JPS6154872B2 - - Google Patents
Info
- Publication number
- JPS6154872B2 JPS6154872B2 JP53132267A JP13226778A JPS6154872B2 JP S6154872 B2 JPS6154872 B2 JP S6154872B2 JP 53132267 A JP53132267 A JP 53132267A JP 13226778 A JP13226778 A JP 13226778A JP S6154872 B2 JPS6154872 B2 JP S6154872B2
- Authority
- JP
- Japan
- Prior art keywords
- compound
- temperature
- titanium
- hafnium
- composite
- 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
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/36—Carbonitrides
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/32—Carbides
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/34—Nitrides
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/448—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for generating reactive gas streams, e.g. by evaporation or sublimation of precursor materials
- C23C16/4488—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for generating reactive gas streams, e.g. by evaporation or sublimation of precursor materials by in situ generation of reactive gas by chemical or electrochemical reaction
Landscapes
- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Electrochemistry (AREA)
- Chemical Vapour Deposition (AREA)
Description
本発明は、複合化合物を被覆した超硬合金に関
する。
炭化タングステンを主成分とし、主としてコバ
ルトで結合した超硬合金を母材とし、表面に母材
より耐摩耗性に富むTi，Zr，Hfの炭化物、窒化
物、炭窒化物を数ミクロンの厚さにて被覆した、
いわゆるコーテイングチツプは母材の靭性と、表
面被覆層の耐摩耗性を兼ねそなえており、切削工
具としては、従来の超硬合金より優れた切削性能
を有することは広く知られた事実である。
しかし、切削材及び切削方法の進歩に伴なつて
さらに高性能、長寿命化を目的に改良された切削
工具が要望され、開発がなされている。
これらの対策として、最近、炭化物及び窒化物
の単層膜のみを用いるのではなく、材料の特徴を
生かした使いかたがなされてきている。例えば、
特開昭49−3841号に示してあるように、多層膜コ
ーテイングがその一例である。つまり、TiC皮膜
は硬度が高いことから耐フランク摩耗はあるが、
耐クレータ摩耗に対して劣る欠点がある。また、
TiN皮膜は、硬度が低いことから耐フランク摩耗
に対しては劣るが、化学的安定性、つまり生成自
由エネルギーOGが大きいことから耐クレータ摩
耗に優れている。おのおのの特徴を生かすため、
TiC＋TiN＋Ti（Ｃ・Ｎ）などの多層膜、複合皮
膜のコーテイング材料が開発され、市場にまでま
わつている。さらに、コーテイング材料としては
高温においてより安定なものが要求され、例えば
特開昭51−42029号のようにTiC皮膜の上にＡ
2O3をコーテイングしたTiC＋Ａ2O3コーテイン
グチツプもある。
これらの多層膜は異種の炭化物、窒化物及び酸
化膜を積層し、TiC＋TiN，TiC＋Ａ2O3したも
のであり、異種層間の密着性が悪く、切削時に皮
膜のはく離およびチツピングが起こる場合があつ
た。また、複合皮膜としては、ほとんどが金属の
炭窒化物、例えばTi（Ｃ・Ｎ），Zr（Ｃ・Ｎ），
Hf（Ｃ・Ｎ）であつた。これらの複合膜では一
種金属、例えばTiのみの性質しか特徴をだせな
い欠点がある。
そこで、本発明者らは２種金属の炭化物、窒化
物を組合せ、２種の金属の特徴を持つた複合皮
膜、特に耐フランク摩耗に優れているチタン化合
物と耐クレータ摩耗に優れているハフニウム化合
物を組合せた（Ti，Hf）Ｃ，（Ti，Hf）Ｎなるも
のを作成し、特徴あるコーテイング皮膜をつくる
ことを試みた。しかし、（Ti，Hf）Ｃ，（Ti，
Hf）ＮはTi（Ｃ・Ｎ）に比較して生成過程が複
雑であることから従来まつたく試みられた例がな
い。Ti（Ｃ・Ｎ）は、原料ガスTiC４に、キヤ
リヤガスとしてH2を導入し、かつ反応ガスとし
てCH4，NH3を一緒に混合することにより容易に
生成される。しかし、（Ti，Hf）Ｃの場合は、原
料ガスが２種類必要とし、かつ反応条件がことな
る問題がある。さらにHfCの生成に関してはまつ
たくやられていないのが現状であつた。そこで本
発明者らは、まずHfCの生成に成功し、得られた
皮膜が耐摩耗性があることを確認している。こ
の、HfC生成方法に関しては、特許申請中（特開
昭54−109098号）であるが、この方法を基に生成
方法を改良することにより、（Ti，Hf）Ｃの生成
が非常に容易であることに気づき、本発明に至つ
た。本発明はこれらの方法により得ることができ
た複合化合物を被覆した超硬合金に関するもので
ある。
以下に本発明の実施例とその効果についてのべ
る。
本発明は、超硬合金の表面に耐摩耗性に優れた
チタン化合物とハフニウム化合物の複合化合物、
（Ti，Hf）Ｃ，（Ti，Hf）Ｎ及び（Ti，If）Ｃ・
Ｎを被覆した超硬合金を得ることを目的とする。
本発明に用いた減圧CVD（Chemicee Vapor
Deposition）装置を第１図に示す。原料ガスとし
てはヨウ素（I2）とチタン（Ti）、ハフニウム
（Hf）とを反応させ、TiI4及びHfI4を生成し、そ
れを用いた。まず、恒温槽の温度をコントロール
して、一定量のヨウ素ガスを加熱されたTi及び
Hfに導入して、チタン及びハフニウムヨウ化物
を生成する。その際の反応式は
Hf＋2I2→HfI4
Ti＋2I2→TiI4
で示される。これらのヨウ化物の生成は、Tiお
よびハフニウムの加熱温度によつて決まる。HfI4
はHfの加熱温度を300℃以上にすることにより、
生成し、かつ850℃以上で分解出来ることを確認
している。これに関しては特許申請中（特開昭55
−60016号）である。チタンヨウ化物はTi温度を
250℃以上にすることにより生成できる。しか
し、チタンヨウ化物はTi温度により、生成され
る組成がことなり、250〜300℃はTiI4、300℃以
上ではTiI3，TiI2が生成される。TiI3，TiI2は蒸
気圧が小さいため好ましくない。したがつて、チ
タンヨウ化物は蒸気圧が大きいTiI4を用いる必要
があり、そのためにはTi温度は250〜300℃が最
適であることがわかつた。
これらの結果から、Ti及びHf温度は300℃とす
ることにした。なお、Ti及びHf原料は好ましく
はスポンジ状のものがよく、かつ粒度はそろえた
方がよい。TiI4及びHfI4の生成量はI2の蒸発量、
つまりヨウ素温度によつて決定され、本実験では
30℃にした。なお、ヨウ素温度は、過剰のヨウ素
（未反応のヨウ素）が流れないように装置の大き
さ原料のチヤージ量（Hf，Ti）によつてきめな
ければいけない。
このようにして生成されたTiI4，HfI4は反応ガ
スと一緒に所定温度に加熱された基体上に導び
く。反応ガスとして、例えば炭化水素、C4H10を
導入して、（Ti，Hf）Ｃを生成する場合、下記の
ようになる。
4HfI4＋C4H10→4HfC＋10HI＋3I2
4TiI4＋C4H10→4TiC＋10HI＋3I2
その際の基体の加熱温度（以下反応温度と表わ
す）は850℃〜1250℃の範囲がよい。このように
して、基体上にTiC、とHfCとが共析し、（Ti，
Hf）Ｃなる複合皮膜が生成される。反応温度が
850℃以下の場合TiC及びHfCが生成しない。
1250℃以上の場合、基体（wc−Co合金）の液相
温度が1270℃にあるため基体自体の物性が低下
し、好ましくない。かつ、得られる（Ti，Hf）
Ｃは、柱状晶組織になり、表面が荒れ、切削時の
チツピング現象が起こる。さらに皮膜形成時には
反応圧力を0.25Torr以下にする必要がある。減圧
にすることにより、膜厚の均一性が良くなること
は既知のことであるが、0.25Torr以上になると膜
厚分布が悪くなり、かつ得られる皮膜が極端な柱
状晶組織になる欠点がある。
（Ti，Hf）Ｃの生成速度は、反応温度、反応
圧力、原料ガス（TiI4，HfI4）及びC4H10により、
影響されるのはもちろんである。
（Ti，Hf）Ｃの中のTiCとHfCとの固溶比は、
Ti及びHf中に導入されるヨウ素ガスにより左右
され、その際の生成速度に影響される。
反応ガスとして、炭化水素の代りにNH3を用い
ることにより、（Ti，Hf）Ｎが生成でき、かつ炭
化水素とNH3の混合ガスを用いることにより
（Ti，Hf）Ｃ・Ｎが生成される。
実施例 １
超硬チツプ素材72wc−9Co−8TiC−11TaCの
上に下記の条件で（Ti，Hf）Ｃ複合皮膜を被覆
した。
＜形成条件＞
反応圧力：0.2Torr
反応温度：950℃
C4H10：0.2ml／min
Hf温度：300℃
Ti温度：300℃
I2温度：30℃
であり、その際の生成速度は約20μｍ／ｈであ
り、5.0μｍ被覆した。このコーテイングチツプ
を下記の切削条件で切削した。
＜切削条件＞
被削材：SCM3（Hs 30〜35）
切削速度：140m／min
送 り：0.2mm／rev
切込み：7.5mm
切削テストの評価結果を第２図に示す。これか
ら明らかなように、（Ti，Hf）Ｃの耐摩耗性は、
ノンコーテイングチツプに比較して数倍優れてお
り、かつ、TiCコーテイングチツプに比較して２
倍優れていることがわかる。
実施例 ２
超硬チツプ素材83.5WC―6.5Co―5TaC―
5TiCNの上に、下記の条件で（Hf，Ti）CNおよ
び（Hf，Ti）Ｎ複合皮膜を被覆した。
＜形成条件＞
（Hf，Ti）Ｃ・Ｎ （Hf，Ti）Ｎ
反応圧力：0.15Torr反応圧力：0.2Torr
反応温度：950℃反応温度：900℃
CH4：１ml／minNH3：３ml／min
NH3：２ml／minHf温度：300℃
Hf温度：300℃Ti温度：300℃
Ti温度300℃I2温度：30℃
I2温度：30℃
であり、その際の（Hf，Ti）Ｃ・Ｎおよび
（Hf，Ti）Ｎの生成速度は2.5μｍ／ｈおよび2.0
μｍ／ｈであり、それぞれ上記素材に6.0μｍ被
覆した。尚、比較チツプとして上記超硬チツプ素
材にTiNおよびTiC・Ｎをそれぞれ6.0μｍ被覆し
たものを用いた。
＜切削条件＞
被削材：SCM3（Hs38〜40）
切削速度：180m／min
送 り：0.3mm／rev.
切込み：2.0mm
寿命判定基準：フランク摩耗幅 0.3mm
切削テストの結果を第１表に示す。
The present invention relates to a cemented carbide coated with a composite compound. The base material is a cemented carbide mainly composed of tungsten carbide and bonded with cobalt, and the surface is coated with carbides, nitrides, and carbonitrides of Ti, Zr, and Hf, which are more wear resistant than the base material, to a thickness of several microns. coated with
It is a well-known fact that so-called coating chips have both the toughness of the base material and the wear resistance of the surface coating layer, and have superior cutting performance to conventional cemented carbides as cutting tools. However, as cutting materials and cutting methods progress, improved cutting tools with higher performance and longer life are desired and are being developed. As a countermeasure against these problems, recently, instead of using only a single layer film of carbides and nitrides, methods have been used that take advantage of the characteristics of the materials. for example,
One example is a multilayer coating, as shown in Japanese Patent Application Laid-Open No. 49-3841. In other words, TiC film has flank wear resistance due to its high hardness, but
It has the disadvantage of poor crater wear resistance. Also,
TiN coatings are inferior in flank wear resistance due to their low hardness, but are superior in crater wear resistance due to their chemical stability, that is, their large free energy of formation OG. In order to take advantage of each person's characteristics,
Coating materials such as multilayer films and composite films such as TiC + TiN + Ti (C/N) have been developed and are now on the market. Furthermore, coating materials that are more stable at high temperatures are required, and for example, A
There is also a TiC+A 2 O 3 coated chip that is coated with 2 O 3 . These multilayer films are made by laminating different types of carbide, nitride, and oxide films, such as TiC + TiN, TiC + A 2 O 3 , and the adhesion between the different types of layers is poor, and peeling and chipping of the film may occur during cutting. . In addition, most of the composite films are made of metal carbonitrides, such as Ti (C/N), Zr (C/N),
It was Hf(C・N). These composite films have the disadvantage that they can only exhibit the characteristics of one metal, such as Ti. Therefore, the present inventors have combined carbides and nitrides of two types of metals to create a composite film that has the characteristics of two types of metals, a titanium compound that has excellent flank wear resistance and a hafnium compound that has excellent crater wear resistance. We created a combination of (Ti, Hf)C and (Ti, Hf)N, and attempted to create a distinctive coating film. However, (Ti, Hf)C, (Ti,
Since the production process of Hf)N is more complicated than that of Ti(C.N), no attempts have been made to date. Ti(C.N) is easily produced by introducing H 2 as a carrier gas into the source gas TiC 4 and mixing together CH 4 and NH 3 as reaction gases. However, in the case of (Ti, Hf)C, there are problems in that two types of raw material gases are required and the reaction conditions are different. Furthermore, the current situation is that little effort has been made regarding the generation of HfC. Therefore, the present inventors first succeeded in producing HfC and confirmed that the resulting film was wear resistant. This HfC production method is currently under patent application (Japanese Unexamined Patent Publication No. 109098/1989), but by improving the production method based on this method, (Ti, Hf)C can be produced very easily. This realization led to the present invention. The present invention relates to a cemented carbide coated with a composite compound obtained by these methods. Examples of the present invention and their effects will be described below. The present invention uses a composite compound of a titanium compound and a hafnium compound with excellent wear resistance on the surface of a cemented carbide.
(Ti, Hf)C, (Ti,Hf)N and (Ti,If)C・
The purpose is to obtain a cemented carbide coated with N. Reduced pressure CVD (Chemicee Vapor CVD) used in the present invention
The deposition apparatus is shown in FIG. As a raw material gas, iodine (I 2 ), titanium (Ti), and hafnium (Hf) were reacted to generate TiI 4 and HfI 4 , which were used. First, by controlling the temperature of the thermostatic chamber, a certain amount of iodine gas was added to the heated Ti and
Hf is introduced to produce titanium and hafnium iodide. The reaction formula at that time is shown as Hf+2I 2 →HfI 4 Ti+2I 2 →TiI 4 . The formation of these iodides is determined by the heating temperature of Ti and hafnium. HfI 4
By increasing the heating temperature of Hf to 300℃ or higher,
It has been confirmed that it can be generated and decomposed at temperatures above 850℃. A patent application is currently being applied for this (Japanese Unexamined Patent Publication No. 55
-60016). Titanium iodide increases Ti temperature
It can be produced by raising the temperature to 250℃ or higher. However, the composition of titanium iodide produced differs depending on the Ti temperature; TiI 4 is produced at 250 to 300°C, and TiI 3 and TiI 2 are produced above 300°C. TiI 3 and TiI 2 are not preferred because their vapor pressures are low. Therefore, it is necessary to use TiI4 , which has a high vapor pressure, as the titanium iodide, and it has been found that the optimal Ti temperature is 250 to 300°C for this purpose. Based on these results, the Ti and Hf temperatures were decided to be 300°C. Note that the Ti and Hf raw materials are preferably spongy and have the same particle size. The amount of TiI 4 and HfI 4 produced is the amount of evaporation of I 2 ,
In other words, it is determined by the iodine temperature, and in this experiment
The temperature was set to 30℃. Note that the iodine temperature must be determined based on the size of the device and the charge amount (Hf, Ti) of the raw materials so that excess iodine (unreacted iodine) does not flow. TiI 4 and HfI 4 thus produced are guided together with the reaction gas onto a substrate heated to a predetermined temperature. When (Ti, Hf)C is produced by introducing, for example, a hydrocarbon, C 4 H 10 , as a reaction gas, the process is as follows. 4HfI 4 +C 4 H 10 →4HfC+ 10 HI+3I 2 4TiI 4 +C 4 H 10 →4TiC+ 10 HI+3I 2The heating temperature of the substrate at that time (hereinafter referred to as reaction temperature) is preferably in the range of 850°C to 1250°C. In this way, TiC and HfC eutectoid on the substrate (Ti,
A composite film called Hf)C is produced. The reaction temperature is
TiC and HfC are not generated at temperatures below 850℃.
If the temperature is 1250°C or higher, the liquidus temperature of the substrate (wc-Co alloy) is 1270°C, so the physical properties of the substrate itself deteriorate, which is not preferable. And obtained (Ti, Hf)
C has a columnar crystal structure, the surface is rough, and a chipping phenomenon occurs during cutting. Furthermore, during film formation, the reaction pressure must be kept below 0.25 Torr. It is known that reducing the pressure improves the uniformity of the film thickness, but when the pressure exceeds 0.25 Torr, the film thickness distribution deteriorates and the resulting film has an extremely columnar crystal structure. . The production rate of (Ti, Hf)C depends on the reaction temperature, reaction pressure, raw material gas (TiI 4 , HfI 4 ) and C 4 H 10 .
Of course it will be influenced. The solid solution ratio of TiC and HfC in (Ti, Hf)C is
It depends on the iodine gas introduced into Ti and Hf, and is influenced by the production rate at that time. By using NH 3 instead of hydrocarbon as a reaction gas, (Ti, Hf)N can be generated, and by using a mixed gas of hydrocarbon and NH 3 , (Ti, Hf)C・N can be generated. Ru. Example 1 A (Ti, Hf)C composite film was coated on a carbide chip material 72wc-9Co-8TiC-11TaC under the following conditions. <Formation conditions> Reaction pressure: 0.2Torr Reaction temperature: 950℃ C 4 H 10 : 0.2ml/min Hf temperature: 300℃ Ti temperature: 300℃ I 2 temperature: 30℃, and the formation rate is approximately 20μm /h, and the coating was 5.0 μm. This coating chip was cut under the following cutting conditions. <Cutting conditions> Work material: SCM3 (Hs 30-35) Cutting speed: 140m/min Feed: 0.2mm/rev Depth of cut: 7.5mm The evaluation results of the cutting test are shown in Figure 2. As is clear from this, the wear resistance of (Ti, Hf)C is
It is several times better than non-coated chips and 2 times better than TiC coated chips.
It turns out it's twice as good. Example 2 Carbide chip material 83.5WC―6.5Co―5TaC―
5TiCN was coated with (Hf,Ti)CN and (Hf,Ti)N composite films under the following conditions. <Formation conditions> (Hf,Ti)C・N (Hf,Ti)N Reaction pressure: 0.15Torr Reaction pressure: 0.2Torr Reaction temperature: 950℃ Reaction temperature: 900℃ CH 4 : 1ml/minNH 3 : 3ml/min NH 3 :2ml/minHf temperature: 300℃ Hf temperature: 300℃Ti temperature: 300℃ Ti temperature 300℃I 2 temperature: 30℃ I 2 temperature: 30℃, and (Hf, Ti)C/N and (Hf,Ti)N production rate is 2.5μm/h and 2.0
μm/h, and each of the above materials was coated with a thickness of 6.0 μm. As comparative chips, the above-mentioned carbide chip material coated with TiN and TiC.N to a thickness of 6.0 μm each was used. <Cutting conditions> Work material: SCM3 (Hs38~40) Cutting speed: 180m/min Feed: 0.3mm/rev. Depth of cut: 2.0mm Life evaluation criteria: Flank wear width 0.3mm Cutting test results are shown in Table 1 show.
【表】
本発明品は比較品に比べて、２倍以上の切削寿
命であつた。
また、上記の実施例１及び実施例２のどちらの
切削テストにおいても、切削の際のピツチングお
よびはく離もなく、チツプ素材との密着性もよい
ことがわかつた。[Table] The cutting life of the product of the present invention was more than twice that of the comparative product. Furthermore, in both the cutting tests of Examples 1 and 2, it was found that there was no pitting or peeling during cutting, and that the adhesiveness with the chip material was good.
第１図は本発明に用いた装置の概略図、第２図
は本発明のコーテイングチツプの切削テスト結果
を示す図である。
１：トラツプ、２：油回転ポンプ、３：基体ホ
ルダー、４：基体、５：基体加熱用高周波加熱
炉、６：ガス均一分散液、７：サブヒータ、８：
チタンスポンジ、９：ハフニウムスポンジ、１
０：恒温槽、１１：ヨウ素、１２：温度制御装
置、１３：反応管。
FIG. 1 is a schematic diagram of the apparatus used in the present invention, and FIG. 2 is a diagram showing the results of a cutting test of the coating chip of the present invention. 1: Trap, 2: Oil rotary pump, 3: Substrate holder, 4: Substrate, 5: High frequency heating furnace for heating the substrate, 6: Uniform gas dispersion liquid, 7: Subheater, 8:
Titanium sponge, 9: Hafnium sponge, 1
0: constant temperature bath, 11: iodine, 12: temperature controller, 13: reaction tube.
Claims (1)
バルトで結合した超硬合金表面に、ハフニウム化
合物とチタン化合物との複合化物であるハフニウ
ム及びチタンの化合物被覆層を形成したことを特
徴とする複合化合物を被覆した超硬合金。 ２ 特許請求の範囲第１項において、ハフニウム
化合物は炭化ハフニウム（HfC）、窒化ハフニウ
ム（HfN）であり、チタン化合物は炭化チタン
（TiC）、窒化チタン（TiN）であることを特徴と
する複合化合物を被覆した超硬合金。 ３ 特許請求の範囲第１項において、複合化合物
であるハフニウム及びチタンの化合物被覆層は
（Hf・Ti）Ｃ，（Hf・Ti）Ｎ，（Hf・Ti）Ｃ・Ｎ
の組成であることを特徴とする複合化合物を被覆
した超硬合金。[Claims] 1. A compound coating layer of hafnium and titanium, which is a composite of a hafnium compound and a titanium compound, is formed on the surface of a cemented carbide made of tungsten carbide as a main component and bonded mainly with cobalt. Cemented carbide coated with a composite compound. 2. A composite compound according to claim 1, wherein the hafnium compound is hafnium carbide (HfC) or hafnium nitride (HfN), and the titanium compound is titanium carbide (TiC) or titanium nitride (TiN). Cemented carbide coated with. 3 In claim 1, the compound coating layer of hafnium and titanium which is a composite compound is (Hf・Ti)C, (Hf・Ti)N, (Hf・Ti)C・N
A cemented carbide coated with a composite compound characterized by a composition of:
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13226778A JPS5558364A (en) | 1978-10-27 | 1978-10-27 | Ultra hard alloy coated composite compounds |
| US06/053,731 US4264682A (en) | 1978-10-27 | 1979-07-02 | Surface hafnium-titanium compound coated hard alloy material and method of producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13226778A JPS5558364A (en) | 1978-10-27 | 1978-10-27 | Ultra hard alloy coated composite compounds |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5558364A JPS5558364A (en) | 1980-05-01 |
| JPS6154872B2 true JPS6154872B2 (en) | 1986-11-25 |
Family
ID=15077277
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP13226778A Granted JPS5558364A (en) | 1978-10-27 | 1978-10-27 | Ultra hard alloy coated composite compounds |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5558364A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6456865A (en) * | 1987-08-28 | 1989-03-03 | Sumitomo Cement Co | High-hardness coating film and its production |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS52225B2 (en) * | 1972-09-20 | 1977-01-06 | ||
| JPS53116285A (en) * | 1977-03-22 | 1978-10-11 | Mitsubishi Metal Corp | Coated super hard alloy product and its manufacture |
-
1978
- 1978-10-27 JP JP13226778A patent/JPS5558364A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5558364A (en) | 1980-05-01 |
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