JP3130734B2 - Heat resistant coating - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a metal material represented by stainless steel, high speed steel, die steel, Ti alloy, Al alloy, heat resistant alloy, or a sintered alloy represented by cemented carbide, cermet, Alternatively, a titanium / aluminum carbonitride is formed on a ceramic sintered body represented by an Al ₂ O ₃ based sintered body, a ZrO ₂ based sintered body, a SiC based sintered body, or a Si ₃ N ₄ based sintered body. A coating member formed by coating a hard layer of an oxide, specifically, for example, a cutting tool represented by a turning tool, a milling tool, an end mill, a drill, a wear resistance represented by a slitter, a can-making tool, and a mold The present invention relates to a heat-resistant covering member suitable as a tool or a sporting member typified by a fishing tackle, a golf club, a watch part, a frame of glasses, a tie pin, a broach, and an earring or a decorative member.

[0002]

2. Description of the Related Art Carbides, nitrides, carbonates, nitrides and their mutual solid solutions of metals of groups 4a, 5a and 6a of the periodic table are formed on a base material of a metal material, a sintered alloy or a ceramic sintered body. Or one kind of monolayer in aluminum oxide,
Alternatively, a large number of coating members formed by coating two or more types of multi-layer coatings have been proposed, and some of these coating members include cutting tools, wear-resistant tools, sports members, decorative members, and the like. It has been put to practical use.

[0003] Among these conventional coating members, a coating member coated with a coating of a Ti compound does not exhibit satisfactory abrasion resistance when used for a cutting tool or a wear-resistant tool, and has a relatively short time. However, a typical solution to this problem is disclosed in JP-A-62-565.
No. 65 is known.

[0004]

Problems to be Solved by the Invention
In Japanese Patent Application Laid-Open No. 5 (1993) -205, a hard coating layer composed of a single layer or a multilayer of two or more of carbides, nitrides and carbonitrides of Ti and Al is provided on the surface of a base material in an amount of 0.5 to 10 μm. It describes a hard-coated surface-coated hard member having excellent wear resistance.

[0005] The surface-coated hard member described in the publication is an excellent coated hard member having improved abrasion resistance. However, when used as a cutting tool, for example, a high-speed cutting or heavy cutting is required. When used under high temperature conditions, the hard coating layer rapidly oxidizes and wears, and has poor thermal shock resistance.
There is a problem that welding to a work material as a mating material is apt to occur and the life is shortened.

The present invention has solved the above-mentioned problems. Specifically, in a wide range from a low-temperature region to a high-temperature region, the present invention has abrasion resistance, oxidation resistance, thermal shock resistance, and thermal shock resistance. An object of the present invention is to provide a heat-resistant covering member having excellent chipping and welding resistance.

[0007]

Means for Solving the Problems The present inventors show that a coated member in which a coating of a compound of Ti and Al is coated on a cemented carbide substrate has a relatively excellent effect when used in a low temperature range. On the other hand, while studying the problem that the effect is reduced when used in a high-temperature region, when a small amount of oxygen element is contained in a compound film of Ti and Al, the wear resistance from a low-temperature region to a high-temperature region is reduced. The inventors have found that the reduction does not occur, the characteristics are excellent in a well-balanced manner, and the life is remarkably improved, and the present invention has been completed.

That is, the heat-resistant coated member of the present invention comprises a hard layer of titanium / aluminum carbonitride represented by the following formula (A) on a base material of a metal material, a sintered alloy or a ceramic sintered body. Is coated with a film thickness of 0.1 to 15 μm. (Ti _a , Al _b ) (C _X N _{YO Z} ) _R (A) {wherein, in the formula (A), Ti is titanium, Al is aluminum, and C is carbon. , N represents nitrogen, O represents oxygen, a and b
Represents the atomic ratio of each of the metal elements Ti and Al, X, Y and Z represent the atomic ratios of the non-metal elements C, N and O, and R represents the total of Ti and Al Represents the atomic ratio of the nonmetallic element obtained by adding C, N and O to the element, where a + b = 1 and 0.95 ≧ a ≧ 0.
05, X + Y + Z = 1, 0.89 ≧ X ≧ 0.1, 0.8
9 ≧ Y ≧ 0.1, 0.25 ≧ Z ≧ 0.01, 1.10 ≧
R ≧ 0.80.

The base material of the coating member of the present invention is made of a metal material, a sintered alloy or a ceramic sintered body which can withstand the heating temperature when coating the hard layer.
Specifically, for example, stainless steel, high speed steel, die steel, titanium alloy, Al alloy, heat-resistant alloy metal material, cemented carbide, cermet sintered alloy, Al ₂ O ₃ based sintered body, Si ₃ N ₄ based sintered body, Sialon based sintered body, ZrO ₂
A ceramic sintered body of a system sintered body can be exemplified.
Among these, when used as a cutting tool or a wear-resistant tool, a cemented carbide, a nitrogen-containing TiC-based cermet or a ceramic sintered body is particularly preferable.

When the hard layer coated on the base material is coated directly adjacent to the base material, it is also preferable that the content of the oxygen element in the hard layer particularly varies depending on the material of the base material. Specifically, for example, in a sintered alloy substrate, it is preferable that the oxygen element is gradually reduced from the surface of the hard layer toward the substrate side. It is preferable that the oxygen element gradually increases from the surface of the layer toward the base material from the viewpoint of the adhesion between the hard layer and the base material. This hard layer may be of stoichiometric or non-stoichiometric composition, but in particular (Tia, Alb)
(C _X , N _Y , O _Z ) _R [where Ti is titanium, Al is aluminum, C is carbon, N is nitrogen, O
Represents oxygen, and a and b are metal elements Ti and Al
X, Y and Z represent the respective atomic ratios of nonmetallic elements C, N and O, and R
Are C, N and O with respect to the total metal element of Ti and Al
A + b =
1, 0.95 ≧ a ≧ 0.05, X + Y + Z = 1, 0.8
9 ≧ X ≧ 0.1, 0.89 ≧ Y ≧ 0.1, 0.25 ≧ Z
It is particularly preferable to use titanium / aluminum carbonitride satisfying the conditions of ≧ 0.01 and 1.10 ≧ R ≧ 0.80 in view of strength, wear resistance and welding resistance.

Further, the coating composition of the coating member of the present invention.
As between the base material and the hard layer, the base material and the hard layer
An inner layer that mainly enhances adhesion to the layer may be interposed
Preferably, as the inner layer, specifically, for example, T
i, Zr, Hf, V, Nb, Ta, Cr, Mo, W gold
Genus, TiC, ZrC, HfC, VC, NbC, TaC,
Cr_ThreeC_Two, Mo_TwoC , WC, TiN, ZrN, CrN,
Ti (C, N), Ti (C, O), Ti (N, O), T
i (C, N, O), (Ti, Zr) C, (Ti, Z)
N, (Ti, Z) (C, N), (Ti, Ta) C, (T
i, W) C, (Ti, Ta, W) (CN), (Ti, T
a, W) N and (Ti, Zr, Ta) C.
Wear. These inner layers should be selected according to the material of the base material.
When the substrate is a sintered alloy, for example, Ti
C, TiN, Ti (C, N), Ti (C, O), Ti
(N, O), Ti (C, N, O), (Ti, Zr) C,
(Ti, Hf) C, (Ti, V) C, (Ti, Nb)
C, (Ti, Cr) C, (Ti, Mo) C, (Ti,
W) C, (Ti, Zr) N, (Ti, V) N, (Ti,
Cr) N, (Ti, Zr) (C, N), (Ti, Zr)
(C, O), (Ti, Zr) (N, O), (Ti, Z
r) one single layer or two or more layers of (C, N, O)
It is the mediation of adhesion between the substrate and the hard layer,
Especially preferred from the viewpoint of wear resistance and fracture resistance
It is.

Further, it is also preferable to adopt a coating structure in which an outer layer is formed adjacent to the hard layer. When the outer layer is made of aluminum oxide, it has high resistance to welding and oxidation at high temperatures.
This is preferable because it has excellent wear resistance. When the outermost surface of these coating layers, specifically, the surface of the hard layer or the surface of the outer layer of aluminum oxide, is further coated with the outer layer of titanium nitride, titanium oxynitride, or titanium carbonitride, the decorative effect, before and after use This is preferable because it also has the effect of facilitating the determination of the color and the effect of preventing color unevenness.

[0013] In the coating composition of the coating member of the present invention,
In the case of a configuration having only a hard layer, the coating thickness is 0.1 to
When the thickness is less than 0.1 μm, the effect of the hard layer is weak, and the abrasion resistance is remarkably reduced. Conversely, when the thickness exceeds 15 μm, peeling of the coating film tends to occur. The thickness of the hard layer is preferably 0.5 to 10 μm
m, especially 0.5 from the industrial production including film formation time
８8 μm is preferred. In the case where the inner layer is interposed in addition to the hard layer, the thickness of the inner layer is 0.1 to 5 μm.
In the case where the outer layer is formed, the thickness of the outer layer is preferably 0.1 to 5 μm, and the total thickness of the inner layer and the hard layer or the inner layer, the hard layer, and the outer layer is preferably Is preferably 0.5 to 15 μm.

The coating member of the present invention can be prepared by using various types of substrates that have been commercially available or conventionally proposed, using a conventional chemical vapor deposition method (CVD method) or physical vapor deposition method (PVD method).
Can be produced by applying Specifically, in the case of a CVD method, a plasma CVD method is preferable, and adjustment of a gas pressure in the plasma CVD method or the PVD method, particularly adjustment of a gas pressure for supplying an oxygen element is important. Further, it is preferable to form a film by a PVD method such as an ion plating method or a sputtering method since a large compressive stress can be left in the film and the fracture resistance is remarkably improved.

[0015]

According to the coating member of the present invention, a hard layer of titanium / aluminum carbonitride coated on a base material has an effect of enhancing heat resistance, and as a result, abrasion resistance, welding resistance and acid resistance at high temperatures are obtained. In the case of a sintered alloy base material, an effect of leaving a large compressive stress in the hard layer occurs, and as a result, indirectly increases the strength and wear resistance of the coating. It has become a functional effect.

[0016]

Example 1 A commercially available cemented carbide (JIS standard, P30 equivalent grade, S) was placed in a reaction vessel of an ion plating apparatus.
After installing the base material (DKN42ZTN shape), a heating step, an Ar etching step, and a coating step were performed to obtain inventive products 1 to 5 and comparative products 1 to 3. Among them, the present invention products 1 to 5 are 1 × in an electron heating type reaction vessel in which a base material is installed.
After evacuating to a high vacuum of 10 ^-5 Torr, Ar gas was introduced to a pressure of 2 × 10 ^-3 Torr. ° C, output 12 for products 4 and 5 of the present invention
The substrate was heated at kw for 60 minutes to maintain the substrate at 420 ° C. Next, the pressure in the reaction vessel was increased to 1 × 10 ⁻³ Torr.
r, a voltage of -300 V was applied to the substrate side, a glow discharge was generated between the reaction container and the substrate, and the substrate surface was subjected to Ar etching by Ar ion bombardment for 30 minutes. Next, coating was performed under the coating conditions shown in Table 1 (using a nitrogen gas purity of 5N) to obtain the product 1 of the present invention.
~ 5.

On the other hand, the comparative products 1 to 3 were evacuated to 1 × 10 ^-4 Torr in the resistance heating type reaction vessel in which the base material was placed, and then introduced with Ar gas to obtain 4 × 10 ^-4 to 1 ×. 10 ^-4 To
The substrate was heated at an output of 20 kW for 60 minutes at a pressure of rr to maintain the substrate at 500 ° C. Next, a DC voltage of −600 V was applied to the substrate side in Ar gas of 8 × 10 ⁻² Torr in the reaction vessel, and the substrate surface was subjected to Ar etching by Ar ion bombardment for 10 minutes. Next, coating was performed under the coating conditions shown in Table 1 to obtain Comparative Products 1 to 3.

The coating composition components of the inventive products 1 to 5 and comparative products 1 to 3 thus obtained were analyzed by an X-ray diffractometer and a glow discharge optical emission analyzer, and are shown in Table 2. The thickness of each coating film was examined by a scanning electron microscope, and the residual stress of the coating film was determined from the surface of each coating film by X-ray diffraction using Cu-Kα radiation.

Next, products 1 to 5 of the present invention and comparative products 1 to 3
Work material: SCM440, Tool shape: SDKN
42ZTN, cutting speed: 161m / min, depth of cut: 2
mm, Feed: 0.2 mm / blade, a 100 × 150 mm ² surface in conditions of dry milling seeking average flank wear after 20 pass cutting, are also shown in Table 2.

[0020]

[Table 1]

[0021]

[Table 2]

[0022]

Example 2 Except that a base material was used for a commercially available cemented carbide (JIS standard, K10 grade), the formation of the hard layer of the products 6 to 10 of the present invention was the same as that of the products 1 to 1 of the present invention. Comparative example 4 was prepared in substantially the same manner as in Example 5 (mainly adjusting the reaction gas composition and gas pressure).
The hard layers Nos. 6 to 6 were formed in substantially the same manner as Comparative Examples 1 to 3 of Example 1, and the inner layer was formed under the conditions of a conventional ion plating method.

The coating composition components of the products 6 to 10 of the present invention and the comparative products 4 to 6 were determined in the same manner as in Example 1, and the results are shown in Table 3. Inventive product 6 shown in Table 3
-10 and comparative products 4-6, work material: S48
C, cutting speed: 150 m / min, cutting depth: 1.5 m
m, feed: 0.3 mm / rev, cutting time: 30 mi
n, first cutting conditions by dry turning, work material: FC3
5. Cutting speed: 150m / min, depth of cut: 1.5m
m, feed: 0.3 mm / rev, cutting time: 10 mi
n, a cutting test is performed under the second cutting conditions by dry turning, and an average flank wear amount at that time is obtained,
The results are shown in Table 3.

[0024]

[Table 3]

[0025]

Example 3 A commercially available cemented carbide (JIS P30 equivalent grade, SNMG120408 shape) was used as a base material.
The product 11 of the present invention obtained by coating an inner layer, a hard layer and an outer layer on a substrate
Comparative Examples 7 and 8 were prepared by sequentially coating the first to fourth layers on a substrate. The coatings of the inner layer, the outer layer, and the comparative product in the product of the present invention are coated by a conventional plasma thermal CVD method, and the hard layers of the products 11 to 14 of the present invention correspond to the products 1 to 5 of the present invention in Example 1. (Adjust reaction gas composition and gas pressure mainly)
The hard layer of No. 6 is made of TiCl: 40 cc / min, AlCl
_{3: 30~35cc / min, NH 3} : 150~200c
_{c / min, H 2: 2000cc} / min, CH 4: 25
0 cc / min, O ₂ : reaction gas composition of 40 cc / min, furnace pressure 1.0 Torr, bias voltage −500
V, coated with 45 minutes coating time.

The coating composition components of the inventive products 11 to 16 and the comparative products 7 and 8 thus obtained were determined in the same manner as in Example 1, and the results are shown in Table 4. Using the present invention product 11 to 16 and Comparative products 7 and 8 shown in Table 4, Workpiece: S45C (H _B 190), Cutting speed: 300 meters /
min, feed: 0.5 mm / rev, depth of cut: 2.0 m
The turning test was performed under the conditions of m, cutting time: 60 min, and the results are shown in Table 4. In addition, the present invention products 11 to 11
A scratch strength test was carried out with a device equivalent to a scratch hardness tester from the surface of the coating of Comparative Examples 16 and 7 and 8,
The maximum load at which the coating was not peeled off at that time was determined and is shown in Table 4. Further, the products 11 to 16 of the present invention and the comparative product 7,
The residual stress of the coating No. 8 was determined in the same manner as in Example 1, and the results are shown in Table 4.

[0027]

[Table 4]

[0028]

The heat-resistant coated member of the present invention has a higher compressive stress remaining in the coating and is superior in the peeling resistance of the coating as compared with the conventional coated member coated with a titanium / aluminum carbonitride coating. As a result, when used as a cutting tool, there is a remarkable effect that the wear resistance (abrasion including peeling of the coating film and fine chipping) is about 3 to 4 times as excellent.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI C23C 16/34 C23C 16/34 // C23C 30/00 30/00 C Examiner Naoyuki Miyazawa (56) References JP-A-7- 180071 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C23C 14/00-14/58 C23C 16/00-16/56 C23C 30/00 B23B 27/14 C04B 41/87 C22C 29/04

Claims (5)

(57) [Claims] 1. A hard layer of titanium / aluminum carbonitride represented by the following formula (A) having a thickness of 0.1 to 15 μm on a base material of a metal material, a sintered alloy or a ceramic sintered body. A heat-resistant covering member characterized by being coated with: (Ti _a , Al _b ) (C _X N _{YO Z} ) _R (A) {wherein, in the formula (A), Ti is titanium, Al is aluminum, and C is carbon. , N represents nitrogen, O represents oxygen, a and b
Represents the atomic ratio of each of the metal elements Ti and Al, X, Y and Z represent the atomic ratios of the non-metal elements C, N and O, and R represents the total of Ti and Al Represents the atomic ratio of the nonmetallic element obtained by adding C, N and O to the element, where a + b = 1 and 0.95 ≧ a ≧ 0.
05, X + Y + Z = 1, 0.89 ≧ X ≧ 0.1, 0.8
9 ≧ Y ≧ 0.1, 0.25 ≧ Z ≧ 0.01, 1.10 ≧
R ≧ 0.80. 2. Between the base material and the hard layer, a metal of Group 4a, 5a, or 6a of the periodic table and their carbides, nitrides, carbonates, oxynitrides, their mutual solid solutions, or their solid solutions. The heat-resistant coated member according to claim 1, wherein one or more single layers selected from the mixture or two or more inner layers are coated. 3. The base material is made of a sintered alloy, and the inner layer is made of Ti carbide, nitride, carbonitride, carbonate, nitride oxide, carbonitride or Zr, Hf, V, Nb, T
a, Cr, Mo, W at least one element and Ti
It is characterized by being composed of a single layer or two or more layers selected from composite carbides, composite nitrides, composite carbonitrides, composite carbonates, composite nitrides, and composite carbonitrides The heat-resistant covering member according to claim 2, wherein 4. An aluminum oxide adjacent to said hard layer,
4. The method according to claim 1, wherein an outer layer comprising one kind of a single layer or two or more kinds of titanium nitride, titanium carbonitride, titanium nitride oxide, titanium carbonitride oxide is coated. A heat-resistant covering member as described in the above. 5. The heat-resistant coating according to claim 1, wherein the hard layer has an oxygen element gradually reduced from the surface of the hard layer toward the substrate. Element.