TWI477616B - Articles and mathod for making the same - Google Patents

Description

Covered member and method of manufacturing same

The present invention relates to a coated member and a method of manufacturing the same.

A molding die of a conventional low-melting material such as magnesium or a magnesium alloy, aluminum or aluminum alloy is usually made of stainless steel. However, in the high temperature oxidizing environment, the surface of the stainless steel substrate is liable to form a loose layer of chromium oxide (Cr ₂ O ₃ ); when the temperature is gradually increased, the Cr ₂ O ₃ layer becomes unstable and begins to decompose, making the interior of the stainless steel substrate The metal ions such as Fe and Ni diffuse into the Cr ₂ O ₃ layer, causing cracking and spalling of the Cr ₂ O ₃ layer, which greatly reduces the high temperature oxidation resistance of the stainless steel substrate.

In addition, the formation of the Cr ₂ O ₃ layer will roughen the surface of the molding die, which will affect the appearance of the molded product, lower the yield of the molded product, and also shorten the service life of the molding die.

In view of this, it is necessary to provide a covering member that can better solve the above problems.

Further, a method of manufacturing the above-described covering member is also provided.

A coated member includes a substrate, a chromium layer sequentially formed on the substrate, a chromium oxynitride layer, and a titanium nitride layer.

A method of manufacturing a coated member, comprising the steps of:

Providing a substrate;

Using a chromium target as a target, magnetron sputtering a chromium layer on the substrate;

Using a chromium target as a target, using nitrogen and oxygen as reaction gases, magnetron sputtering a chromium oxynitride layer on the chromium layer;

A titanium target was used as a target, and a titanium nitride layer was magnetron-sputtered on the chromium oxynitride layer using nitrogen as a reaction gas.

In the method for producing a coated article of the present invention, a chromium layer, a chromium oxynitride layer and a titanium nitride layer are sequentially formed on the substrate by a magnetron sputtering coating method. Since the chromium layer and the CrON layer can effectively prevent oxidation of the substrate under high temperature oxidation conditions, the high temperature oxidation resistance of the substrate can be effectively improved; the formation of the TiN layer can prevent the CrON layer from being scratched. Thereby the coated member has good wear resistance.

Further, when the covering member is a molding die for molding a low melting point material such as magnesium, a magnesium alloy, aluminum or an aluminum alloy, the high temperature oxidation resistance of the coated member is improved, the yield of the molded product can be improved, and the coating can be extended. The service life of the piece.

Referring to FIG. 1, a covering member 10 according to a preferred embodiment of the present invention includes a base 11, a chromium layer 13 sequentially formed on the base 11, a chromium oxynitride (CrON) layer 15, and a titanium nitride (TiN) layer 17.

The material of the base 11 is stainless steel, die steel or high speed steel.

The covering member 10 may be a molding die for molding a low melting point material such as magnesium, magnesium alloy, aluminum or aluminum alloy.

The chromium layer 13, the CrON layer 15, and the TiN layer 17 can be formed by magnetron sputtering coating, respectively.

The chromium layer 13 has a thickness of 100 to 200 nm.

The CrON layer 15 has a thickness of 0.5 to 1 μm. The content of chromium in the CrON layer 15 is 40% to 60%, the mass percentage of oxygen is 30% to 50%, and the mass percentage of nitrogen is 5% to 15%.

The TiN layer 17 has a thickness of 0.4 to 1.2 μm.

As shown in FIG. 2, the manufacturing method of the covering member 10 according to a preferred embodiment of the present invention mainly includes the following steps:

A substrate 11 is provided. The base 11 can be obtained by press forming.

The substrate 11 is pretreated. The pretreatment may include conventional steps of chemical degreasing, wax removal, pickling, ultrasonic cleaning, and drying of the substrate 11.

A coating machine 100 is provided, and the substrate 11 is placed in the coating machine 100, and a chromium layer 13, a CrON layer 15, and a TiN layer 17 are sequentially formed on the substrate 11 by magnetron sputtering.

As shown in FIG. 2, the coater 100 includes a coating chamber 20 and a vacuum pump 30 connected to the coating chamber 20. The vacuum pump 30 is used to evacuate the coating chamber 20. A rotating frame (not shown), two first targets 22, and two second targets 23 are provided in the coating chamber 20. The turret drives the base body 11 to revolve along the circular trajectory 21, and the base body 11 also rotates when revolving along the trajectory 21. The two first targets 22 and the two second targets 23 are symmetrically disposed with respect to the center of the track 21, and the two first targets 22 are oppositely disposed on the inner and outer sides of the track 21, and the second targets 23 are oppositely disposed on the track 21 Inside and outside. A gas source passage 24 is disposed at each end of each of the first target 22 and each of the second targets 23, and the gas enters the coating chamber 20 through the gas source passage 24. When the substrate 11 passes between the two first targets 22, particles sputtered on the surface of the first target 22 may be plated; similarly, when the substrate 11 passes between the second targets 23, it may be plated. Particles sputtered on the surface of the second target 23. In the present example, the first target 22 is a chromium target and the second target 23 is a titanium target.

The chromium layer 13 is magnetron sputtered on the surface of the substrate 11. The specific operation method and process parameters for forming the chromium layer 13 are: vacuuming the coating chamber 20 to a background vacuum of 8.0×10 ⁻³ Pa, and using argon as a working gas, passing through the coating chamber 20 The argon gas having a flow rate of 100 to 200 sccm is applied with a bias of -100 to -300 V on the substrate 11, and the coating chamber is heated to a temperature of 20 to 150 ° C (that is, a coating temperature of 100 to 150 ° C) to open the first target. The power source of 22 is set to have a power of 5 to 10 kW, and the chromium layer 13 is deposited. The time for depositing the chromium layer 13 is 5 to 15 minutes.

The Cr atoms in the chromium layer 13 can be combined with O atoms to form a Cr ₂ O ₃ protective film in a high-temperature oxidation environment, thereby effectively preventing oxidation of the substrate 11 and failing.

A CrON layer 15 is formed on the chromium layer 13. The specific operation method and process parameters for forming the CrON layer 15 are: maintaining the argon flow rate, the coating temperature, the power of the first target 22, and the bias voltage applied to the substrate 11, and setting the nitrogen gas and the oxygen gas as the reaction gas. The flow rate of nitrogen is 10 to 100 sccm, and the flow rate of oxygen is 10 to 100 sccm, and the CrON layer 15 is deposited. The time for depositing the CrON layer 15 is 30 to 60 minutes, and the power of the first target 22 is turned off after the deposition is completed.

The CrON layer 15 can form a Cr-O and a Cr-N two-phase compound during the formation thereof, and the two-phase compound can simultaneously inhibit the growth of crystal grains of each phase, thereby reducing the size of crystal grains of each phase. The denseness of the CrON layer 15 is enhanced to prevent the diffusion of oxygen into the interior of the CrON layer 15, and the oxidation of the substrate 11 can be further prevented.

A TiN layer 17 is formed on the CrON layer 15. The specific operation method and process parameters for forming the TiN layer 17 are: maintaining the argon flow rate, the coating temperature, and the bias voltage applied to the substrate 11 unchanged, using nitrogen as the reaction gas, and setting the flow rate of the nitrogen gas to 60 to 120 sccm to open the The power source of the second target 23 is set to have a power of 8 to 10 kW, and the TiN layer 17 is deposited. The time for depositing the TiN layer 17 is 30 to 90 minutes.

The TiN layer 17 has a high melting point, high hardness, and excellent wear resistance, so that the TiN layer 17 can protect the CrON layer 15 from being scratched by the CrON layer 15.

The power supply of the negative bias and the target is turned off, and the argon gas and the oxygen gas are stopped. After the TiN layer 17 is cooled, air is introduced into the coating film, the coating chamber door is opened, and the covering member 10 is taken out.

In the manufacturing method of the coated member 10 of the preferred embodiment of the present invention, the chromium layer 13, the CrON layer 15, and the TiN layer 17 are sequentially formed on the substrate 11 by magnetron sputtering. Since the chromium layer 13 and the CrON layer 15 can effectively prevent oxidation of the substrate 11 under high temperature oxidizing conditions, the high temperature oxidation resistance of the substrate 11 can be effectively improved; the formation of the TiN layer 17 can prevent CrON. The layer 15 is scratched so that the covering member 10 has good wear resistance.

In addition, when the covering member 10 is a molding die for molding a low melting point material such as magnesium, magnesium alloy, aluminum or aluminum alloy, the high temperature oxidation resistance of the covering member 10 can improve the yield of the molded product, and Extend the service life of the covering member 10.

The invention will now be specifically described by way of examples.

Example 1

(1) Magnetron sputtering to form a chromium layer 13

The coating chamber 20 has a background vacuum of 8×10 ⁻³ Pa, an argon flow rate of 150 sccm, a bias voltage applied to the substrate 11 of −200 V, and a plating temperature of 120° C., and the first target 22 is disposed. The power of the power is 8 kW, and the time for depositing the chrome layer 13 is 5 minutes.

(2) Magnetron sputtering to form CrON layer 15

The argon flow rate, the coating temperature, the power of the first target 22, and the bias voltage applied to the substrate 11 were maintained, and the flow rate of nitrogen gas was set to 30 sccm, the flow rate of oxygen gas was 40 sccm, and the time for depositing the CrON layer 15 was 40 min.

(3) Magnetron sputtering to form TiN layer 17

The flow rate of the argon gas, the coating temperature, and the bias voltage applied to the substrate 11 were kept constant, the flow rate of the nitrogen gas was set to 60 sccm, the power source of the second target 23 was 8 kW, and the time for depositing the TiN layer 17 was 60 min.

Example 2

(1) Magnetron sputtering to form a chromium layer 13

The coating chamber 20 has a background vacuum of 8×10 ⁻³ Pa, an argon flow rate of 150 sccm, a bias voltage applied to the substrate 11 of −200 V, and a plating temperature of 120° C., and the first target 22 is disposed. The power supply was 5 kW, and the chrome layer 13 was deposited for 10 minutes.

(2) Magnetron sputtering to form CrON layer 15

The argon flow rate, the coating temperature, the power of the first target 22, and the bias voltage applied to the substrate 11 were maintained, and the flow rate of nitrogen gas was set to 60 sccm, the flow rate of oxygen gas was 80 sccm, and the time for depositing the CrON layer 15 was 60 min.

(3) Magnetron sputtering to form TiN layer 17

The flow rate of the argon gas, the coating temperature, and the bias voltage applied to the substrate 11 were maintained, the flow rate of the nitrogen gas was set to 100 sccm, the power source of the second target 23 was 8 kW, and the time for depositing the TiN layer 17 was 30 min.

Performance Testing

The coated member 10 prepared above is subjected to an electromagnetic masking effectiveness test, a hundred-square test, a salt spray test, and a high-temperature and high-humidity test. The specific test methods and results are as follows:

(1) High temperature oxidation test

The tube heat treatment furnace was used, and the temperature was raised to 800 ° C at a heating rate of 10 ° C / min, and the temperature was maintained at 800 ° C for 10 hours, and then the heat treatment furnace was cooled.

Tests have shown that the coated member 10 obtained in the first and second embodiments of the present invention has not been oxidized or peeled off after being heat-treated at 800 ° C for 10 hours. It can be seen that the coated member 10 obtained by the method of the embodiment of the present invention has good high temperature oxidation resistance.

(2) Abrasion resistance test

The surface of the covering member 10 was rubbed with a load of 1 kg using a 5700 type linear abrasion resistance tester at a cycle speed of 2 inches and a cycle speed of 25 cycles/minute.

The results showed that the coated members 10 obtained in the inventive examples 1 and 2 did not expose the substrate after 20 cycles. It can be seen that the covering member 10 has better wear resistance.

10. . . Covered piece

11. . . Matrix

13. . . Chrome layer

15. . . Chromium oxynitride layer

17. . . Titanium nitride layer

100. . . Coating machine

20. . . Coating chamber

30. . . Vacuum pump

twenty one. . . Trajectory

twenty two. . . First target

twenty three. . . Second target

twenty four. . . Air source channel

Figure 1 is a cross-sectional view of a coated member in accordance with a preferred embodiment of the present invention;

Figure 2 is a schematic view of a vacuum coater used to manufacture the coated member of Figure 1.

10. . . Covered piece

11. . . Matrix

13. . . Chrome layer

15. . . Chromium oxynitride layer

17. . . Titanium nitride layer

Claims (10)

A covering member comprising a base body, wherein the covering member further comprises a chromium layer, a chromium oxynitride layer and a titanium nitride layer which are sequentially formed on the substrate. The covering member according to claim 1, wherein the chromium layer, the chromium oxynitride layer and the titanium nitride layer are respectively formed by a magnetron sputtering coating method. The coated article of claim 1 or 2, wherein the titanium nitride layer has a mass percentage of aluminum of 40% to 65%, and an oxygen element content of 30% to 45%. %, the mass percentage of nitrogen is 5% to 15%. The covering member according to claim 1, wherein the chromium layer has a thickness of 100 to 200 nm. The covering member according to Item 1, wherein the chromium oxynitride layer has a thickness of 0.5 to 1 μm, and the titanium nitride layer has a thickness of 0.3 to 0.5 μm. The coated article of claim 1, wherein the substrate is stainless steel, die steel or high speed steel. A method of manufacturing a coated member, comprising the steps of:
Providing a substrate;
Using a chromium target as a target, magnetron sputtering a chromium layer on the substrate;
Using a chromium target as a target, using nitrogen and oxygen as reaction gases, magnetron sputtering a chromium oxynitride layer on the chromium layer;
A titanium target was used as a target, and a titanium nitride layer was magnetron-sputtered on the chromium oxynitride layer using nitrogen as a reaction gas. The method for manufacturing a coated member according to claim 7 , wherein the step of magnetron sputtering the chromium layer is carried out by using argon gas as a working gas, and setting an argon gas flow rate of 100 to 200 sccm to be applied on the substrate. The bias voltage of -100~-300V, the coating temperature is 100~150°C, the power supply of the chrome target is 5~10kW, and the deposition time is 5~15min. The method for manufacturing a coated member according to claim 7 , wherein the step of magnetron sputtering the chromium oxynitride layer is carried out by using argon gas as a working gas, setting an argon gas flow rate of 100 to 200 sccm, and setting a nitrogen gas. The flow rate is 10~100sccm, the flow rate of oxygen is 10~100sccm, the bias voltage of -100~-300V is applied to the substrate, the coating temperature is 100~150°C, the power supply of the chromium target is 5~10kW, and the coating temperature is 100~150 °C, deposition time is 30~60min. The method for manufacturing a coated member according to claim 7 , wherein the step of magnetron sputtering the titanium nitride layer is carried out by using argon gas as a working gas and setting an argon gas flow rate of 100 to 200 sccm to the substrate. Apply a bias voltage of -100~-300V, set the flow rate of nitrogen to 60~120sccm, set the power supply of the titanium target to 8~10kW, the coating temperature is 100~150°C, and the deposition time is 30~90min.