JPH083750A - Heat resistant coating member - Google Patents

Abstract

PURPOSE:To obtain a heat resistant coating member excellent in wear resis tance, etc., over the region from low to high temp. by coating the top of a substrate of a metallic material, etc., with a hard layer of titanium-aluminum oxycarbonitride in a specified thickness. CONSTITUTION:The top of a substrate of a metallic material such as stainless steel, a sintered alloy such as a cemented carbide or a ceramic sintered compact such as an Al2O3 sintered compact is coated with a hard layer of titanium- aluminum oxycarbonitride by CVD or PVD in 0.1-1.5mm thickness. The hard layer is represented by the formula (TiaAlb)(CxNyOz)R (where 0.95>=a>=0.05, a+b=1, 0.89>=X>=0.1, 0.89>=Y>=0.1, X+Y+Z:1 and 1.10>=R>=0.8). The objective heat resistant coating member excellent in resistance to oxidation, thermal shock, chipping and fusion over the region from low to high temp. is obtd.

Description

Detailed Description of the Invention

[0001]

The present invention relates to a metal material typified by stainless steel, high speed steel, die steel, Ti alloy, Al alloy, heat resistant alloy, or cemented carbide, and sintered alloy typified by cermet. Alternatively, titanium / aluminum carbonitride is formed on the base material of a ceramics sintered body represented by an Al ₂ O ₃ system sintered body, a ZrO ₂ system sintered body, a SiC system sintered body, and a Si ₃ N ₄ system sintered body. Regarding a covering member formed by coating a hard oxide layer, specifically, for example, turning tools, milling tools, end mills, cutting tools typified by drills, slitters, can-making tools, and wear resistance typified by dies. The present invention relates to a heat-resistant covering member suitable as a sports member or a decorative member represented by tools, fishing tackles, golf clubs, watch parts, eyeglass frames, tie pins, broaches, and earrings.

[0002]

2. Description of the Related Art Carbides, nitrides, carbonates, nitrous oxides of the metals of groups 4a, 5a and 6a of the periodic table and their mutual solid solutions are formed on a base material of a metal material, a sintered alloy or a ceramics sintered body. Or a single layer of 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, and decorative members. Has been put to practical use.

Among these conventional coated members, a coated member coated with a Ti compound coating does not exhibit sufficient wear resistance when used as a cutting tool or wear resistant tool, and is relatively short in time. However, there is a problem of reaching the end of life, and a typical example that attempts to solve this problem is JP-A-62-565.
There is a publication No. 65.

[0004]

Problems to be Solved by the Invention JP-A-62-5656
JP-A No. 5-55 discloses that a hard coating layer composed of a single layer of Ti and Al carbides, nitrides, and carbonitrides of Ti and Al or a multi-layer of two or more layers is formed on the surface of a base material at 0.5 to 10 μm. It describes a surface-coated hard member formed of a thickness and having excellent wear resistance.

The surface-coated hard member described in the above publication is an excellent coated hard member having improved wear resistance, but when it is used as a cutting tool, for example, high-speed cutting or heavy cutting, When used under high temperature conditions, the hard coating layer rapidly oxidizes and wears, resulting in poor thermal shock resistance.
There is also a problem that welding with a work material which is a mating material easily occurs and the life becomes short.

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

[0007]

Means for Solving the Problems The inventors of the present invention exert a particularly excellent effect when a coating member obtained by coating a film of a compound of Ti and Al on a base material of cemented carbide is used in a low temperature region. On the other hand, when the problem that the effect is reduced when used in the high temperature region was investigated, when a trace amount of oxygen element was contained in the compound film of Ti and Al, the wear resistance from the low temperature region to the high temperature region was improved. The present invention has been completed based on the knowledge that the characteristics are well-balanced and the life is remarkably improved without reduction.

That is, in the heat resistant coating member of the present invention, a hard layer of titanium / aluminum oxycarbonitride is 0.1 to 15 μm on a base material of a metal, alloy or ceramics sintered body.
It is characterized by being coated with a film thickness of.

The base material in the coating member of the present invention is made of a metal material, a sintered alloy or a ceramics sintered body capable of withstanding the temperature of heating 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 system sintered body, Si ₃ N ₄ type sintered body, sialon type sintered body, ZrO ₂
A ceramic sintered body of a system sintered body can be mentioned.
Among these, when used as a cutting tool or an abrasion resistant tool, a cemented carbide, a nitrogen-containing TiC-based cermet or a ceramics sintered body is particularly preferable.

It is also preferable that the hard layer coated on the substrate has a variable oxygen element content, particularly in the hard layer, depending on the material of the substrate when the hard layer is coated directly on the substrate. Specifically, for example, in a sintered alloy base material, it is preferable that the oxygen element gradually decreases from the surface of the hard layer toward the base material side. It is preferable that the oxygen element gradually increases from the surface of the layer toward the base material side from the viewpoint of adhesion between the hard layer and the base material. The hard layer may be stoichiometric or non-stoichiometric, but in particular (Tia, Alb)
When expressed as (C _X , N _Y , O _Z ) _R , [wherein Ti is titanium, Al is aluminum, C is carbon, N is nitrogen, O is
Indicates oxygen, and a and b are metal elements Ti and Al.
And X, Y, and Z represent the atomic ratios of C, N, and O, which are nonmetallic elements, and R
Is C, N and O for the metal element which is the sum of Ti and Al.
Represents the atomic ratio of the non-metal elements, which is the sum of) and 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 oxide satisfying the conditions of ≧ 0.01 and 1.10 ≧ R ≧ 0.80 from the viewpoint of strength, wear resistance and welding resistance.

Further, the coating composition in the coating member of the present invention
As between the base material and the hard layer described above, the base material and the hard layer
It is also possible to interpose an inner layer that mainly improves adhesion with the layer.
The inner layer is preferably, for example, T
i, Zr, Hf, V, Nb, Ta, Cr, Mo, W gold
Genus, TiC, ZrC, HfC, VC, NbC, TaC,
Cr₃C₂, Mo₂C , 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, (Ti, Zr, Ta) C
Wear. These inner layers can be selected according to the material of the base material.
Is preferable, and when the base material 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 of (C, N, O) or multiple layers of two or more
Consists of the mediation of the adhesion between the base material and the hard layer, the covering member
Is particularly preferable from the viewpoint of wear resistance and fracture resistance as
Is.

Further, it is also preferable that the outer layer is formed adjacent to the hard layer, and when the outer layer is made of aluminum oxide, the welding resistance, the oxidation resistance at high temperature,
It 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 oxycarbonitride, the decorative effect, before and after use It is also preferable because it has an effect of facilitating the discrimination of or the effect of preventing color unevenness.

Of the film constitutions in the covering member of the present invention,
When the hard layer only is used, 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 wear resistance is significantly deteriorated. On the contrary, when the thickness exceeds 15 μm, peeling of the coating is likely to occur. The hard layer preferably has a thickness of 0.5 to 10 μm.
m, especially 0.5 in terms of industrial production including film forming time
-8 μm is preferable. When the inner layer is formed in addition to the hard layer, the inner layer has a thickness of 0.1 to 5 μm.
When the outer layer is formed, the outer layer preferably has a thickness of 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 0.5 to 15 μm.

The coated member of the present invention uses various types of base materials that are commercially available or conventionally proposed, and the conventional chemical vapor deposition method (CVD method) or physical vapor deposition method (PVD method) is used.
Can be produced by applying. Specifically, in the case of the CVD method, the plasma CVD method is preferable, and it is important to adjust the gas pressure in the plasma CVD method or the PVD method, particularly to adjust the gas pressure for supplying oxygen element. Further, it is preferable to form the film by the PVD method such as the ion plating method or the sputtering method because a large compressive stress can be left in the film and the fracture resistance is remarkably improved.

[0015]

In the coated member of the present invention, the hard layer of titanium / aluminum oxycarbonitride coated on the base material acts to enhance heat resistance, and as a result, wear resistance, welding resistance and acid resistance at high temperature. It has the effect of improving the chemical conversion property, especially when it is made of a sintered alloy base material, it causes the effect of leaving a large compressive stress in the hard layer, resulting in an increase in the strength and wear resistance of the coating. It has become an action.

[0016]

Example 1 A commercially available cemented carbide (JIS standard, P30 equivalent grade, S
After a base material of DKN42ZTN shape) was installed, 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 these, the products 1 to 5 of the present invention have 1 ×
After exhausting to a high vacuum state of 10 ⁻⁵ Torr, Ar gas was introduced to make a pressure state of 2 × 10 ⁻³ Torr, and for the products 1 to 3 of the present invention, the output was 10 kw, and the substrate was heated for 60 minutes to 400 times. Hold at ℃, output 12 for products 4 and 5 of the present invention
The base material was heated at 420 ° C. by heating for 60 minutes with kw. Next, the pressure inside the reaction vessel is set to 1 × 10 ⁻³ Tor.
The voltage was changed to r and a voltage of −300 V was applied to the base material side to generate glow discharge between the reaction vessel and the base material, and the base material surface was subjected to Ar etching by Ar ion bombardment for 30 minutes. Then, 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 was obtained.

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

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

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, the average flank wear amount after cutting 20 passes of 100 × 150 mm ² surface under the condition of dry milling cutting was also shown in Table 2.

[0020]

[Table 1]

[0021]

[Table 2]

[0022]

Example 2 The hard layers of the products 6 to 10 of the present invention were formed in the same manner as the products 1 to 1 of the present invention except that the substrate was used for a commercially available cemented carbide (JIS standard, K10 equivalent grade). Comparative product 4 in the same manner as 5 (mainly adjusting reaction gas composition and gas pressure)
The hard layers of Nos. 6 to 6 were formed in substantially the same manner as the comparative products 1 to 3 of Example 1, and the inner layers were formed under the conditions of the ion plating method which has been conventionally used.

The coating composition components of the invention products 6 to 10 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. Invention product 6 shown in Table 3
-10 and comparative products 4-6, work material: S48
C, cutting speed: 150 m / min, depth of cut: 1.5 m
m, feed: 0.3 mm / rev, cutting time: 30 mi
n, the first cutting conditions by dry turning and the 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 condition by dry turning, and the average flank wear amount at each time is obtained,
The results are shown in Table 3.

[0024]

[Table 3]

[0025]

Example 3 Using a commercially available cemented carbide (JIS standard P30 equivalent grade, SNMG120408 shape) as a base material,
The present invention product 11 obtained by coating a base material with an inner layer, a hard layer and an outer layer.
To 16 were produced, and the first to fourth layers were sequentially coated on the base material to produce comparative products 7 and 8. The inner and outer layers of the product of the present invention and the coatings of the comparative product are coated by the conventional plasma thermal CVD method, and the hard layers of the products 11 to 14 of the present invention are the hard layers of the products of Example 1 to 1 to 5 of the invention. In the same manner as described above (mainly adjusting the reaction gas composition and gas pressure), the product of the present invention 15, 1
The hard layer of 6 is TiCl: 40 cc / min, AlCl
₃ : 30 to 35 cc / min, NH ₃ : 150 to 200 c
c / min, H ₂ : 2000 cc / min, CH ₄ : 25
0 cc / min, O ₂ : 40 cc / min reaction gas composition, furnace pressure 1.0 Torr, bias voltage −500
V, coating time 45 minutes.

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 inventive products 11 to 16 and the comparative products 7 and 8 shown in Table 4, a work material: S45C (H _B 190), a cutting speed: 300 m /
min, feed: 0.5 mm / rev, depth of cut: 2.0 m
A turning test was conducted under the conditions of m, cutting time: 60 min, and the results are also shown in Table 4. Further, the products 11 to 11 of the present invention
Scratch strength test was carried out from the coating surface of 16 and comparative products 7 and 8 with a device equivalent to a scratch hardness tester,
The maximum load at which the coating film did not peel off at that time was determined and listed in Table 4. Further, the present invention products 11 to 16 and the comparative product 7,
The residual stress of the coating film No. 8 was determined in the same manner as in Example 1, and the results are also shown in Table 4.

[0027]

[Table 4]

[0028]

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

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Claims (6)

[Claims] 1. A hard material layer of titanium / aluminum carbonitride oxide is coated on a base material of a metal material, a sintered alloy or a ceramics sintered body in a film thickness of 0.1 to 15 μm. A heat resistant covering member. 2. A metal of group 4a, 5a, 6a of the periodic table, and their carbides, nitrides, carbonates, oxynitrides and mutual solid solutions thereof, or a mutual solid solution thereof, between the base material and the hard layer. The heat-resistant coated member according to claim 1, characterized in that the heat-resistant coated member is coated with an inner layer composed of one kind of single layer or two or more kinds of multilayers selected from the mixture. 3. The base material is made of a sintered alloy, and the inner layer is made of Ti carbide, nitride, carbonitride, carbon oxide, oxynitride, oxycarbonitride, or Zr, Hf, V, Nb, T
at least one element of a, Cr, Mo and W and Ti
Characterized by being composed of one kind of single layer or two or more kinds of layers selected from compound carbide, compound nitride, compound carbonitride, compound carbon oxide, compound carbon monoxide, and compound carbon monoxide. The heat resistant coating member according to claim 2. 4. An outer layer formed of a single layer of aluminum oxide, titanium nitride, titanium carbonitride, titanium oxynitride, or titanium oxycarbonitride or a multilayer of two or more types is coated adjacent to the hard layer. The heat-resistant coating member according to claim 1, 2, or 3, characterized in that. 5. The heat resistant coating member according to claim 1, wherein the hard layer has oxygen elements gradually decreasing from the surface of the hard layer toward the base material side. . 6. The heat resistant coating member according to claim 1, wherein the hard layer is made of titanium / aluminum carbonitride oxide represented by the following formula (A). _{(Tia, Alb) (C X} , N Y, O Z) R ‥‥‥‥‥ (A) [where, Ti is titanium in the formula (A), Al is aluminum, C is carbon, N is the nitrogen, O Represents oxygen, and a and b
Represents the atomic ratio of each of the metal elements Ti and Al, X, Y and Z represent the atomic ratio of each of the non-metal elements C, N and O, and R represents the metal which is the sum of Ti and Al. Represents the atomic ratio of the non-metal element, which is the sum of C, N, and O with respect to the element, and a + b = 1, 0.95 ≧ a, respectively.
≧ 0.05, X + Y + Z = 1, 0.89 ≧ X ≧ 0.1,
0.89 ≧ Y ≧ 0.1, 0.25 ≧ Z ≧ 0.01, 1.
10 ≧ R ≧ 0.80]