JPH0860340A - High hardness coated member - Google Patents

Abstract

PURPOSE: To produce a high hardness coated member excellent in wear, thermal impact, chipping, welding resistances or the like and having a long service life by coating the surface of a base material with a hard layer of titanium- aluminium carbon nitride constituted of a specified nonstoichiometric compsn. CONSTITUTION: The surface of a base material of a metallic material, a sintered alloy, a ceramic sintered body or the like is coated with a hard layer of titanium-aluminum carbonitride by a chemical or physical vapor depositing method or the like. This hard layer is constituted of a nonstoichiometric compsn. expressed by the formula of (Tia , Alb ) (CX(NY)R (where a+b=1, 0.8>=a>=0.2, X+Y=1, 0.9>=X>=0.1 and 1.50>=R>1.00). The film thickness of this hard layer is preferably regulated to 0.5 to 10 (m. If required, the space between the base material and hard layer may be provided with an internal layer of Ti carbide or the like, or adjacently to the hard layer, an external layer of Al2 O3 or the like may be provided. At this time, the thickness of the internal and external layers is respectively preferably regulated to 0.1 to 5μm.

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 high hardness coating 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 film is not yet satisfactory when used for a cutting tool or a wear resistant tool, for example, a low speed area in a cutting tool or In the wet cutting region, there is a problem that the life is reached in a relatively short time. Some of these problems are attempted to be solved by using a hard layer composed of one single layer or two or more multi-layers of Ti and Al carbides, nitrides and carbonitrides. Japanese Patent Laid-Open No. 62-56565, Japanese Patent Laid-Open No. 1-252304, Japanese Laid-Open Patent Publication No. 2-194159, and Japanese Laid-Open Patent Publication No. 4-224104.

[0004]

Carbides of Ti and Al,
Single layer of one or more of nitrides and carbonitrides
About the coated member coated with the hard layer consisting of the above multiple layers
Among the prior art, Japanese Patent Application Laid-Open No. 62-56565 discloses
Stoichiometric composition (Ti, Al) C, (Ti, Al)
N , (Ti, Al) (C , N ) Coating of 0.5-10μ
A coating member coated with a thickness of m is disclosed.
In Kaihei 1-252304, the film thickness is 0.5 to 10 μm.
m TiC, TiN , Ti (C , N ) Adhesion-strengthening layer
(Ti, Al) with a stoichiometric composition through the film of
C, (Ti, Al) N , (Ti, Al) (C , N ) Cover
Opening of the covering member in which the film is covered in a thickness of 0.5 to 5 μm
Japanese Patent Application Laid-Open No. 2-194159,
(Ti, Al) (C , N ) Of Al and N in the coating of
A limited amount of stoichiometric nitride and carbonitride coatings
Is disclosed by the arc discharge method.
In Japanese Patent Laid-Open No. 4-224104, 1-10
Single-phase crystallinity (Ti, Al) (C ,
N ) Stoichiometry limiting the content of Ti and C in the film
A theoretical carbonitride is disclosed.

The carbonitride coatings of Ti and Al described in these four publications have the effect of being superior in wear resistance as compared with conventional coatings of titanium carbide, titanium nitride and titanium carbonitride. However, there is almost no difference in hardness of the coating film between the two, and for example, there is a problem that when the cutting edge becomes high temperature during continuous cutting for a long time, the wear rapidly progresses and the life becomes short.

The present invention solves the above-mentioned problems. Specifically, in a wide range from a low temperature region to a high temperature region, Ti and Al having a conventional stoichiometric composition are combined. Compared to carbonitride coatings, the properties such as thermal shock resistance, fracture resistance, and welding resistance have been improved to the same level or slightly, and especially wear resistance has been further improved to achieve longer life. It is intended to provide a hardness coating member.

[0007]

Means for Solving the Problems The inventors of the present invention have found that a coating member obtained by coating a carbonitride film of Ti and Al on a cemented carbide substrate is titanium carbide, titanium nitride, or titanium carbonitride. It was confirmed that the effect of the ratio was excellent in the low temperature region as compared with the coating film of the compound, and the cause was examined, and it also affected the content ratio of Ti and Al and the content ratio of carbon and nitrogen. However, when a large amount of a non-metal element obtained by summing carbon and nitrogen is added to a metal element obtained by summing Ti and Al, distortion occurs in the crystal lattice, resulting in a high hardness coating. The crystal structure of the film changes depending on the ratio of Ti to Al at that time, and it has been found that the film can be made to have a much higher hardness by selecting this crystal structure, and the present invention has been completed. .

The high-hardness coated member of the present invention is formed by applying (Ti
a, Alb) (C _X , N _Y ) _R [where Ti is titanium, A
l is aluminum, C is carbon, N is nitrogen, a and b are atomic ratios of Ti and Al which are metal elements, and X and Y are atomic ratios of C and N which are non-metal elements. And R represents an atomic ratio of a non-metal element obtained by summing C and N with respect to a metal element obtained by summing Ti and Al, and a + b = 1, 0.8 ≧ a ≧ 0.2,
X + Y = 1, 0.9 ≧ X ≧ 0.1, 1.50 ≧ R> 1.
00]] is coated with a hard layer of titanium-aluminum carbonitride having a non-stoichiometric composition.

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.

The hard layer coated on the base material may have various arrangements depending on the material of the base material and the use and shape of the covering member. Specifically, the first configuration in which the hard layer is directly adjacent to the base material, and the second configuration in which the hard layer is directly adjacent to the base material and the outer surface of the hard layer is coated. A third structure in which the inner layer is covered between the base material and the hard layer, and a fourth structure in which the inner layer is covered between the base material and the hard layer and the outer layer is covered on the surface of the hard layer are typical. It is a typical layout configuration.

In the coated member of the present invention (Tia, Al
b) In the hard layer having a non-stoichiometric composition represented by (C _X , N _Y ) _{R, when a,} which represents the atomic ratio of Ti, exceeds 0.8, the relative atomic ratio of Al is relatively represented b. Is less than 0.2, the oxidation resistance is significantly reduced, and conversely, when a is less than 0.2, b representing the atomic ratio of Al is 0.8.
, And as a result, the number of crystals having a hexagonal crystal structure increases, and the hardness and wear resistance decrease significantly. Further, when X representing the carbon atom ratio in the non-metallic element of the hard layer exceeds 0.9 and increases, Y representing the nitrogen atom ratio becomes relatively small.
When it is less than 1, and when X is less than 0.1, Y relatively representing the carbon atom ratio exceeds 0.9 and increases, and in each case, the oxidation resistance and wear resistance are significantly reduced. Becomes Further, the atomic ratio R of the non-metal element in which carbon and nitrogen are added to the metal element in which Ti and Al are added in the hard layer
When R is 1 or less, the hardness is low and the wear resistance is significantly reduced. On the other hand, when R exceeds 1.50 and is large, it is difficult to manufacture and further effects cannot be expected.

Further, the coating composition in the coating member of the present invention
Among the above, between the base material and the hard layer, the base material and the hard layer
As the inner layer mainly for improving the adhesiveness, specifically,
For example, Ti, Zr, Hf, V, Nb, Ta, Cr, M
o, W metal, TiC, ZrC, HfC, VC, Nb
C, TaC, Cr₃C₂, Mo₂C , WC, TiN, Zr
N, CrN, Ti (C, N), Ti (C, O), Ti
(N, O), Ti (C, N, O), (Ti, Zr) C,
(Ti, Z) N, (Ti, Z) (C, N), (Ti, T
a) C, (Ti, W) C, (Ti, Ta, W) (C
N), (Ti, Ta, W) N, (Ti, Zr, Ta) C
Can be mentioned. These inner layers are the base materials
Therefore, it is preferable to select it. When the base material is a sintered alloy
For example, TiC, 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, M
o) 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, Zr) (C, N, O)
It is a dense layer of the base material and the hard layer that it consists of two or more layers.
Adhesion mediation, wear resistance and fracture resistance as a covering member
It is particularly preferable from the viewpoint of sex.

Further, in the coating composition for forming the outer layer adjacent to the hard layer, the outer layer made of aluminum oxide is preferable because it has excellent welding resistance, oxidation resistance and wear resistance at high temperature. That is. 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 an outer layer of titanium nitride, titanium oxynitride, or titanium carbonitride oxide, a decorative effect,
It is preferable because it has an effect of easy discrimination before and after use or an effect of preventing color unevenness.

Among 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
The thickness is preferably 15 μm, more preferably 0.5 to 10 μm, and particularly preferably 0.5 to 8 μm from the viewpoint of industrial production including film forming time. In addition to this hard layer, the thickness of the inner layer is preferably 0.1 to 5 μm when the inner layer is interposed, and the thickness of the outer layer is further formed when the outer layer is formed. Is 0.1
5 μm is preferable, and the total thickness of the coating including the inner layer and the hard layer or the inner layer, the hard layer and the outer layer is 0.5 to 15 μm.
It is preferable that

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. In particular, as a concrete method for forming the hard layer, in the case of the CVD method, the plasma CVD method is preferable, and in the case of the plasma CVD method, it is important to promote the activation reaction, Therefore, it is necessary to particularly adjust the H ₂ gas flow rate, the total gas pressure amount in the reaction furnace, and the bias voltage amount applied to the substrate. Further, in the case of the PVD method, it is important to use a solid substance as a source of the non-metal element in the hard layer, and a sputtering method in which a hard material target is sputtered to form a hard layer, or a solid substance is used. It is important to use an ion plating method in which vaporized ions are vaporized by arc discharge or the like and vaporized ions are accelerated to form a hard layer. In addition to these, there is also a method of implanting nitrogen ions or carbon ions, but the above-mentioned sputtering method is preferable because it is easy to adjust the composition components of the hard layer.

[0016]

In the coated member of the present invention, the hard layer of titanium / aluminum carbonitride having a non-stoichiometric composition has a high hardness and acts to particularly enhance wear resistance and welding resistance, and the base material is fire-bonded. In the case of using gold, the synergistic effect of the strength of the base material and the high hardness of the hard layer acts more strongly, and as a result, the usage area is extended or the life is extended.

[0017]

Example 1 A commercially available cemented carbide (JIS standard, P30 equivalent grade, SNGN120) was placed in the reaction vessel of the sputtering apparatus.
After setting the base material of 408 shape), 5.0 in the reaction vessel
Pre-evacuation to × 10 ^-6 Torr, heating step, Ar etching step and Ar gas pressure 2.0 × 10 ^-3 Torr
The coating process is performed in r, and the invention products 1 to 5 and the comparative products 1 to
3 was obtained. The coating at this time was performed under the respective conditions shown in Table 1, and the coating composition components were adjusted according to the material of the target used.

Further, by using an ion plating apparatus, the gas composition in the reaction furnace was adjusted by the Ti-Al evaporation source, and comparative products 4 to 6 which were coating members substantially similar to the conventional ones were obtained. The coating conditions for obtaining the comparative products 4 to 6 are also shown in Table 1.

The coating composition components of the products 1 to 5 of the present invention and the comparative products 1 to 6 thus obtained were analyzed by an X-ray diffractometer and a glow discharge emission spectrometer, and shown in Table 2. Further, the hardness and the film thickness of each film were examined by a micro Vickers hardness meter and a scanning electron microscope, and the results are also shown in Table 2.

Next, products 1 to 5 of the present invention and comparative products 1 to 6
Work material: S48C (250 mm diameter round bar), cutting speed: 200 m / min, feed: 0.3 mm
/ Min, depth of cut: 1.5 mm, a cutting test was performed under wet cutting conditions with a water-soluble cutting oil, the cutting time was calculated when the average flank wear width was 0.3 mm, and the results are also shown in Table 2. did.

[0021]

[Table 1]

[0022]

[Table 2]

[0023]

[Example 2] In a reaction container of an ion plating apparatus
In addition, commercially available cemented carbide (JIS standard K10 equivalent, 8 mm diameter
After installing the base material of the 2-flute solid end mill of
× 10 ^-FourPre-evacuate to Torr, then introduce Ar gas
4x10^-Four~ 1 × 10^-FourOutput in the pressure state of Torr
Heat at 12 kW for 60 minutes to keep the substrate at 420 ° C
It was Then, the pressure inside the reaction vessel is set to 1 × 10.^-3With Torr
Then, a voltage of -300 V is applied to the base material side, the reaction container and the base material.
A glow discharge is generated in the meantime and the surface of the substrate is exposed to Ar for 30 minutes.
Ar etching was performed by an on-bombard process. So
After that, the inner and outer layers are formed by the conventional coating process.
And the hard layer is formed by the ion pretreatment shown in Table 3.
Coating under the coating conditions, especially the carbon of the evaporation source
When I emitted it, I added carbon ions with an ion accelerator.
The products 6 to 8 of the present invention are accelerated to form a hard layer.
Obtained.

For comparison, base materials having the same shapes and materials as those of the products 6 to 8 of the present invention were coated under the same coating conditions as those of the comparative product 4 of Example 1 to obtain comparative products 7 to 9.

Inventive products 6 to 8 and comparative products 7 to 8 thus obtained
Work Material: SKD61 (HRC41), Feed: 0.08 mm / rev, Depth: Ad = 12 mm,
A cutting test was performed under Rd = 0.8 mm, cutting speed: 60 m / min, and water-soluble cutting conditions, and the flank wear width at a cutting length of 50 m was examined. The results are shown in Table 4.
The compositional components of the film and the film thickness were determined in the same manner as in Example 1, and the results are also shown in Table 4.

[0026]

[Table 3]

[0027]

[Table 4]

[0028]

The high hardness coated member of the present invention has a higher hardness than the conventional coated member coated with titanium / aluminum carbonitride or titanium / aluminum carbide or nitride having a stoichiometric composition. It has a remarkable effect that the life is improved by 1.4 to 2.8 times when it is used as a cutting tool.

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Claims (6)

[Claims] 1. A hard layer of titanium / aluminum carbonitride having a non-stoichiometric composition represented by the following formula (A) is coated on a base material of a metal material, a sintered alloy or a ceramics sintered body. A high hardness coating member characterized by being (Tia, Alb) (C _X , N _Y ,) _R ···· (A) [In the formula (A), Ti is titanium, Al is aluminum, C is carbon, and N is nitrogen. And b represent atomic ratios of Ti and Al that are metal elements, X and Y represent atomic ratios of C and N that are non-metal elements, and R represents a metal element that is the sum of Ti and Al. C
And N represent the atomic ratio of the non-metallic elements, a + b = 1, 0.8 ≧ a ≧ 0.2, X + Y = 1,
0.9 ≧ X ≧ 0.1, 1.50 ≧ R> 1.00] 2. The high hardness coating member according to claim 1, wherein the hard layer has a film thickness of 0.5 to 10 μm. 3. A Ti carbide, a nitride, a carbonitride, a carbon oxide, a nitric oxide, a carbonitride oxide, or Zr, Hf, V, Nb, Ta between the base material and the hard layer. , Cr, M
At least one element selected from the group consisting of complex carbides, complex nitrides, complex carbonitrides, complex carbonates, complex oxynitrides, and complex oxycarbonitrides of at least one element of O and W and Ti. The high hardness coated member according to claim 1 or 2, wherein an inner layer composed of a single layer or a multilayer of two or more types is coated. 4. The high hardness coating member according to claim 3, wherein the inner layer has a film thickness of 0.1 to 5 μm. 5. An outer layer consisting of a single layer of aluminum oxide, titanium nitride, titanium carbonitride, titanium oxynitride, or titanium oxycarbonitride or a multilayer consisting of two or more types is coated adjacent to the hard layer. The high hardness coating member according to claim 1, 2 or 3, characterized in that. 6. The high hardness coated member according to claim 5, wherein the outer layer has a film thickness of 0.1 to 5 μm.