JP2003039207A - Clad tool - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a clad tool remarkably excellent in cutting durable property in comparison with a conventional one by increasing the film adhesion between the strength in the field of a crystal grain within a film containing zirconium and the film of an upper layer. SOLUTION: The clad tool is made to have either a single layer film made of any one kind of a group of 4, 5 and 6 in the periodic table and the carbide, nitride, oxide, carbo-nitride, carbo-oxide, nitro-oxide and carbo-nitro-oxide of aluminum or a multi-layer film made of two or more kinds among them, and at least one layer among the above films is forced to contain zirconium and said film containing zirconium is forced to contain crystal grains having twin crystal structures.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a coated tool, and more particularly to a tool coated with a film containing zirconium.

[0002]

2. Description of the Related Art Generally, a coated tool is produced by forming a hard coating on the surface of a substrate made of superhard alloy, high speed steel or special steel by chemical vapor deposition or physical vapor deposition. Such a coated tool has both the wear resistance of the coating and the toughness of the substrate, and is widely put to practical use. Generally, when a high hardness material is cut at high speed without using a cutting fluid (hereinafter referred to as dry cutting), the cutting edge temperature of the cutting tool rises to around 1000 ° C. Cutting tools must withstand wear due to contact with the work material under such a high temperature environment and mechanical shock due to intermittent cutting, etc., and coated tools having both wear resistance and toughness are useful. . The above hard coating includes carbides, nitrides, carbonitrides, carbonates, and nitrites of metals of Groups 4, 5 and 6 of the Periodic Table, which have excellent wear resistance and toughness.
A coated tool in which a film made of oxycarbonitride and an aluminum oxide film having excellent oxidation resistance are coated as a single layer or a multi-layer film is generally used. Also, the above Periodic Table 4,
Group 5 and 6 metals include titanium, especially its carbide (TiC),
Nitride (TiN) and carbonitride (TiCN) are mainly used. Therefore, in order to avoid complication, titanium will be specifically described below as a representative of metals of Groups 4, 5, and 6 of the Periodic Table.

These TiC, TiN and TiCN films have a Vickers hardness Hv of about 3200, 2100, 2 at room temperature.
It is extremely hard at 700 and has excellent wear resistance at room temperature.
However, the hardness of these films sharply decreases as the temperature rises, so there is a problem that the wear resistance sharply decreases in dry cutting in which the temperature of the cutting edge reaches around 1000 ° C. In order to improve the wear resistance of these hard films, a method has been proposed in which a film of titanium zirconium carbonitride or the like is coated on a tool substrate (Japanese Patent Publication No. 11-510856). This method is a method in which a carbonitride film containing at least two kinds of metal elements is coated by a CVD method using a CN compound gas. The obtained titanium zirconium carbonitride film had a large crystal grain size and was not always satisfactory in wear resistance and chipping resistance as a tool.

The inventors of the present invention have conducted extensive studies in order to solve the above-mentioned drawbacks of the coated tool, and as a result, a hard film containing zirconium and titanium as metal components,
For example, in a (Ti, Zr) CN film, a (Ti, Zr) CNO film, etc., when the specific conditions are satisfied, the film hardness does not drop sharply even at high temperature, and the film adhesion and wear resistance are It has been found that an excellent film can be realized, and the method described in JP 20
01-11632 and JP 2001-170804 A,
Japanese Patent Application No. 2000-394137, Japanese Patent Application 2000-396
568, Japanese Patent Application No. 2001-3044, Japanese Patent Application No. 2001-
No. 3060 and Japanese Patent Application No. 2001-23821 were filed to disclose the technique. As a tool coated with a hard coating containing both zirconium and titanium, a cutting tool coated with a mixed layer of titanium carbonitride crystal grains having a granular crystal structure and zirconium carbonitride crystal grains (Japanese Patent Laid-Open No. 2001-2001).
9604) has recently been proposed, but in the above mixed layer, T
iCN and ZrCN individually form crystal grains, and T
It is not formed from crystal grains in which i, Zr, C, and N are integrated. For this reason, the disadvantages such as the decrease in film hardness of TiCN crystal grains at high temperature and the insufficiency of film hardness of ZrCN crystal grains at room temperature have not been solved, or the bonding force between these crystal grains is not sufficient. The abrasion resistance and chipping resistance obtained are not always satisfactory.

[0005]

The present invention further develops the above-mentioned invention previously proposed by the present inventors, that is, an invention relating to a hard film containing zirconium, titanium or the like as a metal component, and containing zirconium. By increasing the strength of the crystal grain boundaries in the film (twin crystals) and the film adhesion to the upper layer film (continuous twins), it is possible to provide a coated tool with significantly superior cutting durability characteristics compared to conventional products. is there.

[0006]

The inventors of the present invention have conducted extensive studies to solve the above-mentioned problems. As a result, at least a part of the crystal grains constituting the zirconium-containing film has a twin crystal structure. As the strength of the crystal grain boundaries in the film increases, the upper layer film also has a twin crystal structure, and the twin boundary between the two is formed continuously, increasing the grain boundary strength and film adhesion of the upper layer film itself. Further, they have found that a tool having further excellent cutting durability characteristics can be obtained, and have reached the present invention. That is, the present invention provides a substrate surface on which any one of carbides, nitrides, oxides, carbonitrides, carbonates, nitriding oxides, and carbonitriding oxides of Groups 4, 5 and 6 of the Periodic Table. A coated tool having a layer coating or a multi-layer coating of two or more types, at least one layer of said coating containing zirconium, and said zirconium-containing coating containing crystal grains having a twin structure. is there. In the coated tool of the present invention, since the zirconium-containing film has a twin structure, the grain boundary strength is high and good cutting durability characteristics are realized.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION In the coated tool of the present invention, it is preferable that a layer containing crystal grains having a twin structure is formed on the zirconium-containing film. Since the upper layer contains crystal grains having a twin structure, the grain boundary strength in the upper layer is increased, and more excellent cutting durability characteristics are realized. Further, in the coated tool of the present invention, it is preferable that the twin boundary portion of the layer formed on the zirconium-containing film is continuous from the twin boundary portion of the zirconium-containing film. Since the twin boundaries are continuous, the film between the zirconium-containing film and the layer formed on it is continuously formed at the crystal lattice plane level, and high adhesion is achieved between both layers. In addition, since both layers have a twin structure, the strength of the crystal grain boundary of each layer is high, and further excellent cutting durability characteristics are realized. This effect is particularly strong when two or more zirconium-containing films are formed in a multi-layered film form. Further, in the coated tool of the present invention, it is preferable that the twin boundary portion (twin plane) constituting the twin structure is composed of {111} planes. Since the twin boundary portion forming the twin structure is composed of {111} planes having many lattice points, the twin boundary portion is densely formed, and the twin crystal boundary portions are bounded by crystal grains that are in contact with each other. It is judged that the grain boundary strength is further increased and further excellent cutting durability characteristics are obtained.

Further, the coated tool of the present invention is zirconium.
A film formed on the inclusion film is a zirconium-containing film.
It is preferably grown in the axial direction. do this
As a result, excellent adhesion was obtained between both layers,
Cutting durability characteristics can be obtained. In the coated tool of the present invention,
Titanium is shown as a representative of Group 4, 5 and 6 metals in the periodic table
Other homologous metals such as Zr, Hf,
Whether it is V, Nb, Ta, Cr, Mo, or W
A substantially similar effect can be obtained. In addition, the zirconium-containing film
Not limited to TiZrCN and TiZrCNO films, but T
iZrC, TiZrCO, TiZrN, TiZrNO film
But good. In addition, the TiZrCN film and the TiZrCNO film are
CH_ThreeCN and TiCl_FourOr CH_ThreeCN and TiCl_Four
And oxidizing gas (eg CO_TwoOr CO alone gas,
Or CO_TwoAnd mixed gas of CO) react to form a film
CH is not limited to_Four, N_Two, TiCl_Four
And CH _Four, N_Two, TiCl_FourReact with the oxidizing gas
It may be a TiZrCN film or a TiZrCNO film to be formed.
The zirconium-containing film is not limited to the above films.
In addition, for example, Cr, Hf, Ta, Nb, Mg,
One or more of Y, Si, B, W, Mo, S
A film containing 0.3 to 10% by mass may be used. 0.3 mass%
If it is less than 10% by weight, the effect of adding these does not appear,
If it exceeds the above, the effects of abrasion resistance and high toughness of the above-mentioned film will be reduced
Appears.

The zirconium-containing film, the titanium carbide layer, the titanium carbonitride layer, the titanium carbonate layer, and the aluminum oxide film that can form the coated tool of the present invention are not necessarily the outermost layers. For example, a compound of at least one layer of titanium, zirconium or hafnium (eg Ti
N, ZrN, HfN, TiCN layer, ZrCN, HfCN
Alternatively, a multi-layer film or the like in which these are combined may be coated. Further, the above film is allowed to contain inevitable additives and impurities, for example, up to about several mass% within a range not deteriorating the cutting durability characteristics of the coated tool of the present invention. The coated tool of the present invention can be manufactured by a known film forming method. For example,
A normal chemical vapor deposition method (thermal CVD), a chemical vapor deposition method with plasma added (PACVD), an ion plating method, or the like can be used. The application is not limited to the cutting tool, and may be a wear-resistant material coated with a hard coating, a mold, a molten metal component, or the like. Next, the coated tool of the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples.

(Example 1) WC: 80% by mass, TiC:
On a throw-away chip made of cemented carbide having a composition of 5% by mass, (Ta, Nb) C: 6% by mass, and Co: 9% by mass, a film thickness of 0.4 μ was formed at a film forming temperature of 900 ° C. by a thermal CVD method.
First, a titanium nitride film of m was formed. Subsequently, the film forming temperature 8
50 ° C., the raw material gas is TiCl ₄ gas: 1.5 vol%,
CH ₃ CN gas: 1.0 vol%, N ₂ gas: 45 vo
A raw material gas composed of 1% and the remaining H2 carrier gas was flowed into the CVD furnace at a flow rate of 6000 ml per minute to form a film at a deposition pressure of:
A titanium carbonitride film having a thickness of 1 μm was formed at 5.0 kPa. Next, TiCl ₄ gas 1.5 vol%, ZrCl ₄
Gas 1.5 vol%, CH ₃ CN gas 1 vol%, CO
Gas of 1 vol%, N ₂ gas of 45 vol%, and a raw material gas composed of the remaining H ₂ carrier gas was flowed into the CVD furnace at a rate of 6000 ml per minute, a film forming pressure of 5 kPa and a film forming temperature of 85.
By reacting at 0 ° C., a titanium zirconium oxycarbonitride film composed of Ti and Zr, C, N and O was formed. Subsequently, ZrCl ₄ gas: 1.5 vol%, CH ₃ CN gas: 1.0 vol%, N ₂ gas: 45 vol%, and the remaining H
Raw material gas composed of ₂ carrier gases 6000 min.
Flowing only ml into the CVD furnace, the same film forming temperature as above 850
A zirconium carbonitride layer was formed at a temperature of 5 ° C. and a film forming pressure of 5 kPa. A multi-layered structure including a set of the zirconium carbonitride oxide layer and the zirconium carbonitride layer as a unit layer
By laminating a set of multi-layer structure unit layers, a multilayer film having a total thickness of 9 μm composed of a titanium zirconium oxycarbonitride layer and a zirconium carbonitride layer was formed.

The cross section of the thus-prepared multilayer film of Example 1 of the present invention was taken with a transmission electron microscope (TEM, manufactured by Hitachi,
A photograph taken by H-800, 200 kV) is shown in FIG. FIG. 2 is a dark STEM image near the center upper right portion in FIG. This is an image of transmitted scattered electrons, and the atomic number effect is emphasized, and an image similar to a normal SEM image is taken. That is, the layer photographed in a bright striped pattern is the ZrCN film, and the striped layer photographed darkly above and below it is the TiZrCNO film. FIG. 3 shows the distribution of Ti in the region near FIG. 2, and FIG. 4 shows the analysis of the distribution of Zr. This element map was analyzed by an energy dispersive X-ray analyzer (EDX, manufactured by NORAN) incorporated in the TEM device. From FIGS. 1 to 4, TiZrCNO film and ZrCN
It can be seen that the film and the film are formed in a multi-layered film with high density. No vacancies were observed between the films or between the crystal grains. Further, it can be seen that, for example, from the lower right to the upper left of FIG. 2, a large number of crystal grain boundaries linearly penetrate between the multilayer films. In addition, in FIG. 1, there are several portions that are particularly darkly photographed. This is because the crystal plane of this portion matches the incident electron beam and the electron beam is diffracted due to Bragg reflection. This is because the electron beam transmittance is low. This is not because of cracks or holes in the film.

FIG. 5 is a high-resolution image (using Hitachi's HF-2100, 200 kV) in the center of FIG. Figure 5
The ZrCN film is photographed in the upper half, the TiZrCNO film is photographed in the lower half, and the grain boundaries ab are photographed from the lower right to the upper left. As shown in FIG. 5, TiZrC is parallel to the grain boundaries ab.
It can be seen that both the lattice fringes of the NO film and the ZrCN film are continuously formed in a straight line and are symmetrical to each other with the grain boundary ab as a boundary. That is, both the TiZrCNO film and the ZrCN film have a twin structure, and the grain boundary a
-B is a twin plane, and this twin plane is TiZr
It can be seen that the CNO film and the ZrCN film are continuous in a straight line. As a result of Fourier transform of the lattice image of FIG. 5, Zr
It was found that the crystal lattices of both the CN film and the TiZrCNO film are face-centered cubic crystals, and the lattice fringes ab are {111} planes. Further, in FIG. 5, the TiZrCNO film and the Z
Since the lattice stripes of the rCN film are continuous in a straight line across the interface (in the vicinity of the center of FIG. 5), it can be seen that both are epitaxially grown.

The transmission electron micrographs of FIGS. 1 to 5 show that the cross section of the film-forming surface was polished to a thickness of 20 μm or less, and then further thinned by ion milling to form a microscopic area of the film cross section.
The image was taken through an electron beam. Therefore, it is considered that the probability of actually observing the twinned portion contained in the zirconium-containing film or the layer formed thereon is low. Therefore, as shown in FIG.
The fact that the twinned portion is observed in the photograph can be judged that the twinned portion is present in the zirconium-containing film and the upper layer film quite frequently. In addition, when the conditions of the observation sample are bad such as the observation sample is thick, the twinning relation may not be confirmed in the electron diffraction image. Also in this case, it should be noted that the above twinning relationship may be confirmed by reworking the sample and observing the lattice image.

Five cutting tools manufactured under the conditions of Example 1 of the present invention were intermittently cut under the following conditions, and the state of chipping of the tip of the cutting edge was observed with a stereoscopic microscope at a magnification of 50, until chipping or film peeling occurred on the cutting edge. The number of intermittent cuttings was calculated. Work Material: SCM435 Material (Four Grooves) Tool Shape: CNMG433 Cutting Conditions: 200m / min Feed: 0.3mm / rev Cutting Depth: 1.5mm Cutting Fluid: Not Used (Dry Cutting) As a result, the present invention product The cutting edge is sound even after interrupted cutting up to 8000 times, chipping and peeling are not seen, the grain boundary strength of the film and the adhesion between films are excellent, and the durability as an interrupting tool is excellent as a cutting tool. I understood it.

Example 2 As Comparative Example 2, zirconium
Cutting with and without twin crystal structure
In order to clarify the effect on the characteristics, the following Comparative Example 2 was created.
Made Of a cemented carbide substrate having the same composition as in Example 1
TiN and TiCNO were applied to the surface in the same manner as in Example 1.
After forming the film, next, TiCl_FourGas 1.5vol
%, ZrCl _FourGas 1 vol%, CH_ThreeCN gas 0.5
vol%, CO_TwoGas 1 vol%, N _TwoGas 45vol
%, Remaining H_TwoSource gas composed of carrier gas is supplied every minute
Flowing only 6000 ml into the CVD furnace, film forming pressure 10 kP
a, at a film forming temperature of 750 ° C., consisting of Ti, Zr, C, N and O
A titanium zirconium oxycarbonitride film was formed. continue,
Source gas is ZrCl_FourGas: 1.5vol%, CH_ThreeC
N gas: 0.5 vol%, N_TwoGas: 45 vol%, balance
Ri H_Two60 minutes per minute of raw material gas composed of carrier gas
Only 00 ml was flown into the CVD furnace and the film formation temperature was 950 ° C.
A zirconium carbonitride layer was formed at a film pressure of 10 kPa.
This zirconium carbonitride oxide layer and zirconium carbonitride
16 layers of multi-layered structure with one layer as a unit layer
By stacking multi-layer structural unit layers, titanium oxycarbonitride
The total thickness of the ruconium layer and the zirconium carbonitride layer is
Comparative Example 2 is prepared by forming a 9 μm multilayer film.
did.

The vicinity of the zirconium-containing film of Comparative Example 2 was observed with a transmission electron microscope in the same manner as in Example 1.
No twin structure was found in the zirconium-containing film. Next, an intermittent cutting test was performed under the same conditions as in Example 1 using 5 cutting tools manufactured under the conditions of Comparative Example 2, and the chipped state of the cutting edge was observed with a stereoscopic microscope at a magnification of 50.
It was revealed that chipping occurred on the cutting edge after any of the 000 times of impact cutting and that the cutting tool was inferior. Also,
Microscopic observation of the part where film peeling or chipping occurred in this intermittent cutting test revealed that film peeling occurred from the zirconium-containing film, and this caused chipping.

Example 3 As Example 3 of the present invention, WC: 8
0% by mass, TiC: 5% by mass, (Ta, Nb) C: 6% by mass, Co: 9% by mass on a throw-away tip made of cemented carbide under the same conditions as in Example 1 .4
A titanium nitride film having a thickness of 1 μm and a titanium carbonitride film having a thickness of 1 μm were formed. Next, TiCl ₄ gas 1.5 vol%, ZrC
l ₄ gas 1.5 vol%, CH ₃ CN gas 2.0 vol
%, N ₂ gas 45 vol%, and a raw material gas composed of the residual H ₂ carrier gas at a flow rate of 6000 ml / min in the CVD furnace, and the reaction is performed at a film forming pressure of 5 kPa and a film forming temperature of 850 ° C. , N was formed into a titanium zirconium carbonitride film. Subsequently, ZrCl ₄ gas 1.5 vol%, CH ₃ CN gas 1.0 vol%, N ₂
A raw material gas composed of 45 vol% of gas and the residual H ₂ carrier gas was flowed into the CVD furnace at 6000 ml per minute, and a zirconium carbonitride layer was formed at the same film forming temperature of 850 ° C. and a film forming pressure of 5 kPa. The titanium zirconium carbonitride layer and the zirconium carbonitride layer are used as a unit layer, and 12 sets of multilayer structure unit layers are laminated to form a titanium zirconium carbonitride layer and a zirconium carbonitride layer. A multilayer film having a total thickness of 7 μm was formed.
After that, 200 ml / min of a raw material gas ₂ composed of TiCl ₄ gas, CH ₄ gas, and H ₂ carrier gas was flowed for 30 minutes, and the raw material gas of the present composition was further added with 2 more times.
By adding 0 ml / min of CO ₂ gas for 30 minutes, a layer (bonding film) made of titanium carbide and titanium carbonate was formed at a film forming temperature of 950 ° C. Then Al
H ₂ gas 3 in a small tube filled with small metal pieces and kept at 350 ℃
AlCl ₃ gas generated by flowing 10 ml / min and 130 ml / min of HCl gas, ₂ l / min of H ₂ gas and 100 ml / min of CO ₂ gas were caused to flow in the CVD furnace, and 10
After a 2 μm thick α-type aluminum oxide film was formed by reacting at 10 ° C., a 0.8 μm thick titanium nitride film was further formed at a film forming temperature of 1010 ° C. to obtain a coated tool of Inventive Example 3. It was

In Example 3 of the present invention, an X-ray diffractometer (RU-200BH) manufactured by Rigaku Denki Co., Ltd. was used as an X-ray source for CuKα1 rays (λ
= 0.15405 nm), the X-ray diffraction pattern was measured by the 2θ-θ scanning method, and then the cross section of the multilayer film of the present invention was examined by a transmission electron microscope (TEM, manufactured by Hitachi Ltd.) in the same manner as in Example 1. H-800, 200 kV) and an energy dispersive X-ray analyzer (EDX, manufactured by NORAN) as a result of microanalysis. As a result, TiN and TiC were formed on the surface of the cemented carbide substrate.
It was confirmed that a multilayer film composed of TiZrCN and ZrCN was formed at a high density via the N film, and an α-type aluminum oxide and a TiN film were formed thereon via a coupling film. Then, it was confirmed that both the TiZrCN crystal grains and the ZrCN crystal grains had a twin crystal structure in the multilayer film portion, and the twin planes were linearly continuous between both crystal grains.

Using the coated tool of the present invention obtained as described above, intermittent cutting was performed under the following conditions, and the damage state of the cutting edge was observed with a tool microscope at a magnification of 50 times. Work material: SCM435 (with four grooves) Tool shape: CNMG433 Cutting speed: 220 m / min Feed: 0.20 mm / rev Cutting depth: 1.5 mm Cutting fluid: Not used (dry cutting) As a result of this cutting test, In each of the invention products, no chipping or peeling was observed in the zirconium-containing film or the alumina film at the cutting edge after the intermittent cutting up to 7,000 times of the intermittent cutting, and the crystal grain boundary strength of the film of Inventive Example 3 and the inter-film It was found that the adhesion was excellent and the tool life was long.

Example 4 As Comparative Example 4, the following Comparative Example 4 was prepared in order to clarify the difference between the case where the zirconium-containing film has the twin structure and the case where it does not have the twin structure. Example 3 was formed on the surface of a cemented carbide substrate having the same composition as in Example 3.
After forming a TiN film and a TiCN film by the same method as described above, next, TiCl ₄ gas 1.5 vol%, ZrCl ₄
Gas 0.5 vol%, CH ₃ CN gas 0.5 vol%,
A raw material gas composed of 45% by volume of N ₂ gas and the residual H ₂ carrier gas was flowed into the CVD furnace at a rate of 6000 ml / min to form Ti and Z at a film forming pressure of 15 kPa and a film forming temperature of 750 ° C.
A titanium zirconium carbonitride film composed of r, C and N was formed. Subsequently, the film forming temperature is 950 ° C., the source gas is ZrC.
l ₄ Gas: 1.5vol%, _CH 3 CN gas: 0.5 v
CV of raw material gas composed of ol%, N ₂ gas: 45 vol% and the remaining H ₂ carrier gas at 6000 ml / min
The zirconium carbonitride layer was formed at a film forming pressure of 15 kPa. The titanium zirconium carbonitride layer and the zirconium carbonitride layer are used as a unit layer, and 12 sets of multilayer structure unit layers are laminated to form a titanium zirconium carbonitride layer and a zirconium carbonitride layer. A multilayer film having a total thickness of 7 μm was formed. Further, a layer (bonding film) made of a titanium carbide and a titanium carbonate was prepared under the same conditions as in Example 2, and the thickness was 2 μm.
A coated tool of Comparative Example 4 was prepared by depositing the α-type aluminum oxide film and the titanium nitride film having a thickness of 0.8 μm.

The vicinity of the zirconium-containing film of Comparative Example 4 was observed with a transmission electron microscope in the same manner as in Example 3, but no twin structure portion was found in the zirconium-containing film. next,
An interrupted cutting test was conducted under the same conditions as in Example 3 using 5 cutting tools produced under the conditions of Comparative Example 4, and the chipping occurrence state at the tip of the cutting edge was observed with a stereoscopic microscope at a magnification of 50. As a result, impact cutting was performed 4500 times. Later, it was found that chipping and film peeling occurred in all of them and it was inferior as a cutting tool. In addition, microscopic observation of the part where film peeling or chipping occurred in this intermittent cutting test revealed that chipping or film peeling had occurred in the zirconium-containing film, and this is considered to be the cause of chipping. all right.

[0022]

INDUSTRIAL APPLICABILITY As described above, by applying the present invention, a useful zirconium-containing film coating excellent in the strength of the crystal grain boundary of the zirconium-containing film and the adhesion to the upper layer film and having excellent cutting durability characteristics. A tool can be realized.

[Brief description of drawings]

FIG. 1 is a microstructure photograph of a cross section of a multilayer film of a coated tool of the present invention, observed by a transmission electron microscope.

FIG. 2 is a dark STEM near the upper right part of the center of FIG.
Show the image.

FIG. 3 shows the distribution of Ti in the region near FIG.

FIG. 4 shows a distribution of Zr in a region near FIG.

5 is a high-resolution image of the central portion of FIG. 2, in which the ZrCN film is photographed in the upper half of FIG. 5 and the TiZrCNO film is photographed in the lower half, and grain boundaries ab are photographed from the lower right to the upper left. S
A TEM image is shown.

Continued front page    (72) Inventor Koichi Sawano             2 Hitachi Tool, 13 Shinizumi, Narita City, Chiba Prefecture             Narita Factory Co., Ltd. F-term (reference) 3C046 FF02 FF11 FF17                 4K029 BA41 BA44 BA54 BA55 BA58                       BB02 BB07 BC00 BD05                 4K030 BA02 BA22 BA35 BA36 BA38                       BA41 BB01 BB12 LA01 LA22

Claims (7)

[Claims] 1. A single surface selected from the group consisting of carbides, nitrides, oxides, carbonitrides, carbooxides, nitric oxides and carbonitride oxides of groups 4, 5 and 6 of the periodic table and aluminum on the surface of a substrate. A coated tool having a layer coating or a multi-layer coating of two or more types, at least one layer of the coating containing zirconium, and the zirconium-containing coating containing crystal grains having a twin structure. 2. The coated tool according to claim 1, wherein a film containing crystal grains having a twin structure is formed on the zirconium-containing film. 3. The coated tool according to claim 2, wherein the twin boundary portion of the film formed on the zirconium-containing film is continuous from the twin boundary portion of the zirconium-containing film. Coated tool. 4. A coated tool according to claim 1, wherein:
A coated tool characterized in that a twin boundary portion constituting the twin structure is composed of a {111} plane. 5. A coated tool according to claim 1, wherein:
A coated tool, wherein a layer formed on the zirconium-containing film is epitaxially grown on the zirconium-containing film. 6. The coated tool according to claim 1, wherein:
A coated tool, wherein the zirconium-containing film is composed of Ti, Zr, C and N. 7. A coated tool according to claim 1, wherein:
A coated tool, wherein the zirconium-containing film is composed of Ti, Zr, C, N, and O.