# Patent

## Title
Oxide coated cutting tool

## Abstract

A body is at least partially coated with one or more refractory layers of which at least one layer is of a fine grained κ-Al2O3. Said κ-Al2O3 layer has equiaxed grains with an average grain size of <0.5 μm. The Al2O3 layer also has at least one sublayer containing Al, Si and O. The fine grained κ-Al2O3 microstructure is obtained by periodically introducing a silicon halide, preferably SiCl4, during the Al2O3-process.

## Background
This application is a divisional application of application Ser. No. 10/155,168, filed on May 28, 2002 now U.S. Pat. No. 6,673,393, and claims priority under 35 U.S.C. §§ 119 and/or 365 to Application No. 0101902-5 filed in Sweden on May 30, 2001, the entire contents of each of these documents is hereby incorporated by reference.


FIELD OF THE INVENTION
The present invention relates to a coated cutting tool for chipforming machining. The coating includes at least one alumina (Al2O3) layer characterized by fine, equiaxed grains.
BACKGROUND OF THE INVENTION
In the description of the background of the present invention that follows reference is made to certain structures and methods, however, such references should not necessarily be construed as an admission that these structures and methods qualify as prior art under the applicable statutory provisions. Applicants reserve the right to demonstrate that any of the referenced subject matter does not constitute prior art with regard to the present invention.
Cemented carbide cutting tools coated with various types of Al2O3 layers using Chemical Vapour Deposition (CVD), e.g., pure κ-Al2O3, mixtures of κ- and α-Al2O3 coarse grained α-Al2O3 and fine grained textured α-Al2O3 have been commercially available for years generally in multilayer combinations with other metal carbide and/or nitride layers, the metal being selected from transition metals of the IVB, VB and VIB groups of the Periodic Table.
Al2O3 crystallises in several different phases: α, κ, γ, δ, θ etc. The two most frequently occurring phases of CVD-produced wear resistant layers are the thermodynamically stable, α-phase and the metastable κ-phase or a mixture thereof. Generally, the κ-phase exhibits a grain size in the range 0.5-3.0 μm (dependent on the layer thickness) and the grains predominately grow through the whole coating forming a columnar type coating morphology.
Furthermore, the κ-Al2O3 layers are free from crystallographic defects and also free from micropores and voids.
Coarse grained (3-6 μm) α-Al2O3 often possesses porosity and crystallographic defects, while fine grained textured α-Al2O3 is free of defects with very pronounced columnar-shaped grains.
In U.S. Pat. No. 5,674,564 a method is disclosed of growing a fine grained κ-Al2O3 layer by employing a low deposition temperature and a high concentration of a sulphur compound.
In U.S. Pat. No. 5,487,625 a method is disclosed for obtaining a fine grained, (012)-textured α-Al2O3 layer consisting of columnar grains with a small cross section (about 1 μm).
In U.S. Pat. No. 5,766,782 a method is disclosed for obtaining a columnar fine grained (104)-textured α-Al2O3 layer.
The lifetime and the performance of a coated cutting tool are closely related to the microstructure of the coating materials used. Although, coatings produced according to above-mentioned prior art patents show good cutting properties there is still a strong desire to further improve coating microstructures to suit specific cutting conditions and workpiece materials.
As has been mentioned above, all Al2O3 layers produced by the CVD technique possess a more or less columnarlike grain structure. An Al2O3 layer with an equiaxed grain structure is, however, expected to show some favourable mechanical properties, e.g., resistance to crack propagation and higher cutting edge toughness, as compared to a layer with a columnar grain structure. In addition, fine grained layers generally have smoother surfaces than coarse grained layers. During cutting less workpiece materials will adhere onto a smooth coating surface which in turn will imply lower cutting forces and less tendency for the coating to flake off. Nowadays coated cutting inserts are often brushed with SiC based brushes or blasted with fine grained Al2O3 powder in order to obtain a smooth coating surfaces, a rather costly production step.
One well-known and possible technique to produce a fine grained structure and to restrain a columnar grain growth is to deposit a so-called multilayer structure in which the columnar growth of, e.g., Al2O3, is periodically interrupted by the growth of a 0.05-1 μm thick layer of a different material such as disclosed in U.S. Pat. No. 4,984,940 and U.S. Pat. No. 5,700,569. The latter layer should preferably have a different crystal structure or at least different lattice spacings in order to be able to initiate renucleation of the original layer. One example of such a technique is when the Al2O3 growth periodically is interrupted by a short TiN deposition process resulting in a (Al2O3+TiN)×n multilayer structure with a thickness of each individual TiN layer in the range 0.1-1 μm, e.g., see Proceedings of the 12th European CVD Conference page pr. 8-349. However such multilayer structures very often suffer from a low adherence between the two different types of layers.
In Swedish patent application SE 0004272-1 a method is disclosed for obtaining a fine grained α-Al2O3 layer consisting of essentially equiaxed grains with a grain size <1 μm. The grain refinement is accomplished by periodically interrupting the Al2O3 process and treating the Al2O3 surface with a mixture of TiCl4/H2. When the Al2O3 process is restarted renucleation of the α-Al2O3 will take place.
It is not possible to use this method to produce fine grained κ-Al2O3 since only the α-Al2O3 phase will nucleate on the TiCl4/H2 treated Al2O3 surface.
κ-Al2O3 and α-Al2O3 coatings used as tool materials have slightly different wear properties when cutting different materials. It is therefore also desirable to have means to produce fine grained κ-Al2O3 with a controllable grain structure.
SUMMARY OF THE INVENTION
It is the object of the present invention to provide onto a hard substrate, or preferably onto a hard substrate coated with a TiCxNyOz and/or ZrCxNyOz-layer (x+y+z=1 and x,y,z≧0) at least one fine grained single phase κ-Al2O3 layer with a microstructure which is different from the prior art columnar κ-Al2O3 CVD layers mentioned above.
It is also the object of the present invention to provide a high performance tool coating comprising the invented Al2O3 layer.
It is a further object of the invention to provide an alumina coated cutting tool insert with improved cutting performance in steel and nodular cast iron.
According to one aspect of the present invention there is provided a cutting tool comprising a body of sintered cemented carbide, cermet or ceramic, and a hard and wear resistant coating applied on at least a functioning portion of a surface of the body. The coating comprises a structure of one or more refractory layers of which at least one layer consists essentially of an equiaxed fine grained κ-Al2O3 with a thickness of 0.5-25 μm and with a grain size of less than 0.5 μm, and said fine grained κ-Al2O3 layer comprises at least one sub-layer with a thickness between 0.02 and 3 μm containing Al, Si and O with a Si concentration between 4-34 at %, Al concentration of 0-37 at % and O concentration of 60-67 at %.
According to another aspect, the present invention provides a method of coating a body with at least one fine grained κ-Al2O3 layer comprising contacting the body with a reaction mixture comprising a hydrogen carrier gas, one or more halides of aluminium and a hydrolysing and/or oxidising agent at 800-1050° C., adding a sulphur agent to the reaction mixture to enhance the growth rate, and depositing at least one silicon enriched sublayer in the κ-Al2O3 layer by periodically introducing a silicon halide.



BRIEF DESCRIPTION OF THE DRAWINGS
FIGS. 1a-c show Scanning Electron Microscope (SEM) micrographs of the present invention. FIG. 1a shows an SEM micrograph of an Al2O3 layer according to the present invention at a high magnification in top view projection, FIG. 1b shows an SEM micrograph of a cross sectioned sample according to the present invention at a high magnification, and FIG. 1c shows an SEM micrograph of a polished cross-section of an Al2O3 layer with Si-rich layers, A, according to the present invention in so called backscatter mode at high magnification.
FIGS. 2a-b show SEM micrographs of a prior art κ-Al2O3 layer. FIG. 2a shows an SEM micrograph at a high magnification in top view projection and FIG. 2b shows an SEM micrograph in so called backscatter mode at high magnification of a polished cross-section.
FIGS. 3a-b show SEM micrographs of a prior art multilayer κ-Al2O3+TiN coating. FIG. 3a shows an SEM micrograph at a high magnification in top view projection and FIG. 3b shows an SEM micrograph in so called backscatter mode at high magnification of a polished cross-section.
FIG. 4 shows a SEM micrograph of a cross sectioned sample according to the present invention.



DETAILED DESCRIPTION OF THE INVENTION
Surprisingly, it has been found that a non-columinar, fine grained, equiaxed κ-Al2O3 layer can be deposited by repeatedly introducing a controlled amount of a silicon halide, preferably SiCl4, during an Al2O3-deposition process
The duration of the treatment periods as well as the silicon halide concentration are important parameters which must be optimised in order to obtain the desired result. If the silicon halide concentration is too low or/and treatment time is too short, the renucleation of the Al2O3 layer will not be sufficiently dense to cover a sufficient portion of the whole coating surface. If, on the other hand, the silicon halide concentration is too high and/or the treatment time is too long, the cohesion between the grains will be too weak resulting in a low quality coating.
The method of the present invention thus relates to the coating of a body with a κ-Al2O3 layer during which the body is brought in contact with a hydrogen carrier gas containing one or more halides of aluminium, preferably AlCl3, and a hydrolysing and/or oxidising agent, preferably CO2, at temperature of the body between 800 and 1050° C. During the Al2O3 growth, a silicon halide, preferably SiCl4, is added to the reaction mixture at intervals of 1-5 minutes in a concentration of 20-50% of the AlCl3 flow. This procedure is repeatedly carried out in order to obtain a fine grained κ-Al2O3 layer structure with the desired grain size.
In contrast to the columnar grains of prior art Al2O3 layers, the grains of the κ-Al2O3 layers according to the present invention are essentially equiaxed. The resulting grain size and the distribution of the same are dependent on the number of SiCl4 treatments carried out. The more frequently the Al2O3 process is subjected to SiCl4 treatments, the smaller the Al2O3 grains will be. Up to 200 SiCl4 treatments are possible to be carried out, however, generally less than 100 treatments are preferred. The introduction of SiCl4 will initiate a growth of a super fine grained layer comprising Al, Si and O in concentrations, which are dependent on the used AlCl3/SiCl4-flow ratio. When the SiCl4-flow is turned off, renucleation of κ-Al2O3 grains will take place.
One advantage of the invented method is that only one foreign element (Si) can be added during the Al2O3 process in order to create the grain refinement, this is in contrast to prior art techniques which use renucleation layers consisting of TiN or (Tix,Aly)(Cz,Ow,Nj) which is quite different materials from Al2O3.
The resulted grain size of the κ-Al2O3 layer can be determined from a SEM micrograph at high magnification taken from cross-sectioned samples.
More specifically, the coated body comprises a cutting tool with a substrate of cemented carbide, cermet or a ceramic and a coating consisting of a hard wear resistant material and in said coating at least one layer is essentially a single phase fine grained κ-Al2O3 with a thickness of 0.5-25 μm and with a grain size of less than 0.5 μm. The fine grained κ-Al2O3 layer comprises at least one sublayer with a thickness between 0.02 and 3 μm containing Al, Si and O. The Si concentration is in the range 4-34 at %, the Al concentration in the range 0-37 at % and the O concentration in the range 60-67 at %. The other layers in the coating structure may be α-Al2O3, prior art coarse grained κ-Al2O3 (0.5-3.5 μm), ZrO2, TiC or related carbide, nitride, carbonitride, oxycarbide and oxycarbonitride of a metal selected from the Groups IVB, VB, and VIB of the Periodic Table, the elements B, Al and Si and/or mixtures thereof. Such other layers may be deposited by CVD, PACVD (Plasma CVD), PVD (Physical Vapour Deposition) or MTCVD (Moderate Temperature CVD). At least one of such other layers is in contact with the substrate. The total thickness of the coating of the cutting tool can vary between 1 and 30 μm.
Aluminium, silicon and oxygen may exist together in some minerals like andalusite, silliminite, kayanite and mullite (Al6Si4O13). A method to deposit mullite coatings by CVD is disclosed in U.S. Pat. No. 5,763,008, a gas mixture of AlCl3, SiCl4, CO2 and H2 is used.
The present invention uses the same chemical compounds but a sulphur compound is added to form and control the growth of the mentioned sublayer containing silicon. Under the invented process conditions, no mullite has been observed.
EXAMPLE
A) Cemented carbide cutting inserts in style CNMG 120408-PM with the composition 7.5 weight-% Co, 1.8 wt % TiC, 0.5 wt % TiN, 3 wt % TaC, 0.4 wt % NbC and balance WC were coated with a 1 μm thick layer of TiN using conventional CVD-technique followed by a 6 μm TiCN layer employing the MTCVD-technique using TiCl4, H2, N2 and CH3CN as process gasses. In subsequent process steps during the same coating cycle, a 0.5 μm TiCxNyOz layer with an approximate composition corresponding to x=0.5, y=0.3 and z=0.2 was deposited followed by a 6 μm thick layer of κ-Al2O3 deposited according to the invented coating process. Prior to the nucleation of the Al2O3 the oxidation potential of the carrier gas H2 (only gas present in the reactor), i.e., the water vapour concentration, was explicitly set forth to a low level, such as than 5 ppm. Then the Al2O3-process was started up. The process conditions during the Al2O3 deposition were as below:














Step
1
2
3
4







CO2:
4%
4%
4%
4%


AlCl3:
4%
4%
4%
4%


H2S
—
0.15
0.2%
0.2%


HCl
1.5%
5%
5%
5%


H2
balance
balance
balance
balance


SiCl4
—
—
—
2%


Pressure:
60 mbar
60 mbar
60 mbar
60 mbar


Temperature:
1000° C.
1000° C.
1000° C.
1000° C.


Duration:
30 min
20 min
22 min
2 min









The Al2O3 layer was deposited by proceeding through step 1, 2, 3 and 4 and then looping between step 4 and step 3 eight times. Hence, the Al2O3-process was treated with SiCl4 altogether nine times.
XRD-analysis of the deposited Al2O3 layer showed that it consisted essentially of the kappa phase. No diffraction peaks from the mullite-phase (Al6Si2O13) could be detected.
From the SEM-micrographs taken from a polished cross sectioned sample, similar to FIG. 1c, it was possible to observe nine Al2O3-layers with a thickness of approx. 0.5 μm and nine extremely fine grained layers corresponding to the SiCl4-treatment steps 4 with a thickness of approx. 0.15 μm. The grain size was estimated from a fractured sample at 70,000 times magnification to be 0.5 μm for the Al2O3-layers and less than 0.1 μm for the Si containing layers. The inserts appeared multicoloured due to light interference in the transparent layer structure. The coating surfaces were very smooth.
A chemical analysis of the thin sublayers was carried out on a cross sectioned sample in a Hitachi S-4300 FEG-SEM equipped with an EDS-system with a Link Si(Li)-detector. The analysis resulted in the following estimated concentrations Al=32 at %, Si=8 at % and O=60 at %.
B) Cemented carbide cutting inserts in style CNMG 120408-PM with the same composition as in A) were coated with a 1 μm thick layer of TiN using conventional CVD-technique followed by a 6 μm TiCN layer employing the MTCVD-technique using TiCl4, H2, N2 and CH3CN as process gasses. In subsequent process steps during the same coating cycle, a 0.5 μm TiCxNyOz layer with an approximate composition corresponding to x=0.5, y=0.3 and z=0.2 was deposited followed by a 6 μm thick layer of κ-Al2O3 deposited according to the invented coating process. Prior to the nucleation of the Al2O3 the oxidation potential of the carrier gas H2 (only gas present in the reactor), i.e., the water vapour concentration, was explicitly set forth to a low level, such as less than 5 ppm.
Then the first Al2O3 layer step 1 was started up. The process conditions during the Al2O3 deposition were as below:
















Step
1
2
3









CO2:
4%
4%
4%



AlCl3:
4%
4%
4%



H2S
—
0.2%
0.2%



HCl
1.5%
5%
5%



H2
balance
balance
balance



SiCl4
—
—
2%



Pressure:
60 mbar
60 mbar
60 mbar



Temperature:
1000° C.
1000° C.
1000° C.



Duration:
30 min
5 min
1.5 min










The Al2O3 layer was deposited by proceeding through step 1, 2 and 3 and then looping between step 3 and step 2 altogether 35 times. Hence, the Al2O3-process was treated with SiCl4 altogether 36 times.
XRD-analysis of the deposited Al2O3 layer showed that it consisted essentially of the kappa phase. No diffraction peaks from the mullite-phase (Al6Si2O13) could be detected.
From a SEM-micrograph taken from a cross sectioned sample at a magnification of 70,000 times, the grain size was estimated to be 0.13 μm for the Al2O3 layers and less than 0.04 μm for the layers corresponding to the SiCl4 treatment steps 3. The inserts appeared violet/green in colour and had extremely smooth coating surfaces.
C) The cemented carbide substrate of A) was coated with TiCN (5 μm), a 0.5 μm TiCxNyOz layer and 6 μm Al2O3 as set forth in A) except for that the Al2O3 process was carried out according to prior art technique that is, only step 1 and 2 as described under A) and the process time of step 2 was 290 min. This resulted in an Al2O3 layer consisting essentially of the κ-Al2O3 phase with an average grain size of about 2 μm with a grain structure similar to what is shown in FIG. 2a. 
D) The cemented carbide substrate of A) was coated with TiCN (5 μm), a 0.5 μm TiCxNyOz layer and a 6 μm of multilayered Al2O3/TiN-coating as below:














Step
1
2
3
4







CO2
4%
4%
0%
4%


AlCl3
4%
4%
0%
4%


H2S
—
0.2%
0%
0.2%


HCl
1.5%
5%
0%
5%


H2
balance
balance
balance
balance


TiCl4
—
—
2%
—


N2
—
—
40%
—


Pressure:
60 mbar
60 mbar
60 mbar
60 mbar


Temperature:
1000° C.
1000° C.
1000° C.
1000° C.


Duration:
30 min
20 min
3 min
20 min









The Al2O3 layer was deposited by proceeding through step 1, 2, 3 and 4 and then looping between step 4 and step 3 nine times. Hence, the Al2O3-process was interrupted ten times by a TiN-process.

This resulted in a multilayer coating consisting of 11 layers of Al2O3 and 10 thin layers of TiN. The Al2O3 layer was determined to consist of essentially the kappa phase.
Some of the inserts from A), B), C) and D) were brushed with a cylindrical nylon brush containing SiC grains.
Brushed and unbrushed cutting inserts from A), B), C) and D) were then tested with respect to edge line and rake face flaking in two types of workpiece materials under different cutting conditions.
Cutting operation 1: A facing operation in nodular cast iron (AISI 60-40-18, DIN CGC40). The shape of the machined workpiece was such that the cutting edge was out of cut twice per revolution of the workpiece.
Cutting Data:
Speed=160 m/min,
Feed=0.1 mm/rev.
Depth of cut=2.0 mm
The inserts were run one cut over the face of the workpiece. This test is very decisive and demanding when cutting nodular cast iron.
The percentage of the edge line in cut that obtained flaking was recorded for each insert tested as well as to what extent flaking occurred on the rake face of the cutting insert. The results are expressed in Table 1 below as an average value of the four inserts (four edges).
Cutting operation 2: A facing operation in an alloyed steel (AISI 1518, W-no 1.0580). The shape of the workpiece was such that the cutting edge was out of cut three times per revolution.










Cutting data:


















Speed:
130-220 m/min



Feed:
0.2 mm/rev.



Depth of cut:
2.0 mm










Five inserts (edges) were run one cut over the workpiece. The results in Table 2 are expressed as percentage of the edge-line in cut that obtained flaking of the coating.







TABLE 1







Cutting operation 1










Variant
Edge line flaking







A unbrushed (acc. to invention)
5%



A brushed (acc. to invention)
0%



B unbrushed (acc. to invention)
0%



B brushed (acc. to invention)
0%



C unbrushed (prior art)
65% 



C brushed (prior art)
5%



D unbrushed (prior art)
30% 



D brushed (prior art)
0%

















TABLE 2







Cutting operation 2










Edge line



Variant
flaking
Rake face Flaking





A brushed (acc. to
 5%
Only spot wise Al2O3


invention)

Flaking


B brushed (acc. to
 3%
Only spot wise Al2O3


invention)

Flaking


C brushed (prior art)
90%
Severe Al2O3 flaking


D brushed (prior art)
70%
Flaking of Al2O3 and step wise




between TiN and Al2O3 layers









The results from Table 1 show that unbrushed coatings according to the present invention work equally well as the brushed inserts in alloyed steel and results in Table 2 show that the inserts according to invention also work surprisingly well in nodular cast iron and far better than prior art inserts.

## Claims

1. A cutting tool comprising:
a body of sintered cemented carbide, cermet or ceramic; and 
a hard and wear resistant coating applied on at least a functioning portion of a surface of the body, wherein said coating comprises a structure of one or more refractory layers of which at least one layer consists essentially of an equiaxed fine grained κ-Al2O3 with a thickness of 0.5-25 μm and with a grain size of less than 0.5 μm, and said fine grained κ-Al2O3 layer comprises at least one sublayer with a thickness between 0.02 and 3 μm containing Al, Si and O with a Si concentration between 4-34 at %, Al concentration of greater than 0 to 37 at % and O concentration of 60-67 at %.

2. The cutting tool according to claim 1, wherein the fine grained κ-Al2O3 is in contact with a TiCxNyOz layer.

3. The cutting tool according to claim 1, wherein the fine grained κ-Al2O3 is in contact with an α-Al2O3 layer.

4. The cutting tool according to claim 1, wherein the fine grained κ-Al2O3 layer has 1-200 sublayers containing Al, Si and O.

5. The cutting tool according to claim 4, wherein the fine grained κ-Al2O3 layer has less than 100 sublayers.

6. The cutting tool according to claim 1, wherein the Si concentration is about 8 at %.

7. The cutting tool according to claim 1, wherein the O concentration is about 60 at %.

8. The cutting tool according to claim 1, wherein the Al concentration is about 32 at %.

9. The cutting tool according to claim 8, wherein the fine grained κ-Al2O3 is in contact with a TiCxNyOz layer.

10. The cutting tool according to claim 8, wherein the fine grained κ-Al2O3 is in contact with an α-Al2O3 layer.

11. The cutting tool according to claim 8, wherein the fine grained κ-Al2O3 layer has 1-200 sublayers containing Al, Si and O.

12. The cutting tool according to claim 11, wherein the fine grained κ-Al2O3 layer has less than 100 sublayers.

13. A cutting tool comprising:
a body of sintered cemented carbide, cermet or ceramic; and 
a hard and wear resistant coating applied on at least a functioning portion of a surface of the body, 
wherein said coating comprises a structure of one or more refractory layers of which at least one layer consists essentially of an equiaxed fine grained κ-Al2O3 with a thickness of 0.5-25 μm and with a grain size of less than 0.5 μm, and said fine grained κ-Al2O3 layer comprises 1-200 sublayers containing Al, Si and O and at least one sublayer has a thickness between 0.02 and 3 μm containing Al, Si and O with a Si concentration about 8 at %, Al concentration of about 32 at % and O concentration of about 60 at %, and 
wherein the fine grained κ-Al2O3 is in contact with a TiCxNyOz layer or in contact with an α-Al2O3 layer.

14. The cutting tool according to claim 13, wherein the fine grained κ-Al2O3 layer has less than 100 sublayers.