JP4868534B2 - Method for depositing a high melting point metal carbide layer - Google Patents

Description

  The present invention relates to a method for depositing a hard material layer comprising a carbide of a refractory metal such as titanium, tungsten, zirconium or an alloy composed mainly of a refractory element. The high melting point in the meaning of the present invention is an element having a melting point of 1400 ° C. or higher. Objects with such a hard material layer are advantageously used for cutting tools or press elements that are subject to wear by friction and / or pressure or when it is desired to achieve anticorrosive properties. The main requirements imposed on a hard material layer made of a carbide of high melting point metal are high hardness and wear resistance and good adhesion to each substrate.

  For example, it is known to deposit a titanium carbide layer or a tungsten carbide layer on an object by plasma spraying (A. Haefer, “Overflachen-und Dunnschich-Technology, Tail 1 Beschichengen von Oberchen, 1st publishing, 29th year, 1987, Spr. See page below). However, the layers produced by this method have only high roughness, high porosity and limited wear protection.

Titanium carbide or titanium carbonitride is deposited by CVD (Chemical Vapor Deposition) on the Internet page “ https://www.balzer-technik.ch/Technische Hinweise / overflachenchenhandling.htm” on March 30, 2004 A method is disclosed. The deposition of the layer takes place at a temperature of 1000 ° C. This limits the body material that one wishes to coat. Furthermore, this method guarantees only a small precipitation rate.

  For example, another possibility for depositing titanium carbonitride is arc evaporation (see Ueberschism information Nr. 401/2003 of METAPLAS IONON). However, even with this method, only a small precipitation rate can be obtained for a small coated surface. The publication discloses a method of depositing tungsten carbide on an amorphous carbon matrix by PVD (physical vapor deposition) magnetron sputtering technique to form a so-called “WC: H layer”. Although magnetron sputtering makes it possible to deposit a hard material layer with good wear properties, here again the deposition rate with a maximum of about 10 nm / s is not satisfactory from an economic point of view.

  Therefore, a technical problem of the present invention is to provide a method capable of depositing a hard material layer made of a carbide of a high melting point metal at a deposition rate of at least 20 nm / s. It is desirable for the deposited layer to have high hardness, abrasion resistance and abrasion resistance.

  The solution to this technical problem is obtained by an object with the features of claim 1. Further advantageous embodiments of the invention result from the dependent claims.

  According to the present invention, a carbon-containing atmosphere is generated by inflow of a reactive gas into a vacuum chamber; a refractory metal is evaporated by an electron beam; precipitation is aided by a plasma, in which case the plasma is diffused into a diffusion arc Generated on the surface of the high melting point metal to be evaporated by discharge; the coverage is at least 20 nm / s and at least one is maintained by keeping the object temperature between 50 ° C. and 500 ° C. during the deposition. A layer of a kind of refractory metal carbide is deposited on the at least one object in a vacuum chamber by high rate electron beam evaporation.

  As refractory metal, for example tungsten, zirconium or preferably titanium may be used. These elements are suitable for forming hard material layers with good wear properties. However, a high melting point metal in the sense of the present invention also means an alloy in which one of the aforementioned metals is preferentially superior.

  The main step of the method according to the invention is the generation of a plasma by a diffuse arc discharge. In this case, the high-energy electron beam impinging on the surface of the evaporating material is deflected rapidly and periodically at high frequencies, so that at least a part of the surface of the material to be evaporated is heated, so to speak, finally. Is evaporated. At the same time, the material to be evaporated, for example located in the crucible, is connected as the cathode of a strong arc discharge. A so-called “diffusion arc” is formed which burns mainly in the area of the surface of the evaporated material heated by the electron beam. Compared to normal arc discharges that form routes with extremely high current densities, diffuse arc discharges have a diffusive and planar spread in the evaporate. This spread substantially corresponds to the surface of the evaporant, which is so uniformly heated. This ionizes a major proportion of the generated metal vapor, thus achieving a high degree of ionization overall. This contributes to the formation of a dense layer with high hardness. Furthermore, the use of a diffusion arc discharge has the advantage that this diffusion arc discharge does not sputter and is therefore particularly suitable for plasma activated deposition over large surfaces.

In one embodiment, acetylene (C ₂ H ₂ ) is flowed into the vacuum chamber as a reactive gas, thus creating a carbon-containing atmosphere in the vacuum chamber. Due to the triple bond between both carbon atoms, this gas has a particularly high reactivity. However, in order to generate a carbon-containing atmosphere in the vacuum chamber, for example, methane or butane may be flowed into the vacuum chamber.

It is also advantageous to allow a reactive gas to flow into the vacuum chamber, thereby depositing a stoichiometric layer. This is because this layer has a high hardness value. For this purpose, a reactive gas pressure in the vacuum chamber of 1 × 10 ⁻³ mbar to 5 × 10 ⁻² mbar is suitable.

  The hardness of the carbide layer deposited according to the invention can also be increased by flowing a nitrogen-containing and / or oxygen-containing gas into the vacuum chamber as an additional reactive gas. Applying a negative bias voltage in the range of 50V to 300V to the object to be coated, which accelerates the ionized vapor or reactive gas particles towards the surface of the object, can also be applied to the layer properties, eg layer It advantageously affects the wear resistance, hardness and density of the steel. This negative bias voltage may be switched, for example with respect to the crucible or anode where the evaporant is located. As a bias voltage, a DC voltage or a voltage pulsed to an intermediate frequency or to a high frequency may be applied to an object to be coated. The use of a pulse bias has a particularly advantageous effect on the stability of the process guide, particularly during the deposition of poorly conductive carbide layers.

  In order to achieve a minimum amount of plasma activation, an arc current of at least 100 A of diffuse arc discharge to the surface of the evaporated material must be formed. For example, when a carbide hard material layer is deposited by magnetron sputtering, a maximum deposition rate of about 10 nm / s can be obtained, whereas the method according to the present invention enables a deposition rate of several hundred nm / s. Very good layer properties are obtained with a deposition rate in the range of 50 nm / s to 250 nm / s and a layer thickness of 10 nm to 10 μm, preferably 1 μm to 5 μm.

  In another embodiment, at least one lower layer is deposited between the carbide hard material layer and the object to be coated. This compensates for the mechanical stresses that are generated, and thus a better anchoring of the hard material layer is achieved.

  In the following, the invention will be described in detail with reference to advantageous embodiments. FIG. 1 schematically shows an apparatus in which the method according to the invention can be carried out. An evaporation crucible 2 is arranged in the vacuum chamber 1. In the evaporation crucible 2, titanium is evaporated as the evaporation material 3. A high-power axial electron beam gun 4 is connected to the vacuum chamber. The high output axial electron beam gun 4 generates an electron beam 5. The electron beam 5 is diverted to the surface of the evaporating material 3 located in the evaporating crucible 2 by an electromagnetic diverting device (not shown). Therefore, the evaporating material 3 is heated and finally evaporated. An electrode 6 is disposed above the evaporation crucible 2. This electrode 6 surrounds the vapor chamber and can be adjusted to a positive voltage with respect to the evaporation crucible 2. A steel object 8 that is moved in the conveying device 7 above the electrode 6 is coated with evaporated material.

  The electron beam gun 4 quickly deflects the high-energy electron beam 5 with an output of about 50 kw at high frequency and periodically, so that at least a part of the surface of the evaporation material 3 is heated uniformly, so to speak. Evaporate. A DC voltage of about 30 V applied between the electrode 6 and the evaporation crucible 2 by the power supply device 9 results in the formation of a so-called “diffusion arc discharge” with a current of about 300 A. This diffusion arc discharge mainly burns the surface of the evaporation material 3 which is heated to a uniform level by the electron beam 5. Thereby, a high degree of ionization of the vapor is obtained. A bias voltage of −100 V applied to the object 8 by the power supply device 10 causes acceleration of ionized vapor particles to the surface of the object 8.

  The inflow of acetylene gas by the gas inflow system 11 into the vacuum chamber 1 during titanium evaporation causes a 3 μm thick stoichiometric TiC layer to deposit on the object 8 at a constant coverage of about 100 nm / s. Is done. In this case, the object 8 is maintained at a temperature of 200 ° C. Testing has shown that the TiC layer thus produced has a high hardness of 33 GPa and a high wear resistance.

1 schematically shows an apparatus in which the method according to the invention can be carried out.

Explanation of symbols

  DESCRIPTION OF SYMBOLS 1 Vacuum chamber, 2 Evaporation crucible, 3 Evaporation material, 4 High output axial electron beam gun, 5 Electron beam, 6 Electrode, 7 Conveyance apparatus, 8 Object, 9 Power supply apparatus, 10 Power supply apparatus, 11 Gas inflow system

Claims (12)

In a method for depositing a layer of carbide of at least one refractory metal (3) on at least one object (8) in a vacuum chamber (1) by electron beam evaporation, in the vacuum chamber (1) An atmosphere containing carbon is generated by inflow of a reactive gas to the metal; a high melting point metal (3) is evaporated by an electron beam (5); precipitation is supported by plasma, and in this case, the electron beam (5) is converted to a high melting point. The metal (3) is deflected rapidly and periodically at high frequency over at least a predetermined area of the surface of the metal (3), whereby the high melting point metal (3) is heated and evaporated uniformly in that area, An evaporation crucible (2) where the melting point metal (3) is located is formed as a cathode, whereby the surface of the high melting point metal (3) where the plasma is to be evaporated by diffusion arc discharge. Consisting of at least one refractory metal carbide, characterized in that the coverage is at least 20 nm / s and the object temperature during deposition is kept between 50 ° C. and 500 ° C. the method for depositing in a vacuum chamber by means of at least electron beam evaporation to one object layers.   2. The method according to claim 1, wherein tungsten, zirconium or titanium is used as the refractory metal (3).   The method according to claim 1 or 2, wherein the carbon-containing atmosphere is generated by inflow of acetylene, methane or butane into the vacuum chamber.   4. The method according to claim 1, wherein a reactive gas is allowed to flow into the vacuum chamber (1), thereby depositing a stoichiometric carbide layer on the object (8).   The method according to claim 1, wherein a nitrogen-containing and / or oxygen-containing gas is introduced as an additional reactive gas.   The method according to any one of claims 1 to 5, wherein a negative bias voltage of 50V to 300V is applied to the object (8).   The method according to claim 6, wherein the bias voltage is applied as a DC voltage or as a voltage pulsed to an intermediate frequency or to a high frequency. The method according to claim 1, wherein a reactive gas pressure of 1 × 10 ⁻³ mbar to 5 × 10 ⁻² mbar is generated in the vacuum chamber (1).   9. A method according to any one of claims 1 to 8, wherein an arc current of at least 100A is formed upon plasma activation.   The method according to any one of claims 1 to 9, wherein the coverage is formed within a range of 50 nm / s to 250 nm / s.   The method according to claim 1, wherein a layer thickness of 10 nm to 10 μm is deposited.   The method according to claim 11, wherein the layer thickness is 1 μm to 5 μm.

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