# Patent

## Title
Tool and method for the chemical vapor deposition of a two-phase layer on a substrate member

## Abstract

The invention relates to a tool, especially a cutting tool, comprising a substrate member onto which at least one layer is deposited by means of CVD, and a method for the chemical vapor deposition of a two-phase layer on a sintered part. According to the invention, the single deposited layer or at least one of the layers is provided with a TiCN phase, TiOCN phase, TiOC phase, or TiC phase and an additional phase consisting of ZrO2 and/or HfO2. CH3CN, C5H5N, or C6H6 is used in the gas atmosphere for producing such a layer in addition to TiCl4, HfCl4, and/or ZrCl4 and CO2, the remainder being composed of H2 and/or Ar.

## Background
CROSS REFERENCE TO RELATED APPLICATIONS
This application is the US national phase of PCT application PCT/DE2004/000845 filed 23 Apr. 2004 with a claim to the priority of German patent application 10320652.3 itself filed 7 May 2003 and German patent application 102004010594.4 itself filed 2 Mar. 2004.
FIELD OF THE INVENTION
The invention relates to a tool, especially a cutting tool, comprised of a substrate body upon which a layer is deposited by CVD. The invention also relates to a method of CVD deposition of a two phase-layer on a substrate body.
BACKGROUND OF THE INVENTION
Coated substrate bodies for use as cutting elements are basically known.
Thus, for example in German Patent Document 100 17 909 A1, substrate bodies on a tungsten carbide basis and provided with a hard coating are known which have a titanum composite layer with at least one coating of TiC, TiN, TiCN, TiCO and TiCNO and an Al2O3 and/or Al2O3—ZrO2 composite layer. In the last mentioned case, ZrO2 particles are dispersed in an Al2O3 phase.
Furthermore, it is also known to provide layer sequences in the form of TiN—TiCN—TiN layers, optionally with an additional outer Al2O3 layer. Al2O3 layers which are deposited by means of a CVD process can, depending upon the process conditions, be in the form of α-Al2O3, κ-N2O3 or amorphous Al2O3. The German Patent Document DE 100 17 909 A1 discloses for the production of a TiCN layer, a CVD process in which at an average temperature range between 700° C. and 950° C., a reaction gas mixture is used which contains CH3CN.
OBJECT OF THE INVENTION
It is the object of the present invention to provide an improved tool and especially a cutting tool of the aforedescribed type that because of its coating has an improved life in dry machining as well as wet machining and especially in the turning of cast workpieces or heat treatable steels (CK45).
SUMMARY OF THE INVENTION
This object is achieved with the tool according to claim 1 which is characterized in accordance with the invention that the single deposited layer or at least one of the first layers, apart from a TiCN phase or a TiOCN phase or a TiC phase or a TiOC phase has a further comprised of ZrO2 and HfO2. This multiphase layer can be the single layer, an intermediate layer (a layer between two other layers) or an outer layer or coating, whereby, depending upon the use, the procedures can be varied based upon the consideration that with increasing ZrO2 and/or HfO2 proportions, the hardness of the respective layer drops.
Further features of the tool are described in the dependent claims.
Thus the mentioned further phase of ZrO2 and HfO2 can be present in a monoclinic and/or tetragonal form.
Upon the layer defined herein above, according to a further feature, an Al2O3 layer can also be deposited, preferably as an outer layer or coating and preferably also as an α-Al2O3 layer. The substrate body can be comprised of a hard metal, a is cermet or a ceramic.
Preferably the ratio of the TiCN— phase, the TiOCN phase, TiC phase or TiOC phase to the further phase of ZrO2 and/or HfO2, should lie between 4:1 and 1:4 preferably between 2:1 and 1:1.
As has already been indicated, for example the first phase of TiCN or TiOCN also can be replaced by TiC or TiOC so that the ratio of C:N of 0.5:0.5 can be replaced by 1.0:0.
The present invention encompasses also such tools in which in the TiCN-phase or TiOCN phase or TiOC phase or TiC phase, the titanium is replaced to a small proportion by Hf in the compound TiCxNyOz with 0≦x, y, z≦1 so that less than half the titanium can be replaced by Zr or Hf. Preferably a maximum of 20%, and even more preferably a maximum of 10% of the titanium is so replaced. Such compounds can be produced for example when the gas atmosphere from which the respective phase is deposited, contains a substoichiometric amount of oxygen.
According to a further feature or variant of the invention, the two-phase layer can be provided as an intermediate layer which is disposed between TiCN and Al2O3 and on which a ZrCN coating is externally deposited.
To produce the tool according to the invention it is proposed that upon the sintered substrate body for the CVD deposition of the aforementioned multiphase layer, a method can be used and which is characterized in that, in the gas atmosphere, apart from TiCl4, HfCl4 and/or ZrCl4 and CO2, additionally CH3CN (acetonitrile) or C5H5N (pyridine) or C6H6 (benzene) is provided, the balance being H2 and/or Ar. When acetonitrile is used the following simultaneous reactions run in the gas phase:

2TiCl4+CH3CN+4.5H2→2TiC0.5N0.5+CH4+8HCl

ZrCl4+2CO2+2H2→ZrO2+2CO+4HCl

or

2TiCl4+CH3CN+4.5H2→2TiCO5N0.5+CH4+8HCl

HfCl4+2CO2+2H2→HfO2+2CO+4HCl

Corresponding reactions occur when instead of acetone, pyridine is used, whereby as a reaction product a TiCxNy-phase will also arise. However, in the case of use of pyridine in the gas phase the C:N proportion changes from 0.5:0.5 to 0.7:0.3 and when benzene is used the proportion becomes 1.0:0, that is in the first phase less or no nitrogen is contained.
Preferably the following gas proportions are used: TiCl4:1:4 vol. %, preferably 1:2 vol. %
ZrCl4 and/or HfCl4:0.3 to 4 Vol. % preferably 0.5 to 2 vol. % C5H5N or CH3CN or C6H6: 0.2 to 2 vol. % preferably 0.5 to 1 vol %.
CO2:0.1 to 3 Vol. %, preferably 0.3 to 2 Vol. %.
Balance Ar and/or H2.
The deposition temperature in a preferred application of the invention lies between 800° and 1000° C. and the gas atmosphere pressure is 5×103 Pa to 6×104 Pa.
In a concrete example, a hard metal substrate body has a hard material phase of WC and a binder phase of 6% by weight Co upon which a layer sequence of TiN—TiCN/HfO2—TiN is deposited and for the deposition of the intermediate layer, the following gas phase composition is chosen:
1.4 vol. % TicCl4, 1.4 vol. % HfCl4, 0.8 vol. % CH3CN, 0.5 Vol. % CO2, balance H2.
The other TiN layers are respectively produced using a convention CVD coating process.
In a corresponding way on a hard metal substrate body, layer sequences of TiN—TiCN—TiCN/HfO2-αAl2O3 can be deposited. It has been found surprisingly that using the multiphase intermediate layer TiCN/HfO2 in accordance with the invention with a CVD process, stable α-Al2O3 can be generated.



BRIEF DESCRIPTION OF THE DRAWINGS
The advantages of the invention which are described in greater detail hereinafter will be apparent from the drawings:
FIGS. 1 to 3 are each a set of comparative bar graphs comparing the life of a cutting tool with a two phase coating or layer according to the invention with the life of a cutting tool with a three phase coating or layer according to the prior art.



As previously described, on a hard metal substrate body which has the form of a cutting insert of the type SNUN 120408, in the first case, a layer sequence according to the invention of TiN/TiCN/HfO2—TiN is applied. The intermediate layer thus is comprised of two phases namely, TiCN on the one hand and HfO2 on the other.
By comparison therewith, a substrate body of the same composition and the same type is provided with a three layer coating of TiN—TiCN—TiN. In a dry turning of a steel of the type CK45N with the parameters vc=200 m/min, aρ=2.0 mm and f=0.4 mm/revolution, the life of the coating according to the invention was about 15 min whereas the life of the comparative body in accordance with the state of the art was less than 12 min.
Also by comparison with a cutting body in accordance with the coating techniques of the state of the art, with a layer sequence of TiN—TiCN—K —Al2O3, the coating sequence according to the invention of TiN—TiCN—TiCN/HfO2-α-Al2O3 can provide a continuous cut in turn of the workpiece using a coolant/lubricant, that is a wet cut, and with a significant improvement in the life of the tool.
While with the layer sequence in accordance with the state of the art in which the intermediate TiCN layer is deposited with a deposition temperature between 800° C. and 1000° C. and the gas phase only deposits K Al2O3, the tool has a useful life of only six minutes, whereas the life with the layer sequence in which between the TiCN layer and the Al2O3 layer a two phase intermediate layer of TriCN and HfO2 has been interposed, the life is substantially greater. This intermediate layer allows, at the same process conditions, the deposition of α-Al2O3. The life of the tool is 9 minutes which is a 50% improvement. In the composition tests the workpiece was a cast body of GG25 and the cutting insert was of the type CNMG120412-5 and the following turning parameters were used: vc=450 m/min, aρ=2.5 mm and f=0.315 mm/revolution.
As can be seen from FIG. 3, the coating according to the invention also provides in wet turning with a continuous cut a significant improvement in the life of the tool. On a substrate body of the same composition as type CNMG120412-5, a layer sequence of the composition TiN—TiCN(MT)—TiCN/HfO2-α-Al2O3 was applied in a first case and in the second case a layer sequence of TiN—TiCN(MT)K—Al2O3—ZrCN was applied.
Both cutting inserts were used for the turning of a cast iron body of the type GG25 with the following machining parameters vc=400 m/min, aρ=2.5 mm, f=0.315 mm/revolution.
The life of the insert which was made with the layer composition according to the invention in which a two-phase intermediate layer TiCN/HfO2 was introduced, was 12.5 min whereas the cutting insert according to the state of the art had a life of 10.2 min.
The aforedescribed test results show clearly that both is with dry turning and also with turning in a wet state, significant improvements in the life of the tool can be achieved.

## Claims

1. A tool, especially a cutting tool comprised of a substrate body upon which a single coating or at least one layer is deposited by means of CVD, wherein said single coating or at least one deposited layer consists of two phases, wherein the single deposited coating or at least one of the layers has apart from a first TiCN phase or a TiOCN phase or a TiOC phase or a TiC phase, a further phase consisting of ZrO2 or HfO2.

2. The tool according to claim 1 wherein the further phase is present in monoclinic and/or tetragonal form.

3. The tool according to claim 1 wherein on the coating or layer which consists of a first TiCN phase or a TiOCN phase or a TiOC phase or a TiC phase and a ZrO2 or HfO2 as a further phase, Al2O3 is deposited.

4. The tool according to claim 3 wherein the Al2O3 is deposited as an outer coating.

5. The tool according to claim 4 wherein the Al2O3 deposited as an outer coating is deposited as α-Al2O3.

6. The tool according to claim 1, wherein the substrate body is comprised of a hard metal, a cermet or a ceramic.

7. The tool according to claim 1, wherein the ratio of the TiCN phase, TiOCN phase, TiC phase or TiOC phase to the further phase lies between 4:1 and 1:4.

8. The tool according to claim 7, wherein the ratio of the TiCN phase, TiOCN phase, TiC phase or TiOC phase to the further phase lies between 2:1 and 1:2.

9. The tool according to claim 1, wherein in the TiCN phase, or TiOCN phase, or TiOC phase or TiC phase, the titanium is replaced to a small proportion by Zr or Hf.

10. The tool according to claim 1, wherein the layer consisting of two phases is an intermediate layer between two TiN layers.

11. A method of CVD deposition of a layer consisting of two phases upon a substrate body according to claim 1, comprising the step of introducing during said CVD deposition, into a gas atmosphere apart from TiCl4, HfCl4 or ZrCl4 and CO2, acetonitrile or pyridine or benzene, the balance being H2 and/or Ar.

12. The method of CVD deposition according to claim 11 wherein the gas atmosphere has the following gas proportions:
TiCl4: 1 to 4 vol. %, ZrCl4 or HfCl40.3 to 4 vol. %, pyridine or acetonitrile or benzene: 0.2 to 2 vol. %; CO2: 0.1 to 3 vol. %, balance Ar and/or H2.

13. The method of CVD deposition according to claim 12 wherein the gas atmosphere has the following gas proportions: TiCl4: 1 to 2 vol. %, ZrCl4 or HfCl4: 0.5 to 2 vol. %, pyridine or acetonitrile or benzene: 0.5 to 1 vol. %; CO2: 0.3 to 2 vol. %.

14. The method of CVD deposition according to claim 12 carried out at a deposition temperature between 800° C. and 1000° C. and at a gas atmosphere pressure between 5×103 and 6×104 Pa.