JPH10317123A - Crystalline oriented hard coated member - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a crystalline oriented hard coated material excellent in various properties in the wide range from the low temperature to the high temperature and excellent in service life by forming a coating film consisting of a single layer of one kind of, or a multilayer of two or more kinds of nitride, carbonitride, nitrooxide, carbooxide and carbonitride oxide of Ti and Al on a base material, and maximizing the peak intensity of the crystal face of the film in the (200) crystal face. SOLUTION: When this coated material is used as a cutting tool or a wear- resistant tool, the base material such as cemented carbide and TiC cermet containing nitrogen is preferable. When the atomic ratio of Ti and Al incorporated in the coating film is 48-75: 52-25, the hardness becomes high, the peelability resistance, the oxidation resistance and the thermal impact resistance are excellent, and the service life becomes excellent. In the case of a rotary cutting tool of heavy-duty applications, the film thickness is preferably 0.5-5 μm. The strength ratio of the (200) crystal face to the (111) crystal face in a case of the X-ray diffraction from the film surface, is preferably 2-100.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a nitride, carbonitride, nitride oxide, and carbonate of titanium and aluminum having a (200) crystal plane grown on a base material of a metal, alloy or ceramic sintered body. Orientated hard coating member coated with a coating of a (TiAl) compound composed of oxides and carbonitrides, specifically, a metal, alloy or ceramic sintered body having a high exfoliation resistance excellent on a base material. Hardness and high toughness of the (TiAl) compound film are coated, for example, turning tools, milling tools, drills, cutting tools typified by end mills, cutting blades such as slitters, cutting blades and dies, punches and other molds. The present invention relates to a crystal-oriented hard covering member that is most suitable as a wear-resistant tool represented by a corrosion-resistant wear-resistant member such as a tool and a nozzle, a tunnel drill bit, and a construction tool represented by a construction tool.

[0002]

2. Description of the Related Art Metal, alloy and ceramic substrates are coated with a ceramic film having a thickness of 20 μm or less,
Many coating members have been proposed that attempt to achieve a long life by effectively extracting the characteristics of the substrate and the coating. The method of coating the coating on the coating member is roughly classified into a chemical vapor deposition method (CVD method) and a physical vapor deposition method (PVD method). Among them, a coating coated by the PVD method has an advantage of increasing abrasion resistance without deteriorating the strength of the substrate. For this reason, coatings of coated cutting tools typified by drills, end mills, and throw-away inserts for milling, which generally emphasize strength and fracture resistance, are currently coated by a PVD method.

[0003] It is well known that a coating of a Ti compound typified by titanium nitride is applied to improve abrasion resistance. However, metal nitrides typified by titanium nitride are liable to be oxidized at high temperatures, and have a problem that wear resistance is significantly deteriorated. In order to improve the problem of oxidation of the titanium nitride film, there has been proposed a coating member represented by a (TiAl) compound film in the middle of the 1980's. No. 56565, JP-A-6-2105
No. 02, JP-A-6-210511 and JP-A-7-197235.

On the other hand, it has been proposed to improve the adhesion of a film by crystallizing a film to be coated on the surface of a substrate, as a typical example of which is disclosed in JP-A-56-156767.
JP, JP-A-2-159363, JP-A-5-2
87322, JP-A-5-287323 and JP-A-5-295517.

[0005]

A prior art relating to a coating of a (TiAl) compound is disclosed in JP-A-62-56565.
JP, JP-A-6-210502, JP-A-6-2502
Japanese Patent Application Laid-Open No. 10511 and JP-A-7-197235 disclose a hard coating layer comprising a single layer or a multilayer of two or more of carbides, nitrides and carbonitrides of (TiAl) on the surface of a substrate. A surface-coated hard member having excellent abrasion resistance and having formed thereon is disclosed.

[0006] Conventional (TiAl) compound coatings typified by surface-coated hard members disclosed in these publications are coatings having improved oxidation resistance and abrasion resistance as compared with Ti compound coatings as originally developed. However, since the (111) crystal face is a (TiAl) compound film grown on the substrate, the adhesion between the film and the substrate is poor, and the mechanical properties of the film itself are liable to deteriorate. When applied to a cutting tool used under severe conditions, there is a problem that cutting performance is reduced. In other words, the surface-coated hard member described in the publication, by incorporating Al in the coating, achieved improved chemical properties on the coating surface as compared to the coating of the Ti compound, but the base material and the coating Because consideration is not given to the crystal structure at the interface, the peel resistance and strength of the coating are inferior, and the fracture toughness value and fracture resistance of the surface-coated hard member are reduced, especially when used as a high-speed cutting tool, Oxidation of the coating due to high temperature, rapid wear, deterioration due to thermal shock, and short life due to welding with the work material.

On the other hand, JP-A-56-156767 and JP-A-Hei 2 156767 as prior art relating to a crystal oriented film.
JP-A-159363, JP-A-5-287322, JP-A-5-287323 and JP-A-5-2-2
No. 95517 discloses a coated hard member in which a Ti compound film made of titanium nitride, titanium carbide, and titanium carbonitride is crystal-oriented and coated on the surface of a base material.

The coated hard members disclosed in these publications regarding crystal orientation improve the adhesion between the coating and the substrate by orienting the crystal plane of the coating,
Since the coating is made of a Ti compound containing no Al, the mechanical properties of the coating itself are low and the strength, hardness, abrasion resistance, heat resistance and oxidation resistance of the coating cannot be satisfied. is there.

The present invention has solved the above-mentioned problems, and specifically, has high toughness, high hardness, wear resistance, and oxidation resistance in a wide range from a low temperature range to a high temperature range. It is an object of the present invention to provide a crystal-oriented hard coating member having a longer life by coating with a coating having heat resistance, thermal shock resistance, fracture resistance, welding resistance and a peeling-resistant coating.

[Means for Solving the Problems]

The present inventors have proposed that (Ti)
A study has been conducted on the problem that the coated member coated with the Al) compound coating exhibits an excellent effect when used in a low-temperature region, whereas the effect is reduced when used in a high-temperature region. Although the reason is not clear, the conventional (TiAl) compound coating on the substrate is (1)
11) A coating film having a crystal plane grown thereon.
11) A (200) crystal plane was grown (TiAl) in contrast to the (TiAl) compound coating on which the crystal plane was grown.
That the compound coating tends to have a slightly higher hardness, exfoliation resistance, oxidation resistance, and thermal shock resistance, and that the wear resistance does not decrease from low to high temperatures. The inventor has found that these compounds are combined to have a long life, and have completed the present invention.

[0011] The hard coating member of the present invention comprises, on a substrate, a nitride, a carbonitride, a nitride oxide of titanium and aluminum,
A coating member coated with a coating composed of one kind of single layer or two or more kinds of carbon oxides or carbonitrides, wherein the peak intensity of the crystal plane of the coating obtained by X-ray diffraction is (20
0) characterized by having a maximum height on the crystal plane.

[0012]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The material of the hard coating member of the present invention is not particularly limited in terms of material, and a material capable of withstanding the heating temperature when coating the coating, for example, a metal member There is no problem if it is a sintered alloy or a ceramic sintered body. Specifically, for example, metal members represented by stainless steel, heat-resistant alloy, high-speed steel, die steel, Ti alloy, Al alloy, cemented carbide, Cermet, sintered alloys represented by powdered high-speed steel, Al ₂ O ₃ based sintered body, Si
Ceramic sintered bodies represented by ₃ N ₄ based sintered bodies, sialon based sintered bodies, and ZrO ₂ based sintered bodies can be given. Among these, when used as a cutting tool or a wear-resistant tool, a substrate of a cemented carbide, a nitrogen-containing TiC-based cermet, or a ceramic sintered body is preferable.

The composition of the coating film coated on the substrate is, for example, (Ti, Al) N, (Ti, A
1) CN, (Ti, Al) NO, (Ti, Al) CO,
One type of single layer or two or more types of multilayers in (Ti, Al) CNO can be mentioned. This coating has a high hardness when the atomic ratio of Ti element to Al element, which is a metal element contained in the coating, is 48 to 75:52 to 25.
This is preferable because it has excellent peeling resistance, oxidation resistance, and thermal shock resistance and has a long life. The coating may be of stoichiometric or non-stoichiometric composition.

Further, when X-ray diffraction is performed from the coating surface,
The conventional (TiAl) compound coating is a coating in which the (111) crystal plane has the maximum intensity peak and is crystallographically oriented to the (111) plane, whereas the coating in the hard coating member of the present invention is (200). ) A film in which the crystal plane is crystallographically oriented to the (200) plane at which the maximum intensity peak is obtained. In other words, the coating on the hard-coated member of the present invention is represented by X
The heights of the intensity peaks due to the (200) crystal plane and the (111) crystal plane in the line diffraction are h (200),
When (111) is set, h (200)> h (111)
It is only necessary to have the relationship of
It is preferable that the intensity ratio of the (200) crystal plane to the (111) crystal plane has a relationship of 2 to 100. That is, the (200) crystal plane and (11)
1) It is preferable that the heights of the respective intensity peaks determined from the crystal plane have a relationship of h (200) / h (111) = 2 to 100. It is necessary to select the film thickness of this coating depending on the application or shape. For the application as a tool, it is preferable that the coating has a thickness of 0.1 to 10 μm, and particularly for severe applications such as drills, end mills, In the case of a rotary cutting tool represented by a reamer, the thickness is preferably 0.5 to 5 μm.

The hard coated member of the present invention has the effect of improving the adhesion to the above-mentioned substrate by the crystal oriented film. May have little effect on gender. In this case, it is also preferable that an intermediate layer is interposed between the substrate and the coating. As the middle layer,
It can be formed of a substance having a coefficient of thermal expansion intermediate between the base material and the coating, a gradient composition component, or the like. It is also preferable to form the uppermost layer on the surface of the crystal-oriented film.

The intermediate layer is made of, for example, Ti
C, ZrC, HfC, TaC, NbC, VC, WC, M
o ₂ C, Cr ₃ C ₂ , TiN, ZrN, HfN, TaN,
CrN, Ti (CN), (TiW) C, (TiTa)
C, (TiTa) CN, and (TiTa) N. These intermediate layers can be formed as one kind of single layer or two or more kinds of multilayers. Further, an underlayer having a high affinity for the substrate, for example, T
_{i, TiAl, Ti 3 Al,} TiAl 3, W, typified by a metal or _{alloy, WC, Mo 2 C, Cr} 2 N, TaN,
VB ₂ , NbB ₂ , TaB ₂ , W ₂ B ₅ , MoB ₂ , CrB ₂
It is also preferable to form an underlayer consisting of one kind of single layer selected from ceramics having a hexagonal crystal structure or two or more kinds of multilayers. The thickness of this intermediate layer is
Any thickness is possible as long as the hard film coated on the surface of the intermediate layer can increase the adhesion.
It is preferable that the thickness be from 0.01 to 5 μm, particularly from 0.01 to 1 μm.

The uppermost layer coated on the surface of the crystal-oriented film is formed for the purpose of further improving heat resistance and oxidation resistance, for coloring the surface, and for discriminating before and after use. ₂ O ₃ , (AlSi) ON, (TiAlSi)
N, (TiAlSi) ON, TiC, ZrC, HfC,
TaC, NbC, VC, WC, Mo ₂ C, Cr ₃ C ₂ , T
iN, ZrN, HfN, TaN, CrN, Ti (C
N), (TiW) C, (TiTa) C, (TiTa) C
N, (TiTa) N may be a single layer or two or more layers. Although the thickness of the uppermost layer varies depending on the purpose, it is specifically, for example, 0.1 mm.
The thickness is preferably 1 to 5 μm.

When producing the hard covering member of the present invention,
First, the base material is a metal member represented by stainless steel, heat-resistant alloy, high-speed steel, die steel, Ti alloy, Al alloy, cemented carbide, cermet, and sintered alloy of powdered high-speed steel which are conventionally commercially available. The base material is a ceramic sintered body of Al ₂ O ₃ based sintered body, Si ₃ N ₄ based sintered body, sialon based sintered body, ZrO ₂ based sintered body, preferably a cemented carbide of JIS B4053 P20-P classified in the use selection criteria of
40, M20 to 40 and K10 to K20 equivalent hard metal materials, particularly preferably P30, M20, M30, K1
A base material made of a cemented carbide material equivalent to 0 may be used. The surface of the base material is polished as necessary and subjected to a cleaning treatment using ultrasonic waves, an organic solvent, or the like, and then a conventional physical vapor deposition method (PVD method), chemical vapor deposition method (CVD method) or It can be manufactured by coating a film on a substrate by a plasma CVD method.

When a film is coated on a substrate, a PVD method, a CVD method, or a plasma CVD method can be used depending on the film quality, including an underlayer and an intermediate layer to be coated, if necessary. . Among these, it is preferable to perform all coatings from the manufacturing process by a PVD method typified by an ion plating method or a sputtering method. Among them, coating treatment is preferably performed by an ion plating method, particularly an arc ion plating method. Is preferred.

The case where the coating of the high-strength coating member of the present invention is produced by the ion plating method will be described in more detail. Two types of metal titanium and metal aluminum may be used independently as evaporation sources. -Al alloy or TiAl intermetallic compound may be used. The method of ionizing the metal may be arc discharge, glow discharge, high-frequency heating, or the like. The gas used in the ion plating method may be a gas for generating nitride, that is, a nitrogen source gas such as ammonia containing nitrogen, in addition to a nitrogen gas. This reaction gas is introduced into the furnace,
It is preferable to ionize a metal, an alloy, or an intermetallic compound as an evaporation source and apply a negative bias to the base material, because the crystal orientation of the film becomes easy. In particular, in order to increase the content of the (200) crystal plane to form a (TiAl) compound film which is crystallographically oriented, bombard conditions for cleaning the substrate surface before the film formation and nitrogen gas during the film formation It is important to adjust the partial pressure of the nitrogen source gas and the bias voltage to the substrate.

[0021]

According to the hard coated member of the present invention, the coating of the (Ti, Al) compound oriented on the (200) crystal plane enhances the hardness of the coating, and has the effect of improving the fracture toughness value and wear resistance of the entire film. And acts to alleviate the stress remaining near the interface between the substrate and the coating, especially in the case of a substrate made of cemented carbide, increasing the residual compressive stress in the coating, It acts to enhance the adhesion.

[0022]

Embodiment 1 Commercially available shape SNGA120408
Cemented carbide (material equivalent to K10 of JIS B4053)
After cleaning the surface of the substrate with an organic solvent, the substrate is placed in a chamber of an arc discharge plasma PVD apparatus,
(Installed using a jig that can simultaneously cover the flank face and the rake face), initial conditions in the chamber were a temperature of 600 ° C. and a pressure of 1 × 10 ⁻⁴ Torr, and were maintained for 60 minutes. Then, the pressure was reduced to 1 × 10 ⁻³ Torr, the arc current was set to 60 A, the substrate bias was set to −600 V, and the bombardment treatment was performed for the holding time shown in Table 1. Then, using an evaporation source containing a TiAl intermetallic compound, Table 1 was used.
The coating was applied to the surface of the substrate by treating with the pressure, the arc current, the substrate bias, the nitrogen flow rate, and the holding time described in the above section, to thereby obtain products 1 to 16 of the present invention.

For comparison, the bombarding conditions were as follows: a pressure of 1 × 10 ⁻⁵ Torr and a vacuum of 10 × 10 ^-5 Torr.
A comparative product 1 was obtained in the same manner as the product 1 of the present invention except that the treatment was performed under the conditions described in Table 1 except that 0 A and the substrate bias were set to -800 V. Invention products 1 to 16 thus obtained
Comparative products 2 and 3 coated with a commercially available (TiAl) N coating film were added to Comparative product 1 and X-ray diffraction was performed on each of the films to determine the composition and crystal face of the film. The strength ratio was examined and it was confirmed that the coatings were all composed of the composition of (TiAl) N, and that the strength ratio of the crystal plane of the coating was the result shown in Table 2. Further, the atomic ratio of the Ti element to the Al element present in the coatings of the products 1 to 16 of the present invention and the comparative product 1 was obtained using an X-ray diffractometer and a glow discharge optical emission analyzer. 60-62: 40-3
8 was a (TiAl) N coating.

Next, the film thickness and the film hardness of the products 1 to 16 of the present invention and the comparative products 1 to 3 were measured using a film peeling tester corresponding to a scanning electron microscope, a Vickers hardness tester and a scratch wear tester. Measurement, and as the peeling resistance of the coating, the scratch strength for determining the critical peeling load until the coating was peeled was measured.
m, the hardness of the coating and the scratch strength of the coating are shown in Table 2.
Was confirmed.

Next, products 1 to 16 of the present invention and comparative products 1 to
3, the work material: S48C (HB205 to 223),
Cutting speed 150m / min, feed: 0.3mm / re
v, depth of cut: 1.5 mm, chip shape: SNGA120
408, a turning test was performed under the cutting conditions of the dry cutting test, and when the peeling of the coating, chipping or the average flank wear width reached 0.1 mm, the life was determined, and the cutting time until the life was calculated and also shown in Table 2. .

[0026]

[Table 1]

[0027]

[Table 2]

[0028]

Example 2 The initial conditions in the chamber were changed except that the coating conditions were as shown in Table 3. The bombarding conditions were substantially the same as those of the product 3 of the present invention in Example 1, whereby products 17 to 22 of the present invention having different coating thicknesses were obtained. In addition, in the same manner as in Example 1,
The composition ratio of the coating and the crystal plane intensity ratio were investigated to confirm that all the coatings were composed of (TiAl) N, and that the intensity ratio h (200) / h (111) of the crystal plane of the coating was about 5.
0 was confirmed. Similarly, using an X-ray diffractometer and a glow discharge optical emission spectrometer, the atomic ratio of the Ti element to the Al element present in the coatings of the products 17 to 22 of the present invention was obtained. As a result, almost Ti: Al = 60 to 62: It was a coating of (TiAl) N having a range of 40 to 38. Next, in the same manner as in Example 1, the film thickness, the film hardness, the scratch strength of the film, and the cutting time up to the life of these inventive products 17 to 22 were determined, and the results are shown in Table 4.

[0029]

[Table 3]

[0030]

[Table 4]

[0031]

Example 3 Initial conditions and bombarding conditions in the chamber were almost the same as those of the product 3 of the present invention in Example 1, except that the target used and other conditions under the coating conditions of the coating were performed under the conditions shown in Table 5. And the Ti in the coating
Inventive products 23 to 31 having different atomic ratios of element and Al element
I got Further, in the same manner as in Example 1, the composition of the coatings of these inventive products 23 to 31 and the strength ratio of the crystal plane were investigated.
That the coatings are all composed of (TiAl) N;
It was confirmed that the intensity ratio h (200) / h (111) of the crystal plane of the coating film was about 5.0. Similarly, using the X-ray diffraction apparatus and the glow discharge optical emission analyzer, the products of the present invention 23 to 3
The atomic ratio between the Ti element and the Al element present in the coating No. 1 was determined, and the results are shown in Table 6. Then, in the same manner as in Example 1, the film thicknesses of these invention products 23 to 31 were determined.
The hardness of the coating, the scratch strength of the coating, and the cutting time until the service life were determined, and the results are shown in Table 6.

[0032]

[Table 5]

[0033]

[Table 6]

[0034]

Example 4 The present invention was carried out in substantially the same manner as in Example 3 of the present invention except that a nitrogen gas was introduced at the time of coating and a mixed gas of ammonia gas and methane gas was used. Product 32 was obtained. In addition, except that nitrogen gas was introduced at the time of coating, a mixed gas of ammonia gas and carbon monoxide was used, and the conditions of product 3 of the present invention were substantially the same as those of product 3 of the present invention. 33 was obtained. further,
While the nitrogen gas was introduced at the time of coating the film, the conditions of the invention product 3 of Example 1 were substantially the same as those of the invention product 3 of Example 1 except that a mixed gas of ammonia gas, methane gas and carbon monoxide was used. 34 was obtained.

The coatings of the inventive products 32 to 34 thus obtained were examined in the same manner as in Example 1.
Is a composition of (TiAl) NC, and is a product 3 of the present invention.
The coating of No. 3 had a composition of (TiAl) NO, and the coating of the present invention product 34 had a composition of (TiAl) NCO. As to the products of the present invention 32 to 33, as in Example 1, the scratch strength of the coating film and the cutting time until the life were examined. As a result, the same tendency as that of the product of the present invention 3 was shown.

[0036]

The hard coated member of the present invention is a conventional (11)
1) Compared with a comparative product coated with a (TiAl) N film oriented on the crystal plane, the film has excellent exfoliation resistance, and the film itself has high hardness, high toughness, abrasion resistance, and oxidation resistance. , Heat shock resistance, chipping resistance, and welding resistance, it has an effect of extending the life in a region corresponding to a medium speed cutting region to a high speed cutting region in this field. Therefore, the hard coated member of the present invention has an excellent effect that a long life can be achieved in a wide range from the low-speed cutting region to the high-speed cutting region, which is the region of the conventional coated member. It is expected that a long life is expected especially as a cutting tool for milling, a rotary cutting tool as an end mill and a drill, and a coated member coated with a coating of high toughness and high hardness. Excellent effects can be exhibited also in the region.

────────────────────────────────────────────────── ─── Continued on the front page (51) Int.Cl. ⁶ Identification code FI C23C 30/00 C23C 30/00 C // B23B 27/14 B23B 27/14 A

Claims (6)

[Claims] 1. A single layer or a multilayer of two or more of nitride, carbonitride, nitride, carbonate and carbonitride of titanium and aluminum on a substrate. A crystal-oriented hard coated member, wherein the coated film has a peak intensity of a crystal plane determined by X-ray diffraction having a maximum height at a (200) crystal plane. 2. The crystal-oriented hard coating member according to claim 1, wherein the base material is made of a cemented carbide or a sintered cermet alloy. 3. The film is obtained by X-ray diffraction (1).
11) The intensity ratio of the (200) crystal plane to the crystal plane is 2
The crystal-oriented hard covering member according to claim 1 or 2, wherein the number is 100. 4. The film according to claim 1, wherein the film has a thickness of 0.5 μm to 5 μm.
4. The crystal-oriented hard coating member according to claim 1, wherein m is m. 5. The coating film according to claim 1, wherein the atomic ratio of a Ti element, which is a metal element contained in the coating, to an Al element is 48-7.
5:52 to 25.
5. The crystal-oriented hard covering member according to 3 or 4. 6. The crystal-oriented hard coating member according to claim 1, wherein the hard coating member is used as a rotary cutting tool.