Process for producing cermet cutting tools having both longitudinal and granular crystal structures

BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention is a continuation-in-part application of U.S. patent application Ser. No. 644,446, now abandoned, and relates to a cermet cutting tool, and process for producing the same, in which a hard coating layer is formed onto the surface of a titanium carbo-nitride based cermet substrate. In particular, the present invention pertains to improvements for enhancing the chipping resistance and wear resistance of the blade member.
2. Background Art
Conventionally, cermets, containing at least one metal of carbide, nitride and carbo-nitride of titanium (Ti), zirconium (Zr), hafnium (Hf), tantalum (Ta), niobium (Nb), tungsten (W), molybdenum (Mo) and chromium (Cr) as a hard phase-constituting component and iron family metals such as cobalt (Co), nickel (Ni) and the like as binder metals, have been widely used to form blade members or inserts for use in finish cutting of steel.
In recent years, the aforementioned cermets possessing surface coatings composed of TiC, TiCN and the like, which further improve wear resistance, are being produced.
For example, Japanese Patent Application First Publication No. Sho 54-117510 discloses a cermet cutting tool which is formed by applying to a titanium carbo-nitride based cermet substrate using a chemical vapor deposition process, a hard coating layer of thickness 0.5.about.20 .mu.m which is formed from at least one layer of a compound selected from the group consisting of titanium carbide (TiC), titanium nitride (TiN), titanium carbo-nitride (TiCN), titanium carbo-oxide (TiCO), titanium carbo-oxi-nitride (TiCNO) and aluminum oxide (Al.sub.2 O.sub.3). In addition, as the substrate, use of a TiCN based cermet in which the incorporated amount of binding phase-constituting component, Co or Ni, is comparatively higher in the surface layer portion when compared to the substrate interior, is known.
In this case, as the chemical vapor deposition process, a conventional process is employed in which a TiCN coating layer is formed onto the cermet surface using a mixed gas composed of 4% of TiCl.sub.4, 3% of CH.sub.4, 4% of N.sub.2, and 89% of H.sub.2 (% by volume) at a temperature of 1000.degree. C. and a pressure of 100 Torr inside the chemical vapor deposition apparatus. The reaction in this case is represented by the following formula:
TiCl.sub.4 +CH.sub.4 + 1/2N.sub.2 +H.sub.2 .fwdarw.TiCN+4HCl+H.sub.2
However, when the aforementioned prior art cermet cutting tools are used in steel and cast-iron high-speed cutting inserts, chipping of the cutting insert occurs easily due to the lack of toughness of the hard coating layer, and considerable wear occurs due to this chipping, thereby exhausting the tool life in a comparatively short time.
One source generating the aforementioned problems lies in the fact that the binding phase-constituting component (Ni or Co) diffuses into the TiCN layer during chemical vapor deposition, creating a materially inferior TiCN layer. In other words, the iron family metals such as Co and Ni which comprise the binding phase-constituting components, due to the high coating temperature (1000.degree. C.) of prior art chemical vapor deposition processes, diffuse into the TiCN layer and cause loss of the original wear resistance, resulting in formation of a coating layer possessing a low wear resistance. However, if chemical vapor deposition is attempted at a temperature of 900.degree. C. or less where it is difficult for the binding phase-constituting component to diffuse into the TiCN layer, the activity of reaction gases such as methane, nitrogen and the like is reduced, and the reaction does not occur, which results in the TiCN coating layer being unobtainable. Consequently, under the aforementioned temperature conditions of the prior art, a coating layer cannot be formed.
The inventors of the present invention have conducted various research in order to obtain a TiCN coating layer with superior wear resistance by efficient chemical vapor deposition of a TiCN layer at a temperature of 900.degree. C. or less, where it is difficult for the aforementioned binding phase-constituting component to diffuse into the TiCN layer. As a result, when adding acetonitrile (CH.sub.3 CN) to the mixed gas used in the chemical vapor deposition, highly efficient formation of a TiCN coating layer is possible even when chemical vapor deposition is performed at a temperature of 900.degree. C. or less: the TiCN coating layer formed in this manner, due to non-diffusion of the aforementioned binding phase-constituting component, was confirmed by observation to possess a superior wear resistance.
Furthermore, the inventors of the present invention, in order to further improve the wear resistance of the TiCN layer, have continued their research. As a result, they have discovered a novel development in that when chemical vapor deposition is performed using a reaction gas composed of 1.about.5% of TiCl.sub.4, 0.1.about.1% of CH.sub.3 CN, 0.about.25% of N.sub.2 with the remaining portion being composed of H.sub.2, under a reaction temperature of 800.degree..about.900.degree. C. and a reaction pressure of 30.about.200 Torr, at least one portion of the TiCN layer comprises a longitudinal growth crystal structure, which is a change from the normal granular crystal structure, resulting in further improvement of both the chipping resistance and the wear resistance.
SUMMARY OF THE INVENTION
The present invention is based on this aforementioned discovery, and it is therefore an object of the present invention to provide, by means of improving the toughness of the hard coating layer, a cermet cutting tool, and process for producing the same, with improved chipping resistance and wear resistance of the cutting insert.
In order to achieve this objective, a first aspect of the present invention is directed to providing a cermet cutting tool comprising the following:
a. a substrate formed from titanium carbo-nitride based cermet; and
b. a hard coating layer of average thickness 0.5.about.20 .mu.m, formed onto the surface of the aforementioned substrate; this layer being formed from at least one layer of a compound selected from the group consisting of titanium carbide (TiC), titanium nitride (TiN), titanium carbo-nitride (TiCN), titanium carbo-oxide (TiCO), titanium carbo-oxi-nitride (TiCNO) and aluminum oxide (Al.sub.2 O.sub.3); wherein at least one of the layers comprising the aforementioned hard coating layer is a titanium carbo-nitride layer, and at least one layer of this titanium carbo-nitride layer comprises a longitudinal growth crystal structure.
In addition, a second aspect of the present invention is directed to providing a cermet cutting tool comprising the following:
a. a substrate formed from titanium carbo-nitride based cermet; and
b. a hard coating layer of average thickness 0.5.about.20 .mu.m, formed onto the surface of the aforementioned substrate comprising at least one layer of the compound titanium carbo-nitride; the aforementioned at least one layer of the compound titanium carbo-nitride comprising the above-mentioned hard coating layer comprises at least one of the following crystal structures:
(1) a crystal structure which changes from a granular crystal structure to a longitudinal growth crystal structure as it progresses away from the aforementioned substrate;
(2) a crystal structure which changes from a granular crystal structure to a longitudinal growth crystal structure and back to a granular crystal structure as it progresses away from the aforementioned substrate; and
(3) a crystal structure which changes from a longitudinal growth crystal structure to a granular crystal structure as it progresses away from the aforementioned substrate.
Furthermore, a third aspect of the present invention is directed to providing a cermet cutting tool comprising the following:
a. a substrate formed from titanium carbo-nitride based cermet; and
b. a hard coating layer of average thickness 0.5.about.20 .mu.m, formed onto the surface of the aforementioned substrate comprising a lower layer composed of at least one layer of the compound titanium carbo-nitride, and an upper layer formed from at least one layer of a compound selected from the group consisting of titanium carbide (TiC), titanium nitride (TiN), titanium carbo-nitride (TiCN), titanium carbo-oxide (TiCO), titanium carbo-oxi-nitride (TiCNO) and aluminum oxide (Al.sub.2 O.sub.3); the entire aforementioned lower layer comprises at least one of the following crystal structures:
(1) a crystal structure which changes from a granular crystal structure to a longitudinal growth crystal structure as it progresses away from the aforementioned substrate;
(2) a crystal structure which changes from a granular crystal structure to a longitudinal growth crystal structure and back to a granular crystal structure as it progresses away from the aforementioned substrate; and
(3) a crystal structure which changes from a longitudinal growth crystal structure to a granular crystal structure as it progresses away from the aforementioned substrate.
A fourth aspect of the present invention is directed to providing a cermet cutting tool comprising the following:
a. a substrate formed from titanium carbo-nitride based cermet; and
b. a hard coating layer of average thickness 0.5.about.20 .mu.m, formed onto the surface of the aforementioned substrate comprising a lower layer formed from at least one layer of a compound selected from the group consisting of titanium carbide (TiC), titanium nitride (TiN), titanium carbo-nitride (TiCN), titanium carbo-oxide (TiCO) and titanium carbo-oxi-nitride (TiCNO), and an upper layer formed from at least one layer of a compound selected from the group consisting of titanium carbide (TiC), titanium nitride (TiN), titanium carbo-nitride (TiCN), titanium carbo-oxide (TiCO), titanium carbo-oxi-nitride (TiCNO) and aluminum oxide (Al.sub.2 O.sub.3); wherein at least one of the layers comprising the aforementioned upper layer is a titanium carbo-nitride layer, and at least one layer of this titanium carbo-nitride layer comprises at least one of the following crystal structures:
(1) a crystal structure which changes from a granular crystal structure to a longitudinal growth crystal structure as it progresses away from the aforementioned substrate;
(2) a crystal structure which changes from a granular crystal structure to a longitudinal growth crystal structure and back to a granular crystal structure as it progresses away from the aforementioned substrate; and
(3) a crystal structure which changes from a longitudinal growth crystal structure to a granular crystal structure as it progresses away from the aforementioned substrate.
In all of the cermet cutting tools provided in aforementioned first through fourth aspects of the present invention, if the average thickness of the hard coating layer is less than 0.5 .mu.m, sufficient wear resistance is unobtainable due to this hard coating layer. On the other hand, if the average thickness of the hard coating layer exceeds 20 .mu.m, chipping of the cutting insert occurs easily and a superior wear resistance becomes impossible to obtain.
The cermet comprising the aforementioned substrate contains 70.about.95% by weight of a solid solution of carbo-nitride represented by the formula (Ti.sub.x M.sub.y)(C.sub.u N.sub.v), (wherein M is at least one metal selected from the group consisting of transition metals in groups IV.sub.A, V.sub.A and VI.sub.A of the Periodic Table with the exception of titanium, and x, y, u and v are molar ratios which satisfy the relations of x+y=1, u+v=1, 0.5.ltoreq.x.ltoreq.0.95, 0.05.ltoreq.y.ltoreq.0.5, 0.2.ltoreq.u.ltoreq.0.8 and 0.2.ltoreq.v.ltoreq.0.8) as the hard-dispersed phase-constituting component, with the remainder comprising one or two metals selected from the group consisting of cobalt and nickel as a binder phase-constituting component.
If the content of the aforementioned hard-dispersed phase-constituting component is less than 70% by weight and the content of the binder phase-constituting component exceeds 30% by weight, the wear resistance of the cermet substrate is lowered. On the other hand, if the content of hard-dispersed phase-constituting component exceeds 95% by weight and the content of the binder phase-constituting component is less than 5% by weight, the cermet substrate becomes susceptible to chipping, in other words, the chipping resistance is poor, both of which are undesirable results.
It is possible for the incorporated amount of the aforementioned binder phase-constituting component to be relatively greater in the surface portion of the aforementioned cermet when compared with that of the substrate interior. In the case when the incorporated amount of the binder phase-constituting component is greater at the substrate surface, the chipping resistance of the cermet cutting tool is further improved.
Each of the cermet cutting tools of the present invention having the aforementioned respective structures, as a result of possessing a hard coating layer with a high toughness at least one portion of which comprises a TiCN layer with a longitudinal growth crystal structure, displayed a superior wear resistance when used in steel and cast-iron high-speed cutting inserts which, in particular, demand a high resistance to chipping. Consequently, superior cutting properties can be maintained over a long period of time.
In addition, the process for producing the cermet cutting tool of the present invention comprises the following steps:
a. a step for preparing a substrate from a titanium carbo-nitride based cermet;
b. a step for forming a hard coating layer onto the surface of the aforementioned substrate using a chemical vapor deposition method wherein in at least one part of this step, chemical vapor deposition is performed using a reaction gas composed of 1.about.5% of TiCl.sub.4, 0.1.about.1% of CH.sub.3 CN, 0.about.25% of N.sub.2 with the remaining portion being composed of H.sub.2, under a reaction temperature of 800.degree..about.900.degree. C. and a reaction pressure of 30.about.200 Torr.
In this process, the reaction in which TiCN is formed is represented by the following formula:
TiCl.sub.4 +CH.sub.3 CN+ 5/2H.sub.2 .fwdarw.TiCN+4HCl+CH.sub.4
By means of the aforementioned process, a hard coating layer incorporating a TiCN layer with at least one portion containing longitudinal growth crystal structure can be formed, and the chipping and wear resistances of this hard coating layer can be improved. In addition, in accordance with this process, diffusion of the binding phase-constituting component of the titanium carbo-nitride based cermet into the TiCN layer is extremely low, thus reduction of the material quality of the TiCN layer stemming from diffusion of the binding phase-constituting component can be prevented, resulting in the enhancement of both chipping and wear resistances.
However, if the aforementioned reaction temperature is less than 800.degree. C., it becomes impossible to form a TiCN layer with longitudinal growth crystal structure. However, if this reaction temperature exceeds 900.degree. C., the binding phase-constituting component diffuses into the TiCN coating layer resulting in formation of a coating layer with low wear resistance, both of which are undesirable. In addition, if the reaction pressure is less than 30 Torr, the reaction time is too long, which is an industrially undesirable result. On the other hand, if the reaction pressure exceeds 200 Torr, the reaction speed is too fast resulting in a non-uniform membrane thickness. In addition, if any of the concentrations of the TiCl.sub.4, CH.sub.3 CN, and N.sub.2 components of the aforementioned reaction gas fall outside the above prescribed ranges, formation of a TiCN layer with longitudinal growth crystal structure becomes difficult.
It is also possible to form a TiN layer above and/or below the TiCN layer. As the method for forming this TiN layer, conventional methods known in the prior art in which chemical vapor deposition is performed using nitrogen gas or ammonium gas may be employed. In forming the TiN layer, a reaction temperature of 900.degree. C. or greater is required. In addition, the wettability of the TiN layer with the binding phase-constituting component of the cermet substrate (ie. Co or Ni) is low, which results in greater prevention of diffusion of the binding phase-constituting component into the TiCN layer. In this case, the membrane thickness of the TiN layer is preferably less than 4 .mu.m.

BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is an enlarged photograph displaying a cross-sectional view of the surface portion of a cermet cutting tool (cutting tool 2 of the present invention) according to the present invention taken by scanning electron microscope.
FIG. 2 is an enlarged photograph displaying a cross-sectional view of the surface portion of a prior art cermet cutting tool (prior art cutting tool 2) taken by scanning electron microscope.
FIG. 3 is an enlarged photograph displaying a cross-sectional view of the surface portion of a cermet cutting tool (cutting tool 13 of the present invention) according to the present invention taken by scanning electron microscope.
FIG. 4 is an enlarged photograph displaying a cross-sectional view of the surface portion of a prior art cermet cutting tool (prior art cutting tool 15) taken by scanning electron microscope.
FIG. 5 is an enlarged photograph displaying a cross-sectional view of the surface portion of a cermet cutting tool (cutting tool 31 of the present invention) according to the present invention taken by scanning electron microscope.
FIG. 6 is an enlarged photograph displaying a cross-sectional view of the surface portion of a prior art cermet cutting tool (prior art cutting tool 26) taken by scanning electron microscope.
FIG. 7 is an enlarged photograph displaying a cross-sectional view of the surface portion of a cermet cutting tool (cutting tool 38 of the present invention) according to the present invention taken by scanning electron microscope.
FIG. 8 is an enlarged photograph displaying a cross-sectional view of the surface portion of a prior art cermet cutting tool (prior art cutting tool 27) taken by scanning electron microscope.

EXAMPLES
The present invention will now be explained with reference to the Examples.
Example 1
Powders of TiCN, TiC, TiN, TaC, NbC, WC, Mo.sub.2 C, ZrC, Co and Ni each having a predetermined average particle size within the range of 1.about.3 .mu.m, were prepared as starting materials. These starting materials were combined so as to produce the composition shown in TABLE 1, and were mixed together for 72 hours using a ball mill under wet conditions. After drying, the resultant mixed powder was pressed and a large number of green compact bodies were formed.
A portion of these compacted bodies were then sintered at a fixed temperature from 1450.degree..about.1500.degree. C. for one hour under 10.sup.-2 Torr in a vacuum to produce TiCN based cermet substrates A.about.D in which the binding phase-constituting component was not contained in a relatively larger amount at the surface layer portion.
The remainder of the aforementioned compacted bodies were first heated under rising temperature and brought to sintering temperature under 10.sup.-2 Torr in a vacuum; after reaching a predetermined temperature within the range of 1450.degree..about.1550.degree. C., the sintering conditions were changed to 10 Torr in N.sub.2 environment and maintained for one hour; and cooling from sintering temperature was performed in a vacuum under 0.1 Torr to produce TiCN based cermet substrates E and F in which the binding phase-constituting component was contained in a relatively larger amount at the surface layer portion. The respective thicknesses of the surface layer portions of these substrates E and F, and the maximum amount of binding phase-constituting component incorporated into these surface layer portions are shown in TABLE 1.
Furthermore, all of the aforementioned TiCN based cermet substrates A.about.F were shaped to conform to cutting chip standards of ISO-CNMG120408.
Each respective type of coating layer comprising granular crystal structures, and TiCN layers comprising longitudinal growth crystal structures were formed onto the surfaces of the aforementioned TiCN based cermet substrates A.about.F using a conventional chemical vapor deposition apparatus, according to the layer constructions shown in TABLES 3 and 4, to produce cutting tools 1.about.12 of the present invention. The coating layers comprising granular crystal structures were formed under the conditions shown in TABLE 2, while the TiCN layers comprising longitudinal growth crystal structures were formed under the following conditions.
Conditions for Forming Longitudinal Growth Crystal Structure
Reaction gas composition:
TiCl.sub.4 --1.5% by volume
CH.sub.3 CN--0.5% by volume
N.sub.2 --25% by volume
H.sub.2 --73% by volume
Reaction temperature: 860.degree. C.
Pressure: 50 Torr
On the other hand, under the conditions shown in TABLE 2, the hard coating layers, comprising granular crystal structures and having the respective average thicknesses and compositions shown in TABLES 4 and 5, were formed onto the surfaces of the aforementioned TiCN based cermet substrates A.about.F to produce prior art TiCN based cermet cutting tools 1.about.12.
Subsequently, all of the cermet cutting tools were subjected to both a steel wet-type continuous hitch-speed cutting test and a steel dry-type intermittent high-speed cutting test. The continuous cutting test measured the amount of flank wear of the cutting edge, while the intermittent cutting test measured the amount of time necessary to reach the limits of tool life with chipping as the source. The results of these tests are shown in TABLE 6, with the cutting test conditions as follows:
Continuous cutting test conditions
Workpiece: Round bar (JIS. SCM440)
Cutting speed: 250 m/min.
Feed rate: 0.2 mm/rev.
Depth of cut: 1 mm
Cutting time: 30 min.
Intermittent Cutting Test Conditions
Workpiece: Round bar with 4 longitudinal grooves (JIS. SNCM439)
Cutting speed: 200 m/min.
Feed rate: 0.2 mm/rev.
Depth of cut: 1 mm
In addition, photographs enlarged 5000 times displaying the longitudinal cross-sectional structures of the surface portions of cutting tool 2 of the present invention and cutting tool 2 of the prior art, as taken by scanning electron microscope, are shown in FIGS. 1 and 2.
As seen from the results of TABLES 1.about.6 and FIGS. 1.about.2, cermet cutting tools 1.about.12 of the present invention possessing at least one TiCN layer in their hard coating layer, and at least one layer within this TiCN layer comprising a longitudinal growth crystal structure, display superior wear resistance in steel high-speed continuous cutting and superior chipping resistance in high-speed intermittent cutting, and consequently display superior cutting properties over a long period of time when compared with prior art cutting tools 1.about.12, all of which are formed with a hard coating layer consisting of granular crystal structure.
Example 2
Powders of TiCN, TiC, TiN, TaC, NbC, WC, Mo.sub.2 C, ZrC, Co and Ni each having a predetermined average particle size within the range of 1.about.2 .mu.m, were prepared as starting materials. These starting materials were combined so as to produce the compositions shown in TABLE 7, and processed under the same conditions as in Example 1 to produce TiCN based cermet substrates G.about.I, in which the binding phase-constituting component was not contained in a relatively larger amount at the surface layer portion, and TiCN based cermet substrates J.about.L, in which the binding phase-constituting component was contained in a relatively larger amount at the surface layer portion. The thicknesses of the surface layer portions of the substrates containing the binding phase-constituting component in a relatively larger amount, and the maximum amount of binding phase-constituting component incorporated into these surface layer portions are shown together in TABLE 7.
Subsequently, TiCN layers comprising granular crystal structures, and TiCN layers comprising longitudinal growth crystal structures were formed onto the surfaces of the aforementioned TiCN based cermet substrates G.about.L using a conventional chemical vapor deposition apparatus under the following conditions, according to the respective layer constructions and thicknesses shown in TABLES 8 and 9, to produce cutting tools 13.about.24 of the present invention.
Conditions for Forming TiCN Granular Crystal Structure
Reaction gas composition:
TiCl.sub.4 --3% by volume
CH.sub.4 --5% by volume
N.sub.2 --25% by volume
H.sub.2 --67% by volume
Reaction temperature: 1020.degree. C.
Pressure: 100 Torr
Conditions for Forming Longitudinal Growth Crystal Structure
Reaction gas composition:
TiCl.sub.4 --1.5% by volume
CH.sub.3 CN--0.5% by volume
N.sub.2 --25% by volume
H.sub.2 --73% by volume
Reaction temperature: 860.degree. C.
Pressure: 50 Torr
On the other hand, TiCN layers all comprising granular crystal structures were formed onto the surfaces of the aforementioned TiCN based cermet substrates G.about.L, as shown in TABLE 9, under exactly the same conditions as the aforementioned products of the present invention to produce prior art TiCN based cermet cutting tools 13.about.18.
Subsequently, all of the cermet cutting tools were subjected to both a steel dry-type continuous high-speed cutting test and a cast-iron wet-type high-speed cutting test under the conditions outlined below, and the amount of flank wear of the cutting edge was measured. The results of these tests are shown in TABLES 8 and 9.
Steel Dry-Type High-Speed Cutting Test Conditions
Workpiece: SCM440; Hardness: H.sub.B 220
Cutting speed: 250 m/min.
Feed rate: 0.2 mm/rev.
Depth of cut: 1 mm
Cutting time: 30 min.
Cast-Iron Wet-Type High-Speed Cutting Test Conditions
Workpiece: FC30; Hardness: H.sub.B 200
Cutting speed: 300 m/min.
Feed rate: 0.2 mm/rev.
Depth of cut: 1 mm
Cutting time: 30 min.
In addition, photographs enlarged 5000 times displaying the longitudinal cross-sectional structures of the surface portions of cutting tool 13 of the present invention and cutting tool 15 of the prior art, as taken by scanning electron microscope, are shown in FIGS. 3 and 4. As shown in FIG. 3, cutting tool 13 of the present invention is formed with a crystal structure which changes from a granular crystal structure to a longitudinal growth crystal structure and then back to a granular crystal structure as it progresses away from the substrate. In contrast, prior art cutting tool 15, as shown in FIG. 4, comprises a TiCN layer comprising only a granular crystal structure.
As seen from the results of TABLES 8.about.9 and FIGS. 3.about.4, cermet cutting tools 13.about.24 of the present invention possessing within a TiCN layer comprising the hard coating layer, at least one layer consisting of a crystal structure which changes from a granular crystal structure to a longitudinal growth crystal structure, a crystal structure which changes from a granular crystal structure to a longitudinal growth crystal structure and then back to a granular crystal structure, or a crystal structure which changes from a longitudinal growth crystal structure to a granular crystal structure, as it progresses away from the substrate, display superior wear resistance and chipping resistance in steel and cast-iron high-speed cutting where chipping occurs easily, when compared with prior art cutting tools 13.about.18.
Example 3
TiCN based cermet substrates G.about.I, in which the binding phase-constituting component was not contained in a relatively larger amount at the surface layer portion, and TiCN based cermet substrates J.about.L, in which the binding phase-constituting component was contained in a relatively larger amount at the surface layer portion were produced using the same composition and process as with the cermet substrates of Example 2.
Subsequently, TiCN layers consisting of granular crystal structures, and TiCN layers consisting of longitudinal growth crystal structures were formed onto the surfaces of the aforementioned TiCN based cermet substrates G.about.L using a conventional chemical vapor deposition apparatus, under the same conditions as in Example 2, to produce a TiCN lower layer. Furthermore, on top of this lower layer an upper layer, comprising a granular crystal structure and possessing the compositions and thicknesses shown in TABLE 10, was formed using a conventional chemical vapor deposition apparatus under the general conditions shown in TABLE 11 to produce cermet cutting tools 25.about.32 of the present invention.
On the other hand, hard coating layers, comprising granular crystal structures and possessing the respective compositions and thicknesses shown in TABLE 12, were formed onto the surfaces of the aforementioned TiCN based cermet substrates G.about.L, under the general conditions shown in TABLE 11, to produce prior art TiCN based cermet cutting tools 19.about.26.
Subsequently, all of the cermet cutting tools were subjected to both a steel dry-type high-speed cutting test and an cast-iron wet-type high-speed cutting test as in Example 2, and the amount of flank wear of the cutting edge was measured. The results of these tests are shown in TABLE 13.
In addition, photographs enlarged 5000 times displaying the longitudinal cross-sectional structures of the surface portions of cutting tool 31 of the present invention and cutting tool 25 of the prior art, as taken by scanning electron microscope, are shown in FIGS. 5 and 6. As shown in FIG. 5, cutting tool 31 of the present invention is formed with a hard coating layer comprising a lower TiCN layer which changes from a granular crystal structure to a longitudinal growth crystal structure as it progresses away from the substrate, and an upper TiCN layer comprising a granular crystal structure. In contrast, prior art cutting tool 25, as shown in FIG. 6, comprises TiCN and TiN layers formed with only a granular crystal structure.
As seen from the results of TABLES 10.about.13 and FIGS. 5.about.6, cermet cutting tools 25.about.32 of the present invention possessing a hard coating layer comprising a TiCN layer in which at least one layer comprises a crystal structure which changes from a granular crystal structure to a longitudinal growth crystal structure, a crystal structure which changes from a granular crystal structure to a longitudinal growth crystal structure and then back to a granular crystal structure, or a crystal structure which changes from a longitudinal growth crystal structure to a granular crystal structure, as it progresses away from the substrate, display superior wear resistance and chipping resistance in steel and cast-iron high-speed cutting where chipping occurs easily, when compared with prior art cutting tools 19.about.26.
Example 4
TiCN based cermet substrates G.about.I, in which the binding phase-constituting component was not contained in a relatively larger amount at the surface layer portion, and TiCN based cermet substrates J.about.L, in which the binding phase-constituting component was contained in a relatively larger amount at the surface layer portion, were produced using the same composition and process as with the cermet substrates of Example 2.
Subsequently, onto each surface of the aforementioned TiCN based cermet substrates G.about.L, a lower layer comprising at least one layer consisting of a granular crystal structure and possessing the respective compositions and thicknesses shown in TABLE 14, was formed using a conventional chemical vapor deposition apparatus under the conditions shown in TABLE 11.
Following this, under the same conditions as shown in TABLE 11, the upper layers, each comprising at least one layer and possessing the respective compositions and thicknesses shown in TABLE 14, were formed. These upper layers each comprise at least one TiCN layer, and at least one layer within each respective TiCN layer was combined under the granular crystal structure forming conditions or longitudinal growth crystal structure forming conditions described below, to produce cermet cutting tools 33.about.40 of the present invention possessing the crystal structures shown in TABLE 14.
Conditions for Forming TiCN Granular Crystal Structure
Reaction gas composition:
TiCl.sub.4 --3% by volume
CH.sub.4 --5% by volume
N.sub.2 --25% by volume
H.sub.2 --67% by volume
Reaction temperature: 950.degree. C.
Pressure: 100 Torr
Conditions for Forming Longitudinal Growth Crystal Structure
Reaction gas composition:
TiCl.sub.4 --1.5% by volume
CH.sub.3 CN--0.5% by volume
N.sub.2 --25% by volume
H.sub.2 --73% by volume
Reaction temperature: 860.degree. C.
Pressure: 50 Torr
On the other hand, hard coating layers, comprising granular crystal structures and possessing the respective compositions and thicknesses shown in TABLE 15, were formed onto the surfaces of the aforementioned TiCN based cermet substrates G.about.L, under the general conditions shown in TABLE 11, to produce prior art TiCN based cermet cutting tools 27.about.34.
Subsequently, all of the cermet cutting tools were subjected to both a steel dry-type high-speed cutting test and an cast-iron wet-type high-speed cutting test as in Example 2, and the amount of flank wear of the cutting edge was measured. The results of these tests are shown in TABLE 16.
In addition, photographs enlarged 5000 times displaying the longitudinal cross-sectional structures of the surface portions of cutting tool 38 of the present invention and cutting tool 32 of the prior art, as taken by scanning electron microscope, are shown in FIGS. 7 and 8.
As seen from the results of TABLES 14.about.16 and FIGS. 7.about.8, cermet cutting tools 33.about.40 of the present invention, comprising as the upper layer of the hard coating layer, at least one TiCN layer comprising a crystal structure which changes from a granular crystal structure to a longitudinal growth crystal structure, a crystal structure which changes from a granular crystal structure to a longitudinal growth crystal structure and then back to a granular crystal structure, or a crystal structure which changes from a longitudinal growth crystal structure to a granular crystal structure, as it progresses away from the substrate, display superior wear resistance and chipping resistance in steel and cast-iron high-speed cutting where chipping occurs easily, when compared with prior art cutting tools 27.about.34.
TABLE 1__________________________________________________________________________ Binding phaseCermet enhanced surface portionsubstrate Mix incorporated Thick-classifi- Distributional Composition (% by weight) amt. of binding nesscation Co Ni TaC NbC WC Mo.sub.2 C ZrC TiC TiN TiCN phase (% by wt) (.mu.m)__________________________________________________________________________A 8 4 9 1 15 8 0.5 R 20 -- -- --B 8 6 10 1 10 8 -- -- 5 -- --C 12 6 9 1 15 9 0.5 R 20 -- -- --D 14 4 15 2 16 -- 0.3 R 20 -- --E 12 4 10 1 15 -- 0.5 18 R -- 26 20F 7 7 12 1 16 -- 0.2 -- 5 R 21 30__________________________________________________________________________ R = Remaining portion
TABLE 2__________________________________________________________________________Hard cover- Conditions for forming the hard covering layer granular crystal structureing layer Reaction environmentcomposition Reaction gas composition (% by volume) Pressure (Torr) Temp (.degree.C.)__________________________________________________________________________TiC TiCl.sub.4 : 4%, CH.sub.4 : 5%, H.sub.2 : 91% 100 1030TiN TiCl.sub.4 : 4%, N.sub.2 : 8%, H.sub.2 : 88% 100 980TiCN TiCl.sub.4 : 4%, CH.sub.4 : 3%, N.sub.2 : 4%, H.sub.2 : 100 1000TiCO TiCl.sub.4 : 4%, CO: 6%, H.sub.2 : 90% 100 1000TiCNO TiCl.sub.4 : 4%, CO: 3%, N.sub.2 : 3%, H.sub.2 : 100 1000Al.sub.2 O.sub.3 AlCl.sub.3 : 3%, CO.sub.2 : 5%, H.sub.2 : 92% 100 1000__________________________________________________________________________
TABLE 3__________________________________________________________________________ Hard covering layerClassi- First Layer Second Layerfication Aver- Aver-(Cutting Sub- age age Third Layer Fourth Layer Fifth Layertool of strate Com- thick- Com- thick Com- Average Com- Average Com- Averagethe present num- position ness position ness position thickness position thickness position thicknessinvention) ber (structure) (.mu.m) (structure) (.mu.m) (structure) (.mu.m) (structure) (.mu.m) (structure) (.mu.m)__________________________________________________________________________1 A TiN (P) 1 TiCN (L) 6 TiN (P) 0.5 -- -- -- --2 TiC (P) 1 TiCN (L) 6 -- -- -- -- -- --3 B TiN (P) 1 TiCN (L) 6 TiN (P) 1 -- -- -- --4 TiC (P) 1 TiCN (P) 1 TiCN (L) 5 TiCN (P) 1 TiN 1P)5 C TiC (P) 1 TiCN (L) 4 TiN (P) 0.5 -- -- -- --6 TiC (P) 1 TiCN (L) 4 TiCO (P) 0.5 Al.sub.2 O.sub.3 1.5 TiN 0.57 D TiN (P) 0.5 TiCN (L) 3 TiN (P) 0.5 -- -- -- --8 TiCN (P) 1 TiCN (L) 3 TiCN (P) 1 TiCN (L) 2 TiN 0.5__________________________________________________________________________ P = Granular crystal structure; L = Longitudinal crystal structure
TABLE 4__________________________________________________________________________ Hard covering layerSub- First Layer Second Layer Third Layer Fourth Layer Fifth LayerClas- strate Com- Average Com- Average Com- Average Com- Average Com- Averagesifi- num- position thickness position thickness position thickness position thickness position thicknesscation ber (structure) (.mu.m) (structure) (.mu.m) (structure) (.mu.m) (structure) (.mu.m) (structure) (.mu.m)__________________________________________________________________________Cutting tool covering ofthe present invention9 E TiN (P) 1 TiCN (L) 6 TiN (P) 0.5 -- -- -- --10 TiC (P) 1 TiCN (L) 2 TiCN (P) 1 TiCN (L) 2 TiN 1P)11 F TiN (P) 1 TiCN (L) 6 TiCNO (P) 0.5 Al.sub.2 O.sub.3 1P) TiN 0.512 TiN (P) 1 TiCN (L) 5 -- -- -- -- -- --Prior art cutting tool covering1 A TiN (P) 1 TiCN (P) 6 TiN (P) 0.5 -- -- -- --2 TiC (P) 1 TiCN (P) 6 -- -- -- -- -- --3 B TiN (P) 1 TiCN (P) 6 TiN (P) 1 -- -- -- --4 TiC (P) 1 TiCN (P) 7 TiN (P) 1 -- -- -- --__________________________________________________________________________ P = Granular crystal structure; L = Longitudinal crystal structure
TABLE 5__________________________________________________________________________ Hard covering layerSub- First Layer Second Layer Third Layer Fourth Layer Fifth LayerClas- strate Com- Average Com- Average Com- Average Com- Average Com- Averagesifi- num- position thickness position thickness position thickness position thickness position thicknesscation ber (structure) (.mu.m) (structure) (.mu.m) (structure) (.mu.m) (structure) (.mu.m) (structure) (.mu.m)__________________________________________________________________________Prior art cutting tool coverings5 C TiN (P) 1 TiCN (P) 4 TiN (P) 0.5 -- -- -- --6 TiC (P) 1 TiCN (P) 4 TiCO (P) 0.5 Al.sub.2 O.sub.3 1.5 TiN 0.57 D TiN (P) 0.5 TiCN (P) 3 TiN (P) 0.5 -- -- -- --8 TiCN (P) 7 TiN (P) 0.5 -- -- -- -- -- --9 E TiN (P) 1 TiCN (P) 6 TiN (P) 0.5 -- -- -- --10 TiC (P) 1 TiCN (P) 6 TiN (P) 1 -- -- -- --11 F TiN (P) 1 TiCN (P) 6 TiCNO (P) 0.5 Al.sub.2 O.sub.3 1P) TiN 0.512 TiN (P) 1 TiCN (P) 5 -- -- -- -- -- --__________________________________________________________________________ P = Granular crystal structure; L = Longitudinal crystal structure
TABLE 6__________________________________________________________________________ Continuous Intermittent Continuous Intermittent cutting cutting cutting cutting Amount of Cutting Amount of Cutting flak wear time flak wear timeClassification (mm) (min.) Classification (mm) (min.)__________________________________________________________________________Cutting tool covering of the present inventionPrior art cutting tool covering1 0.11 7.4 1 0.23 1.02 0.12 7.2 2 0.27 1.23 0.13 8.0 3 0.26 0.94 0.12 8.6 4 0.28 1.15 0.15 12.0 5 0.27 1.46 0.13 8.5 6 0.27 1.67 0.22 13.6 7 0.34 2.38 0.15 10.9 8 0.26 2.09 0.12 12.5 9 0.22 1.810 0.14 12.8 10 0.24 2.211 0.12 9.0 11 0.21 2.112 0.20 9.7 12 0.38 1.9__________________________________________________________________________
TABLE 7__________________________________________________________________________ Binding phase enhanced surface portion Mix incorporated amount of Thick-Classifi- Distributional Composition (% by weight) binding phase nesscation Co Ni TaC NbC WC Mo.sub.2 C ZrC TiC TiN TiCN (% by wt) (.mu.m)__________________________________________________________________________Cermet substrateG 4 8 10 1 10 10 -- R 30 -- -- --H 12 6 8 -- 15 10 0.5 R 20 -- -- --I 10 10 -- 10 10 6 -- -- 10 R -- --J 7 7 10 1 8 8 -- -- 5 R 20 10K 12 4 12 -- 15 -- -- R 35 -- 28 20L 13 5 15 -- 15 -- 0.5 -- -- R 22 15__________________________________________________________________________ R = Remaining portion
TABLE 8__________________________________________________________________________ Amount of flank wear (mm) Crystal structure of the TiCN layer Cutting CuttingClassifi- Substrate First layer Second layer Third layer Fourth layer Fifth layer Material: Material:cation number (Thickness: .mu.m) (Thickness: .mu.m) (Thickness: .mu.m) (Thickness: .mu.m) (Thickness: .mu.m) Steel Cast-iron__________________________________________________________________________Cutting tool covering of the present invention13 G P + L (U) (6) -- -- -- -- 0.17 0.1614 P + L (I) + P L (B) + P (2) P (1) -- -- 0.16 0.15 (4)15 H P + L (I) + P -- -- -- -- 0.14 0.21 (8)16 P + L (U) (3) P + L (U) (3) P + L (U) (3) P + L (U) (3) P + L (I) + P 0.12 0.18 (3)17 I L (B) + P (4) -- -- -- -- 0.19 0.2218 P + L (U) (4) P + L (I) + P L (B) + P (2) -- -- 0.15 0.19 (3)19 J P + L (U) (6) P (1) -- -- -- 0.16 0.1420 P (1) L (B) + P (4) L (B) + P (3) L (B) + P (2) -- 0.12 0.1321 K P + L (U) (7) P + L (U) (1) -- -- -- 0.14 0.16__________________________________________________________________________ Note: P = Granular crystal structure; L = Longitudinal growth crystal structure U = Upper layer; I = Intermediate layer; B = Lower layer *Thickness represents the average thickness
TABLE 9__________________________________________________________________________ Amount of flank wear (mm) Crystal structure of the TiCN layer Cutting CuttingClassifi- Substrate First layer Second layer Third layer Fourth layer Fifth layer Material: Material:cation number (Thickness: .mu.m) (Thickness: .mu.m) (Thickness: .mu.m) (Thickness: .mu.m) (Thickness: .mu.m) Steel Cast-iron__________________________________________________________________________Cutting tool covering of thepresent invention22 K P (0.5) L (B) + P (4) P (1) L (B) + P (4) P (0.5) 0.13 0.1423 L P + L (I) + P P (1) -- -- -- 0.21 0.23 (3)24 P + L (I) + P L (B) + P (3) L (B) + P (3) -- -- 0.14 0.21 (5)Prior art cutting tool coverings13 G P (6) -- -- -- -- 9 min. 7 min. tool life due life due to chipping chipping14 H P (8) -- -- -- -- 6 min. 2 min. tool life due life due to chipping chipping15 I P (4) -- -- -- -- 11 min. 9 min. tool life due life due to chipping chipping16 J P (10) -- -- -- -- 5 min. 3 min. tool life due life due to chipping chipping17 K P (10) -- -- -- -- 4 min. 2 min. tool life due life due to chipping chipping18 L P (11) -- -- -- -- 6 min. 5 min. tool life due life due to chipping chipping__________________________________________________________________________ Note: P = Granular crystal structure; L = Longitudinal growth crystal structure U = Upper layer; I = Intermediate layer; B = Lower layer *Thickness represents the average thickness
TABLE 10__________________________________________________________________________ Hard covering layer Crystal structure of the lower layer (TiCN layer) Composition of the upper layer and averageClas- and average thickness of each layer (.mu.m) thickness of each layer (.mu.m)sifi- Substrate First Second Third Fourth First Second Third Fourthcation number layer layer layer layer layer layer layer layer__________________________________________________________________________Cutting tool covering of thepresent invention25 G P + L (U) -- -- -- TiCO (0.5) Al.sub.2 O.sub.3 --) -- (5)26 P + L (I) + P L (B) + P (2) -- -- TiN (0.5) -- -- -- (6)27 H L (B) + P (4) -- -- -- TiC (2) TiN (1) -- --28 I P + L (U) (2) P + L (U) (2) P + L (U) P + L (U) (2) TiCNO (0.5) Al.sub.2 O.sub.3 (1) (2)29 J P + L (I) + P -- -- -- TiC (2) TiCNO (0.5) Al.sub.2 O.sub.3 TiN (0.5) (2)30 P + L (U) (2) P + L (I) + P L (B) + P -- TiN (1) -- -- -- (3) (2)31 K P + L (U) (7) -- -- -- TiN (1) -- -- --32 L P + L (I) + P L (B) + P P + L (U) P + L (U) (2) TiN (0.5) -- -- -- (2.5) (2) (2)__________________________________________________________________________ Note: P = Granular crystal structure; L = Longitudinal growth crystal structure U = Upper layer; I = Intermediate layer; B = Lower layer
TABLE 11__________________________________________________________________________Hardcovering Conditions for forming the hard covering layer granular structurelayer Reaction environmentcomposi- Pressure Temption Reaction gas composition (% by volume) (Torr) (.degree.C.)__________________________________________________________________________TiC TiCl.sub.4 : 4%, CH.sub.4 : 5%, H.sub.2 : 91% 100 1030TiN TiCl.sub.4 : 4%, N.sub.2 : 8%, H.sub.2 : 88% 1000TiCN TiCl.sub.4 : 4%, CH.sub.4 : 3%, N.sub.2 : 4%, H.sub.2 : 980TiCO TiCl.sub.4 : 4%, CO: 6%, H.sub.2 : 90% 1000TiCNO TiCl.sub.4 : 4%, CO: 3%, N.sub.2 : 3%, H.sub.2 : 90% 1000Al.sub.2 O.sub.3 Al.sub.2 O.sub.3 : 3%, CO.sub.2 : 5%, H.sub.2 : 92% 1050__________________________________________________________________________
TABLE 12__________________________________________________________________________ Composition of the hard covering layer and thickness of each layer (.mu.m)Classifi- Substrate First Second Third Fourth Fifthcation number layer layer layer layer layer__________________________________________________________________________Prior art cutting tool covering19 G TiCN (5) TiCO (0.5) Al.sub.2 O.sub.3 (1) -- --20 TiCN (8) TiN (0.5) -- -- --21 H TiCN (4) TiC (2) TiN (1) -- --22 I TiCN (8) TiCNO (0.5) Al.sub.2 O.sub.3 (1) -- --23 J TiCN (2) TiC (2) TiCNO (0.5) Al.sub.2 O.sub.3 (1) TiN (0.5)24 TiCN (8) TiN (1) -- -- --25 K TiCN (7) TiN (1) -- -- --26 L TiCN (5) TiN (0.5) -- -- --__________________________________________________________________________
TABLE 13______________________________________Amountof flank wear Amount of flank wear(mm) (mm)Clas- Cutting Cutting Cutting Cuttingsifi- Material: Material: Classifi- Material: Material:cation Steel Cast-iron cation Steel Cast-iron______________________________________Cutting tool covering of Prior art cuttingthe present invention tool covering25 0.15 0.12 19 7 min. tool 5 min. tool life due to life due to chipping chipping26 0.13 0.12 20 6 min. tool 4 min. tool life due to life due to chipping chipping27 0.16 0.14 21 8 min. tool 8 min. tool life due to life due to chipping chipping28 0.18 0.16 22 3 min. tool 2 min. tool life due to life due to chipping chipping29 0.15 0.14 23 9 min. tool 10 min. tool life due to life due to chipping chipping30 0.14 0.16 24 7 min. tool 4 min. tool life due to life due to chipping chipping31 0.13 0.15 25 8 min. tool 5 min. tool life due to life due to chipping chipping32 0.17 0.18 26 6 min. tool 8 min. tool life due to life due to chipping chipping______________________________________
TABLE 14__________________________________________________________________________ Hard covering layer Crystal structure of the lower layer (TiCN layer) Composition of the upper layer and averageClas- and average thickness of each layer (.mu.m) thickness of each layer (.mu.m)sifi- Substrate First Second Third Fourth First Second Third Fourthcation number layer layer layer layer layer layer layer layer__________________________________________________________________________Cutting tool covering ofthe present invention33 G TiN (1) -- -- -- P + L (U) P + L (I) + P Al.sub.2 O.sub.3 (2) TiN (1) (2) (2)34 TiCN (1) TiCO (1) -- -- P + L -- -- -- (I) + P (3)35 H TiCNO (0.5) TiC (1) -- -- TiCN (1) L (B) + P (3) TiC P + L (I) + P (3)36 I TiCN (1) TiN (1) -- -- P + L (U) P + L (U) (2) TiCN Al.sub.2 O.sub.3 (2) (2) (0.5)37 J TiCN (1) TiC (1.5) TiN (0.5) -- L (B) + P TiN (1) -- -- (3)38 TiC (0.5) -- -- -- P + L TiN -- -- (I) + P (5) (0.5)39 K TiCN (1) -- -- -- P + P + L (I) + P L -- L (U) (2) (2) (B) + P (2)40 L TiN (1) TiC (1) TiCO (0.5) Al.sub.2 O.sub.3 (2) TiCN (0.5) P + L (U) (2) -- --__________________________________________________________________________ Note: P = Granular crystal structure; L = Longitudinal growth crystal structure U = Upper layer; I = Intermediate layer; B = Lower layer
TABLE 15__________________________________________________________________________Classi- Substrate Composition and average thickness of the hard covering layer (.mu.m)fiction number First layer Second layer Third layer Fourth layer Fifth layer__________________________________________________________________________Prior art cutting tool covering27 G TiN (1) TiCN (4) Al.sub.2 O.sub.3 (2) TiN (1) --28 TiCN (1) TiCO (0.5) TiCN (3) -- --29 H TiCNO (0.5) TiC (1) TiCN (4) TiC (0.5) TiCN (3)30 TiCN (1) TiN (1) TiCN (4) TiCNO (0.5) Al.sub.2 O.sub.3 (2)31 I TiCN (6) TiN (1) -- -- --32 TiC (0.5) TiCN (5) TiN (0.5) -- --33 J TiCN (1) TiC (1) TiCN (6) -- --34 TiN (1) TiC (1) TiCO (0.5) Al.sub.2 O.sub.3 (2) TiCN (3)__________________________________________________________________________
TABLE 16__________________________________________________________________________Amount of flank wear (mm)Classi- Cutting Cutting material Classi- Amount of flank wear (mm)fication material: steel cast-iron fication Cutting material: steel Cutting material: cast-iron__________________________________________________________________________Cutting tool covering of Prior art cuttingthe present invention tool covering33 0.15 0.17 27 6 min. tool life due to 7 min. tool life due to chipping chipping34 0.20 0.21 28 9 min. tool life due to 9 min. tool life due to chipping chipping35 0.13 0.17 29 5 min. tool life due to 3 min. tool life due to chipping chipping36 0.18 0.16 30 4 min. tool life due to 6 min. tool life due to chipping chipping37 0.15 0.13 31 9 min. tool life due to 8 min. tool life due to chipping chipping38 0.16 0.17 32 10 min. tool life due to 9 min. tool life due to chipping chipping39 0.13 0.16 33 6 min. tool life due to 4 min. tool life due to chipping chipping40 0.19 0.17 34 4 min. tool life due to 3 min. tool life due to chipping chipping__________________________________________________________________________

Number	Date	Country
2-21048	Jan 1990	JPX
4-227874	Aug 1992	JPX
4-235265	Aug 1992	JPX
4-235266	Aug 1992	JPX
4-235267	Aug 1992	JPX

Number	Name	Date
4769070	Tobioka et al.	Sep 1988
4781989	Yoshimura et al.	Nov 1988
4902395	Yoshimura	Feb 1990
5935057	Yoshimura et al.	Jun 1990

Number	Date	Country
54-117510	Sep 1979	JPX
60-33353	Feb 1985	JPX
61-213339	Sep 1986	JPX
63-35753	Feb 1988	JPX
1-34616	Feb 1989	JPX
1-104773	Apr 1989	JPX
1-129971	May 1989	JPX
2-22455	Jan 1990	JPX

Process for producing cermet cutting tools having both longitudinal and granular crystal structures

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CPC

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Abstract

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Entry
Kubel, E., "New CVD-coatings for carbide inserts", Adv. Hard Mater. Prod., Conf. Proc. (1988) pp. 27/1-27/9.
Bonetti-Lang, M. et al., "Carbonitride coatings at moderate temperature obtained from organic carbon/nitrogen compounds", Int. J. Refract. Hard Met. (1982), 1(4), pp. 161-165. (no months availabe).