having a particle diameter of 1 μm or less is determined for the first hard phase. (hereinafter, the total area is referred to as a particle area (1)), and the total area of particles having a particle diameter of 1 μm or less is calculated for the second hard phase (hereinafter, the total area is referred to as a particle area (2)). The total area of the hard phase is set for the total area of the coarse grain area (1), the coarse grain area (2), the coarse grain area (3), the coarse grain area (4), the particle area (1), and the particle area (2). The total ratio of the coarse-grained areas (1) to (4) to the total area of the hard phase, that is, the coarse-grained area ratio "total coarse/hard phase" (%) 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 particle area (2) are relative to the total area of the hard phase. The respective area ratios (%) are 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 to S1, the area ratio of the coarse grain area (2) to the total area of the hard phase is S2, and the coarse grain area (3) is relative. The area ratio of the total area of the hard phase is S3, and the area ratio of the coarse grain area (4) to the total area of the hard phase is S4, and the (S1+S2), S1/(S1+) is obtained at this time. S2), S3/(S3+S4). The results are shown in Table 4. Further, when the particle area (1) is SS1 and the particle area (2) is SS2: SS1/(SS1+SS2) is obtained, and the area of the third hard phase and the area of the fourth hard phase are obtained. The area ratio of the total area to the area of the entire cermet (hard phase + bonding phase) (here, the field of view of the observed image): (3rd + 4th) / (total cermet). The results are also shown in Table 4. Further, in any of the samples of the third hard phase or the fourth hard phase, the particle diameter of the particles of the third hard phase or the fourth hard phase is mostly more than 1 μm, and the particle diameter is hardly observed. Particles of the third hard phase or particles of the fourth hard phase of 1 μm or less.
[表4][Table 4]
對所獲得之各煅燒體之表面分別實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)，對耐磨損性、耐缺損性、加工面之表面粗糙度進行調查。將其結果示於表6。表面粗糙度Ra係依據JIS B 0601(2001)進行測定。Each of the obtained calcined bodies was subjected to a surface grinding treatment and a tip treatment to prepare a cutting insert (cutting tool) having a CNMG120408-shaped crushing member. 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 abrasion resistance, the defect resistance, and the surface roughness of the machined surface were investigated. . The results are shown in Table 6. The surface roughness Ra was measured in accordance with JIS B 0601 (2001).
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No. 1~19係與不存在上述四種相中之某一種之樣品No. 100~105相比，耐磨損性優異，並且耐缺損性亦優異。且可知，使用該等樣品No. 1~19時，被切削材之加工面之表面粗糙度Ra較小，且加工面之面品質較高。As shown in Table 6, it is found that there are samples No. 1 to 19 in which all of the first hard phase, the second hard phase, the third hard phase, and the fourth hard phase are present, and there is no one of the above four phases. Sample No. 100 to 105 were superior in abrasion resistance and excellent in defect resistance. It is also known that when these samples No. 1 to 19 are used, the surface roughness Ra of the machined surface of the workpiece is small, and the surface quality of the machined surface is high.
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0.1以上且0.5以下之樣品或S1/(S1+S2)滿足0.1以上且0.4以下、及S3/(S3+S4)滿足0.4以上且0.9以下之樣品，存在表面粗糙度Ra變得更小之傾向，且面品質優異。可知，於樣品No. 1~19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。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. . Further, in Sample Nos. 1 to 19, in particular, (S1+S2) satisfies 0.1 or more and 0.5 or less samples, or S1/(S1+S2) satisfies 0.1 or more and 0.4 or less, and S3/(S3+S4) satisfies In the sample of 0.4 or more and 0.9 or less, the surface roughness Ra tends to be smaller, and the surface quality is excellent. In the sample Nos. 1 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.
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、Al)N膜(厚度為4 μm)之被覆刀片，並於表5所示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，上述實施形態可於不脫離本發明主旨之範圍內進行適當變更，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。On the surface of the cutting insert of Sample Nos. 1 to 19, a coated blade formed of a (Ti, Al)N film (thickness: 4 μm) by arc ion plating was formed under the test conditions shown in 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. In addition, the above-described embodiment can be appropriately modified without departing from the spirit and scope of the invention, and is 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.
本發明金屬陶瓷係可較佳地用於切削工具之原材料。本發明被覆金屬陶瓷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。The cermet system of the present invention can be preferably used as a raw material for a cutting tool. The coated cermet tool system of the present invention can be preferably used for rotary cutting, grinding and cutting, and particularly for steel cutting.
1．．．第1硬質相1. . . First hard phase
1b．．．周邊部1b. . . Peripheral part
2．．．第2硬質相2. . . Second hard phase
2a、3a．．．芯部2a, 3a. . . Core
2b、3b．．．周邊部2b, 3b. . . Peripheral part
3．．．第3硬質相3. . . Third hard phase
4．．．第4硬質相4. . . 4th hard phase
10．．．鍵結相10. . . Bond phase
圖1係示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。Fig. 1 is a schematic view showing four hard phases present in the cermet of the present invention.
1．．．第1硬質相1. . . First hard phase
1b．．．周邊部1b. . . Peripheral part
2．．．第2硬質相2. . . Second hard phase
2a、3a．．．芯部2a, 3a. . . Core
2b、3b．．．周邊部2b, 3b. . . Peripheral part
3．．．第3硬質相3. . . Third hard phase
4．．．第4硬質相4. . . 4th hard phase
10．．．鍵結相10. . . Bond phase
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- 2010-03-19 SE SE1051204A patent/SE536731C2/en unknown
- 2010-03-19 CN CN201080001593.3A patent/CN102046823B/en active Active
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Also Published As
| Publication number | Publication date |
|---|---|
| KR20100135941A (en) | 2010-12-27 |
| KR101253853B1 (en) | 2013-04-12 |
| SE1051204A1 (en) | 2011-02-08 |
| WO2010110197A1 (en) | 2010-09-30 |
| CN102046823B (en) | 2013-02-13 |
| JP4690475B2 (en) | 2011-06-01 |
| SE536731C2 (en) | 2014-07-01 |
| CN102046823A (en) | 2011-05-04 |
| TW201042054A (en) | 2010-12-01 |
| JP2010222650A (en) | 2010-10-07 |
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