JP4709223B2 - Sintered body, manufacturing method thereof, sliding member using the sintered body, film forming material, hot extrusion die, hot extrusion molding apparatus and hot extrusion using the hot extrusion die Molding method - Google Patents

Sintered body, manufacturing method thereof, sliding member using the sintered body, film forming material, hot extrusion die, hot extrusion molding apparatus and hot extrusion using the hot extrusion die Molding method Download PDF

Info

Publication number
JP4709223B2
JP4709223B2 JP2007537741A JP2007537741A JP4709223B2 JP 4709223 B2 JP4709223 B2 JP 4709223B2 JP 2007537741 A JP2007537741 A JP 2007537741A JP 2007537741 A JP2007537741 A JP 2007537741A JP 4709223 B2 JP4709223 B2 JP 4709223B2
Authority
JP
Japan
Prior art keywords
hot extrusion
sintered body
mass
die
ticn
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
JP2007537741A
Other languages
Japanese (ja)
Other versions
JPWO2007037431A1 (en
Inventor
浩 浜島
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Kyocera Corp
Original Assignee
Kyocera Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Kyocera Corp filed Critical Kyocera Corp
Priority to JP2007537741A priority Critical patent/JP4709223B2/en
Publication of JPWO2007037431A1 publication Critical patent/JPWO2007037431A1/en
Application granted granted Critical
Publication of JP4709223B2 publication Critical patent/JP4709223B2/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21C—MANUFACTURE OF METAL SHEETS, WIRE, RODS, TUBES OR PROFILES, OTHERWISE THAN BY ROLLING; AUXILIARY OPERATIONS USED IN CONNECTION WITH METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL
    • B21C25/00—Profiling tools for metal extruding
    • B21C25/02—Dies
    • B21C25/025—Selection of materials therefor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21C—MANUFACTURE OF METAL SHEETS, WIRE, RODS, TUBES OR PROFILES, OTHERWISE THAN BY ROLLING; AUXILIARY OPERATIONS USED IN CONNECTION WITH METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL
    • B21C25/00—Profiling tools for metal extruding
    • B21C25/02—Dies
    • 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
    • B22F5/00—Manufacture of workpieces or articles from metallic powder characterised by the special shape of the product
    • B22F5/10—Manufacture of workpieces or articles from metallic powder characterised by the special shape of the product of articles with cavities or holes, not otherwise provided for in the preceding subgroups
    • 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
    • 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
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/24—After-treatment of workpieces or articles
    • B22F2003/241—Chemical after-treatment on the surface
    • B22F2003/242—Coating
    • 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
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/24—After-treatment of workpieces or articles
    • B22F2003/247—Removing material: carving, cleaning, grinding, hobbing, honing, lapping, polishing, milling, shaving, skiving, turning the surface
    • 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
    • B22F2998/10—Processes characterised by the sequence of their steps

Description

本発明は、焼結体とその製造方法とその焼結体を用いた摺動部材、成膜用材料並びに熱間押出成形用ダイスとその熱間押出成形用ダイスを用いた熱間押出成形装置及び熱間押出成形方法に関する。   The present invention relates to a sintered body, a manufacturing method thereof, a sliding member using the sintered body, a film forming material, a hot extrusion die, and a hot extrusion molding apparatus using the hot extrusion die. And a hot extrusion molding method.

従来、アルミニウム合金などの熱間押出により押出材を成形する場合、図５及び９に示すような、熱間押出成形装置１１１のダイケース１０２に組み込まれたベアリング部となる熱間押出成形用ダイス１０１の誘導部となる貫通孔１０１ａから、約４００〜５００℃に加熱されたアルミニウム合金のビレット５を押出成形することにより、所望の形状の押出材６が成形されてきた。   Conventionally, when an extruded material is formed by hot extrusion of aluminum alloy or the like, as shown in FIGS. 5 and 9, a hot extrusion die that serves as a bearing portion incorporated in the die case 102 of the hot extrusion molding device 111. An extruded material 6 having a desired shape has been formed by extruding an aluminum alloy billet 5 heated to about 400 to 500 ° C. from a through-hole 101 a serving as a guide portion 101.

そして、熱間押出成形用ダイス１０１の材質としては、通常、超硬合金（以下で、超硬という）やＳＫＤ６１が用いられていて、超硬は、高硬度で且つ金属材に匹敵する高強度が得られること、ＳＫＤ６１は高温下での硬度・強度の劣化が出難いという理由で広く使用されている。   And as a material of the hot extrusion molding die 101, usually a cemented carbide (hereinafter referred to as cemented carbide) or SKD61 is used, and the cemented carbide has a high hardness and a high strength comparable to a metal material. SKD61 is widely used because it is difficult to deteriorate hardness and strength at high temperatures.

しかしながら、前述した高温下によるアルミニウム合金等の熱間押出成形用ダイス１０１の材質として超硬やＳＫＤ６１を用いると、超硬では約４００〜５００℃の高温下での熱劣化により、著しく硬度および強度が低下する。またＳＫＤ６１では使用上十分に耐えうるだけの高硬度が得られず、更には例えば、アルミニウム合金の押出材６を成形時に誘導部となる貫通孔１０１ａの内周面１０１ｂにアルミニウムが凝着する。これらのことにより、超硬やＳＫＤ６１は長時間の成形に耐えるものではなく、熱間押出成形用ダイス１０１が破損または摩耗により成形された押出材６への傷の発生や寸法不良といった問題が発生していた。   However, if cemented carbide or SKD61 is used as the material for the hot extrusion molding die 101 such as the aluminum alloy at a high temperature described above, the hardness and strength of the cemented carbide are remarkably increased due to thermal degradation at a high temperature of about 400 to 500 ° C. Decreases. In addition, the SKD 61 cannot obtain a high hardness enough to withstand use, and, for example, aluminum adheres to the inner peripheral surface 101b of the through-hole 101a that serves as a guide portion when the extruded material 6 of an aluminum alloy is formed. As a result, carbide and SKD61 do not endure long-time molding, and problems such as generation of flaws and defective dimensions in the extruded material 6 formed due to damage or wear of the hot extrusion die 101 occur. Was.

最近では、このような問題を解決するために、従来の超硬やＳＫＤ６１で作製した熱間押出成形用ダイス１０１の誘導部となる貫通孔１０１ａの内周面１０１ｂの部分にセラミックやサーメットをコーティングまたは厚くすることや、熱間押出成形用ダイス１０１をセラミックで作製することが模索されている。しかしながら、多くの問題が解決されないことから一般に普及していないのが現状である。   Recently, in order to solve such a problem, a ceramic or cermet is coated on the inner peripheral surface 101b of the through hole 101a serving as a guiding portion of a hot extrusion die 101 made of conventional carbide or SKD61. Alternatively, it has been sought to increase the thickness and to produce the hot extrusion die 101 with ceramic. However, since many problems are not solved, it is not widely used in general.

例えば、アルミニウム合金の熱間押出成形に使用されるベアリング部となる熱間押出成形用ダイス１０１の貫通孔１０１ａの内周面１０１ｂにセラミックスをコーティングすることが、特許文献１、特許文献２、特許文献３に開示されている。   For example, it is possible to coat ceramics on the inner peripheral surface 101b of the through hole 101a of the hot extrusion die 101 that becomes a bearing part used for hot extrusion of an aluminum alloy. It is disclosed in Document 3.

特許文献１、２では、熱間押出成形用ダイス１０１の母材をハイス鋼とし、少なくとも押出材料との摺動面となる部分にＴｉＣを１μｍの厚みでコーティングすることにより、押出材６と熱間押出成形用ダイス１０１の誘導部となる貫通孔１０１ａの内周面１０１ｂの摺動抵抗が低減でき、押出速度を従来比２０％向上できたことが開示されている。   In Patent Documents 1 and 2, the base material of the hot extrusion molding die 101 is made of high-speed steel, and at least a portion that becomes a sliding surface with the extruded material is coated with TiC to a thickness of 1 μm, whereby the extruded material 6 and the heat It is disclosed that the sliding resistance of the inner peripheral surface 101b of the through hole 101a serving as the guiding portion of the inter-extrusion molding die 101 can be reduced, and the extrusion speed can be improved by 20% compared to the conventional technique.

また、特許文献３では、熱間押出成形用ダイス１０１の誘導部となる貫通孔１０１ａの内周面１０１ｂにＴｉＣ、ＶＣ、ＴａＣ、ＷＣなどのセラミックス層を放電硬化処理により厚み２〜１０μｍの範囲で被覆することが提案されており、熱間押出成形用ダイス１０１の母材については触れられてはいないが、被覆されたセラミックス層により、耐摩耗性が向上することが開示されている。   Moreover, in patent document 3, ceramic layers, such as TiC, VC, TaC, and WC, are 2-10 micrometers in thickness by the electric discharge hardening process on the internal peripheral surface 101b of the through-hole 101a used as the induction | guidance | derivation part of the die | dye 101 for hot extrusion molding. Although it has been proposed that the base material of the hot extrusion die 101 is not mentioned, it is disclosed that the wear resistance is improved by the coated ceramic layer.

また、特許文献４では、ＳＫＤ材の熱間押出成形用ダイス１０１の誘導部となる貫通孔１０１ａの内周面１０１ｂの表面にサーメットを厚み４〜１５ｍｍの範囲で厚くすることが提案されている。そこではサーメットの組成として、Ｃｒ3Ｃ2、ＮｂＣ、ＷＣ、ＴｉＣ、ＳｉＣの炭化物系セラミックスの一種または二種以上から選択され、Ｎｉ基またはＮｉＣｒ基の合金マトリックスからなり、前記セラミックスが１０〜３０ｗｔ％含有してなるものである。これにより熱間押出成形時における貫通孔１０１ａの内周面１０１ｂの表面から深さ４ｍｍの位置で７００℃に達したと仮定しても硬度を確保でき摩耗を防止できることと、さらに、熱間押出成形時の熱衝撃によるクラックを抑制し補強した部分の剥離を防止できることが開示されている。Further, Patent Document 4 proposes that the cermet is thickened in the thickness range of 4 to 15 mm on the surface of the inner peripheral surface 101b of the through hole 101a serving as the guide portion of the hot extrusion molding die 101 of the SKD material. . In this case, the composition of the cermet is selected from one or more of Cr 3 C 2 , NbC, WC, TiC, SiC carbide ceramics, and is made of an Ni-based or NiCr-based alloy matrix, and the ceramic is 10 to 30 wt. % Content. As a result, even when it is assumed that the temperature reaches 700 ° C. at a depth of 4 mm from the surface of the inner peripheral surface 101b of the through-hole 101a at the time of hot extrusion molding, hardness can be secured and wear can be prevented. It has been disclosed that cracking due to thermal shock during molding can be suppressed and peeling of the reinforced portion can be prevented.

さらに、特許文献５では、熱間押出成形用ダイス１０１の本体を、ＺｒＯ2−Ｙ2Ｏ3、ＺｒＯ2−ＭｇＯ等のジルコニア系セラミックスまたは、Ｓｉ3Ｎ4窒化珪素等のセラミックスにすることが提案されている。そこではアルミニウムの熱間押出成形時の押出材６への表面欠陥の発生を抑止しつつ、押出速度の増大を図ることが開示されている。Further, in Patent Document 5, the main body of the hot extrusion die 101 is made of zirconia ceramics such as ZrO 2 —Y 2 O 3 , ZrO 2 —MgO, or ceramics such as Si 3 N 4 silicon nitride. Proposed. There, it is disclosed to increase the extrusion speed while suppressing the occurrence of surface defects on the extruded material 6 during the hot extrusion of aluminum.

一方、特許文献６では、アルミニウム溶湯の鋳造等における高温加圧強度が要求される射出成形材やダイキャストスリーブに適した材質として、炭窒化チタン（ＴｉＣＮ）焼結体が提案されていて、炭窒化チタン（ＴｉＣＮ）粉体６４重量部、炭化チタン（ＴｉＣ）粉体３０重量部、助剤としてＡＭＦ合金鉄粉体６重量部を使用し炭窒化チタン系サーメット焼結体を作製することが開示されている。
特開２０００−６３９７２号公報 特開２０００−６３９７３号公報 特開２０００−１０２８１６号公報 特開２０００−６３９７５号公報 特許第２５３５０２５号公報 特開２００３−３２１７１８号公報 On the other hand, in Patent Document 6, a titanium carbonitride (TiCN) sintered body has been proposed as a material suitable for injection molding materials and die-cast sleeves that require high-temperature pressure strength in casting of molten aluminum, etc. Disclosed is a titanium carbonitride-based cermet sintered body using 64 parts by weight of titanium nitride (TiCN) powder, 30 parts by weight of titanium carbide (TiC) powder, and 6 parts by weight of AMF alloy iron powder as an auxiliary. Has been.
JP 2000-63972 A JP 2000-63973 A JP 2000-102816 A JP 2000-63975 A Japanese Patent No. 2535025 Japanese Patent Laid-Open No. 2003-321718

しかしながら、特許文献１、２で提案されたハイス鋼からなる貫通孔１０１ａの内周面１０１ｂにＴｉＣを１μｍコーティングした場合、母材のハイス鋼とコーティングされたＴｉＣの熱膨張係数差が大きいことからコーティングの剥離が生じやすい。また、ＴｉＣは４５０℃以上の環境下で酸化現象が起こり易くなり、高硬度材のＴｉＣから著しく硬度劣化となるＴｉＯ2に置換反応が生じる熱劣化の問題があった。However, when 1 μm of TiC is coated on the inner peripheral surface 101b of the through hole 101a made of high-speed steel proposed in Patent Documents 1 and 2, the difference in thermal expansion coefficient between the high-speed steel and the coated TiC is large. The coating tends to peel off. In addition, TiC is susceptible to an oxidation phenomenon in an environment of 450 ° C. or higher, and there is a problem of thermal deterioration in which a substitution reaction occurs in TiO 2 that is significantly hardened from TiC of a high-hardness material.

また、特許文献３で提案されたセラミックス層を貫通孔１０１ａの内周面１０１ｂに放電加工処理により厚み２〜１０μｍの範囲でコーティングしたものにおいては、母材とコーティングされたセラミック層の熱膨張係数差が大きいことからコーティングの剥離の発生を回避出来るものではなかった。   Further, in the case where the ceramic layer proposed in Patent Document 3 is coated on the inner peripheral surface 101b of the through hole 101a in a thickness range of 2 to 10 μm by electric discharge machining, the thermal expansion coefficient of the base material and the coated ceramic layer is obtained. Due to the large difference, it was not possible to avoid the occurrence of peeling of the coating.

また、特許文献４で提案されたＳＫＤ材の貫通孔１０１ａの内周面１０１ｂに炭化物系のサーメットを厚み４〜１５ｍｍの範囲で厚くしたものにおいては、炭化物系サーメットの組成として、Ｃｒ3Ｃ2、ＮｂＣ、ＷＣ、ＴｉＣ、ＳｉＣの炭化物系セラミックスの一種または二種以上から選択されるが、これらの何れの炭化物系セラミックを僅か１０〜３０ｗｔ％含有使用しても、例えばアルミニウム合金との高い摺動特性が得られない。そのためアルミニウム合金の押出材６の成形時に誘導部となる貫通孔１０１ａの内周面１０１ｂにアルミニウムが凝着し易くなり、破損するという問題や、または摩耗により成形された押出材６への傷の発生や寸法不良といった問題を回避出来るものではなかった。Further, in the case where the carbide cermet is thickened in the thickness range of 4 to 15 mm on the inner peripheral surface 101b of the through hole 101a of the SKD material proposed in Patent Document 4, the composition of the carbide cermet is Cr 3 C 2. NbC, WC, TiC and SiC are selected from one or two or more kinds of carbide ceramics. Even if these carbide ceramics are used in an amount of only 10 to 30 wt%, for example, a high slip with an aluminum alloy is used. Dynamic characteristics cannot be obtained. Therefore, aluminum is likely to adhere to the inner peripheral surface 101b of the through-hole 101a serving as a guide portion during the molding of the aluminum alloy extrudate 6 and may be damaged, or damage to the extrudate 6 formed by wear may be caused. Problems such as generation and dimensional defects could not be avoided.

また、特許文献５で提案された熱間押出成形用ダイス１０１本体をジルコニア系セラミックス或いは窒化珪素セラミックスで作製したものにおいては、アルミニウム合金の熱間押出成形に耐えられる十分な高強度が得られないと言う理由から貫通孔１０１ａの内周面１０１ｂが破損または摩耗により成形された押出材６への傷の発生や寸法不良といった問題を回避出来るものではなかった。   Further, in the case where the hot extrusion molding die 101 main body proposed in Patent Document 5 is made of zirconia ceramics or silicon nitride ceramics, sufficient high strength that can withstand hot extrusion molding of an aluminum alloy cannot be obtained. For this reason, it has not been possible to avoid problems such as generation of scratches and defective dimensions in the extruded material 6 formed by breakage or wear of the inner peripheral surface 101b of the through hole 101a.

また、特許文献６では、アルミニウム溶湯鋳造材に適した材質として、ＴｉＣＮ−ＴｉＣ系サーメット焼結体の製造方法が開示されているものの、ＴｉＣは４５０℃以上の環境下で酸化現象が起こり易くなり、高硬度材のＴｉＣから著しく硬度劣化となるＴｉＯ2に置換反応が生じる熱劣化の理由から、アルミニウム合金等の熱間押出成形用のダイス材としては相応しいものではなかった。Patent Document 6 discloses a method for producing a TiCN-TiC cermet sintered body as a material suitable for a molten aluminum casting material, but TiC is liable to undergo an oxidation phenomenon in an environment of 450 ° C. or higher. The die material for hot extrusion molding of aluminum alloy or the like is not suitable because of the heat deterioration in which a substitution reaction occurs in TiO 2 which is remarkably deteriorated in hardness from TiC as a high hardness material.

本発明は、上記課題に鑑み、特に約４００〜６００℃の環境下において、高強度、高硬度、高靭性、高摺動性を備えた焼結体、およびこれを用いた摺動部材、成膜用材料並びに熱間押出成形用ダイスとその熱間押出成形用ダイスを用いた熱間押出成形装置を提供することを目的とする。   In view of the above problems, the present invention has a sintered body having high strength, high hardness, high toughness, and high slidability, and a sliding member using the same, particularly in an environment of about 400 to 600 ° C. An object of the present invention is to provide a film material, a hot extrusion die, and a hot extrusion molding apparatus using the hot extrusion die.

本発明の焼結体は、ＴｉＣＮが５８〜９２．５質量％、Ｔｉが０．０１〜１質量％、ＴｉＣが０．０１〜２質量％、ＴｉＮが０．０１〜２質量％、残部がＴａＣ、Ｎｉ、Ｃｒからなる。そしてＴａＣを１〜１１質量％、Ｎｉを３〜１３質量％、Ｃｒを３〜１３質量％有するのがよい。   In the sintered body of the present invention, TiCN is 58 to 92.5 mass%, Ti is 0.01 to 1 mass%, TiC is 0.01 to 2 mass%, TiN is 0.01 to 2 mass%, and the balance is It consists of TaC, Ni, Cr. And it is good to have 1-11 mass% of TaC, 3-13 mass% of Ni, and 3-13 mass% of Cr.

また、前記焼結体はその粒度分布に２つのピークを有することが好ましく、１つのピークは１．０〜１．３μｍの粒度範囲、他のピークは１．４〜１．７μｍの粒度範囲にあり、前記粒度分布における１．０〜１．３μｍの粒度範囲の結晶粒と１．４〜１．７μｍの粒度範囲の結晶粒とが３：２〜１：１の重量比率であるのがよい。さらに、前記焼結体の結晶粒は球状であるのがよい。   The sintered body preferably has two peaks in its particle size distribution, one peak in the particle size range of 1.0 to 1.3 μm and the other peak in the particle size range of 1.4 to 1.7 μm. The crystal grains in the particle size range of 1.0 to 1.3 μm and the crystal grains in the particle size range of 1.4 to 1.7 μm in the particle size distribution may have a weight ratio of 3: 2 to 1: 1. . Furthermore, the crystal grains of the sintered body are preferably spherical.

本発明の摺動部材および成膜用材料は、前記焼結体を用いて形成されており、例えばスライダーやターゲット材などがある。   The sliding member and film forming material of the present invention are formed using the sintered body, and examples thereof include a slider and a target material.

そして、本発明の熱間押出成形用ダイスは、前記焼結体を用いて形成されている。そして、この熱間押出成形用ダイスは、板形状の中心付近に貫通孔を有し、少なくとも該貫通孔の内周面にアモルファス膜を形成されているのがよい。さらに、前記アモルファス膜がアルミナもしくはシリコンカーバイドからなり、該アモルファス膜が厚み０．２〜１．２μｍであるのがよい。   And the die | dye for hot extrusion molding of this invention is formed using the said sintered compact. The hot extrusion die preferably has a through hole in the vicinity of the center of the plate shape, and an amorphous film is preferably formed at least on the inner peripheral surface of the through hole. Further, it is preferable that the amorphous film is made of alumina or silicon carbide, and the amorphous film has a thickness of 0.2 to 1.2 μm.

本発明の熱間押出成形装置は、前記熱間押出成形用ダイスを筒状のダイケースの一方端側に装着し、上記ダイケースの他方端側を筒状のコンテナの一方端側に装着し、押出材をコンテナから押出すための押し出し機構を上記コンテナに配置したものである。   In the hot extrusion molding apparatus of the present invention, the hot extrusion molding die is attached to one end side of a cylindrical die case, and the other end side of the die case is attached to one end side of a cylindrical container. The extrusion mechanism for extruding the extruded material from the container is arranged in the container.

本発明の熱間押出成形用ダイスの製造方法は、平均粒径０．３〜０．７μｍのＴｉＣＮ粉末と、平均粒径１．２〜２μｍのＴｉＣＮ粉末とを７：３〜９：１の比率で混合し、さらに平均粒径１．５μｍ以下のＴａＣ粉末と、平均粒径２μｍ以下のＮｉ粉末及びＣｒ粉末とを加えて、溶媒とともに粉砕混合してスラリーとする工程を有する。   The method for producing a hot extrusion die of the present invention comprises a TiCN powder having an average particle size of 0.3 to 0.7 μm and a TiCN powder having an average particle size of 1.2 to 2 μm of 7: 3 to 9: 1. Mixing at a ratio, and further adding TaC powder having an average particle size of 1.5 μm or less, Ni powder and Cr powder having an average particle size of 2 μm or less, and pulverizing and mixing with a solvent to form a slurry.

本発明の焼結体は、ＴｉＣＮが５８〜９２．５質量％、Ｔｉが０．０１〜１質量％、ＴｉＣが０．０１〜２質量％、ＴｉＮが０．０１〜２質量％からなるので、前記焼結体を用いて形成した本発明の熱間押出成形用ダイスは、特に約４００〜６００℃の高温環境下においても、高強度、高靭性が保持できるとともに、押出材の摺動抵抗を低く抑制できるという効果がある。   The sintered body of the present invention is composed of 58 to 92.5% by mass of TiCN, 0.01 to 1% by mass of Ti, 0.01 to 2% by mass of TiC, and 0.01 to 2% by mass of TiN. The die for hot extrusion molding of the present invention formed using the sintered body can maintain high strength and high toughness even in a high temperature environment of about 400 to 600 ° C., and the sliding resistance of the extruded material. Can be suppressed low.

また、前記熱間押出成形用ダイス１は、板形状の中心付近に貫通孔を有し、少なくとも該貫通孔の内周面にアモルファス膜を形成したことから、熱間押出成形における約４００〜６００℃付近の予備加熱時に、前記アモルファス膜が貫通孔の内周面の酸化を防止するので熱間押出成形前の熱間押出成形用ダイスの強度低下（粒子間結合力低下）を防止できる。   The hot extrusion die 1 has a through hole in the vicinity of the center of the plate shape, and an amorphous film is formed at least on the inner peripheral surface of the through hole. Since the amorphous film prevents oxidation of the inner peripheral surface of the through-hole at the time of preheating near about 0 ° C., it is possible to prevent a decrease in strength (a decrease in bonding strength between particles) of the hot extrusion die before hot extrusion.

さらに、前記アモルファス膜をアルミナもしくはシリコンカーバイドとすることにより約６００℃程度までの耐酸化作用があることから、熱間押出成形前の予備加熱時の熱間押出成形用ダイスの貫通孔の内周面の酸化防止効果をさらに向上できる。   Furthermore, since the amorphous film is made of alumina or silicon carbide, it has an oxidation resistance up to about 600 ° C., so that the inner periphery of the through hole of the hot extrusion die during preheating before hot extrusion molding The surface antioxidant effect can be further improved.

そして、前記アモルファス膜の好ましい厚みは０．２〜１．２μｍであり、厚みが少なくとも０．２μｍ以上であれば、ムラなく熱間押出成形用ダイスの表面を保護でき、高温下での表層からの酸化の問題を防止出来る。そして本来予備加熱時の酸化防止が目的であるので１．２μｍあれば十分である。１．２μｍを大幅に超える程の厚膜にしてしまうと、殊に２μｍを超える様な厚膜では内部応力により膜の密着性が低下してしまい、セッティング時などの作業でアモルファス膜が剥がれる虞がある。そして、予備加熱温度が約５００℃以下の場合はシリコンカーバイドのアモルファス膜、約６５０℃以下の場合はアルミナのアモルファス膜を形成することにより、貫通孔の内周面の酸化を防止できる。   And the preferable thickness of the said amorphous film is 0.2-1.2 micrometers, and if the thickness is at least 0.2 micrometer or more, the surface of the die | dye for hot extrusion molding can be protected evenly, from the surface layer under high temperature Can prevent oxidation problems. And since it is originally intended to prevent oxidation during preheating, 1.2 μm is sufficient. If the film thickness is much larger than 1.2 μm, the adhesion of the film will decrease due to internal stress, especially if the film thickness exceeds 2 μm, and the amorphous film may be peeled off during setting work. There is. By forming a silicon carbide amorphous film when the preheating temperature is about 500 ° C. or less, and forming an alumina amorphous film when the preheating temperature is about 650 ° C. or less, oxidation of the inner peripheral surface of the through hole can be prevented.

そして、前記熱間押出成形用ダイスを筒状のダイケースの一方端側に装着し、上記ダイケースの他方端側を筒状のコンテナの一方端側に装着し、押出材をコンテナから押出すための押し出し機構を上記コンテナに配置して熱間押出成形装置として用いれば、前記熱間押出成形用ダイスは、高温時における強度、硬度、靭性が優れていることから、熱間押出成形用ダイスの摩耗や破損を防止できるとともに、押出材への傷や寸法の問題が抑えられ、熱間押出成形の連続成形時間の大幅な向上が図れる。   Then, the hot extrusion molding die is attached to one end side of a cylindrical die case, the other end side of the die case is attached to one end side of the cylindrical container, and the extruded material is extruded from the container. If the extrusion mechanism for this is arranged in the container and used as a hot extrusion molding device, the hot extrusion die is excellent in strength, hardness and toughness at high temperatures. Can be prevented from being worn and damaged, and the problems of scratches and dimensions on the extruded material can be suppressed, and the continuous molding time of the hot extrusion molding can be greatly improved.

また、本発明の熱間押出成形用ダイスの製造方法は、ＴｉＣＮ系サーメット材となる原料粉体を、平均粒径０．３〜０．７μｍのＴｉＣＮ粉末と、平均粒径１．２〜２μｍのＴｉＣＮ粉末とを７：３〜９：１の比率で混合し、さらに平均粒径１．５μｍ以下のＴａＣ粉末と、平均粒径２μｍ以下のＮｉ粉末及びＣｒ粉末とを加えてなる。そして、該原料粉体を溶媒とともに粉砕混合してスラリーとする工程としたことから、前記粗粒ＴｉＣＮ結晶粒子の周囲を前記微細ＴｉＣＮ結晶粒子で埋め尽くされることによって共有結合焼結または固相結合が促進されるために、ＴｉＣＮ結晶粒子がＴｉ，ＴｉＣ，ＴｉＮへ分解することを低く抑えて焼結させることができる。このようにして得られた焼結体を用いて本発明の熱間押出成形用ダイスを作製するとＴｉ，ＴｉＣ，ＴｉＮの介在が低く抑えられていることから、高温時における耐酸化性の抑制効果があり、その結果、高摺動性が確保できるのである。   Moreover, the manufacturing method of the die | dye for hot extrusion molding of this invention is the raw material powder used as a TiCN type | system | group cermet material, TiCN powder with an average particle diameter of 0.3-0.7 micrometer, and average particle diameter of 1.2-2 micrometers. The TiCN powder is mixed at a ratio of 7: 3 to 9: 1, and TaC powder having an average particle size of 1.5 μm or less, and Ni powder and Cr powder having an average particle size of 2 μm or less are added. Since the raw material powder is pulverized and mixed with a solvent to form a slurry, the surroundings of the coarse TiCN crystal particles are filled with the fine TiCN crystal particles, thereby performing covalent bonding sintering or solid phase bonding. Therefore, the TiCN crystal particles can be sintered while suppressing the decomposition of TiCN crystal particles into Ti, TiC, and TiN. When the hot-extrusion die of the present invention is produced using the sintered body thus obtained, since the intervention of Ti, TiC and TiN is kept low, the effect of suppressing oxidation resistance at high temperatures As a result, high slidability can be secured.

本発明の熱間押出成形用ダイスが組み込まれた熱間押出成形装置の一例を示す断面図である。It is sectional drawing which shows an example of the hot extrusion molding apparatus in which the die | dye for hot extrusion molding of this invention was integrated. 本発明の試験片の斜視図である。It is a perspective view of the test piece of this invention. ３点曲げ抗折強度の測定方法を示す断面図である。It is sectional drawing which shows the measuring method of 3 point | piece bending bending strength. （ａ）は本発明の熱間押出成形用ダイスの平面図、（ｂ）はその断面図である。(A) is a top view of the die for hot extrusion molding of this invention, (b) is the sectional drawing. 従来の熱間押出成形用ダイスの断面図である。It is sectional drawing of the conventional die for hot extrusion molding. 本発明の熱間押出成形用ダイスとなるＴｉＣＮ系サーメット材のＴＧ−ＤＴＡ示差熱分析チャートである。It is a TG-DTA differential thermal analysis chart of the TiCN type cermet material used as the hot extrusion die of the present invention. アルミナアモルファス膜のＴＧ−ＤＴＡ示差熱分析チャートである。It is a TG-DTA differential thermal analysis chart of an alumina amorphous film. シリコンカーバイドアモルファス膜のＴＧ−ＤＴＡ示差熱分析チャートである。It is a TG-DTA differential thermal analysis chart of a silicon carbide amorphous film. 従来の熱間押出成形装置の断面図である。It is sectional drawing of the conventional hot extrusion molding apparatus. 本発明の熱間押出成形用ダイスのＴｉ、ＴｉＣ、ＴｉＮの組成を示すダイアグラムである。It is a diagram which shows the composition of Ti of the hot extrusion die of this invention, TiC, and TiN.

以下、本発明の実施形態について図面を用いて説明する。
本発明の焼結体は、ＴｉＣＮ５８〜９２．５質量％、Ｔｉ０．０１〜１質量％、ＴｉＣ０．０１〜２質量％、ＴｉＮ０．０１〜２質量％、残部がＴａＣ、Ｎｉ、Ｃｒからなることが重要である。さらにＴａＣ１〜１１質量％を有することが望ましい。さらにＮｉ３〜１３質量％、Ｃｒ３〜１３質量％を有することが望ましい。なお残部はＦｅなどの不可避不純物になる。Hereinafter, embodiments of the present invention will be described with reference to the drawings.
The sintered body of the present invention is composed of TiCN 58-92.5% by mass, Ti 0.01-1% by mass, TiC 0.01-2% by mass, TiN 0.01-2% by mass, the balance being TaC, Ni, Cr. is important. Furthermore, it is desirable to have TaC1-11 mass%. Furthermore, it is desirable to have Ni 3-13 mass% and Cr 3-13 mass%. The balance becomes inevitable impurities such as Fe.

前記焼結体は、粒度分布において２つのピークを有することが好ましく、また該ピークがそれぞれ１．０〜１．３μｍと１．４〜１．７μｍの粒度範囲内であることが好ましい。
一方のピークが１．０μｍ未満だと微細粒子のみの凝集が起こりやすく、微細粒子の凝集は異常粒子成長の核となって来るために、脱粒や靭性および強度かが劣化するという不具合があり、１．３μｍより大きいと共有結合焼結または固相結合が不十分であるためにＴｉＣＮ結晶粒子がＴｉ，ＴｉＣ，ＴｉＮへ分解するという不具合がある。
また他方のピークが１．４μｍ未満だと粒径が大きくなりすぎて摺動性が確保できないという不具合があり、１．７μｍより大きいと共有結合焼結または固相結合が不十分であるためにＴｉＣＮ結晶粒子がＴｉ，ＴｉＣ，ＴｉＮへ分解するという不具合がある。The sintered body preferably has two peaks in the particle size distribution, and the peaks are preferably in the particle size ranges of 1.0 to 1.3 μm and 1.4 to 1.7 μm, respectively.
If one peak is less than 1.0 μm, only fine particles tend to aggregate, and the aggregation of fine particles becomes the core of abnormal particle growth, so there is a problem that the grain size and toughness and strength deteriorate, If it is larger than 1.3 μm, there is a problem that the TiCN crystal particles decompose into Ti, TiC and TiN because the covalent bond sintering or the solid phase bond is insufficient.
On the other hand, if the other peak is less than 1.4 μm, there is a problem that the particle size becomes too large to ensure slidability, and if it exceeds 1.7 μm, covalent bond sintering or solid phase bonding is insufficient. There is a problem that TiCN crystal particles decompose into Ti, TiC, and TiN.

また、１．０〜１．３μｍの範囲でのピークと１．４〜１．７μｍでのピークの比が３：２〜１：１の重量比率であることが好ましい。１．０〜１．３μｍでのピークが６０％以上であると微細粒子同士の凝集が起こりやすくなり、異常粒子成長の核となって脱粒や強度劣化するために摺動性が確保できないという不具合があり、５０％未満であると共有結合焼結または固相結合が不十分であるためにＴｉＣＮ結晶粒子がＴｉ，ＴｉＣ，ＴｉＮへ分解するという不具合がある。
なお、前記焼結体の粒度分布における２つのピークは、所定の粒度をもった微細粉末と粗粒粉末を所定の配合比で混合したＴｉＣＮ原料粉体を用いることにより所望の粒度範囲のものを得ることができる。The ratio of the peak in the range of 1.0 to 1.3 μm and the peak in the range of 1.4 to 1.7 μm is preferably a weight ratio of 3: 2 to 1: 1. If the peak at 1.0 to 1.3 μm is 60% or more, the aggregation of fine particles is likely to occur, and it becomes the nucleus of abnormal particle growth, and the slidability cannot be ensured due to degranulation and strength deterioration. If the content is less than 50%, the covalent bonding sintering or solid phase bonding is insufficient, so that there is a problem that the TiCN crystal particles decompose into Ti, TiC and TiN.
The two peaks in the particle size distribution of the sintered body are those in a desired particle size range by using a TiCN raw material powder in which a fine powder having a predetermined particle size and a coarse powder are mixed at a predetermined mixing ratio. Obtainable.

また、前記焼結体の結晶粒は球状であることが好ましい。前記結晶粒が球状であると、焼結体を使ったダイス表面での原料押出時の滑りが安定する。   In addition, the crystal grains of the sintered body are preferably spherical. When the crystal grains are spherical, the slippage at the time of raw material extrusion on the die surface using the sintered body is stabilized.

本発明の焼結体は、摺動部材や成膜用材料に用いることができる。前記焼結体を用いて形成された摺動部材を熱間押出成形用ダイスや熱間絞りダイスに用いた場合、高摺動性を得ることができる。また、前記焼結体を用いて形成された成膜用材料を熱間押出成形用ダイスや熱間絞りダイスの摺動部に形成した場合、高摺動性を得ることができる。   The sintered body of the present invention can be used for sliding members and film forming materials. When the sliding member formed using the sintered body is used for a hot extrusion die or a hot drawing die, high slidability can be obtained. Moreover, when the film-forming material formed using the sintered body is formed on a sliding portion of a hot extrusion die or a hot drawing die, high slidability can be obtained.

図１に、本発明の熱間押出成形用ダイス１が筒状のダイケース２に嵌入された熱間押出成形装置１１の概略の縦断面図を示した。例えば、アルミニウム合金の押出材６の成形は、アルミニウム合金等の柱状鋳塊を加熱したビレット５を筒状のコンテナ３の中に入れ、押出機構４で押し出すことにより口金金型である熱間押出成形用ダイス１から所望の押出材６が成形される。
本発明の熱間押出成形用ダイス１は、前記焼結体を用いて形成されている。前記熱間押出成形用ダイス１を形成する焼結体の成分含有量を、ＴｉＣＮ５８〜９２．５質量％、ＴａＣ１〜１１質量％、Ｎｉ３〜１３質量％、Ｃｒ３〜１３質量％としたのは、ＴｉＣＮが５８質量％未満の場合は、高い滑り性（高摺動性）を得ることができず、ＴｉＣＮが９２．５質量％を超えると焼結性が著しく低下し、高硬度、高強度が得られないからである。FIG. 1 shows a schematic longitudinal sectional view of a hot extrusion molding apparatus 11 in which the hot extrusion molding die 1 of the present invention is fitted in a cylindrical die case 2. For example, the extrusion material 6 made of aluminum alloy is formed by hot extrusion which is a die die by putting a billet 5 in which a columnar ingot such as an aluminum alloy is heated into a cylindrical container 3 and extruding it by an extrusion mechanism 4. A desired extruded material 6 is formed from the forming die 1.
The hot extrusion molding die 1 of the present invention is formed using the sintered body. The component content of the sintered body forming the hot extrusion die 1 was TiCN 58-92.5% by mass, TaC 1-11% by mass, Ni 3-13% by mass, Cr 3-13% by mass, When TiCN is less than 58% by mass, high slipperiness (high slidability) cannot be obtained, and when TiCN exceeds 92.5% by mass, the sinterability is remarkably lowered, and high hardness and high strength are obtained. It is because it cannot be obtained.

また、ＴａＣが１質量％未満の場合は、高温下での耐酸化性及び焼結性が低下し、１１質量％を超えると摺動特性が低下してしまう。また、ＮｉとＣｒがそれぞれに於いて３質量％未満の場合は、焼結性の低下及び緻密化が確保できなくなり、ＮｉとＣｒがそれぞれに於いて１３質量％を超えると高硬度の確保ができず耐磨耗性が低下する。   On the other hand, when TaC is less than 1% by mass, the oxidation resistance and sinterability at high temperatures are lowered, and when it exceeds 11% by mass, the sliding characteristics are lowered. In addition, when Ni and Cr are less than 3% by mass, it is impossible to secure a decrease in sinterability and densification, and when Ni and Cr exceed 13% by mass, high hardness can be ensured. It is not possible to reduce the wear resistance.

そして、Ｔｉ０．０１〜１質量％、ＴｉＣ０．０１〜２質量％、ＴｉＮ０．０１〜２質量％としたのは、前記Ｔｉが１質量％、ＴｉＣが２質量％、ＴｉＮが２質量％を超えるとＴｉＣ、ＴｉＮ及びＴｉ金属が所望量以上で介在することとなり耐酸化性が低下するからである。その結果、高摺動性が著しく低下することになり、本焼結体を熱間押出成形用ダイス１として用いた場合、約４００〜６００℃の高温環境下での熱劣化と摺動性が阻害されると言った問題が生ずる。   And Ti 0.01-1% by mass, TiC 0.01-2% by mass, TiN 0.01-2% by mass, Ti is 1% by mass, TiC is 2% by mass, TiN exceeds 2% by mass. This is because TiC, TiN, and Ti metal are present in a desired amount or more, and the oxidation resistance is lowered. As a result, the high slidability is remarkably lowered, and when this sintered body is used as the hot extrusion die 1, thermal degradation and slidability in a high temperature environment of about 400 to 600 ° C. The problem of being disturbed arises.

また、Ｔｉ、ＴｉＣ、ＴｉＮが０．０１質量％未満であれば、局所的な結晶増大化が進み、結晶粒子状態が不均一となり強度が劣化する虞があることから、Ｔｉ、ＴｉＣ、ＴｉＮのいずれの含有量も０．０１質量％以上であることが重要である。   Further, if Ti, TiC, and TiN are less than 0.01% by mass, local crystal increase proceeds, the crystal particle state becomes non-uniform, and the strength may be deteriorated. It is important that any content is 0.01% by mass or more.

上記したＴｉＣＮ、Ｔｉ、ＴｉＣおよびＴｉＮによれば、所定の微細粉末と粗粉末を所定の配合比で混合した所定量のＴｉＣＮ原料粉体を用いて焼結させることにより、ＴｉＣＮと、ＴｉＣＮの分解により生成されるＴｉ、ＴｉＣおよびＴｉＮがそれぞれ所望の割合となるものを得ることができる。   According to the TiCN, Ti, TiC and TiN described above, the TiCN and the TiCN are decomposed by sintering using a predetermined amount of TiCN raw material powder obtained by mixing a predetermined fine powder and a coarse powder at a predetermined blending ratio. The Ti, TiC, and TiN produced by the above can be obtained in desired ratios.

なお、通常押出材６の成形を一旦中断した際は、熱間押出成形用ダイス１の誘導部となる貫通孔１ａの内周面１ｂをＮａＯＨなどを用いてアルカリ洗浄をし、アルミニウム合金等の付着物を除去し再度使用する場合、従来ダイス素材として使用されていた超硬やＳＫＤ６１ではこれらの洗浄液により表面層が腐食されてしまい表面硬度が著しく低下することがある。しかしながら、本発明の熱間押出成形用ダイス１のＴｉＣＮ−ＴａＣ−Ｎｉ−Ｃｒを主成分とする焼結体はＮａＯＨなどのアルカリ洗浄では腐食されることはなく、摩耗で使えなくなるまで何度でも繰り返し使用することができる。   In addition, when the molding of the extrusion material 6 is temporarily interrupted, the inner peripheral surface 1b of the through hole 1a serving as the guide portion of the hot extrusion molding die 1 is alkali-washed with NaOH or the like to obtain an aluminum alloy or the like. When the deposits are removed and used again, carbide or SKD61, which has been conventionally used as a die material, may corrode the surface layer by these cleaning solutions, and the surface hardness may be significantly reduced. However, the sintered body mainly composed of TiCN-TaC-Ni-Cr of the hot extrusion die 1 of the present invention is not corroded by alkaline cleaning with NaOH or the like, and can be used any number of times until it becomes unusable due to wear. Can be used repeatedly.

また、前記貫通孔１ａの内周面１ｂの好ましい表面粗さＲａは０．０５μｍ以下であり、前記Ｒａが０．０５μｍを超えると押出材６の表面の平滑性が得られなくなる。   Moreover, the preferable surface roughness Ra of the inner peripheral surface 1b of the through hole 1a is 0.05 μm or less, and when the Ra exceeds 0.05 μm, the smoothness of the surface of the extruded material 6 cannot be obtained.

また、前記貫通孔１ａは、板形状の熱間押出成形用ダイス１の中心付近に形成されていて、少なくとも前記貫通孔１ａの内周面１ｂにアモルファス膜１ｃを形成することが好ましい。アルミニウム合金等の熱間押出成形においては、ビレット５の均一加熱と内部に介在する空気脱泡の目的から、約４００〜６００℃の温度で熱間押出成形装置１１の内面の予備加熱を約１時間（ｈｒ）程度行う。そのため、この予備加熱時の貫通孔１ａの内周面１ｂの酸化を防止する目的でアモルファス膜１ｃを形成する。   The through hole 1a is preferably formed in the vicinity of the center of the plate-shaped hot extrusion die 1 and an amorphous film 1c is formed at least on the inner peripheral surface 1b of the through hole 1a. In hot extrusion molding of aluminum alloy or the like, preheating of the inner surface of the hot extrusion molding apparatus 11 is performed at a temperature of about 400 to 600 ° C. for about 1 for the purpose of uniform heating of the billet 5 and air defoaming inside. Perform for about time (hr). Therefore, the amorphous film 1c is formed for the purpose of preventing oxidation of the inner peripheral surface 1b of the through hole 1a during the preheating.

即ち、本発明のＴｉＣＮ系サーメットは、従来の超硬、ＳＫＤ６１、さらには、炭化物系サーメットに比べ高温において酸化し難い材質であるものの、ある程度の酸化は抑止できない。したがって酸化による粒子間結合力が低下することを防止するために、前記貫通孔１ａの内周面１ｂにアモルファス膜１ｃを形成するのが望ましい。   That is, the TiCN-based cermet of the present invention is a material that is difficult to oxidize at a high temperature as compared with conventional carbide, SKD61, and carbide-based cermet, but a certain degree of oxidation cannot be suppressed. Therefore, it is desirable to form the amorphous film 1c on the inner peripheral surface 1b of the through hole 1a in order to prevent the bonding force between particles due to oxidation from decreasing.

さらに、前記アモルファス膜１ｃはアルミナ若しくは、シリコンカーバイドで形成することが好ましい。アルミナやシリコンカーバイドの熱酸化反応は約６００℃超から始まることから、熱間押出成形時の予備加熱温度が約６００℃以下であれば予備加熱時における前記内周面１ｂの酸化による強度低下の防止ができる。より具体的には、押出材６の成形前の予備加熱温度が約５５０℃以下の場合はシリコンカーバイドのアモルファス膜１ｃ、約６００℃以下の場合はアルミナのアモルファス膜１ｃを形成することにより貫通孔１ａの内周面１ｂの酸化を防止できるものであり、予備加熱温度によりアモルファス膜１ｃの材質を適宜選択すれば良い。   Furthermore, the amorphous film 1c is preferably formed of alumina or silicon carbide. Since the thermal oxidation reaction of alumina or silicon carbide starts at about 600 ° C. or more, if the preheating temperature at the time of hot extrusion is about 600 ° C. or less, the strength decreases due to oxidation of the inner peripheral surface 1b at the time of preheating. It can be prevented. More specifically, when the preheating temperature before molding of the extruded material 6 is about 550 ° C. or less, a silicon carbide amorphous film 1c is formed, and when it is about 600 ° C. or less, an alumina amorphous film 1c is formed to form a through hole. It is possible to prevent oxidation of the inner peripheral surface 1b of 1a, and the material of the amorphous film 1c may be appropriately selected depending on the preheating temperature.

尚、前記アモルファス膜１ｃは、必ずしもアルミナまたはシリコンカーバイドに限るのではなく、熱交換機用のアルミ冷媒管用の熱間押出成形用であればシリコンナイトライド、チタンナイトライド、チタニアを用いても何ら問題はない。   The amorphous film 1c is not necessarily limited to alumina or silicon carbide, but any problem may be caused even if silicon nitride, titanium nitride or titania is used for hot extrusion molding for aluminum refrigerant pipes for heat exchangers. There is no.

さらに、前記アモルファス膜１ｃの厚みｔは０．２〜１．２μｍであることが望ましく、アモルファス膜１ｃの厚みｔが少なくとも０．２μｍ以上であれば、ムラなく貫通孔１ａの内周面１ｂを保護でき、高温下での表層からの酸化の問題を防止出来る。一方で、前記アモルファス膜１ｃの厚みｔが１．２μｍを超える程の厚膜にしてしまうと、特には２μｍを超える様な厚膜では膜の密着性が低下してしまい、セッティング時などの作業でアモルファス膜１ｃが剥がれてしまうことがある。尚、より好ましいアモルファス膜１ｃの厚みｔは、０．５〜１．０μｍである。   Further, the thickness t of the amorphous film 1c is preferably 0.2 to 1.2 μm. If the thickness t of the amorphous film 1c is at least 0.2 μm or more, the inner peripheral surface 1b of the through hole 1a is uniformly formed. It can protect and prevent the problem of oxidation from the surface layer under high temperature. On the other hand, if the thickness t of the amorphous film 1c exceeds 1.2 μm, the film adhesion deteriorates particularly in the case of a thick film exceeding 2 μm. As a result, the amorphous film 1c may be peeled off. A more preferable thickness t of the amorphous film 1c is 0.5 to 1.0 μm.

そして、前記アモルファス膜１ｃは、熱間押出成形用ダイス１の貫通孔１ａの内周面１ｂのみならず、側面１ｄに形成すると周囲からの酸化による劣化を抑止できる。   When the amorphous film 1c is formed not only on the inner peripheral surface 1b of the through hole 1a of the hot extrusion die 1 but also on the side surface 1d, deterioration due to oxidation from the surroundings can be suppressed.

また、押出材６の熱間押出成形を開始するとアモルファス膜１ｃはビレット５との摺動抵抗で直ぐに剥離消滅してしまうが、押出材６が酸素と熱を吸収することにより誘導部の接触温度が低下し、酸化が問題となるようなレベルに達しない。   Moreover, when hot extrusion molding of the extruded material 6 is started, the amorphous film 1c is immediately peeled off due to sliding resistance with the billet 5, but the contact temperature of the induction part is absorbed by the extruded material 6 absorbing oxygen and heat. Will not reach a level where oxidation becomes a problem.

しかし、前述したように押出材６の成形を一旦中断し、再度成形を開始する場合、貫通孔１ａの内周面１ｂをＮａＯＨなどのアルカリ洗浄をし、アルミニウム合金の付着物を除去し再度使用することもある。その際は再度予備加熱時の酸化を防止するために、剥離したアモルファス膜１ｃを再度付与すれば、何ら問題なく繰り返し使用することが可能である。   However, as described above, when the molding of the extruded material 6 is temporarily interrupted and the molding is started again, the inner peripheral surface 1b of the through hole 1a is washed with alkali such as NaOH to remove the deposits of the aluminum alloy and used again. Sometimes. In that case, in order to prevent oxidation at the time of preheating again, if the peeled amorphous film 1c is applied again, it can be used repeatedly without any problem.

つぎに、図１に示すように、本発明の熱間押出成形装置１１は本発明の熱間押出成形用ダイス１を筒状のダイケース２の一方端側に装着し、上記ダイケース２の他方端側を筒状のコンテナ３の一方端側に装着し、押出材６をコンテナ３から押出すための押し出し機構４を上記コンテナ３に配置してなる。該熱間押出成形装置１１を約４００〜６００℃の高温下の熱間押出成形に用いると、もっともダメージのかかる熱間押出成形用ダイス１が高温時における強度、硬度、靭性に優れていることからその摩耗や破損の虞が少なく、したがって押出材６への傷や寸法の問題の発生を抑えられ、連続成形時間の大幅な向上が図れる。   Next, as shown in FIG. 1, the hot extrusion molding apparatus 11 of the present invention mounts the hot extrusion molding die 1 of the present invention on one end side of a cylindrical die case 2, and The other end side is mounted on one end side of the cylindrical container 3, and an extrusion mechanism 4 for extruding the extruded material 6 from the container 3 is arranged in the container 3. When the hot extrusion molding apparatus 11 is used for hot extrusion molding at a high temperature of about 400 to 600 ° C., the most damaged hot extrusion die 1 is excellent in strength, hardness, and toughness at high temperatures. Therefore, there is little risk of wear or breakage, and therefore the occurrence of scratches and dimensional problems on the extruded material 6 can be suppressed, and the continuous molding time can be greatly improved.

次に、本発明の熱間押出成形用ダイス１の製造方法について説明する。   Next, the manufacturing method of the hot extrusion die 1 of the present invention will be described.

本発明の熱間押出成形用ダイス１の製造方法は、原料粉体として平均粒径０．３〜０．７μｍの微細ＴｉＣＮ粉末と、平均粒径１．２〜２μｍの粗粒ＴｉＣＮ粉末とを７：３〜９：１の比率で所定量を混合し、さらに平均粒径１．５μｍ以下のＴａＣ粉末と、平均粒径２μｍ以下のＮｉ粉末及びＣｒ粉末とを所定量加えて、溶媒とともに粉砕混合してスラリーとする工程を有してなるものである。   The manufacturing method of the hot extrusion die 1 of the present invention includes a fine TiCN powder having an average particle size of 0.3 to 0.7 μm and a coarse TiCN powder having an average particle size of 1.2 to 2 μm as raw material powders. A predetermined amount is mixed at a ratio of 7: 3 to 9: 1, and a predetermined amount of TaC powder having an average particle size of 1.5 μm or less, and Ni powder and Cr powder having an average particle size of 2 μm or less are added, and pulverized with a solvent. It has the process of mixing and making it a slurry.

ここで、ＴｉＣＮ原料粉体の平均粒径０．３〜０．７μｍの微細ＴｉＣＮ粉末と平均粒径１．２〜２μｍの粗粒ＴｉＣＮ粉末とを７：３〜９：１の比率で所定量を混合する理由は、焼結段階において、粗粒ＴｉＣＮ結晶粒子の周囲が微細ＴｉＣＮ結晶粒子で埋め尽くされることによって、共有結合焼結または固相結合が促進され、ＴｉＣＮ結晶粒子がＴｉ，ＴｉＣ，ＴｉＮへ分解することを抑制して焼結させることができるからである。   Here, a predetermined amount of fine TiCN powder having an average particle size of 0.3 to 0.7 μm and coarse TiCN powder having an average particle size of 1.2 to 2 μm in a ratio of 7: 3 to 9: 1. The reason for mixing is that, in the sintering stage, the surroundings of the coarse TiCN crystal particles are filled with fine TiCN crystal particles, whereby the covalent bond sintering or solid phase bonding is promoted, and the TiCN crystal particles become Ti, TiC, It is because it can sinter while suppressing decomposition to TiN.

そして、得られたスラリーを公知のスプレードライヤーにて乾燥し造粒する。   And the obtained slurry is dried and granulated by a known spray dryer.

つぎに、前記の方法で作製した粉体を公知のラバープレスにて、板状の成形体を成形し、公知の切削加工にて所望の形状を得る。尚、板状の成形体の中心付近に予め貫通孔を形成しておくと、成形体の焼成後にワイヤー放電加工により所望の貫通孔に加工することができる。   Next, the powder produced by the above method is formed into a plate-like molded body by a known rubber press, and a desired shape is obtained by a known cutting process. In addition, if a through-hole is previously formed near the center of a plate-shaped molded body, it can be processed into a desired through-hole by wire electric discharge machining after the molded body is fired.

つぎに、前記成形体を公知の真空炉にて１．３３Ｐａ以下に減圧した雰囲気下にて最高キープ温度１３５０〜１５００℃にて１時間（ｈｒ）焼成する。焼成温度が１３５０℃以下では十分に緻密化せず、１５００℃を超えると金属成分が昇華し、またＴｉＣＮ組成が分解し始めることから、好ましい焼成温度は１３５０〜１５００℃である。   Next, the compact is fired for 1 hour (hr) at a maximum keep temperature of 1350 to 1500 ° C. in an atmosphere reduced to 1.33 Pa or less in a known vacuum furnace. When the firing temperature is 1350 ° C. or lower, it is not sufficiently densified, and when it exceeds 1500 ° C., the metal component is sublimated and the TiCN composition starts to decompose, so the preferred firing temperature is 1350-1500 ° C.

つぎに、得られた焼結体をワイヤー放電加工及び研削加工にて所望の形状にした後、押出材６の貫通孔１ａの内周面１ｂを表面粗さＲａが０．０５μｍ以下となるように流体砥粒にて磨き仕上げる。   Next, after making the obtained sintered body into a desired shape by wire electric discharge machining and grinding, the surface roughness Ra of the inner peripheral surface 1b of the through hole 1a of the extruded material 6 is 0.05 μm or less. Finish with fluid abrasive.

以上の工程で本発明の熱間押出成形用ダイス１が作製されるが、貫通孔１ａの内周面１ｂにアモルファス膜１ｃを形成する場合は、スパッタ法にて、アルミナまたはシリコンカーバイドを厚みｔが０．２〜１．２μｍの範囲で成膜するのが望ましい。尚、アモルファス膜１ｃは、貫通孔１ａの内周面１ｂのみならず、側面１ｄに形成しても何ら問題はなく、その場合、両側面１ｄから施しても良い。   The hot extrusion molding die 1 of the present invention is manufactured through the above steps. When the amorphous film 1c is formed on the inner peripheral surface 1b of the through hole 1a, alumina or silicon carbide is formed with a thickness t by sputtering. Is preferably in the range of 0.2 to 1.2 μm. The amorphous film 1c may be formed not only on the inner peripheral surface 1b of the through hole 1a but also on the side surface 1d. In that case, the amorphous film 1c may be applied on both side surfaces 1d.

以上のように、本発明の熱間押出成形用ダイス１およびこれを用いた本発明の熱間押出成形装置１１は、高温下において高い強度と耐摩耗性を備えたことから、産業用や家庭用のアルミニウム合金押出材の熱間押出成形用として適するが、殊に、車載用のラジエーター、インタークーラー、エアコンコンデンサーなどの冷媒管やフィンの成形用に好適に用いることができる。   As described above, the hot extrusion die 1 of the present invention and the hot extrusion molding apparatus 11 of the present invention using the die 1 have high strength and wear resistance at high temperatures. It is suitable for hot extrusion molding of aluminum alloy extruded materials for use, and in particular, it can be suitably used for molding refrigerant tubes and fins such as in-vehicle radiators, intercoolers, and air conditioner condensers.

また、その用途は、前記アルミニウム合金熱間押出成形用に限らず、銅合金やチタン合金熱間押出成形用としても好適である。   Moreover, the use is not limited to the aluminum alloy hot extrusion molding, but is also suitable for copper alloy and titanium alloy hot extrusion molding.

以下本発明の実施例を具体的に説明するが、本発明はこれらの実施例により限定されるものではない。   Examples of the present invention will be specifically described below, but the present invention is not limited to these examples.

[実施例１]
本発明の熱間押出成形用ダイス１の母材であるＴｉＣＮ系サーメットからなる焼結体を、各々の粉体を６水準の含有量に分けて作製した。ＴｉＣＮ粉末は、平均粒径で０．５μｍの微細ＴｉＣＮ粉末と平均粒径で１．７μｍの粗粒ＴｉＣＮ粉末を８：２の比率で所定量を混合し、残りを所定量の平均粒径で１．２μｍのＴａＣ粉末と、１．６μｍのＮｉ粉末及び１．４μｍのＣｒ粉末をＳＵＳ製のボールミルに入れ、ＳＵＳ製の２Φ５サイズの粉砕用ボールを総粉体相当分と同容量、２倍相当容量のエタノール及びパラフィン系ワックスを総粉体質量比で３％加算して４８時間（ｈｒ）粉砕混合しスラリーを作製した。[Example 1]
A sintered body made of TiCN cermet, which is a base material of the hot extrusion die 1 of the present invention, was prepared by dividing each powder into 6 levels. The TiCN powder is prepared by mixing a predetermined amount of fine TiCN powder having an average particle diameter of 0.5 μm and coarse TiCN powder having an average particle diameter of 1.7 μm at a ratio of 8: 2, and the rest being an average particle diameter of a predetermined amount. 1.2μm TaC powder, 1.6μm Ni powder and 1.4μm Cr powder are put into a SUS ball mill, and SUS 2Φ5 size grinding balls have the same capacity as the total powder equivalent, doubled An equivalent volume of ethanol and paraffin wax were added at a total powder mass ratio of 3% and pulverized and mixed for 48 hours (hr) to prepare a slurry.

ここで、上記ＴｉＣＮ、ＴａＣ、Ｎｉ、Ｃｒの合計含有量を１００質量％としたときの各含有量を、ＴｉＣＮ＝６３質量％、ＴａＣ＝１１質量％、Ｎｉ＝１３質量％、Ｃｒ＝１３質量％としたものが試料Ｎｏ．１、ＴｉＣＮ＝７９質量％、ＴａＣ＝６質量％、Ｎｉ＝７質量％、Ｃｒ＝８質量％としたものが試料Ｎｏ．２、ＴｉＣＮ＝９３質量％、ＴａＣ＝１質量％、Ｎｉ＝３質量％、Ｃｒ＝３質量％としたものを試料Ｎｏ．３とした。   Here, when the total content of TiCN, TaC, Ni and Cr is 100% by mass, the respective contents are as follows: TiCN = 63% by mass, TaC = 11% by mass, Ni = 13% by mass, Cr = 13% by mass % Indicates the sample No. 1, TiCN = 79 mass%, TaC = 6 mass%, Ni = 7 mass%, and Cr = 8 mass%. 2, TiCN = 93 mass%, TaC = 1 mass%, Ni = 3 mass%, and Cr = 3 mass%. It was set to 3.

また、本発明の範囲外の比較例として、ＴｉＣＮ原料粉体の平均粒径ならびに微細ＴｉＣＮ粉末と粗粒ＴｉＣＮ粉末の比率を本発明実施例と同等で８：２とし、上記各成分含有量は、ＴｉＣＮ＝６０質量％、ＴａＣ＝１２質量％、Ｎｉ＝１４質量％、Ｃｒ＝１４質量％としたものを試料Ｎｏ．４、ＴｉＣＮ＝６３質量％、ＴａＣ＝１質量％、Ｎｉ＝１８質量％、Ｃｒ＝１８質量％としたものを試料Ｎｏ．５、ＴｉＣＮ＝９６質量％、ＴａＣ＝０質量％、Ｎｉ＝２質量％、Ｃｒ＝２質量％としたものを試料Ｎｏ．６とした。   Further, as a comparative example outside the scope of the present invention, the average particle diameter of the TiCN raw material powder and the ratio of the fine TiCN powder to the coarse TiCN powder were set to 8: 2 as in the present invention example, TiCN = 60% by mass, TaC = 12% by mass, Ni = 14% by mass, Cr = 14% by mass. 4, TiCN = 63% by mass, TaC = 1% by mass, Ni = 18% by mass, Cr = 18% by mass. 5, TiCN = 96% by mass, TaC = 0% by mass, Ni = 2% by mass, Cr = 2% by mass. It was set to 6.

さらに、微細ＴｉＣＮ粉末と粗粒ＴｉＣＮ粉末の配合比率を変更した試料も追加した。   Furthermore, a sample in which the mixing ratio of the fine TiCN powder and the coarse TiCN powder was changed was also added.

ＴｉＣＮ粉末は、平均粒径０．５μｍの微細ＴｉＣＮ粉末と平均粒径１．７μｍの粗粒ＴｉＣＮ粉末とし、残りを所定量の平均粒径で１．２μｍのＴａＣ粉末と、１．６μｍのＮｉ粉末及び１．４μｍのＣｒ粉末を用い、ＴｉＣＮ＝７９質量％、ＴａＣ＝６質量％、Ｎｉ＝７質量％、Ｃｒ＝８質量％とし、前記微細ＴｉＣＮ粉末と粗粒ＴｉＣＮ粉末の配合比を７：３、９：１としたものを本発明の実施例の試料Ｎｏ．８、９とした。そして、前記配合比を６：４、９．５：０．５としたものを本発明の範囲外の試料Ｎｏ．７、１０とした。その他の添加剤および調合方法は前述したものと同一である。   The TiCN powder is a fine TiCN powder having an average particle size of 0.5 μm and a coarse TiCN powder having an average particle size of 1.7 μm, and the remainder is a predetermined amount of 1.2 μm TaC powder and 1.6 μm Ni. Using powder and 1.4 μm Cr powder, TiCN = 79 mass%, TaC = 6 mass%, Ni = 7 mass%, Cr = 8 mass%, and the mixing ratio of the fine TiCN powder and coarse TiCN powder is 7 : 3 and 9: 1 are sample Nos. Of Examples of the present invention. 8 and 9. And what made the said mixture ratio 6: 4, 9.5: 0.5 sample No. outside the scope of the present invention. 7 and 10. Other additives and preparation methods are the same as those described above.

つぎに、得られたスラリーをスプレードライヤーにて、温度１２０℃、曝露時間１秒で高速乾燥し造粒した。   Next, the obtained slurry was granulated by a high speed drying with a spray dryer at a temperature of 120 ° C. and an exposure time of 1 second.

その後、油圧ハンドプレス機にて、焼結後の３点曲げ抗折強度の試験片となる直方体の成形体を作製した。   Then, the rectangular parallelepiped molded object used as the test piece of 3-point bending strength after sintering was produced with the hydraulic hand press machine.

そして、前記成形体を真空炉を用いて、真空度１．３３Ｐａに減圧した環境下にて最高温度１４５０℃で１時間（ｈｒ）焼成しＴｉＣＮ系サーメットの焼結体を作製した。   The compact was then fired at a maximum temperature of 1450 ° C. for 1 hour (hr) in an environment where the degree of vacuum was reduced to 1.33 Pa using a vacuum furnace to produce a sintered body of TiCN cermet.

そして、前記焼結体を平面研削盤（＃４００番定のレジンダイヤ使用）を用いて研削することにより、図２に示すように、ＪＩＳ−Ｒ１６０１に基づく３点曲げ試験方法の試験片１２となる短辺寸法１２ａが３ｍｍ、長辺寸法１２ｂが４ｍｍ、長さ１２ｃが４０ｍｍの直方体に加工した。   Then, by grinding the sintered body using a surface grinder (using a # 400 standard resin diamond), as shown in FIG. 2, the test piece 12 of the three-point bending test method based on JIS-R1601 This was processed into a rectangular parallelepiped having a short side dimension 12a of 3 mm, a long side dimension 12b of 4 mm, and a length 12c of 40 mm.

前記試験片１２の本発明の実施例の試料Ｎｏ．１〜３、８、９および、本発明の範囲外となる比較例の試料Ｎｏ．４〜７、１０について、焼成後の焼結体の組成分析ならびに、大気雰囲気にて５５０℃にて１時間（ｈｒ）加熱処理した後の３点曲げ抗折強度、ビッカース硬度、破壊靱性値をそれぞれ試料数５個について測定した。   Sample No. of the test piece 12 of the embodiment of the present invention. 1 to 3, 8, 9, and sample Nos. Of comparative examples outside the scope of the present invention. For 4-7 and 10, the composition analysis of the sintered body after firing and the three-point bending strength, Vickers hardness, and fracture toughness value after heat treatment at 550 ° C. for 1 hour in the air atmosphere Each was measured for 5 samples.

組成分析は理学電気株式会社製のＸ線回折装置ＲＩＮＴ１１００型を用いＸ線４０ｋＶ，４０ｍＡで実施した。ここで、各成分の組成比は、試料をＸ線回折装置にて測定したときの各成分の回折ピークから別途作成しておいた検量線に基づいて定量値を求め、それらを合算した値から各成分の比率を求め算出した。また測定限界値が０．０１質量％であるために、０．０１質量％未満については、−と記載した。   The composition analysis was performed using an X-ray diffractometer RINT1100 manufactured by Rigaku Corporation with X-rays of 40 kV and 40 mA. Here, the composition ratio of each component is obtained from a value obtained by calculating a quantitative value based on a calibration curve separately prepared from a diffraction peak of each component when the sample is measured with an X-ray diffractometer, and adding them together. The ratio of each component was calculated and calculated. Further, since the measurement limit value is 0.01% by mass, less than 0.01% by mass is described as “−”.

尚、３点曲げ抗折強度はＪＩＳ−Ｒ１６０１による３点曲げ試験方法に基づき、アイコーエンジニアリング株式会社製デジタル荷重試験機を用い、図３に示すように、スパン１３が３０ｍｍ、クロスヘッド１４のスピードが０．５ｍｍ／ｍｉｎ．で試験片１２が破断する強度を測定した。   The three-point bending strength is based on a three-point bending test method according to JIS-R1601, using a digital load tester manufactured by Aiko Engineering Co., Ltd., as shown in FIG. Is 0.5 mm / min. The strength at which the test piece 12 breaks was measured.

また、ビッカース硬度は、ＪＩＳ−Ｒ１６１０により明石製作所製ＡＶＫ−Ａ型硬度計を用い、ＨｖＬｏａｄ１０ｋｇにて実施した。   Moreover, Vickers hardness was implemented by HvLoad10kg using the AVK-A type hardness meter by Akashi Seisakusho according to JIS-R1610.

また、破壊靭性値はＪＩＳ−Ｒ１６０７によるＳＥＰＢ法（Ｓｉｎｇｌｅ Ｅｄｇｅ Ｐｒｅｃｒａｃｋｅｄ Ｂｅａｍ）により、硬度計を明石製作所製ＡＶＫ−Ａ型、万能試験機をインストロン社製ＭＯＤＥＬ１１２５型、オートグラフを島津製作所社製ＡＧＳ−５００Ｂ型、光学式測長計はミツトヨ社製測定機を用いて測定した。   In addition, fracture toughness values were determined by the SEPB method (Single Edge Precracked Beam) according to JIS-R1607. The -500B type optical length meter was measured using a Mitutoyo measuring machine.

前記３点曲げ抗折強度、ビッカース硬度、破壊靭性値の判定基準については、３点曲げ抗折強度が１１５０ＭＰａ以上、ビッカース硬度が１４００ＧＰａ以上、破壊靭性値が１０ＭＰａ・ｍ1/2以上でいずれも満足したものを総合評価は良（○）とし、そのひとつ以上を満足しなかったものを使用不可（×）とした。また、その理由は３点曲げ抗折強度が１１５０ＭＰａ未満であると熱間押出成形作業時に強度不足による割れが発生し易くなり、またビッカース硬度が１４００ＧＰａ未満であると耐摩耗性が不十分となり、摩耗や変形が発生し易くなる、また破壊靭性値が１０ＭＰａ・ｍ1/2未満であると熱間押出成形作業時に欠けや割れが発生し易くなるからである。Regarding the criteria for determining the three-point bending strength, Vickers hardness, and fracture toughness value, the three-point bending strength is 1150 MPa or more, the Vickers hardness is 1400 GPa or more, and the fracture toughness value is 10 MPa · m 1/2 or more. Those that were satisfied were evaluated as good (◯), and those that did not satisfy one or more of them were considered unusable (×). The reason is that if the three-point bending strength is less than 1150 MPa, cracking due to insufficient strength is likely to occur during hot extrusion molding, and if the Vickers hardness is less than 1400 GPa, the wear resistance is insufficient. This is because wear and deformation are likely to occur, and when the fracture toughness value is less than 10 MPa · m 1/2 , chipping and cracking are likely to occur during hot extrusion.

以上の結果を表１に示す。尚、組成、特性値は試料数５個の平均値である。

Figure 0004709223
The results are shown in Table 1. The composition and characteristic values are average values of 5 samples.
Figure 0004709223

表１からわかるように、本発明の熱間押出成形用ダイス１に用いる焼結体の試料Ｎｏ．１，２，３は、組成の範囲がＴｉＣＮ５８〜９２．５質量％、ＴａＣ１〜１１質量％、Ｎｉ３〜１３質量％、Ｃｒ３〜１３質量％で、ＴｉＣＮが分解することによるＴｉの出現が０．０１〜１質量％、ＴｉＣ、ＴｉＮの出現がいずれも０．０１〜２質量％の範囲であることから、前記焼結体を５５０℃に加熱処理した後でも焼結体の表面が酸化による粒子間結合力が低下することは無く、本来の高強度・高硬度・高靱性の特性が維持できることから３点曲げ抗折強度は１１８０ＭＰａ以上、ビッカース硬度は１４６０ＧＰａ以上、破壊靭性値は１０ＭＰａ・ｍ1/2以上といずれも、高温における表面の劣化が認められず総合評価は良好であった。As can be seen from Table 1, the sintered body sample No. 1 used in the hot extrusion die 1 of the present invention. 1, 2 and 3 have a composition range of TiCN 58-92.5% by mass, TaC 1-11% by mass, Ni 3-13% by mass, Cr 3-13% by mass, and the appearance of Ti due to decomposition of TiCN is 0. Since the appearance of 01 to 1% by mass, TiC, and TiN are all in the range of 0.01 to 2% by mass, the surface of the sintered body is oxidized due to oxidation even after the sintered body is heated to 550 ° C. The bond strength does not decrease, and the original high strength, high hardness, and high toughness characteristics can be maintained. Therefore, the three-point bending strength is 1180 MPa or higher, the Vickers hardness is 1460 GPa or higher, and the fracture toughness value is 10 MPa · m 1. In all of the cases of / 2 or more, no deterioration of the surface at high temperature was observed, and the overall evaluation was good.

これに対し、本発明の範囲外である試料Ｎｏ．４は、５５０℃に加熱処理した後で焼結体の表面の酸化が促進されて、粒子間結合力が低下したことから３点曲げ抗折強度は１０４０ＭＰａ、ビッカース硬度は１０３０ＧＰａと低い値であった。また、試料Ｎｏ．５は、ＴｉＣＮが分解することによるＴｉ、ＴｉＣ、ＴｉＮの出現により特にＴａＣが１質量％未満であったことと、Ｔｉが１質量％を大きく超えたことと、ＴｉＮも２質量％を超えたことから、５５０℃に加熱処理した後で焼結体の表面の酸化が促進されて、粒子間結合力が低下したことおよび、焼結性の低さもあることから、３点曲げ抗折強度は９００ＭＰａ、ビッカース硬度は１０４０ＧＰａ、破壊靭性値は７ＭＰａ・ｍ1/2といずれも低い値であった。また、試料Ｎｏ．６は、ＴｉＣＮが分解することによるＴｉ、ＴｉＣ、ＴｉＮの出現がいずれも０．０１質量％未満であったが、特にＴａＣが１質量％未満であったがために、５５０℃に加熱処理した後で耐熱劣化やそもそもの焼結性の低さがあることから３点曲げ抗折強度は８９０ＭＰａ、ビッカース硬度は１１８０ＧＰａ、破壊靭性値は７ＭＰａ・ｍ1/2といずれも低い値であり、総合評価は試料Ｎｏ．４、５、６共に悪く使用不可であった。On the other hand, sample No. which is outside the scope of the present invention. In No. 4, the oxidation of the surface of the sintered body was promoted after heat treatment at 550 ° C., and the bonding strength between the particles was reduced. Therefore, the three-point bending strength was 1040 MPa and the Vickers hardness was as low as 1030 GPa. It was. Sample No. No. 5, especially due to the appearance of Ti, TiC and TiN due to decomposition of TiCN, TaC was less than 1% by mass, Ti greatly exceeded 1% by mass, and TiN also exceeded 2% by mass Therefore, after the heat treatment at 550 ° C., the oxidation of the surface of the sintered body was promoted, the interparticle bonding force was lowered, and the sinterability was also low. 900 MPa, Vickers hardness was 1040 GPa, and fracture toughness values were 7 MPa · m 1/2 , all low. Sample No. In No. 6, the appearance of Ti, TiC, and TiN due to the decomposition of TiCN was less than 0.01% by mass. However, since TaC was less than 1% by mass, heat treatment was performed at 550 ° C. Later, because of heat resistance degradation and low sinterability, the three-point bending strength is 890 MPa, the Vickers hardness is 1180 GPa, and the fracture toughness is 7 MPa · m 1/2. Evaluation was made with sample no. Both 4, 5, and 6 were bad and could not be used.

尚、不可避不純物として試料Ｎｏ．２〜４、６においてＦｅが０．４５〜０．９７質量％検出された。不可避不純物は０に近いのが望ましいが、酸化による周りに与える劣化の温度が８００℃と高い。よって熱間押出成形用のダイスとして用いるときの温度が、約４００〜６００℃である場合においては強度劣化等の要因にならないので、１質量％程度の含有は問題とならない。   In addition, sample no. In 2 to 4 and 6, Fe was detected in an amount of 0.45 to 0.97 mass%. The inevitable impurities are preferably close to 0, but the deterioration temperature caused by oxidation is as high as 800 ° C. Therefore, when the temperature when used as a die for hot extrusion molding is about 400 to 600 ° C., it does not cause a deterioration of strength or the like, so the content of about 1% by mass does not cause a problem.

さらに、ＴｉＣＮ粉末の微細ＴｉＣＮ粉末と粗粒ＴｉＣＮ粉末の配合比を７：３、９：１とした本発明の実施例の試料Ｎｏ．８、９は、焼結性を活性促進させ、焼結時に異常粒成長が抑制できたことから、Ｔｉ、ＴｉＣ、ＴｉＮの出現を抑えることができ、その結果、高温環境下での酸化が進行せず、３点曲げ抗折強度ならびに、ビッカース硬度、破壊靭性値ともに低下することはなく総合評価は良好であった。   Further, the sample No. of Example of the present invention in which the mixing ratio of the fine TiCN powder of TiCN powder to the coarse TiCN powder was 7: 3, 9: 1. Nos. 8 and 9 promote the activity of sinterability and suppress abnormal grain growth during sintering. Therefore, the appearance of Ti, TiC and TiN can be suppressed, and as a result, oxidation in a high temperature environment proceeds. Neither the 3-point bending strength, the Vickers hardness, or the fracture toughness value decreased, and the overall evaluation was good.

これに対し、ＴｉＣＮ粉末の微細ＴｉＣＮ粉末と粗粒ＴｉＣＮ粉末の配合比を６：４，９．５：０．５とした本発明の範囲外の試料Ｎｏ．７、１０において、試料Ｎｏ．７は、局所的に結晶粒子が分解肥大化したことから、焼結時点においてＴｉ、ＴｉＣ、ＴｉＮの出現量が多く、その結果、高温環境下での酸化が進行したため、試料Ｎｏ．７は３点曲げ抗折強度は１１５０ＭＰａ未満、ビッカース硬度は１４００ＧＰａ未満、破壊靭性値は１０ＭＰａ・ｍ1/2未満となり、試料Ｎｏ．１０は、ビッカース硬度が１４００ＧＰａ未満、破壊靭性値が１０ＭＰａ・ｍ1/2未満となり、いずれも総合評価は悪く使用不可であった。On the other hand, sample Nos. Out of the scope of the present invention in which the mixing ratio of the fine TiCN powder and the coarse TiCN powder of the TiCN powder was 6: 4, 9.5: 0.5. 7 and 10, sample no. In No. 7, since the crystal particles locally decomposed and enlarged, a large amount of Ti, TiC, and TiN appeared at the time of sintering, and as a result, oxidation in a high temperature environment progressed. No. 7 has a three-point bending strength of less than 1150 MPa, Vickers hardness of less than 1400 GPa, and fracture toughness of less than 10 MPa · m 1/2 . No. 10 had a Vickers hardness of less than 1400 GPa and a fracture toughness value of less than 10 MPa · m 1/2 , both of which were poor in overall evaluation and could not be used.

以上の結果より、ＴｉＣＮ５８〜９２．５質量％、ＴａＣ１〜１１質量％、Ｎｉ３〜１３質量％、Ｃｒ３〜１３質量％で、ＴｉＣＮが分解することによるＴｉの出現が０．０１〜１質量％、ＴｉＣ、ＴｉＮの出現がいずれも０．０１〜２質量％であるＴｉＣＮ系サーメット材は、高温環境下における強度、硬度、靭性の低下を招くことが無いことから、熱間押出成形用ダイス１の母材として相応しい材質であることが解る。   From the above results, TiCN 58 to 92.5% by mass, TaC 1 to 11% by mass, Ni 3 to 13% by mass, Cr 3 to 13% by mass, and the appearance of Ti due to decomposition of TiCN is 0.01 to 1% by mass, Since the appearance of TiC and TiN are both 0.01 to 2% by mass, the TiCN cermet material does not cause a decrease in strength, hardness and toughness in a high temperature environment. It can be seen that the material is suitable as a base material.

[実施例２]
図４（ａ）、（ｂ）に示す、熱間押出成形用ダイス１、１０１を作製し、熱間押出成形装置１１，１１１に取り付け熱間押出成形を行い熱間押出成形用ダイス１，１０１の評価を実施した。実施例１の試料Ｎｏ．１〜３の焼結体を用いて熱間押出成形用ダイス１を作製したものが本発明の実施例の試料Ｎｏ．１１〜１３、実施例１の試料Ｎｏ．４、６の焼結体を用いたものが本発明の範囲外となる試料Ｎｏ．１４、１５である。[Example 2]
Hot extrusion molding dies 1 and 101 shown in FIGS. 4 (a) and 4 (b) are manufactured, attached to the hot extrusion molding apparatuses 11 and 111, and hot extrusion molding is performed, so that the hot extrusion molding dies 1 and 101 are produced. Evaluation was conducted. Sample No. 1 of Example 1 Samples No. 1 to No. 3 in the examples of the present invention were produced by using the sintered bodies 1 to 3 to produce the hot extrusion die 1. 11 to 13, Sample No. 1 of Example 1. Samples Nos. 4 and 6 using the sintered bodies are outside the scope of the present invention. 14 and 15.

比較例として、熱間押出成形用ダイス１０１の材質をＺｒＯ2９４質量％、Ｙ2Ｏ3６質量％からなるジルコニア系セラミックスを用いたものを試料Ｎｏ．１６とした。
さらに、比較例として、図５に示すように、熱間押出成形用ダイス１０１の本体をＳＫＤ６１とし、貫通孔１０１ａの内周面１０１ｂにＮｉＣｒ／Ｃｒ3Ｃ2／ＮｂＣからなるサーメット材でＣｒ3Ｃ2−ＮｂＣを２５質量％の組成としたものを厚みｔが５ｍｍの補強した部分７を形成したものを試料Ｎｏ．１７とした。尚、上記サーメット材の補強した部分７は放電融着方法により形成した。As a comparative example, a sample using a zirconia-based ceramic made of ZrO 2 94 mass% and Y 2 O 3 6 mass% was used as a sample No. It was set to 16.
Further, as a comparative example, as shown in FIG. 5, the body of the hot extrusion molding die 101 is SKD61, and the inner peripheral surface 101b of the through hole 101a is a cermet material made of NiCr / Cr 3 C 2 / NbC with Cr 3. A sample in which a portion 7 having a composition of 25% by mass of C 2 -NbC and reinforced with a thickness t of 5 mm was formed as sample No. It was set to 17. The reinforced portion 7 of the cermet material was formed by a discharge fusion method.

尚、本発明の実施例、比較例ともに、熱間押出成形用ダイス１、１０１の厚みＴは２０ｍｍで、外径Φ１が３０ｍｍの円盤状からなり、該円盤状の中心付近に貫通孔１ａ、１０１ａが形成され、該貫通孔１ａ、１０１ａは幅ｄが１．５ｍｍ、長さｌが１５ｍｍの長方形状のスリットで４コーナーは約０．５ｍｍのＣ面ｃからなっている。   In both the examples and comparative examples of the present invention, the hot extrusion dies 1 and 101 have a disk shape with a thickness T of 20 mm and an outer diameter Φ1 of 30 mm. 101a is formed, and the through holes 1a and 101a are rectangular slits having a width d of 1.5 mm and a length l of 15 mm, and the four corners are formed by a C plane c of about 0.5 mm.

前記熱間押出成形用ダイス１、１０１を熱間押出成形装置１１、１１１に取り付けて、５００℃で１時間（ｈｒ）の予備加熱処理を施したあと、４６０℃の温度でアルミニウム合金の熱間押出成形を実施した。その成形条件は、押出速度を３０ｍ／ｍｉｎ．となるように押出機構４の押圧力を制御し成形した。そして、押出材６の表面に異常な傷が発生するまで連続成形を実施した。   The hot extrusion molding dies 1 and 101 are attached to the hot extrusion molding apparatuses 11 and 111, subjected to a preheating treatment at 500 ° C. for 1 hour (hr), and then the aluminum alloy is heated at a temperature of 460 ° C. Extrusion was performed. The molding conditions were such that the extrusion speed was 30 m / min. The pressing force of the extrusion mechanism 4 was controlled so that Then, continuous molding was performed until abnormal flaws occurred on the surface of the extruded material 6.

ここで、押出材６の表面に発生する傷の異常の判定基準は、傷の深さが１０μｍ、幅が２０μｍ以上とした。この基準は、業界標準に基づくものではないが、例えば、カーエアコン用アルミニウム冷媒管は、フロンガスフリーとなるに際し、従来以上に圧力の高いガスを用いる方向にあることから、より厳しい傷規格となることを予測したものである。なお、傷の測定は、小坂研究所社製表面粗さ計を用いて行った。   Here, the criteria for determining the abnormality of the scratches generated on the surface of the extruded material 6 were a scratch depth of 10 μm and a width of 20 μm or more. This standard is not based on industry standards, but for example, aluminum refrigerant pipes for car air conditioners are more severely scratched because they tend to use higher-pressure gas than before when they are free of CFCs. This is a prediction. The scratch was measured using a surface roughness meter manufactured by Kosaka Laboratory.

熱間押出成形において、異常の発生は、まず押出材６の表面状態となって現れるが、同時に熱間押出成形用ダイス１，１０１が破損することや、または、内周面１ｂ，１０１ｂに剥離が発生することもあり、この破損や剥離も含めて確認を実施した。尚、いずれも試料数は１個である。   In the hot extrusion molding, the occurrence of an abnormality first appears in the surface state of the extruded material 6, but at the same time, the hot extrusion molding dies 1, 101 are damaged or peeled off to the inner peripheral surfaces 1 b, 101 b. In some cases, this was confirmed including damage and peeling. In either case, the number of samples is one.

そして、上記いずれかの異常が発生するまでの連続成形時間が２４時間（ｈｒ）未満の場合の総合評価を使用不可（×）、２４時間（ｈｒ）以上、３６時間（ｈｒ）未満を使用可（△）、３６時間（ｈｒ）以上、４８時間（ｈｒ）未満を良（○）とした。その理由は、現状品の超硬やＳＫＤ６１で作製された熱間押出成形用ダイス１０１の寿命が半日〜１日未満しかないことから連続成形時間が従来レベルの２４時間（ｈｒ）未満を使用不可とし、また期待値である１．５日〜２日を良、その中間を使用可としたものである。以上の結果を表２に示す。

Figure 0004709223
And the comprehensive evaluation when the continuous molding time until any of the above-mentioned abnormalities is less than 24 hours (hr) cannot be used (x), more than 24 hours (hr) and less than 36 hours (hr) can be used. (△), 36 hours (hr) or more and less than 48 hours (hr) was determined as good (◯). The reason is that the continuous extrusion time of less than 24 hours (hr), which is the conventional level, cannot be used because the life of the hot extrusion die 101 made of the present carbide or SKD61 is only half a day to less than 1 day. In addition, the expected value of 1.5 to 2 days is good and the middle is usable. The results are shown in Table 2.
Figure 0004709223

表２の結果からわかるように、本発明実施例の試料Ｎｏ．１１〜１３は、アルミニウム合金の押出材６の連続成形時間が少なくとも４２時間（ｈｒ）以上実施でき、異常発生理由は全て押出材６への傷であり、その時点において、熱間押出成形用ダイス１のクラックや破損、および内周面１ｂの剥離の発生は見られず、総合評価は良であった。   As can be seen from the results in Table 2, sample No. Nos. 11 to 13 can be carried out for at least 42 hours (hr) or more of the continuous molding time of the extruded material 6 of the aluminum alloy, and all the reasons for the abnormality are scratches on the extruded material 6. At that time, the hot extrusion molding die No cracks or breakage of 1 or peeling of the inner peripheral surface 1b was observed, and the overall evaluation was good.

また、本発明の範囲外となる試料Ｎｏ．１４，１５は、上記連続成形時間が２７時間（ｈｒ），２９時間（ｈｒ）と本発明実施例より約４０％程度少ないことが解る。この異常はいずれも押出材６への傷であり、その時点における熱間押出成形用ダイス１のクラックや破損、剥離等は見られないものの、高温下における強度、硬度、靭性の低下が影響し、誘導部である貫通孔１ａの内周面１ｂが劣化したためである。尚、総合評価は少なくとも１日以上の連続成形ができたことから使用可とした。   Sample No. which falls outside the scope of the present invention. Nos. 14 and 15 show that the continuous molding time is 27 hours (hr) and 29 hours (hr), which is about 40% shorter than the examples of the present invention. All of these abnormalities are scratches on the extruded material 6, and cracks, breakage, peeling, etc. of the hot extrusion die 1 at that time are not observed, but a decrease in strength, hardness, and toughness at high temperatures has an effect. This is because the inner peripheral surface 1b of the through hole 1a, which is the guiding portion, has deteriorated. The overall evaluation was acceptable because continuous molding was possible for at least one day.

さらに、熱間押出成形用ダイス１０１の本体をジルコニア系セラミックスで作製した比較例の試料Ｎｏ．１６は、前記連続成形時間が僅か５時間（ｈｒ）であり、その原因は、熱間押出成形用ダイス１０１が破損したことによるものである。このことから、ジルコニア系セラミックスは表面が滑らかで摺動性が高いと言う長所もあるが、モノクリ（単斜相）増加による高温強度が低いことから、熱間押出成形用ダイスの材質として相応しいものではなく総合評価は×であった。   Further, the sample No. 1 of the comparative example in which the main body of the hot extrusion die 101 was made of zirconia ceramics. No. 16 is that the continuous molding time is only 5 hours (hr), and the cause thereof is that the hot extrusion die 101 is damaged. As a result, zirconia ceramics have the advantage of a smooth surface and high slidability, but they are suitable as a material for hot extrusion dies due to their low high-temperature strength due to an increase in monoclinic (monoclinic phase). Instead, the overall rating was x.

さらに、熱間押出成形用ダイス１０１の本体がＳＫＤ材で、押出材６の貫通孔１０１ａの内周面１０１ｂにＮｉＣｒ／Ｃｒ3Ｃ2／ＮｂＣからなるサーメットを厚くした比較例の試料Ｎｏ．１７は、連続成形時間が１８時間（ｈｒ）において押出材６に異常な傷が発生し、その原因は内周面１０１ｂの補強した部分７の剥離であった。この補強した部分７の剥離は、ＳＫＤ６１材とＮｉＣｒ／Ｃｒ3Ｃ2／ＮｂＣ系サーメット材の熱膨張係数の差が約６×１０-6と大きいことが大きな要因であると見られる。また、前記剥離が発生しなくても、ＮｉＣｒ／Ｃｒ3Ｃ2／ＮｂＣ系サーメットは炭化物系サーメットからなるものであることから、本発明のＴｉＣＮ系サーメットより高温環境下での酸化による劣化が生じやすい。In addition, the hot extrusion molding die 101 is made of SKD material, and a cermet made of NiCr / Cr 3 C 2 / NbC is thickened on the inner peripheral surface 101 b of the through hole 101 a of the extruded material 6. In No. 17, an abnormal flaw occurred in the extruded material 6 when the continuous molding time was 18 hours (hr), and the cause was peeling of the reinforced portion 7 of the inner peripheral surface 101b. The detachment of the reinforced portion 7 seems to be a major factor due to the large difference in thermal expansion coefficient between the SKD61 material and the NiCr / Cr 3 C 2 / NbC cermet material of about 6 × 10 −6 . Further, even if the peeling does not occur, since the NiCr / Cr 3 C 2 / NbC cermet is composed of a carbide cermet, the TiCN-based cermet of the present invention is deteriorated by oxidation in a high temperature environment. Cheap.

以上の結果から、アルミニウム合金等の熱間押出成形に本発明のＴｉＣＮ系サーメット材からなる熱間押出成形用ダイス１を用いると、従来の超硬、ＳＫＤ６１、ジルコニア系セラミックス、サーメット材ならびに炭化物系サーメット等により作製したものと比較すると少なくとも１〜２日以上の高寿命が期待できることが解る。   From the above results, when the hot extrusion die 1 made of the TiCN cermet material of the present invention is used for hot extrusion molding of aluminum alloy or the like, conventional carbide, SKD61, zirconia ceramics, cermet materials and carbides are used. It can be seen that a long life of at least 1 to 2 days or more can be expected when compared with those produced by cermet or the like.

[実施例３]
本発明の熱間押出成形用ダイス１の貫通孔１ａの内周面１ｂへアモルファス膜１ｃを形成したものと形成していないものならびに、アモルファス膜１ｃをアルミナあるいはシリコンカーバイドとした場合、さらにその厚みｔを０．１〜１．５μｍの範囲で作製した場合における高温環境下での連続成形時間への効果を確認した。[Example 3]
When the amorphous film 1c is formed or not formed on the inner peripheral surface 1b of the through hole 1a of the hot extrusion molding die 1 of the present invention, and when the amorphous film 1c is made of alumina or silicon carbide, the thickness is further increased. The effect on the continuous molding time in a high temperature environment when t was produced in the range of 0.1 to 1.5 μm was confirmed.

熱間押出成形用ダイス１となる焼結体は実施例２の試料Ｎｏ．１２と同一組成、同一形状のものを使用した。そして、図１に示す、貫通孔１ａの内周面１ｂにアルミナおよびシリコンカーバイドのアモルファス膜１ｃを形成し、その厚みｔを、０．１、０．２、０．５、１．０、１．２、１．５μｍの６水準として各々１個作製したものを、熱間押出成形装置１１に取り付け、１ｈｒの予備加熱後、アルミニウム合金の押出材６を３０ｍ／ｍｉｎ．の速度で連続成形を実施した。因みに、アモルファス膜１ｃを形成していないものは実施例２の試料Ｎｏ．１２で、これを基準として比較した。   The sintered body used as the hot extrusion die 1 was sample No. 2 in Example 2. 12 and the same composition and shape were used. Then, an amorphous film 1c of alumina and silicon carbide is formed on the inner peripheral surface 1b of the through hole 1a shown in FIG. 1, and the thickness t is 0.1, 0.2, 0.5, 1.0, 1 2 and 1.5 μm, each of which was produced as one of six levels, was attached to a hot extrusion molding apparatus 11 and, after preheating for 1 hr, the aluminum alloy extruded material 6 was 30 m / min. Continuous molding was carried out at a speed of Incidentally, sample No. 1 in Example 2 in which the amorphous film 1c was not formed. 12 for comparison.

ここで、貫通孔１ａの内周面１ｂにアモルファス膜１ｃを形成していない試料Ｎｏ．１２の予備加熱温度は５００℃で１時間（ｈｒ）、アルミニウム合金の成形温度は４６０℃、前記アモルファス膜１ｃがアルミナのものは、予備加熱温度を５５０℃として成形温度を４８０℃でおこなった。また、前記アモルファス膜１ｃがシリコンカーバイドのものは、予備加熱温度を５００℃とし成形温度は４６０℃でおこなった。従来は予備加熱温度が成形温度より低いのが一般的であり、その理由は予備加熱時の前記貫通孔の内周面の酸化による劣化を防止するためである。しかし、本来は成形開始直後の押出材６の寸法精度、表面状態の品質を保持するための予備加熱であることから成形時の温度より予備加熱の温度を同等以上に設定することが望ましいため、本実施例では成形温度より予備加熱温度を高く設定した。   Here, the sample No. 1 in which the amorphous film 1c is not formed on the inner peripheral surface 1b of the through hole 1a. The preheating temperature of No. 12 was 500 ° C. for 1 hour (hr), the forming temperature of the aluminum alloy was 460 ° C., and the amorphous film 1c was made of alumina, the preheating temperature was 550 ° C. and the forming temperature was 480 ° C. When the amorphous film 1c was silicon carbide, the preheating temperature was 500 ° C. and the molding temperature was 460 ° C. Conventionally, the preheating temperature is generally lower than the molding temperature, in order to prevent deterioration due to oxidation of the inner peripheral surface of the through hole during preheating. However, since it is originally preheating to maintain the dimensional accuracy of the extruded material 6 immediately after the start of molding and the quality of the surface state, it is desirable to set the preheating temperature equal to or higher than the temperature at the time of molding, In this example, the preheating temperature was set higher than the molding temperature.

尚、アルミナ、シリコンカーバイドのアモルファス膜１ｃの形成方法は、スパッタ法で、その条件を２５０℃とした。   The formation method of the amorphous film 1c of alumina or silicon carbide was a sputtering method, and the condition was 250 ° C.

前記アモルファス膜１ｃの材質がアルミナで、その厚みｔが０．１，０．２、０．５、１．０、１．２，１．５μｍとしたものがいずれも本発明の実施例で試料Ｎｏ．２１〜２６とした。   The material of the amorphous film 1c is alumina and the thickness t is 0.1, 0.2, 0.5, 1.0, 1.2, 1.5 μm. No. 21-26.

また、前記アモルファス膜１ｃの材質がシリコンカーバイドで、その厚みｔが０．１，０．２、０．５、１．０、１．２，１．５μｍとしたものが本発明の実施例で試料Ｎｏ．２７〜３２とした。   In the embodiment of the present invention, the amorphous film 1c is made of silicon carbide and has a thickness t of 0.1, 0.2, 0.5, 1.0, 1.2, 1.5 μm. Sample No. 27-32.

そして、前述したように所定の予備加熱後、アルミニウム合金の連続成形を実施し、押出材６の表面に傷の深さが１０μｍ、幅が２０μｍ以上のものが現れた時点の連続成形時間を測定した。そして、総合評価は、実施例２と同様に、連続成形時間が２４時間（ｈｒ）未満の場合の総合評価を使用不可（×）、２４時間（ｈｒ）以上、３６時間（ｈｒ）未満を使用可（△）、３６時間（ｈｒ）以上、４８時間（ｈｒ）未満を良（○）、４８時間（ｈｒ）以上のものを優良（◎）とした。   Then, as described above, after predetermined preheating, continuous forming of the aluminum alloy is performed, and the continuous forming time at the time when the surface of the extruded material 6 has a scratch depth of 10 μm and a width of 20 μm or more is measured. did. Then, as in Example 2, the comprehensive evaluation cannot be used when the continuous molding time is less than 24 hours (hr) (x), 24 hours (hr) or more, and less than 36 hours (hr). Good (Δ), 36 hours (hr) or more, and less than 48 hours (hr) as good (◯), and those over 48 hours (hr) as good (◎).

以上の結果を表３に示す。   The above results are shown in Table 3.

因みに、本発明のＴｉＣＮ系サーメット材の熱間押出成形用ダイス１のＴＧ−ＤＴＡ示差熱分析結果を図６，７，８に示した。図６は、貫通孔１ａの内周面１ｂにアモルファス膜１ｃを形成していないＴｉＣＮ系サーメットの分析チャート、図７は貫通孔１ａの内周面１ｂに形成されたアルミナのアモルファス膜１ｃの分析チャート、図８は貫通孔１ａの内周面１ｂに形成されたシリコンカーバイドのアモルファス膜１ｃの分析チャートである。   Incidentally, the TG-DTA differential thermal analysis results of the die 1 for hot extrusion molding of the TiCN cermet material of the present invention are shown in FIGS. FIG. 6 is an analysis chart of a TiCN cermet in which the amorphous film 1c is not formed on the inner peripheral surface 1b of the through hole 1a, and FIG. 7 is an analysis of the alumina amorphous film 1c formed on the inner peripheral surface 1b of the through hole 1a. FIG. 8 is an analysis chart of the silicon carbide amorphous film 1c formed on the inner peripheral surface 1b of the through hole 1a.

尚、ＴＧ−ＤＴＡ示差熱分析は、セイコー電子工業株式会社製ＳＳＣ５０００型示差熱分析装置を用いた。

Figure 0004709223
In addition, the TG-DTA differential thermal analysis used the SSC5000 type | mold differential thermal analyzer by Seiko Denshi Kogyo Co., Ltd.
Figure 0004709223

表３の結果からわかるように、熱間押出成形用ダイス１の押出材６の貫通孔１ａの内周面１ｂにアモルファス膜１ｃを形成していない試料Ｎｏ．１２と比較し、前記アモルファス膜１ｃを形成したものは、連続成形時間が約２５〜８０％向上していることがわかる。   As can be seen from the results in Table 3, the sample No. 1 in which the amorphous film 1c was not formed on the inner peripheral surface 1b of the through hole 1a of the extruded material 6 of the die 1 for hot extrusion molding. It can be seen that the film formed with the amorphous film 1c has a continuous molding time improved by about 25 to 80% as compared with the film No. 12.

そして、前記アモルファス膜１ｃがアルミナで形成された試料ＮＯ．２１〜２６は、シリコンカーバイドの試料Ｎｏ．２７〜３２より予備加熱温度が５０℃高いにも拘わらず、連続成形時間は約１０％前後向上している。このことから、予備加熱温度ならびに成形温度が約４００〜６００℃でおこなわれるアルミニウム合金等の熱間押出成形において、比較的高温領域ではアルミナのアモルファス膜１ｃ、低温領域においてはシリコンカーバイドのアモルファス膜１ｃを形成した熱間押出成形用ダイス１を用いること好ましい。   Then, the sample No. 1 in which the amorphous film 1c is formed of alumina. 21 to 26 are silicon carbide sample Nos. Although the preheating temperature is 50 ° C. higher than 27 to 32, the continuous molding time is improved by about 10%. Therefore, in the hot extrusion molding of an aluminum alloy or the like performed at a preheating temperature and a molding temperature of about 400 to 600 ° C., an amorphous film 1c of alumina in a relatively high temperature region and an amorphous film 1c of silicon carbide in a low temperature region. It is preferable to use a hot extrusion die 1 in which is formed.

そして、アモルファス膜１ｃの厚みｔと連続成形時間の関係は、アルミナのアモルファス膜１ｃの試料Ｎｏ．２１，２２，２３ならびに、シリコンカーバイドのアモルファス膜１ｃの試料Ｎｏ．２７，２８，２９に見られるように、その厚みｔが０．１，０．２，０．５μｍと厚くなるに従い連続成形時間も向上している。特に、前記アルミナのアモルファス膜１ｃの厚みｔが０．２μｍ以上の試料Ｎｏ．２２〜２６においては、アモルファス膜１ｃを形成していない試料Ｎｏ．１２に比べ連続成形時間は約５５％以上の向上となり、本発明の実施例の試料Ｎｏ．２２〜２６は、約３〜３．５日の連続成形が可能であり、従来の超硬やＳＫＤ６１材からなる熱間押出成形用ダイス１０１の一般に言われている寿命約半日に比較し著しい効果である。   The relationship between the thickness t of the amorphous film 1c and the continuous molding time is as follows. 21, 22, and 23, and sample numbers of silicon carbide amorphous film 1c. 27, 28, and 29, the continuous molding time is improved as the thickness t becomes 0.1, 0.2, and 0.5 μm. In particular, the sample No. 1 in which the thickness t of the alumina amorphous film 1c is 0.2 μm or more. In Nos. 22 to 26, the sample Nos. In which the amorphous film 1c was not formed. The continuous molding time is improved by about 55% or more compared to Sample No. 12, and sample No. 22-26 can be continuously molded for about 3 to 3.5 days, and is significantly more effective than the generally-used life of about half of the conventional die for hot extrusion molding 101 made of carbide or SKD61. It is.

しかし、アモルファス膜１ｃの厚みｔが０．１μｍの試料Ｎｏ．２１，２７はアモルファス膜１ｃを形成していない場合より連続成形時間は向上するもののその効果が少なく、これは薄過ぎるがために、予備加熱時に表面から酸化が起こり始めたことによるものと考える。   However, the sample No. 1 in which the thickness t of the amorphous film 1c is 0.1 μm. Although Nos. 21 and 27 improve the continuous molding time as compared with the case where the amorphous film 1c is not formed, the effect is small, and this is too thin.

また、アモルファス膜１ｃの厚みｔが１．５μｍの試料Ｎｏ．２６，３２は、前記厚みｔが１．０、１．２μｍの場合よりも連続成形時間が落ちていることがわかる。その理由は、アモルファス膜１ｃの微々たる剥離による酸化が起因するものと推測される。この厚みｔをたとえば、２μｍ程度以上と厚く形成すると、今回の実施例には記載しなかったが、熱間押出成形用ダイス１をセッティングする際などに、物当たり等を起こすと容易にアモルファス膜１ｃが剥がれることがあり、また、スパッタによるアモルファス膜１ｃの形成時間が長くなるだけであることを考慮すると、前記アモルファス膜１ｃの好ましい厚みｔは０．２〜１．２μｍであり、より好ましくは０．５〜１．２μｍであることがわかる。   Further, the sample No. 1 in which the thickness t of the amorphous film 1c is 1.5 μm. 26 and 32 show that the continuous molding time is lower than when the thickness t is 1.0 and 1.2 μm. The reason is presumed to be due to oxidation due to slight peeling of the amorphous film 1c. For example, when the thickness t is formed as thick as about 2 μm or more, it is not described in the present embodiment. Considering that 1c may be peeled off and only the formation time of the amorphous film 1c by sputtering is increased, the preferred thickness t of the amorphous film 1c is 0.2 to 1.2 μm, more preferably It turns out that it is 0.5-1.2 micrometers.

そして、図６、７、８に示す、ＴＧ−ＤＴＡ示差熱分析チャートから解るように、本発明の熱間押出成形用ダイス１に用いているＴｉＣＮ系サーメット材の酸化反応は約５５０℃、アルミナのアモルファス膜１ｃの酸化反応は最高６００℃以上、また、シリコンカーバイドのアモルファス膜１ｃの酸化反応は約６００℃以上という結果であった。   As can be seen from the TG-DTA differential thermal analysis charts shown in FIGS. 6, 7, and 8, the oxidation reaction of the TiCN cermet material used in the hot extrusion die 1 of the present invention is about 550 ° C., alumina. As a result, the oxidation reaction of the amorphous film 1c was 600 ° C. or more, and the oxidation reaction of the silicon carbide amorphous film 1c was about 600 ° C. or more.

図６に示すＴＧ−ＤＴＡ示差熱分析チャートにおいて、酸化反応は約５５０℃で始まることが確認出来ることから、本発明の熱間押出成形用ダイス１は押出材６の貫通孔１ａの内周面１ｂにアモルファス膜１ｃを形成していない場合でも、予備加熱温度を５００℃付近としても何ら劣化の心配もない。さらにアルミナまたはシリコンカーバイドのアモルファス膜１ｃを形成したものは、予備加熱温度を６００℃程度まで上げても熱酸化による貫通孔１ａの内周面１ｂの劣化の虞がないことがわかる。   In the TG-DTA differential thermal analysis chart shown in FIG. 6, it can be confirmed that the oxidation reaction starts at about 550 ° C. Therefore, the hot extrusion die 1 of the present invention has the inner peripheral surface of the through hole 1 a of the extruded material 6. Even when the amorphous film 1c is not formed on 1b, there is no fear of deterioration even if the preheating temperature is set to around 500 ° C. Further, it can be seen that in the case where the amorphous film 1c of alumina or silicon carbide is formed, there is no possibility of deterioration of the inner peripheral surface 1b of the through hole 1a due to thermal oxidation even if the preheating temperature is increased to about 600 ° C.

このように、本発明の熱間押出成形用ダイス１を熱間押出成形用として用いると、従来のように成形温度より低い温度での予備加熱温度に制限する必要がないことから、押出材６の成形開始直後から安定した寸法、表面状態の品質のものが得られるとともに、その連続成形時間を著しく向上できるのである。   Thus, when the hot extrusion molding die 1 of the present invention is used for hot extrusion molding, it is not necessary to limit the temperature to a preheating temperature lower than the molding temperature as in the prior art. As a result, stable dimensions and surface quality can be obtained immediately after the start of molding, and the continuous molding time can be remarkably improved.

なお各組成の臨界的意義を以下に説明する。   The critical significance of each composition will be described below.

まずＴｉＣＮ、Ｔｉ、ＴｉＣ、ＴｉＮの組成の臨界的意義を表４に示す。

Figure 0004709223
First, Table 4 shows the critical significance of the composition of TiCN, Ti, TiC, and TiN.
Figure 0004709223

ここでは摺動性の評価として押し出し速度を従来のダイスと比較する試験をおこなった。   Here, as an evaluation of slidability, a test was conducted in which the extrusion speed was compared with that of a conventional die.

なお試料Ｎｏ．４３については焼結性を満たさないので作製できなかった。   Sample No. 43 could not be produced because it did not satisfy the sinterability.

ＴｉＣＮが多ければ摺動性は高く、またＴｉＣＮの分解生成物であるＴｉ、ＴｉＮ、ＴｉＣは上限をこえてはいけないが、適量含まれている方が高い摺動性を示した。これはＴｉ、ＴｉＮ、ＴｉＣが不純物としてある程度含有されていないと、ＴｉＣＮが局所的に結晶化する部分が発生し、ダイス表面の状態が不安定になるからである。   If there is much TiCN, the slidability is high, and Ti, TiN, and TiC, which are decomposition products of TiCN, should not exceed the upper limit. This is because if Ti, TiN, and TiC are not contained as impurities to some extent, a portion where TiCN is locally crystallized occurs, and the state of the die surface becomes unstable.

次にＴａＣの組成の臨界的意義を表５に示す。

Figure 0004709223
Next, Table 5 shows the critical significance of the TaC composition.
Figure 0004709223

ここでは耐酸化性の評価としてＸＰＳ（Ｘ−ｒａｙ Ｐｈｏｔｏｅｌｅｃｔｒｏｎ Ｓｐｅｃｔｒｏｓｃｏｐｙ）分析により表面の酸化面積比を比較した。   Here, the oxidation area ratio of the surface was compared by XPS (X-ray Photoelectron Spectroscopy) analysis as evaluation of oxidation resistance.

ＴａＣは多い方が耐酸化性は高いが、上限を超えると摺動性が低下してダイスとしては使用できなくなる傾向がある。   The more TaC is, the higher the oxidation resistance is. However, when the upper limit is exceeded, there is a tendency that the slidability decreases and the die cannot be used.

次にＮｉ、Ｃｒの組成の臨界的意義を表６に示す。

Figure 0004709223
Next, Table 6 shows the critical significance of the composition of Ni and Cr.
Figure 0004709223

ここでは緻密性に対する評価として、相対密度（アルキメデス法による）、即ち理想密度に対する比を評価した。   Here, relative density (according to Archimedes method), that is, a ratio to the ideal density was evaluated as evaluation for the denseness.

Ｎｉ、Ｃｒが適量含まれていると理想密度に近くなるが上限を超えると耐摩耗性が低下し、下限を下回ると焼結性が低下するという傾向があった。   When appropriate amounts of Ni and Cr are contained, the density becomes close to the ideal density. However, when the upper limit is exceeded, the wear resistance is lowered, and when it is less than the lower limit, the sinterability tends to be lowered.

次に本発明の焼結体の粒度分布における２つのピークについての粒度範囲および重量比率の臨界的意義を表７に示す。

Figure 0004709223
Next, Table 7 shows the critical significance of the particle size range and weight ratio for the two peaks in the particle size distribution of the sintered body of the present invention.
Figure 0004709223

ここでは摺動性、ＴｉＣＮの分解性の評価する試験を行った。
評価する焼結体は実施例１の試料Ｎｏ．１と同一組成のものを使用し、これと同様の方法により調整して得た、粒度分布における２つのピークがそれぞれ異なる試料Ｎｏ．６２〜７３を用いた。また、試料Ｎｏ．７４〜７８は２つのピークの結晶粒の比率を変えたものである。
評価は、焼結体の靭性、強度および摺動性について行った。靭性の規格値は１０ＭＰａ・ｍ1/2以上あり、１０ＭＰａ・ｍ1/2以上を良（○）、７ＭＰａ・ｍ1/2以上１０ＭＰａ・ｍ1/2未満を使用可（△）とした。強度の規格値は１１５０ＭＰａ以上であり、１１５０ＭＰａ以上を良（○）、１０００ＭＰａ以上１１５０ＭＰａ未満を使用可（△）とした。摺動性についてはアルミ材を実際に押し出した２４時間後のアルミ材の傷の有無により、傷が出ないものを良（○）、少し傷が生じたものを使用可（△）とした。Here, tests for evaluating slidability and decomposability of TiCN were performed.
The sintered body to be evaluated is the sample No. 1 of Example 1. Sample No. 1 having the same composition as that of No. 1 and having two peaks in the particle size distribution obtained by adjusting in the same manner as above were used. 62-73 were used. Sample No. 74 to 78 are obtained by changing the ratio of crystal grains of two peaks.
Evaluation was performed about the toughness, strength, and slidability of the sintered body. The standard value of toughness is 10 MPa · m 1/2 or more, 10 MPa · m 1/2 or more is good (◯), and 7 MPa · m 1/2 or more and less than 10 MPa · m 1/2 is usable (Δ). The standard value of the strength is 1150 MPa or more, 1150 MPa or more is good (◯), and 1000 MPa or more and less than 1150 MPa is usable (Δ). With respect to the slidability, no damage was found (good) depending on the presence or absence of scratches on the aluminum material 24 hours after the aluminum material was actually extruded, and the slight damage was acceptable (△).

表７に示したように、本発明の焼結体の粒度分布における２つのピークについての粒度範囲および比率が本発明の範囲内にある場合、ＴｉＣＮの分解が起こらず、摺動性は良好であることが示された。
粒度分布における１つのピークが本発明の範囲の下限値より小さいと、粒度分布が細かくなり過ぎて脱粒による強度劣化や靱性低下により摺動性が悪くなり、上限値より大きいと、強度・靱性が低くなる傾向となっている。
また、粒度分布における他のピークが本発明の範囲の下限値より小さいと、これは粒度分布が細かくなり過ぎるとＴｉＣＮの分解が起こり易くなるため摺動性が悪くなり、上限値より大きいと粗大粒の影響が出易くなるため強度劣化となっている。
そして、２つのピークの結晶粒の比率が本発明の範囲の下限値より小さいと、強度劣化となり、上限値より大きいと、摺動性が悪くなっている。これは比率が小さいと脱粒などの影響が出易くなり、比率が大きいとＴｉＣＮの分解が起こりやすくなるためである。As shown in Table 7, when the particle size range and the ratio of the two peaks in the particle size distribution of the sintered body of the present invention are within the range of the present invention, TiCN does not decompose and the slidability is good. It was shown that there is.
If one peak in the particle size distribution is smaller than the lower limit value of the range of the present invention, the particle size distribution becomes too fine and the slidability is deteriorated due to strength deterioration or toughness reduction due to degranulation. It tends to be lower.
In addition, if the other peak in the particle size distribution is smaller than the lower limit value of the range of the present invention, this is because if the particle size distribution becomes too fine, TiCN is liable to be decomposed, resulting in poor slidability. Since the influence of grains is likely to occur, the strength is deteriorated.
And when the ratio of the crystal grain of two peaks is smaller than the lower limit of the range of the present invention, the strength deteriorates, and when larger than the upper limit, the slidability is deteriorated. This is because if the ratio is small, the effect of degranulation or the like is likely to occur, and if the ratio is large, TiCN is likely to be decomposed.

尚、図１０は本発明の熱間押出成形用ダイスのＴｉ、ＴｉＣ、ＴｉＮに関する組成を示すダイアグラムであり、便宜上Ｔｉ、ＴｉＣ、ＴｉＮの各頂点を３％としているものである。   FIG. 10 is a diagram showing the composition of Ti, TiC, and TiN of the hot extrusion die of the present invention. For convenience, each vertex of Ti, TiC, and TiN is 3%.

「ＣＬ１」と示された６角形の網掛け部分が、本願の請求項１のＴｉ、ＴｉＣ、ＴｉＮに関する範囲である。   The hexagonal shaded portion labeled “CL1” is the range related to Ti, TiC, and TiN in claim 1 of the present application.

Claims (17)

ＴｉＣＮが５８〜９２．５質量％、Ｔｉが０．０１〜１質量％、ＴｉＣが０．０１〜２質量％、ＴｉＮが０．０１〜２質量％、残部がＴａＣ、Ｎｉ、Ｃｒからなることを特徴とする焼結体。  TiCN is 58-92.5% by mass, Ti is 0.01-1% by mass, TiC is 0.01-2% by mass, TiN is 0.01-2% by mass, and the balance is TaC, Ni, Cr. A sintered body characterized by ＴａＣを１〜１１質量％有することを特徴とする請求項１に記載の焼結体。  The sintered body according to claim 1, which has 1 to 11% by mass of TaC. Ｎｉを３〜１３質量％、Ｃｒを３〜１３質量％有することを特徴とする請求項１または２に記載の焼結体。  The sintered body according to claim 1 or 2, comprising 3 to 13 mass% of Ni and 3 to 13 mass% of Cr. 前記焼結体の粒度分布が２つのピークを有することを特徴とする請求項１〜３のいずれかに記載の焼結体。  The sintered body according to any one of claims 1 to 3, wherein a particle size distribution of the sintered body has two peaks. 前記粒度分布における１つのピークは１．０〜１．３μｍの粒度範囲、他のピークは１．４〜１．７μｍの粒度範囲にあることを特徴とする請求項４に記載の焼結体。  5. The sintered body according to claim 4, wherein one peak in the particle size distribution is in a particle size range of 1.0 to 1.3 μm, and the other peak is in a particle size range of 1.4 to 1.7 μm. 前記粒度分布における１．０〜１．３μｍの粒度範囲のピークと１．４〜１．７μｍの粒度範囲のピークとが３：２〜１：１の比率であることを特徴とする請求項５に記載の焼結体。  The peak in the particle size range of 1.0 to 1.3 μm and the peak in the particle size range of 1.4 to 1.7 μm in the particle size distribution are in a ratio of 3: 2 to 1: 1. The sintered body according to 1. 前記焼結体の結晶粒が球状であることを特徴とする請求項１〜６のいずれかに記載の焼結体。  The sintered body according to any one of claims 1 to 6, wherein crystal grains of the sintered body are spherical. 請求項１〜７のいずれかに記載の焼結体を用いて形成されていることを特徴とする摺動部材。  A sliding member characterized by being formed using the sintered body according to claim 1. 請求項１〜７のいずれかに記載の焼結体を用いて形成されていることを特徴とする成膜用材料。  A film-forming material formed using the sintered body according to claim 1. 請求項１〜７のいずれかに記載の焼結体を用いて形成されていることを特徴とする熱間押出成形用ダイス。  A die for hot extrusion molding, which is formed using the sintered body according to any one of claims 1 to 7. 板形状の中心付近に貫通孔を有し、少なくとも該貫通孔の内周面にアモルファス膜を形成したことを特徴とする請求項１０に記載の熱間押出成形用ダイス。  The die for hot extrusion molding according to claim 10, wherein a through-hole is formed near the center of the plate shape, and an amorphous film is formed at least on the inner peripheral surface of the through-hole. 前記アモルファス膜がアルミナもしくはシリコンカーバイドからなることを特徴とする請求項１１に記載の熱間押出成形用ダイス。  The hot extrusion die according to claim 11, wherein the amorphous film is made of alumina or silicon carbide. 前記アモルファス膜が厚み０．２〜１．２μｍであることを特徴とする請求項１１に記載の熱間押出成形用ダイス。  The hot extrusion die according to claim 11, wherein the amorphous film has a thickness of 0.2 to 1.2 μm. 請求項１０〜１３のいずれかに記載の熱間押出成形用ダイスを筒状のダイケースの一方端側に装着し、上記ダイケースの他方端側を筒状のコンテナの一方端側に装着し、押出材をコンテナから押出すための押し出し機構を上記コンテナに配置したことを特徴とする熱間押出成形装置。  The hot extrusion die according to any one of claims 10 to 13 is mounted on one end side of a cylindrical die case, and the other end side of the die case is mounted on one end side of a cylindrical container. A hot extrusion molding apparatus, wherein an extrusion mechanism for extruding the extruded material from the container is disposed in the container. 請求項１０〜１３のいずれかに記載の熱間押出成形用ダイスを用いたことを特徴とする熱間押出成形方法。  A hot extrusion molding method using the hot extrusion die according to any one of claims 10 to 13. 請求項１０〜１３のいずれかに記載の熱間押出成形用ダイスを用いてアルミニウム合金を成形することを特徴とする熱間押出成形方法。  A hot extrusion molding method, comprising: forming an aluminum alloy using the hot extrusion die according to any one of claims 10 to 13. 請求項１〜７のいずれかに記載の焼結体の製造方法であって、平均粒径０．３〜０．７μｍのＴｉＣＮ粉末と、平均粒径１．２〜２μｍのＴｉＣＮ粉末とを７：３〜９：１の重量比率で混合し、さらに平均粒径１．５μｍ以下のＴａＣ粉末と、平均粒径２μｍ以下のＮｉ粉末及びＣｒ粉末とを加えて、溶媒とともに粉砕混合してスラリーとする工程を有することを特徴とする焼結体の製造方法。  It is a manufacturing method of the sintered compact in any one of Claims 1-7, Comprising: 7 TiCN powder with an average particle diameter of 0.3-0.7 micrometer, and TiCN powder with an average particle diameter of 1.2-2 micrometers are 7 : 3-9: 1 by weight ratio, further adding TaC powder with an average particle diameter of 1.5 μm or less, Ni powder and Cr powder with an average particle diameter of 2 μm or less, and pulverizing and mixing with a solvent The manufacturing method of the sintered compact characterized by having the process to do.
JP2007537741A 2005-09-29 2006-09-29 Sintered body, manufacturing method thereof, sliding member using the sintered body, film forming material, hot extrusion die, hot extrusion molding apparatus and hot extrusion using the hot extrusion die Molding method Expired - Fee Related JP4709223B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2007537741A JP4709223B2 (en) 2005-09-29 2006-09-29 Sintered body, manufacturing method thereof, sliding member using the sintered body, film forming material, hot extrusion die, hot extrusion molding apparatus and hot extrusion using the hot extrusion die Molding method

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
JP2005283384 2005-09-29
JP2005283384 2005-09-29
JP2005371016 2005-12-22
JP2005371016 2005-12-22
PCT/JP2006/319577 WO2007037431A1 (en) 2005-09-29 2006-09-29 Sintered body and method for producing same; sliding member, film-forming material and die for hot extrusion molding each using such sintered body; and hot extrusion molding apparatus and hot extrusion molding method each using such die for hot extrusion molding
JP2007537741A JP4709223B2 (en) 2005-09-29 2006-09-29 Sintered body, manufacturing method thereof, sliding member using the sintered body, film forming material, hot extrusion die, hot extrusion molding apparatus and hot extrusion using the hot extrusion die Molding method

Publications (2)

Publication Number Publication Date
JPWO2007037431A1 JPWO2007037431A1 (en) 2009-04-16
JP4709223B2 true JP4709223B2 (en) 2011-06-22

Family

ID=37899851

Family Applications (1)

Application Number Title Priority Date Filing Date
JP2007537741A Expired - Fee Related JP4709223B2 (en) 2005-09-29 2006-09-29 Sintered body, manufacturing method thereof, sliding member using the sintered body, film forming material, hot extrusion die, hot extrusion molding apparatus and hot extrusion using the hot extrusion die Molding method

Country Status (4)

Country Link
EP (1) EP1930457A4 (en)
JP (1) JP4709223B2 (en)
CN (1) CN101273150B (en)
WO (1) WO2007037431A1 (en)

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010024377A1 (en) * 2008-08-29 2010-03-04 昭和電工株式会社 Surface-covered cermet member and method for manufacturing same
JP4527199B1 (en) 2010-01-27 2010-08-18 昭和電工株式会社 Extrusion method
JP5267709B2 (en) * 2011-09-14 2013-08-21 株式会社豊田中央研究所 High heat resistant member, method for producing the same, graphite crucible and method for producing single crystal ingot
EP2757424B1 (en) * 2013-01-17 2018-05-16 Omega SA Part for clockwork
FR3014904B1 (en) * 2013-12-13 2016-05-06 Constellium France PRODUCTS FILES FOR PLASTER FLOORS IN LITHIUM COPPER ALLOY
CN104018017B (en) * 2014-05-27 2016-02-24 南京航空航天大学 The recovery of waste and old Ti (C, N) base metal-ceramic material and renovation process
CN104889186B (en) * 2015-06-18 2017-09-22 燕山大学 A kind of positive and negative Compound Extrusion manufacturing process of ZrTiAlV alloys electric field-assisted
RU2680630C1 (en) * 2018-05-08 2019-02-25 федеральное государственное бюджетное образовательное учреждение высшего образования "Уфимский государственный авиационный технический университет" Method of ion-implantation treatment of compressor monowheel with titanium alloys blades
CN109226757B (en) * 2018-10-18 2021-11-02 湖南德润有色焊材科技股份有限公司 Preparation method and application of material blocking block material for extrusion

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS51101007A (en) * 1975-03-04 1976-09-07 Mitsubishi Metal Corp Saametsuto
JPS51103914A (en) * 1975-03-12 1976-09-14 Mitsubishi Metal Corp Kyojinsaametsuto
JPS51114411A (en) * 1975-04-01 1976-10-08 Mitsubishi Metal Corp Tough cermet

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1085041A (en) * 1965-01-27 1967-09-27 Hitachi Ltd Heat-resisting cemented carbide
DE3503105A1 (en) * 1985-01-30 1986-07-31 Leybold-Heraeus GmbH, 5000 Köln METHOD FOR COATING MACHINE PARTS AND TOOLS WITH CARBIDE MATERIAL AND MACHINE PARTS AND TOOLS PRODUCED BY THE METHOD
KR950014351B1 (en) * 1993-12-24 1995-11-25 포항종합제철주식회사 Method of manufacturing complex chrome carbide system
DE19704242C1 (en) * 1997-02-05 1998-08-27 Starck H C Gmbh Co Kg Carbonitride powder, process for their preparation and their use
DE19711642C2 (en) * 1997-03-20 2000-09-21 Nwm De Kruithoorn Bv Method for producing a steel matrix composite material and composite material, produced by such a method
JP2001181775A (en) * 1999-12-24 2001-07-03 Ngk Spark Plug Co Ltd Cermet sintered body
JP2003236707A (en) * 2001-12-11 2003-08-26 Mitsubishi Materials Corp Cutting tip made of cubic crystal boron nitride group ultrahigh pressure sintered material having excellent resistance to chipping
CN1632150A (en) * 2003-12-22 2005-06-29 山东大学 Titanium carbonitride base ceramic bearing materials
CN1239397C (en) * 2004-03-02 2006-02-01 山东大学 Preparation process for three elemental compound powder material of titanium carbonitride

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS51101007A (en) * 1975-03-04 1976-09-07 Mitsubishi Metal Corp Saametsuto
JPS51103914A (en) * 1975-03-12 1976-09-14 Mitsubishi Metal Corp Kyojinsaametsuto
JPS51114411A (en) * 1975-04-01 1976-10-08 Mitsubishi Metal Corp Tough cermet

Also Published As

Publication number Publication date
JPWO2007037431A1 (en) 2009-04-16
EP1930457A4 (en) 2012-08-22
CN101273150B (en) 2010-10-06
CN101273150A (en) 2008-09-24
EP1930457A1 (en) 2008-06-11
WO2007037431A1 (en) 2007-04-05

Similar Documents

Publication Publication Date Title
JP4709223B2 (en) Sintered body, manufacturing method thereof, sliding member using the sintered body, film forming material, hot extrusion die, hot extrusion molding apparatus and hot extrusion using the hot extrusion die Molding method
JP6257896B2 (en) Consolidated high toughness coated hard particles in high toughness matrix materials.
JP5221951B2 (en) Cemented carbide and cutting tools
JP6193207B2 (en) Ceramic parts and cutting tools
EP2860273B1 (en) Heat-resistant molybdenum alloy
EP1148962B1 (en) Metal-ceramic laminar-band composite
JP3916465B2 (en) Molten metal member made of sintered alloy having excellent corrosion resistance and wear resistance against molten metal, method for producing the same, and machine structure member using the same
JP4953762B2 (en) Hot extrusion dies
WO2011060038A2 (en) Inert high hardness material for tool lens production in imaging applications
US6551954B1 (en) WC-base composite ceramic sintered compact
KR101807629B1 (en) Cermet tool
JP4976626B2 (en) Sintered alloy material, method for producing the same, and mechanical structural member using the same
JP2001049378A (en) Wear resistant cemented carbide sintered compact and its manufacture
JP2002194474A (en) Tungsten carbide matrix super hard composite sintered body
JP2002206155A (en) Immersion member for hot-dip metal coating bath, and its manufacturing method
JP6380016B2 (en) Cermet tools and coated cermet tools
JP2009209022A (en) WC-SiC-Mo2C-BASED SINTERED BODY AND ITS MANUFACTURING METHOD
WO2022208766A1 (en) Superhard alloy and mold
JP4690553B2 (en) Mating ring for shift side guide roll
JP2022136020A (en) Cemented carbide cutter
JPH05237827A (en) Mold and its manufacture
JP2008087985A (en) Al2O3-TiC COMPOSITE CERAMIC SINTERED COMPACT
JP2007008776A (en) Chromium-containing sintered compact

Legal Events

Date Code Title Description
A01 Written decision to grant a patent or to grant a registration (utility model)

Free format text: JAPANESE INTERMEDIATE CODE: A01

Effective date: 20110222

A61 First payment of annual fees (during grant procedure)

Free format text: JAPANESE INTERMEDIATE CODE: A61

Effective date: 20110317

LAPS Cancellation because of no payment of annual fees