A hard coating film to be applied to the surface of a tool, which has a composition of (Cr1-a-bAlaSib) (BxCyN1-x-y) with atomic ratios specified below.
0<a≦0.4
0.05≦b≦0.35
0.25≦1−a−b≦0.9
0≦x≦0.15
0≦y≦0.5
or a composition of (M1-a-bAlaSib) (BxCyN1-x-y) with atomic ratios specified below.
0.05≦a≦0.5
0.1<b≦0.35
0≦x≦0.15
0≦y≦0.5
where M denotes ti and Cr.
The hard coating film for cutting tools has better wear resistance than conventional ones.
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2. A hard coating film to be applied to the surface of a tool, wherein the hard coating film comprises a single comprising at least one first layer having a composition of (M1-a-bAlaSib) (BxCyN1-x-y), where a, b, x and y are atomic ratios and
0.05≦a≦0.3,
0.1<b≦0.35,
0≦x≦0.15,
0≦y≦0.5,
M denotes the presence of both ti and Cr, and
an atomic ratio of ti in (M1-a-bAlaSib) is in a range of from 0.03 to 0.43.
1. A hard coating film to be applied to the surface of a tool, wherein the hard coating film has comprising at least one first layer having a composition of (Cr1-a-bAlaSib) (BxCyN1-x-y), where a, b, x and y are atomic ratios and
0<a≦0.4,
0.05≦b≦0.35,
0.25≦1−a−b≦0.9,
0.03≦x≦0.15, and
0≦y≦0.5; and
the hard coating film has the a crystal structure of rock salt and does not include an amorphous phase.
28. A hard coating film to be applied to the surface of a tool, wherein the hard coating film has comprising at least one layer having a composition of (M1-a-bAlaSib) (BxCyN1-x-y), where a, b, x and y are atomic ratios and
0.05≦a≦0.5,
0.1<b≦0.35,
0.035≦x≦0.15,
0≦y≦0.5, and
M denotes ti and Cr; and
the hard coating film has the a crystal structure of rock salt and does not include an amorphous phase.
0. 30. A hard coating film comprising at least one first layer and at least one second layer laminated alternately, wherein
the first layer has a composition including ti, Cr, Al and N; and
the second layer has a composition of (M1-a-bAlaSib) (BxCyN1-x-y), where a, b, x and y are atomic ratios and
0.05≦a≦0.5,
0.1<b≦0.35,
0≦x≦0.15,
0≦y≦0.5,
M denotes ti and Cr, and
an atomic ratio of ti in (M1-a-bAlaSib) is in a range of from 0.03 to 0.43.
29. A hard coating film to be applied to the surface of a tool, wherein the hard coating film comprises comprising at least one first layer and at least one second layer laminated alternatively; alternately, wherein
the first layer has a composition including ti, Cr, Al and N; and
the second layer has a composition of (M1-a-bAlaSib) (BxCyN1-x-y), where a, b, x and y are atomic ratios and
0.05≦a≦0.3,
0.1<b≦0.35,
0≦x≦0.15,
0≦y≦0.5,
M denotes ti and Cr, and
an atomic ratio of ti in (M1-a-bAlaSib) is in a range of from 0.03 to 0.43.
3. The hard coating film defined in
4. The hard coating film defined in
5. The hard coating film defined in
0.03≦x≦0.15,
0≦y≦0.5,
0<z≦0.5, and
0.35≦1−x−y−z<1.
6. The hard coating film defined in
0≦x≦0.15,
0≦y≦0.5,
0<z≦0.5, and
0.35≦1−x−y−z<1.
7. The hard coating film defined in
8. The hard coating film defined in
9. The hard coating film defined in
10. The hard coating film defined in
11. The hard coating film defined in
12. The hard coating film defined in
13. The hard coating film defined in
14. The hard coating film defined in
15. The hard coating film defined in
16. The hard coating film defined in
17. The hard coating film defined in
18. The hard coating film defined in
19. The hard coating film defined in
20. The hard coating film defined in
21. The hard coating film defined in
22. The hard coating film defined in
23. The hard coating film defined in
24. A method for forming a hard coating film, the method comprising coating on a work the hard coating film defined in
25. A method for forming a hard coating film, the method comprising coating on a work the hard coating film defined in
26. The method defined in
27. The method defined in
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1. Field of the Invention
The present invention relates to a hard coating film and a method for forming the same. The hard coating film is designed to improve the wear resistance of cutting tools (such as tip, drill, and end mill) and jigs (such as forging die and punching die).
2. Description of the Related Art
Coating with a hard film of TiN, TiCN, TiAlN or the like has been a conventional way of improving the wear resistance of cutting tools made of cemented carbide, cermet, or high-speed steel. It has recently been found that a coating film of TiAlN (which is a composite nitride of Ti and Al) excels in wear resistance, as disclosed in Patent Document 1 below. This coating film is finding use in the field of cutting tools for high-speed cutting and hard materials such as hardened steel, in place of the coating film of titanium nitride, carbide, or carbonitride. Another recent development is a coating film of laminate structure composed of layers differing in crystal structure and composition for improved wear resistance (as disclosed in Patent Document 2 below) or a coating film of TiAlSiN incorporated with Cr for improved hardness and oxidation resistance (as disclosed in Patent Document 3 below).
There is an increasing demand for hard coating film to impart better wear resistance (hardness and oxidation resistance) to cutting tools in response to harder works, greater cutting speed, and high-speed dry cutting (which increases the surface temperature of cutting tools).
The present invention was completed in view of the forgoing. It is an object of the present invention to provide a hard coating film for better wear resistance than conventional ones and a method for forming the same.
Among known hard coating films excelling in wear resistance is that of (CrAlSi) (BCN) containing optional Ti, with a large content of Al and Si. It tends to become soft as it assumes the hexagonal crystal structure or amorphous structure owing to much Al and Si contained therein. The present inventors found that it is possible to obtain a hard coating film essentially excelling in hardness and oxidation resistance if the Al content is decreased and the Si content is increased more than before. The present inventors further investigated a hard coating film which exhibits a desirable crystal structure when it has the foregoing composition, and also investigated a method for forming the hard coating film. The results of their investigation led to the present invention.
The first aspect of the present invention is directed to a hard coating film to be applied to the surface of a tool, which has a composition of (Cr1-a-bAlaSib) (BxCyN1-x-y) with atomic ratios specified below.
The second aspect of the present invention is directed to a hard coating film to be applied to the surface of a tool, which has a composition of (M1-a-bAlaSib) (BxCyN1-x-y) with atomic ratios specified below.
The hard coating film defined above essentially excels in hardness and oxidation resistance and has the crystal structure free of hexagonal crystals and amorphous phase.
The third aspect of the present invention is directed to a modification to the hard coating film defined in the first or second aspect of the present invention, with the modified hard coating film containing oxygen.
The fourth aspect of the present invention is directed to a modification to the hard coating film defined in the third aspect of the present invention, with the modified hard coating film having the moiety of (BxCyN1-x-y-zOz) with atomic ratios specified below.
The hard coating film defined above is chemically stable and hence exhibits improved oxidation resistance in high-speed cutting and dry cutting which lead to a high surface temperature of tools.
The fifth aspect of the present invention is directed to a modification to the hard coating film defined in any of the first to fourth aspects of the present invention, with the modified hard coating film consisting of two or more layers differing in composition within the specified range.
The hard coating film of layered structure may be formed such that the layer needing hardness comes in direct contact with a tool and the layer needing oxidation resistance covers the outside.
The sixth aspect of the present invention is directed to a modification to the hard coating film defined in any of the first to fifth aspects of the present invention, with the modified hard coating film having an additional layer on one side or both sides thereof, the additional layer being formed from any of nitride, carbide, boride, carbonitride, carboboride, boronitride, and carboboronitride of metal selected from Groups 4A, 5A, and 6A, Al, and Si, with their composition differing from that of the hard coating film defined above.
The seventh aspect of the present invention is directed to a modification to the hard coating film defined in any of the first to sixth aspects of the present invention, with the modified hard coating film having an additional layer on one side or both sides thereof, the additional layer containing at least one species selected from Groups 4A, 5A, and 6A, Al, and Si.
The modified hard coating film may be formed in such a way that the strongly adhering layer comes in direct contact with a tool and the highly corrosion resistant layer covers the outside. The combination of layers differing in composition (and hence in crystal structure) often contributes to wear resistance.
The eighth aspect of the present invention is directed to a modification to the hard coating film defined in the sixth or seventh aspect of the present invention, with the modified hard coating film having more than one additional layer formed thereon. The modified hard coating film exhibits improved wear resistance while maintaining the characteristic properties of the original hard coating film.
The ninth aspect of the present invention is directed to a hard coating film which has a crystal structure represented by rock salt structure. This crystal structure permits the hard coating film to excel in wear resistance.
The tenth aspect of the present invention is directed to a method for forming a hard coating film by unbalanced magnetron sputtering or cathodic arc ion plating that employs a mechanism to apply a magnetic field.
The eleventh aspect of the present invention is directed to a modification to the method for forming a hard coating film defined above, the modification including a means for generating a magnetic force that extends in the direction parallel or perpendicular to the target's evaporating surface, the magnetic force readily converting the film-forming gas into plasma in the neighborhood of the work being coated.
This modification helps form a coating film having a crystal structure suitable for improved wear resistance.
<Effect of the Invention>
The hard coating film according to the present invention imparts improved hardness, oxidation resistance, and wear resistance to cutting tools and the like. The method for forming the hard coating film according to the present invention gives a hard coating film having a crystal structure suitable for improved wear resistance.
The preferred embodiments for the hard coating film according to the present invention will be described in the following.
The hard coating film according to the present invention covers the surface of cutting tools (such as tip, drill, and end mill) and jigs (such as forging die and punching die), which are made of cemented carbide, cermet, or high-speed steel.
(Composition and Structure of Coating Film)
The coating film based on (CrAlSi) (BCN) has the following composition.
The content (in terms of atomic ratio) of aluminum (Al) should be no more than 0.4, preferably no more than 0.35, and no less than 0.05, preferably no less than 0.15. Without aluminum, the hard coating film will be poor in oxidation resistance and hardness.
The content of silicon (Si) should be no less than 0.05 and no more than 0.35, preferably no less than 0.1 and no more than 0.25.
The content of chromium (Cr) is equivalent to the total amount of Al and Si, which is no less than 0.3 and no more than 0.6, preferably no less than 0.4 and no more than 0.55. Chromium strongly affects oxidation resistance and crystal structure.
The coating film based on (TiCrAlSi)(BCN) has the following composition.
The content of aluminum (Al) should be no less than 0.05 and no more than 0.5. The content of Si should be no less than 0.1 and no more than 0.35. The content of Al or Si lower than specified above is not enough to improve oxidation resistance and hardness. The total amount of Al and Si should be no less than 0.2 and no more than 0.7, preferably no less than 0.3 and no more than 0.6.
The total content of Ti and Cr, which is equivalent to the total amount of Al and Si, should be no less than 0.15. The ratio of Ti to Cr is not specifically restricted. A higher Ti/Cr ratio leads to improved hardness, and a lower Ti/Cr ratio leads to improved oxidation resistance (with slightly decreased hardness). The selection of Ti/Cr ratio depends on the purpose of coating.
The hard coating film according to the present invention contains nitrogen (N) as a basic component. The content (in terms of atomic ratio) of nitrogen should be no less than 0.35. The hard coating film will vary in characteristic properties depending on the content of boron (B) or carbon (C), which should be controlled according to the object.
Boron (B) in the hard coating film combines with nitrogen (N) to form the B—N linkage which contributes to lubricity (or reduced friction and improved wear resistance). Boron (B) also combines with metal to form a hard boride (such as TiB2), which contributes to hardness. The content (in terms of atomic ratio) of B should be no more than 0.15, preferably no more than 0.1. Excess boron makes the hard coating film amorphous.
Carbon (C) in the hard coating film forms a hard carbide, thereby contributing to hardness. The content of C should be no more than 0.5, preferably no more than 0.4. Excess carbon remains unreacted or forms an unstable Al—C linkage.
It follows from the foregoing that the hard coating film according to the present invention may have any of the following compositions, which lead to varied characteristic properties shown in Examples given later.
(CrAlSi)N, (CrAlSi)(BN), (CrAlSi)(CN), (CrAlSi)(BCN), (TiCrAlSi)N, (TiCrAlSi)(BN), (TiCrAlSi)(CN), and (TiCrAlSi)(BCN)
The hard coating film mentioned above may additionally contain oxygen in an amount not harmful to its desired characteristic properties. The resulting hard coating film, which contains an oxide, slightly decreases in harness but increases in chemical stability; therefore, it reacts less with metal works and exhibits improved oxidation resistance. The hard coating film should have the oxygen-containing layer as its outermost layer which comes into contact with the work. This is accomplished by adding oxygen to nitrogen being introduced in the last stage of film forming process. The amount (in terms of atomic ratio) of oxygen should be no more than 0.5, preferably no more than 0.4. Excess oxygen causes the hard coating film to decrease in hardness and hence in wear resistance. The content of nitrogen (as the fundamental component) should be no less than 0.35 irrespective of the introduction of oxygen.
The hard coating film according to the present invention may also be composed of two or more layers in laminate form, each differing in composition within a certain range The additional laminated layers may be formed from any of nitride, carbide, boride, carbonitride, carboboride, boronitride, and carboboronitride of metal selected from Groups 4A, 5A, and 6A, Al, and Si, with their composition differing from that of the hard coating film defined above. These metal compounds may be exemplified by TiN, TiAlN, TiCrAlN, CrAlSiN, TiCrAlSiN, TiCN, TiAlCN, TiCrAlCN, TiC, TiB2, TiBCN, and TiCrAlBN.
The hard coating film of laminate structure according to the present invention may have an additional layer of metal or alloy on one side or both sides thereof, the additional layer containing at least one species of metal selected from Groups 4A, 5A, and 6A, Al, and Si. The metals of Group 4A, 5A, and 6A are exemplified by Cr, Ti, and Nb, and the alloy includes Ti—Al.
The hard coating film of laminate structure formed as mentioned above should preferably have more than one additional layer so that it exhibits improved characteristic properties.
The hard coating film according to the present invention should have a crystal structure represented by rock salt structure. This crystal structure excludes the soft hexagonal crystal structure and amorphous phase. The hard coating film of rock salt structure contributes to cutting tools excelling in wear resistance.
The hard coating film should have a thickness no smaller than 0.5 μm and no larger than 20 μm regardless of its layer structure (single layer or multiple layers). With a thickness smaller than 0.5 μm, the hard coating film is poor in wear resistance. With a thickness larger than 20 μm, the hard coating film is liable to damage and peeling at the time of cutting. A desirable thickness is no smaller than 1 μm and no larger than 15 μm. In the case of laminate structure, each layer should have a thickness smaller than 3000 nm, preferably no larger than 1000 nm, more preferably no larger than 500 nm.
<Method and Apparatus for Film Forming>
The hard coating film having the desirable rock salt crystal structure may be formed by using an evaporation source shown in
One embodiment of the present invention will be briefly described with reference to the arc ion plating (AIP) apparatus shown in
The AIP apparatus consists of the following components:
The vacuum chamber 1 is supplied with a mixture gas composed of nitrogen (N2) methane (CH4), oxygen (O2), and argon (as an inert gas). Selection of the former three depends on the composition of the hard coating film desired
The evaporation source 2A for arc process consists of the following components.
The magnet 8 should be one which generates a magnetic force density no smaller than 10 G (gauss), preferably no smaller than 30 G, in the vicinity of the work W. Incidentally, the term “approximately perpendicular” means that the direction of magnetic force may deviate within about 30° from the normal.
The AIP apparatus used in the present invention differs from the conventional one in how the magnetic field moves the film-forming gas in plasma form in front of the evaporation source for arc process.
The invention will be described in more detail with reference to the following examples, which are not intended to restrict the scope thereof. Adequate modifications may be made to the examples within the scope of the invention.
Coating on several substrates was carried out in the following manner by using the AIP apparatus shown in
First, the cathode of the AIP apparatus was provided with the target 6 of Cr—Al—Si alloy. Then, the support 3 was provided with the work W, which is a mirror-polished tip of cemented carbide, a platinum foil (0.1 mm thick), or a ball end mill of cemented carbide (10 mm in diameter, with six blades).
With the vacuum chamber 1 evacuated, the work W was heated to 550° C. by a heater therein, and the vacuum chamber 1 was fed with nitrogen gas. With the pressure in the vacuum chamber 1 kept at 4 Pa, arc discharging was started to form a coating film (3 μm thick) on the surface of the substrate (work W). To form the coating film containing B, the alloy target mentioned above was replaced by the one containing B. To form the coating film containing C and O, the film-forming gas was incorporated with CH4 and O2 gas. Incidentally, a bias voltage of −30 V to −100 V was applied to the substrate (work W) so that the substrate (work W) remained at a minus potential with respect to the earth potential during the coating process.
The resulting coating film was examined for composition (by EPMA corrected by mass absorption coefficient), crystal structure (by X-ray diffractometry), Vickers hardness, and oxidation starting temperature. The coating film was also examined for wear resistance by cutting with the coated end mill under the following conditions. After cutting, the width of flank wear was measured. (The smaller the wear width, the better the wear resistance.) To examine oxidation resistance, the coated platinum foil was heated in dry air at a rate of 4° C./min and the weight increase due to oxidation was plotted. The temperature at which the sample had begun to increase in weight was regarded as the oxidation starting temperature. A high oxidation starting temperature means that the hard coating film is less reactive with the work and is superior in oxidation resistance.
Table 1 shows the results of evaluation of samples in Example 1. The crystal structure in Table 1 is abbreviated as follows.
Samples No. 1 and 2 represent conventional hard coating film of TiN or TiAlN. Samples Nos. 3 to 19 represent hard coating film of metal nitride containing Cr as an essential component, with the amount of Al and Si varied. It is noted that those samples with a comparatively large amount of Al are low in hardness and oxidation starting temperature (and hence large in wear amount) even though they contain a certain amount of Si. Also, those samples with a comparatively large amount of Si are low in hardness because of transformation into amorphous phase.
Samples Nos. 20 to 36 represent hard coating film of above-mentioned metal nitride, with the amount of boron (B) varied (Nos. 20 to 24), the amount of carbon (C) varied (Nos. 25 to 29), and the amount of oxygen (O) varied (Ns. 31 to 36). These results suggest the adequate amount of individual elements in the coating film.
TABLE 1
Composition of coating film (atomic ratio)
Crystal
Hardness
Oxidation starting
Amount of
No.
Cr
Al
Si
Al + Si
B
C
N
O
structure
(HV)
temperature (° C.)
Wear (μm)
1
Comparative Example
TiN
C
2200
650
140
2
Comparative Example
(Ti0.5Al0.5)N
C
2800
850
75
3
Comparative Example
0.4
0.6
0
0.6
0
0
1
0
C
2800
900
70
4
Comparative Example
0.3
0.65
0.05
0.7
0
0
1
0
H
2900
1050
65
5
Comparative Example
0.3
0.6
0.1
0.7
0
0
1
0
H
2800
1100
69
6
Comparative Example
0.3
0.6
0.15
0.75
0
0
1
0
H
2700
1150
75
7
Example
0.55
0.4
0.05
0.45
0
0
1
0
C
3000
1050
48
8
Example
0.55
0.35
0.1
0.45
0
0
1
0
C
3150
1100
30
9
Example
0.48
0.35
0.17
0.52
0
0
1
0
C
3200
1250
25
10
Example
0.45
0.3
0.25
0.55
0
0
1
0
C
3100
1250
28
11
Example
0.45
0.2
0.35
0.55
0
0
1
0
C + H
2800
1300
54
12
Comparative Example
0.3
0.3
0.4
0.7
0
0
1
0
A
2500
1300
88
13
Comparative Example
0.85
0
0.15
0.15
0
0
1
0
C
2900
900
72
14
Example
0.83
0.02
0.15
0.17
0
0
1
0
C
3000
1050
45
15
Example
0.8
0.05
0.15
0.2
0
0
1
0
C
3100
1100
38
16
Example
0.7
0.15
0.15
0.3
0
0
1
0
C
3150
1150
32
17
Example
0.55
0.3
0.15
0.45
0
0
1
0
C
3200
1250
26
18
Example
0.45
0.4
0.15
0.55
0
0
1
0
C + H
3050
1300
38
19
Comparative Example
0.35
0.5
0.15
0.65
0
0
1
0
H
2700
1300
65
20
Example
0.55
0.3
0.15
0.45
0
0
1
0
C
3200
1250
27
21
Example
0.55
0.3
0.15
0.45
0.03
0
0.97
0
C
3250
1250
25
22
Example
0.55
0.3
0.15
0.45
0.1
0
0.9
0
C
3100
1300
25
23
Example
0.55
0.3
0.15
0.45
0.15
0
0.85
0
C
3100
1300
26
24
Comparative Example
0.55
0.3
0.15
0.45
0.2
0
0.8
0
C + H
2800
1000
55
25
Example
0.52
0.35
0.13
0.48
0
0
1
0
C
3200
1250
28
26
Example
0.52
0.35
0.13
0.48
0
0.1
0.9
0
C
3250
1150
23
27
Example
0.52
0.35
0.13
0.48
0
0.4
0.6
0
C
3300
1100
25
28
Example
0.52
0.35
0.13
0.48
0
0.5
0.5
0
C
3100
1050
29
29
Comparative Example
0.52
0.35
0.13
0.48
0
0.55
0.45
0
C
2900
950
57
30
Example
0.52
0.35
0.13
0.48
0.1
0.4
0.5
0
C
3100
1100
29
31
Example
0.52
0.35
0.13
0.48
0
0
1
0
C
3200
1250
28
32
Example
0.52
0.35
0.13
0.48
0
0
0.97
0.03
C
3200
1250
24
33
Example
0.52
0.35
0.13
0.48
0
0
0.9
0.1
C
3150
1300
24
34
Example
0.52
0.35
0.13
0.48
0
0
0.8
0.2
C
3100
1300
26
35
Example
0.52
0.35
0.13
0.48
0
0
0.6
0.4
C + H
3100
1250
28
36
Comparative Example
0.52
0.35
0.13
0.48
0
0
0.45
0.55
H
2800
1100
57
The same procedure as in Example 1 was repeated except that the target was replaced by the one composed of Ti—Cr—Al—Si alloy and cutting was carried out under the following conditions.
The results of evaluation are shown in Table 2. The samples gave the same results as those in Example 1 even though they additionally contain Ti.
TABLE 2
Oxidation
starting
Amount
Composition of coating film (atomic ratio)
Crystal
Hardness
temperature
of Wear
No.
Ti
Cr
Al
Si
Al + Si
B
C
N
O
structure
(HV)
(° C.)
(μm)
1
Comparative Example
TiN
C
2200
650
200
2
Comparative Example
(Ti0.5Al0.5)N
C
2800
850
125
3
Comparative Example
0.3
0.3
0.4
0
0.4
0
0
1
0
C
2800
800
115
4
Comparative Example
0.3
0.2
0.4
0.1
0.5
0
0
1
0
C
2900
950
97
5
Example
0.23
0.25
0.4
0.12
0.52
0
0
1
0
C
3100
1150
74
6
Example
0.3
0.2
0.3
0.2
0.5
0
0
1
0
C
3200
1250
55
7
Example
0.27
0.2
0.25
0.28
0.53
0
0
1
0
C
3150
1250
57
8
Example
0.25
0.2
0.2
0.35
0.55
0
0
1
0
C + H
3050
1250
68
9
Comparative Example
0.17
0.2
0.23
0.4
0.63
0
0
1
0
A
2600
1150
135
10
Comparative Example
0.45
0.4
0
0.15
0.15
0
0
1
0
C
2850
900
126
11
Example
0.4
0.4
0.05
0.15
0.2
0
0
1
0
C
3000
1100
73
12
Example
0.35
0.3
0.2
0.15
0.35
0
0
1
0
C
3100
1200
65
13
Example
0.25
0.3
0.3
0.15
0.45
0
0
1
0
C
3200
1250
57
14
Example
0.25
0.2
0.4
0.15
0.55
0
0
1
0
C
3150
1250
62
15
Example
0.2
0.15
0.5
0.15
0.65
0
0
1
0
C + H
3100
1200
63
16
Comparative Example
0.2
0.1
0.55
0.15
0.7
0
0
1
0
H
2700
1100
110
17
Example
0.43
0.03
0.4
0.14
0.54
0
0
1
0
C
3250
1150
61
18
Example
0.36
0.1
0.4
0.14
0.54
0
0
1
0
C
3200
1150
58
19
Example
0.23
0.23
0.4
0.14
0.54
0
0
1
0
C
3150
1200
60
20
Example
0.1
0.36
0.4
0.14
0.54
0
0
1
0
C
3100
1250
61
21
Example
0.03
0.43
0.4
0.14
0.54
0
0
1
0
C
3100
1250
62
22
Example
0.32
0.2
0.35
0.13
0.48
0
0
1
0
C
3150
1200
63
23
Example
0.32
0.2
0.35
0.13
0.48
0.03
0
0.97
0
C
3200
1230
60
24
Example
0.32
0.2
0.35
0.13
0.48
0.1
0
0.9
0
C
3200
1250
57
25
Example
0.32
0.2
0.35
0.13
0.48
0.15
0
0.85
0
C
3100
1250
63
26
Comparative Example
0.32
0.2
0.35
0.13
0.48
0.2
0
0.8
0
C + H
2800
1200
87
27
Example
0.32
0.2
0.35
0.13
0.48
0
0
1
0
C
3150
1200
63
28
Example
0.32
0.2
0.35
0.13
0.48
0
0.1
0.9
0
C
3150
1200
60
29
Example
0.32
0.2
0.35
0.13
0.48
0
0.4
0.6
0
C
3200
1150
57
30
Example
0.32
0.2
0.35
0.13
0.48
0
0.5
0.5
0
C
3250
1100
67
31
Comparative Example
0.32
0.2
0.35
0.13
0.48
0
0.55
0.45
0
C
2750
950
88
32
Example
0.27
0.2
0.4
0.13
0.53
0.05
0.1
0.35
0
C
3100
1200
63
33
Example
0.32
0.2
0.35
0.13
0.48
0
0
1
0
C
3150
1200
63
34
Example
0.32
0.2
0.35
0.13
0.48
0
0
0.97
0.03
C
3150
1200
61
35
Example
0.32
0.2
0.35
0.13
0.48
0
0
0.9
0.1
C
3100
1250
59
36
Example
0.32
0.2
0.35
0.13
0.48
0
0
0.8
0.2
C
3050
1250
62
37
Example
0.32
0.2
0.35
0.13
0.48
0
0
0.6
0.4
C + H
3000
1200
65
38
Comparative Example
0.32
0.2
0.35
0.13
0.48
0
0
0.45
0.55
H
2800
1050
92
The AIP apparatus shown in
With the vacuum chamber 1 evacuated, the work W was heated to 550° C. by a heart therein, and the vacuum chamber was fed with nitrogen gas. With the pressure in the vacuum chamber 1 kept at 4 Pa, arc discharging was started to form a laminate coating film (3 μm thick) on the surface of the substrate (work W). (There are two exceptions in which one single coating film was formed or one 6-μm thick coating film was formed.) Those coating films containing C and O were formed by feeding the vacuum chamber with CH4 and O2, respectively. Incidentally, a bias voltage of −30 V to −100 V was applied to the substrate (work W) so that the substrate (work W) remained at a minus potential with respect to the earth potential during the coating process.
The resulting coating films were examined in the same way as in Example 1 (for Samples Nos. 1 to 18) and Example 2 (for Samples Nos. 21 to 35) The results are shown in Table 3.
Samples Nos. 3 to 12 and Nos. 23 to 31 conform to the sixth aspect, and Samples Nos. 13 to 15 and Nos. 32 to 34 conform to the seventh aspect. They are excellent in wear resistance. Those samples having more than one laminate layers conform to the eighth aspect. Samples Nos. 6 to 12 and Nos. 25 to 31, in which the composition and layer thickness are the same but the number of layers is varied, suggest that the coating film composed of many laminate layers, each having a small thickness, exhibit improved hardness and oxidation resistance.
TABLE 3
Film
Oxidation
Amount
Thick-
Thick-
Number
Thick-
Hard-
starting
of
Composition
ness
ness
of
ness
ness
temperature
Wear
No.
of Layer 1
(nm)
Composition of Layer 2
(nm)
layers
(nm)
(HV)
(° C.)
(μm)
1
Comparative
TiN
3000
none
—
—
3000
2200
650
140
Example
2
Comparative
Ti0.5Al0.5N
3000
none
—
—
3000
2800
850
75
Example
3
Example
Ti0.5Al0.5N
2000
(Cr0.5Al0.35Si0.15)N
1000
1
3000
3100
1150
33
4
Example
(Ti0.15Cr0.2Al0.65)N
2500
(Cr0.5Al0.35Si0.15)N
500
1
3000
3150
1200
28
5
Comparative
(Ti0.15Cr0.2Al0.65)N
0.5
(Cr0.5Al0.35Si0.15)(C0.1N0.9)
0.5
3000
3000
3100
1000
49
Example
6
Example
(Ti0.15Cr0.2Al0.65)N
2
(Cr0.5Al0.35Si0.15)N
2
750
3000
3200
1250
34
7
Example
(Ti0.15Cr0.2Al0.65)N
5
(Cr0.5Al0.35Si0.15)N
5
300
3000
3200
1250
27
8
Example
(Ti0.15Cr0.2Al0.65)N
10
(Cr0.5Al0.35Si0.15)N
10
150
3000
3250
1300
23
9
Example
(Ti0.15Cr0.2Al0.65)N
50
(Cr0.5Al0.35Si0.15)N
50
30
3000
3150
1250
28
10
Example
(Ti0.15Cr0.2Al0.65)N
100
(Cr0.5Al0.35Si0.15)N
100
15
3000
3150
1200
32
11
Example
(Ti0.15Cr0.2Al0.65)N
500
(Cr0.5Al0.35Si0.15)N
500
3
3000
3100
1150
36
12
Example
(Ti0.15Cr0.2Al0.65)N
2500
(Cr0.5Al0.35Si0.15)N
500
1
3000
3100
1150
35
13
Example
Ti
100
(Cr0.5Al0.35Si0.15)N
2900
1
3000
3150
1100
27
14
Example
Cr
50
(Cr0.5Al0.35Si0.15)N
2950
1
3000
3100
1150
26
15
Example
Ti0.5Cr0.5
30
(Cr0.5Al0.35Si0.15)N
2970
1
3000
3150
1200
24
16
Comparative
(Cr0.3Al0.65Si0.05)N
3000
—
—
—
3000
2900
1050
65
Example
17
Comparative
(Ti0.15Cr0.2Al0.65)N
3000
(Cr0.3Al0.65Si0.05)N
3000
1
6000
2950
1050
60
Example
18
Example
(Cr0.5Al0.35Si0.15)N
2500
(Cr0.5Al0.35Si0.15)(O0.1N0.9)
500
1
3000
2100
1100
35
21
Comparative
TiN
3000
none
—
—
3000
2200
650
200
Example
22
Comparative
Ti0.5Al0.5N
3000
none
—
—
3000
2800
850
125
Example
23
Example
Ti0.5Al0.5N
2000
(Ti0.3Cr0.25Al0.3Si0.15)N
1000
1
3000
3050
1100
69
24
Example
(Ti0.2Cr0.15Al0.65)N
2500
(Ti0.3Cr0.25Al0.3Si0.15)(B0.3N0.97)
500
1
3000
3150
1250
58
25
Comparative
(Ti0.2Cr0.15Al0.65)N
0.5
(Ti0.3Cr0.25Al0.3Si0.15)N
0.5
3000
3000
3050
1150
71
Example
26
Example
(Ti0.2Cr0.15Al0.65)N
2
(Ti0.3Cr0.25Al0.3Si0.15)N
2
750
3000
3150
1200
58
27
Example
(Ti0.2Cr0.15Al0.65)N
5
(Ti0.3Cr0.25Al0.3Si0.15)N
5
300
3000
3200
1250
55
28
Example
(Ti0.2Cr0.15Al0.65)N
10
(Ti0.3Cr0.25Al0.3Si0.15)N
10
150
3000
3150
1250
61
29
Example
(Ti0.2Cr0.15Al0.65)N
50
(Ti0.3Cr0.25Al0.3Si0.15)N
50
30
3000
3100
1150
65
30
Example
(Ti0.2Cr0.15Al0.65)N
100
(Ti0.3Cr0.25Al0.3Si0.15)N
100
15
3000
3050
1100
68
31
Example
(Ti0.2Cr0.15Al0.65)N
500
(Ti0.3Cr0.25Al0.3Si0.15)N
500
3
3000
3000
1100
72
32
Example
Ti
100
(Ti0.3Cr0.25Al0.3Si0.15)N
2900
1
3000
3150
1200
58
33
Example
Cr
50
(Ti0.3Cr0.25Al0.3Si0.15)N
2950
1
3000
3150
1200
57
34
Example
Ti0.5Cr0.5
30
(Ti0.3Cr0.25Al0.3Si0.15)N
2970
1
3000
3150
1200
58
35
Example
(Ti0.3Cr0.25Al0.3Si0.15)N
2500
(Ti0.3Cr0.25Al0.3Si0.15)(O0.1N0.9)
500
1
3000
3100
1150
57
Coating on substrates was carried out in the same way as in Example 1 by using the AIP apparatus shown in
It is apparent from Table 4 that those samples prepared by either sputtering or arc process according to Examples 1 and 2 are superior to conventional samples in crystal structure, hardness, oxidation starting temperature, and amount of wear, when the target of the same composition was used.
TABLE 4
Type of
Crystal
Hardness
Oxidation starting
Amount of wear
No.
evaporation source
Composition of coating
structure
(HV)
temp (° C.)
(μm)
1
Sputter (conventional)
TiN
C
2000
650
140
2
Arc (conventional)
Ti0.5Al0.5N
C
2800
850
75
3
Arc (present invention)
(Cr0.58Al0.3Si0.12)N
C
3150
1100
31
4
Arc (present invention)
(Cr0.5Al0.3Si0.2)N
C
3250
1200
25
5
Arc (present invention)
(Cr0.45Al0.4Si0.15)N
C
3150
1250
24
6
Arc (present invention)
(Cr0.45Al0.35Si0.2)N
C
3100
1250
27
7
Arc (conventional)
(Cr0.58Al0.3Si0.12)N
C
3100
1100
37
8
Arc (conventional)
(Cr0.5Al0.3Si0.2)N
C
3150
1200
31
9
Arc (conventional)
(Cr0.45Al0.4Si0.15)N
C + H
3100
1200
29
10
Arc (conventional)
(Cr0.45Al0.35Si0.2)N
C + H
3050
1250
33
11
Sputter (present invention)
(Cr0.58Al0.3Si0.12)N
C
3150
1050
34
12
Sputter (present invention)
(Cr0.5Al0.3Si0.2)N
C
3200
1150
27
13
Sputter (present invention)
(Cr0.45Al0.4Si0.15)N
C
3100
1200
26
14
Sputter (present invention)
(Cr0.45Al0.35Si0.2)N
C + H
3100
1200
34
15
Sputter (conventional)
(Cr0.58Al0.3Si0.12)N
C
3100
1000
41
16
Sputter (conventional)
(Cr0.5Al0.3Si0.2)N
C
3100
1100
38
17
Sputter (conventional)
(Cr0.45Al0.4Si0.15)N
C + H
3050
1150
29
18
Sputter (conventional)
(Cr0.45Al0.35Si0.2)N
C + H
3000
1150
37
21
Sputter (conventional)
TiN
C
2000
650
200
22
Arc (conventional)
Ti0.5Al0.5N
C
2800
850
125
23
Arc (present invention)
(Ti0.3Cr0.28Al0.3Si0.12)N
C
3100
1150
65
24
Arc (present invention)
(Ti0.25Cr0.25Al0.3Si0.2)N
C
3200
1200
55
25
Arc (present invention)
(Ti0.2Cr0.25Al0.4Si0.15)N
C
3100
1200
57
26
Arc (present invention)
(Ti0.2Cr0.2Al0.4Si0.2)N
C
3100
1250
61
27
Arc (conventional)
(Ti0.3Cr0.28Al0.3Si0.12)N
C
3100
1100
69
28
Arc (conventional)
(Ti0.25Cr0.25Al0.3Si0.2)N
C
3100
1150
61
29
Arc (conventional)
(Ti0.2Cr0.25Al0.4Si0.15)N
C + H
3050
1200
63
30
Arc (conventional)
(Ti0.2Cr0.2Al0.4Si0.2)N
C + H
3000
1200
69
31
Sputter (present invention)
(Ti0.3Cr0.28Al0.3Si0.12)N
C
3100
1100
65
32
Sputter (present invention)
(Ti0.25Cr0.25Al0.3Si0.2)N
C
3150
1150
59
33
Sputter (present invention)
(Ti0.2Cr0.25Al0.4Si0.15)N
C
3050
1150
61
34
Sputter (present invention)
(Ti0.2Cr0.2Al0.4Si0.2)N
C + H
3050
1200
63
35
Sputter (conventional)
(Ti0.3Cr0.28Al0.3Si0.12)N
C
3050
1050
72
36
Sputter (conventional)
(Ti0.25Cr0.25Al0.3Si0.2)N
C
3100
1100
69
37
Sputter (conventional)
(Ti0.2Cr0.25Al0.4Si0.15)N
C + H
3000
1150
69
38
Sputter (conventional)
(Ti0.2Cr0.2Al0.4Si0.2)N
C + H
3000
1150
72
Yamamoto, Kenji, Kujime, Susumu
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