# Patent

## Title
Surface-coated hard material for cutting tools or wear-resistant tools

## Abstract

The present invention provides a thin film coated on a cutting tool surface made of cemented carbides, cermets or ceramics. According to the present invention, an α-Al2O3thin film is deposited on a TiAlvBwCxNyOz (v+w+x+y+z=1, v, w, x, y, z≧0) thin film in a thickness of 2-15 μm, so that the ratio of TC (104) (denoting the texture coefficient of the (104) crystal plane of the polycrystalline α-Al2O3 thin film) to TC (012) (denoting the texture coefficient of the (012) crystal) is more than 1.3. Cutting tools coated with such a thin film have improved wear resistance and adhesion.

## Background
TECHNICAL FIELD
The present invention relates to a thin film coated on cemented carbide which is used as an indexable insert, and more particularly, to a hard ceramic thin film with excellent wear resistance, which is used to improve the wear resistance of cutting tools, as well as cutting tools coated with such a thin film.
BACKGROUND ART
Generally, in order to improve the service life of cutting tools, a hard ceramic thin film made of titanium carbide (TiC), titanium nitride (TiN), titanium carbon nitride (TICN) or alumina (Al2O3) is coated on the surface of a base metal for cemented carbide by chemical vapor deposition (CVD). Regarding cutting tools coated with Al2O3, a cutting tool comprising an Al2O3 thin film of 0.5-1 μm coated on a TiC thin film was introduced to the world for the first time in the world in 1973. The cutting tool comprising Al2O3 coated on TiC was slightly lower in toughness but significantly higher in wear resistance than a monolayer TiC thin film.
Also, in order to improve the toughness of cutting tools, a TiCN thin film is used which is coated using organic CN compound precursors (acetonitrile, CH3CN) at a temperature of 800-900° C. by middle temperature-chemical vapor deposition (MT-CVD). The deposition of the conventional TiCN thin film by high temperature-chemical vapor deposition (HT-CVD) was performed using gas materials including TiCl4, CH4, N2 and H2, at a temperature of about 1,000-1,200° C., whereas the coating by MT-CVD was performed using TiCl4, CH3CN, N2 and H2, at a temperature of 800-900° C. The TiCN thin film coated by MT-CVD is slightly lower in hardness than the TiC thin film, but it has hardness sufficient to provide an improvement in wear resistance and is excellent in toughness since it has a columnar structure.
In the case of Al2O3 thin films with excellent oxidation resistance, since it was reported in studies on phase control technology for Al2O3 thin films in the 1980s that alpha-alumina (α-Al2O3) and kappa-alumina (κ-Al2O3) thin films are suitable for cast iron and steel, respectively, control technology for the Al2O3 thin films has been rapidly developed and commercially used. The α-Al2O3 thin film among the Al2O3 thin films is a unique stable phase which does not undergo a phase change during processing, and it has the best hardness. Thus, it shows excellent cutting performance in cast iron processing which is performed under high-speed cutting conditions. It was analyzed that the κ-Al2O3 thin film is lower in thermal conductivity than the α-Al2O3 thin film and thus shows excellent wear resistance in steel cutting, which generates much heat.
In currently commercially available cutting tools, since the Al2O3 thin film is always applied to ceramic substrates, TiC or TiCN-coated carbides, the interfacial adhesion between the TiC or TiCN thin film surface and the Al2O3 coating layer is very important. In this regard, the TiC or TiCN thin film may be represented by the formula TiAlvBwCxNyOz (v+w+x+y+z=1, v, w, x, y, z≧0) wherein Ti in the TiC or TiN thin film is completely or partially substituted with Al, and carbon (C) or carbon nitride (CN) is completely or partially substituted with boron, oxygen or nitrogen.
EP Nos. 408535 and 603144 disclose coating the α-Al2O3 thin film on cutting tools in order to increase the wear resistance of the cutting tools in cast iron turning. However, such patents do not disclose the crystallographic structure of the α-Al2O3 thin film which shows excellent cutting performance.
DISCLOSURE OF THE INVENTION
Accordingly, an object of the present invention is to provide an α-Al2O3 thin film with excellent cutting performance, and to provide an α-Al2O3 phase having the desired crystallographic structure on a hard material or a thin film of TiAlvBwCxNyOz (v+w+x+y+z=1, v, w, x, y, z≧0) by controlling the nucleation and growth conditions of an Al2O3 phase.
Another object of the present invention is to provide cutting tools deposited with an α-Al2O3 thin film which has improved cutting performance for steel, stainless steel, and cast iron, particularly general cast iron and spherical graphite cast iron.
In order to achieve the above objects, in one aspect, the present invention provides a polycrystalline α-Al2O3 thin film deposited on a base metal for cutting tools or wear-resistant tools, in which the ratio of TC (104) (denoting the texture coefficient of the (104) crystal plane) to TC (012) (denoting the texture coefficient of the (012) crystal plane) in the α-Al2O3 thin film is more than 1.3. The inventive α-Al2O3 thin film has a characteristic in that it is first grown in the (104) direction when measured by X-ray diffraction (XRD) analysis, and a texture coefficient (TC) for the α-Al2O3 thin film is defined by the following equation:




  
    TC
    ⁡
    
      (
      hkl
      )
    
  
  =
  
    
      
        I
        ⁡
        
          (
          hkl
          )
        
      
      
        
          I
          0
        
        ⁡
        
          (
          hkl
          )
        
      
    
    ⁢
    
      
        {
        
          
            1
            n
          
          ⁢
          
            ∑
            
              
                I
                ⁡
                
                  (
                  hkl
                  )
                
              
              
                
                  I
                  0
                
                ⁡
                
                  (
                  hkl
                  )
                
              
            
          
        
        }
      
      
        -
        1
      
    
  




wherein I(hkl) denotes the diffraction intensity of crystal planes, I0(hkl) denotes the standard diffraction intensity of ASTM standard powder diffraction data, n denotes the number of crystal planes used for calculation, and crystal planes (hkl) used are (012), (104), (110), (113), (024), (116), (124) and (030).
The inventive α-Al2O3 thin film is preferably deposited on a thin film of TiAlvBwCxNyOz(v+w+x+y+z=1, v, w, x, y, z≧0). In depositing the TiAlvBwCxNyOz (v+w+x+y+z=1, v, w, x, y, z≧0) thin film on a surface for cutting tools or wear-resistant tools, BCl3 is preferably used in the amount of 0.1-0.4 vol %.
In another aspect, the present invention provides a surface-coated material comprising: at least one material deposited on a base metal for cutting tools or wear-resistant tools, the deposited material being selected from the group consisting of IV-A group metal nitride, carbide, carbon nitride, oxynitride, carbon oxide and carbon oxynitride, and IV-A group metal carbon nitride and carbon oxynitride with a columnar structure; a thin film of TiAlvBwCxNyOz (v+w+x+y+z=1, v, w, x, y, z≧0) deposited on the deposited material; and at least one material deposited on the TiAlvBwCxNyOz thin film by CVD, the deposited material being selected from the group consisting of Al2O3, ZrO2, HfO2, Y2O3, AlN, CBN, and TiB2.
In the surface-coated material, the phase of Al2O3 is preferably alpha (α), and the Al2O3 thin film is preferably a polycrystalline α-Al2O3 thin film. The Al2O3 thin film is a polycrystalline α-Al2O3 thin film in which the ratio of TC (104) (denoting the texture coefficient of the (104) crystal plane) to TC (012) (denoting the texture coefficient of the (012) crystal plane) is more than 1.3, particularly more than 1.5.
The uppermost thin film coated on the base metal surface for tools preferably contains at least one material selected from the group consisting of IV-A group metal nitride, carbide, carbon nitride, oxynitride, carbon oxide and carbon oxynitride, which are deposited by high temperature-chemical vapor deposition, and IV-A group metal carbon nitride and carbon oxynitride with a columnar structure, which are deposited by middle temperature-chemical vapor deposition.
The uppermost thin film is preferably subjected to dry or wet blasting with Al2O3 powder so as to improve its surface roughness.
Accordingly, the present invention provides the α-Al2O3 thin film which is coated on a cutting tool surface made of materials, such as cemented carbides, cermets or ceramics. In the thin film, the ratio of TC (104) (denoting the texture coefficient of the (104) crystal plane) to TC (012) (denoting the texture coefficient of the (012) crystal plane) is preferably more than 1.3, particularly more than 1.5. In addition, the present invention provides cutting tools coated with such a thin film, in which the thin film is preferably coated in a thickness of 2-15 μm, particularly 3-10 μm, by HT-CVD.
In the present invention, a thin film of TiAlvBwCxNyOz (v+w+x+y+z=1, v, w, x, y, z≧0) was formed by the additional use of a given amount of AlCl3 and BCl3 as raw materials for adding Al and B to a thin film composition, in addition to the prior HT-CVD coating method of forming a thin film of TiCxNyOz (x+y+z=1, x, y, z≧0) using raw material gas including TiCl4, CH4, H2, N2, CO2 and CO, at a temperature of 1,000-1,100° C. At this time, the thickness of the formed thin film is preferably 0.1-5 μm, particularly 0.5-3 μm.



BRIEF DESCRIPTION OF THE DRAWINGS
The above and other objects, features and other advantages of the present invention will be more clearly understood from the following detailed description taken in conjunction with the accompanying drawings, in which:
FIG. 1 is a SEM photograph at 5,000×magnification, which shows the shape of an α-Al2O3 thin film deposited on a TiAlvBwCxNyOz (v+w+x+y+z=1, v, w, x, y, z≧0) thin film formed according to the present invention.



BEST MODE FOR CARRYING OUT THE INVENTION
Hereinafter, the present invention will be described in further detail by way of examples. It is to be understood, however, that these examples are given for illustrative purposes only and are not intended to limit the scope of the present invention.
Example 1
(A) On ISO 15K-cemented carbide for coated cutting tools, a TiCN thin film was deposited in a thickness of 10 μm by MT-CVD. On the deposited TiCN film, a thin film of TiAlvBwCxNyOz (v+w+x+y+z=1, v, w, x, y, z≧0) according to the present invention was deposited in a thickness of 0.5 μm, on which an α-Al2O3 thin film was then deposited in a thickness of 5 μm.
The results of X-ray diffraction analysis showed that the ratio of TC (104) (denoting the texture coefficient of the (104) crystal plane of the polycrystalline α-Al2O3 film) to TC (012) (denoting the texture coefficient of the (012) crystal plane) was 1.55.
(B) On ISO 15K-cemented carbide for coated cutting tools, a TiCN thin film was deposited in a thickness of 10 μm by MT-CVD. On the deposited TiCN film, a thin film of TiCxNyOz (x+y+z=1, x, y, z≧0) according to the prior art was deposited in a thickness of 0.5 μm, on which an α-Al2O3 thin film was then deposited in a thickness of 5 μm.
(C) On ISO 15K-cemented carbide for coated cutting tools, a TiCN thin film was deposited in a thickness of 8 μm by MT-CVD. On the deposited TiCN thin film, a κ-α-Al2O3 thin film was deposited in a thickness of 4 μm.
The coated cutting tools of (A), (B) and (C) were subjected to dry or wet blasting with 200-mesh α-Al2O3 powder so as to improve their surface roughness.
The cutting performance of the coated cutting tools according to the prior art (B and C) and the coated cutting tool according to the present invention (A) were evaluated by processing work pieces with the tools for the same time period of 10 minutes, measuring wear occurring at the tool flank and analyzing tool edge chipping. The evaluation results are given in Table 1. As can be seen in Table 1, the inventive tool (A) had improved chipping resistance and wear resistance as compared to the prior tools (B and C).
<Cutting Test Conditions>
Cutting conditions: V=300 m/min, f=0.3 mm/rev., d=2.0 mm, wet processing;
Work pieces: GC 25 (300-mm diameter and 600-mm length), outer diameter processing; and
Tool Type No.: CNMG120408-GR.











TABLE 1









Tool flank wear



Sample
Edge chipping (%)
(mm)



















Invention
A
0
0.137


Prior art
B
50
0.145


Prior art
C
30
0.167









Example 2
(E) On ISO 15K-cemented carbide for coated cutting tools, a TiCN thin film was deposited in a thickness of 10 μm by MT-CVD. On the deposited TiCN film, a thin film of TiAlvBwCxNyOz (v+w+x+y+z=1, v, w, x, y, z≧0), according to the present invention, was deposited in a thickness of 0.5 μm, on which an α-Al2O3 thin film was then deposited in a thickness of 7 μm.
The results of X-ray diffraction analysis showed that the ratio of TC (104) (denoting the texture coefficient of the polycrystalline α-Al2O3 (104) crystal plane) to TC (012) (denoting the texture coefficient of the (012) crystal plane) was 1.59.
(F) On ISO 15K-cemented carbide for coated cutting tools, a TiCN thin film was deposited in a thickness of 10 μm by MT-CVD. On the deposited TiCN film, a thin film of TiCxNyOz (x+y+z=1, x, y, z≧0) according to the prior art was deposited in a thickness of 0.5 μm, on which an α-Al2O3 thin film was then deposited in a thickness of 7 μm.
(G) On ISO 15K-cemented carbide for coated cutting tools, a TiCN thin film was deposited in a thickness of 8 μm by MT-CVD. On the deposited TiCN thin film, a κ-Al2O3 thin film was deposited in a thickness of 5 μm.
The coated cutting tools of (E), (F) and (G) were subjected to dry or wet blasting with 200-mesh α-Al2O3 powder so as to improve their surface roughness.
The cutting performance of the coated cutting tools according to the prior art (F and G) and the coated cutting tool according to the present invention (E) were evaluated by processing work pieces with the tools for the same time period of 10 minutes, measuring wear occurring at the tool flank and analyzing tool edge chipping. The evaluation results are given in Table 2. As can be seen in Table 2, the inventive tool (E) had improved chipping resistance and wear resistance compared to the prior tools (F and G).
<Cutting Test Conditions>
Cutting conditions: V=400 m/min, f=0.3 mm/rev., d=2.0 mm, wet processing;
Work pieces: GC 25 (300-mm diameter and 600-mm length), outer diameter processing; and
Tool Type No.: CNMG120408-GR.











TABLE 2









Tool flank wear



Sample
Edge chipping (%)
(mm)



















Invention
E
0
0.110


Prior art
F
70
0.154


Prior art
G
50
0.177









INDUSTRIAL APPLICABILITY
As described above, according to the present invention, the TiAlvBwCxNyOz (v+w+x+y+z=1, v, w, x, y, z≧0) thin film is deposited on cutting tools in a thickness of 0.1-5 μm by HT-CVD, on which the α-Al2O3 thin film is then deposited in a thickness of 2-15 μm, so that the ratio of TC (104) (denoting the texture coefficient of the (104) crystal plane of the polycrystalline α-Al2O3 thin film) to TC (012) (denoting the texture coefficient of the (012) crystal) is more than 1.3. In this case, the wear resistance, chipping resistance and toughness of the cutting tools can be greatly improved.
Although the preferred embodiment of the present invention have been disclosed for illustrative purposes, those skilled in the art will appreciate that various modifications, additions and substitutions are possible, without departing from the scope and spirit of the invention as disclosed in the accompanying claims.

## Claims

1. A polycrystalline α-Al2O3 thin film deposited on a base metal for cutting tools or wear-resistant tools by high temperature-chemical vapor deposition, in which the ratio of TC (104) (denoting the texture coefficient of the (104) crystal plane) to TC (012) (denoting the texture coefficient of the (012) crystal plane) in the α-Al2O3 thin film is more than 1.3, the texture coefficient being defined by the following equation:




  
    TC
    ⁡
    
      (
      hkl
      )
    
  
  =
  
    
      
        I
        ⁡
        
          (
          hkl
          )
        
      
      
        
          I
          0
        
        ⁡
        
          (
          hkl
          )
        
      
    
    ⁢
    
      
        {
        
          
            1
            n
          
          ⁢
          
            ∑
            
              
                I
                ⁡
                
                  (
                  hkl
                  )
                
              
              
                
                  I
                  0
                
                ⁡
                
                  (
                  hkl
                  )
                
              
            
          
        
        }
      
      
        -
        1
      
    
  



wherein I(hkl) denotes the diffraction intensity of crystal planes, I0(hkl) denotes the standard diffraction intensity of ASTM standard powder diffraction data, n denotes the number of crystal planes used for calculation, and crystal planes (hkl) used are (012), (104), (110), (113), (024), (116), (124) and (030), and
wherein the α-Al2O3 thin film is deposited on a thin film of TiAlvBwCxNyOz (v+w+x+y+z=1, x, y≧0; v>0; w>0; z>0), and
wherein BC13 is used in an amount of 0.1-0.4 vol% in the deposition of the TiAlvBwCxNyOz (v+w+x+y+z=1, x, y≧0; v>0; w>0; z>0) thin film.

2. The thin film of claim 1, wherein said TiAlvBwCxNyOz (v+w+x+y+z=1, x, y≧0; v>0; w>0; z>0) thin film is 0.1-5μm in thickness and said α-Al2O3 thin film is 2-15μm in thickness.

3. The thin film of claim 1, wherein a phase of said polycrystalline α-Al2O3 thin film consists essentially of α phase.

4. The thin film of claim 1, wherein a phase of said polycrystalline α-Al2O3 thin film consists of α phase.

5. The thin film of claim 1, wherein the ratio of TC (104) to TC (012) in the α-Al2O3 thin film is more than 1.5.

6. The thin film of claim 1, wherein the ratio of TC (104) to TC (012) in the α-Al2O3 thin film is more than 1.55.

7. The thin film of claim 1, wherein the ratio of TC (104) to TC (012) in the α-Al2O3 thin film is more than 1.59.

8. The polycrystalline α-Al2O3 thin film deposited on a base material according to claim 1, wherein v+w+x+y+z=1, and v, w, x, y, z>0.

9. A surface-coated material for cutting tools or wear resistant tools, which comprises:
at least one material deposited on a base material for cutting tools or wear-resistant tools, the deposited material being selected from the group consisting of IV-A group metal nitride, carbide, carbon nitride, oxynitride, carbon oxide and carbon oxynitride, and IV-A group metal carbon nitride and carbon oxynitride with a columnar structure;
a thin film TiAlvBwCxNyOz (v+w+x+y+z=1, x, y≧0; v>0; w>0; z >0) deposited on the deposited material; and
at least one material deposited on the TiAlvBwCxNyOz thin film by chemical vapor deposition, the deposited material being selected from the group consisting of Al2O3, ZrO2, HfO2, Y2O3, AlN, CBN, and TiB2,
wherein BCl3 is used in an amount of 0.1-0.4vol% in the deposition of the TiAlvBwCxNyOz (v+w+x+y+z=1, x, y≧0; v>0; w>0; z>0) thin film.

10. The surface-coated material of claim 9, wherein the material deposited on the TiAlvBwCxNyOz thin film is at least Al2O3 and the phase of the Al2O3 film is alpha (α).

11. The surface-coated material of claim 10, wherein said TiAlvBwCxNyOz (v+w+x+y+z=1, x, y≧0; v>0; w>0; z>0) thin film is 0.1-5μm in thickness and said α-Al2O3 thin film is 2-15μm in thickness.

12. The surface-coated material of claim 9, wherein the material deposited on the TiAlvBwCxNyOz thin film is at least Al2O3 and the Al2O3 thin film is a polycrystalline α-Al2O3 thin film in which the ratio of TC (104) (denoting the texture coefficient of the (104) crystal plane) to TC (012) (denoting the texture coefficient of the (012) crystal plane) in the α-Al2O3 thin film is more than 1.3, the texture coefficient being defined by the following equation:




  
    TC
    ⁡
    
      (
      hkl
      )
    
  
  =
  
    
      
        I
        ⁡
        
          (
          hkl
          )
        
      
      
        
          I
          0
        
        ⁡
        
          (
          hkl
          )
        
      
    
    ⁢
    
      
        {
        
          
            1
            n
          
          ⁢
          
            ∑
            
              
                I
                ⁡
                
                  (
                  hkl
                  )
                
              
              
                
                  I
                  0
                
                ⁡
                
                  (
                  hkl
                  )
                
              
            
          
        
        }
      
      
        -
        1
      
    
  



wherein I(hkl) denotes the diffraction intensity of crystal planes, I0(hkl) denotes the standard diffraction intensity of ASTM standard powder diffraction data, n denotes the number of crystal planes used for calculation, and crystal planes (hkl) used are (012), (104), (110), (113), (024), (116), (124) and (030).

13. The surface-coated material of claim 12, wherein the ratio of TC (104) to TC (012) in the α-Al2O3 thin film is more than 1.5.

14. The surface-coated material of claim 12, wherein the ratio of TC (104) to TC (012) in the α-Al2O3 thin film is more than 1.55.

15. The surface-coated material of claim 12, wherein the ratio of TC (104) to TC (012) in the α-Al2O3 thin film is more than 1.59.

16. The surface-coated material of claim 9, wherein said material deposited on the TiAlvBwCxNyOz thin film consists essentially of an α-Al2O3 thin film.

17. The surface-coated material of claim 9, wherein said material deposited on the TiAlvBwCxNyOz thin film consists of an α-Al2O3 thin film.

18. The surface-coated material of claim 9, wherein v+w+x+y+z=1, and v, w, x, y, z>0.