TWI493063B - Coating, articles coated with the coating, and method for manufacturing the articles - Google Patents

Description

Coating, covering member having the coating, and preparation method of the coated member

The present invention relates to a coating, a coated article having the same, and a method of preparing the coated member, and more particularly to a coating formed by vacuum coating, a coated member having the coating, and a method of preparing the coated member.

The vacuum coating process has a wide range of applications in the industrial field. Among them, the coating of TiN film on the surface of the tool or mold can greatly improve the service life of the tool and the mold. However, as metal cutting progresses toward high cutting speeds, high feed rates, high reliability, long life, high precision, and good cutting control, higher demands are placed on the performance of surface coatings. Conventional TiN coatings have been unable to meet the requirements in terms of hardness and toughness.

ZrN films have attracted much attention due to their hardness and toughness being superior to those of TiN films. However, the single ZrN film has almost no room for improvement in hardness and wear resistance, and it is difficult to meet the needs of modern industry.

Chinese patent CN100480043C mentions the deposition of a ZrN/Al ₂ (O _1-x N _X ) ₃ nanocomposite coating on a hard substrate of metal, cemented carbide or ceramic. The hardness of this nanocomposite coating exceeds 30 GPa, but Its wear resistance has not improved.

Studies have found that ZrB ₂ film has the advantages of high hardness, high corrosion resistance, etc., and can be used as a superhard tool material and a surface protection material. However, since ZrB ₂ itself is a friable material, its toughness and wear resistance are poor, which limits its application to tool or mold coating.

In view of this, it is necessary to provide a coating having high hardness, good corrosion resistance, and abrasion resistance.

In addition, it is necessary to provide a covering having the above coating.

It is also necessary to provide a method of preparing the above-mentioned covering member.

a coating formed on a surface of a hard substrate, the coating comprising a gradient film layer, wherein the gradient film layer is a ZrBN layer, and the number of N atoms and B atoms in the gradient film layer is close to the hard matrix The gradient increases in a direction away from the hard substrate, and the coating further includes a color layer formed on the gradient film layer.

A coated member comprising a hard substrate and a coating formed on the hard substrate, the coating comprising a gradient film layer formed on the hard substrate, the gradient film layer being a ZrBN layer, wherein the gradient film layer The number of N atoms and B atoms increases in a gradient from the hard matrix to a direction away from the hard matrix, and the coating further includes a color layer formed on the gradient film layer.

A method for preparing a coated member, comprising the steps of: providing a hard substrate; magnetron sputtering a gradient film layer on the surface of the hard substrate, the gradient film layer being a ZrBN layer, and the N and B atoms in the gradient film layer The amount of the content increases in a gradient from the hard matrix to a direction away from the hard matrix; A color layer is plated on the surface of the gradient film layer.

Compared with the prior art, the content of the N atom and the B atom in the junction of the gradient film layer and the hard matrix is relatively low, and the gradient film layer mainly exhibits a metal phase of Zr, and has a thermal expansion coefficient similar to that of the hard matrix, so the interface The internal stress is small, so that the gradient film layer has strong bonding force and high toughness; the gradient film layer has a high content of surface N atoms and B atoms, and the gradient film layer mainly exhibits BN phase, ZrB ₂ phase and ZrN. The phase avoids the disadvantages of poor toughness and wear resistance of the coating due to the brittleness of a single ZrB ₂ phase. At the same time, due to the high hardness and high corrosion resistance of BN and ZrB ₂ , the hardness and resistance of the gradient layer are significantly improved. Corrosive. The improvement of the hardness and toughness of the gradient film layer and the enhancement of the bonding force between the gradient film layer and the bonding layer can significantly improve the wear resistance of the coating layer.

10‧‧‧ Coating

11‧‧‧ Gradient film

13‧‧‧ color layer

20‧‧‧bonding layer

30‧‧‧hard substrate

40‧‧‧Cladding

1 is a cross-sectional view of a coating according to a preferred embodiment of the present invention; FIG. 2 is a cross-sectional view of a coated member in accordance with a preferred embodiment of the present invention; and FIG. 3 is a flow chart showing a method of preparing a coated member in accordance with a preferred embodiment of the present invention.

The present invention will be further described in detail below with reference to the accompanying drawings and embodiments.

Referring to FIG. 1, a coating 10 according to a preferred embodiment of the present invention includes a gradient film layer 11 formed on a surface of a rigid substrate 30. The material of the hard substrate 30 may be high speed steel, hard alloy, stainless steel or the like.

The gradient film layer 11 is a ZrBN layer having a thickness of 0.5 to 2 μm. The gradient film layer 11 is formed by magnetron sputtering deposition. In the gradient film layer 11, the number of N atoms and B atoms increases as the thickness of the gradient film layer 11 increases, that is, N atoms and B atoms. The number of contents in the gradient film layer 11 increases in a gradient from the hard substrate 30 to the direction away from the hard substrate 30.

It can be understood that a color layer 13 can also be plated on the surface of the gradient film layer 11 to enhance the aesthetic appearance of the coating layer 10.

Referring to FIG. 2, a covering member 40 according to a preferred embodiment of the present invention includes a rigid substrate 30, a bonding layer 20 formed on the rigid substrate 30, and a coating layer 10 formed on the bonding layer 20. The covering member 40 can be any type of cutting tool, precision measuring tool or mold.

The bonding layer 20 serves to increase the bonding force between the coating 10 and the hard substrate 30. In this embodiment, the bonding layer 20 is a Zr layer having a thickness of 100 to 200 nm. The bonding layer 20 is formed by magnetron sputtering deposition.

Referring to FIG. 3, the method for fabricating the covering member 40 mainly includes the following steps:

S1: A rigid substrate 30 is provided.

S2: Pre-treating the hard substrate 30.

The surface of the hard substrate 30 is wiped with deionized water and absolute ethanol in this order, and the wiped hard substrate 30 is placed in an ultrasonic cleaner containing an acetone solution for vibration cleaning to remove impurities and oil on the surface of the hard substrate 30. . After cleaning, blow dry and set aside.

The surface of the hard substrate 30 subjected to the above treatment is subjected to plasma cleaning to remove impurities on the surface of the hard substrate 30 while increasing the roughness of the surface of the hard substrate 30 to improve the bonding force between the surface of the hard substrate 30 and the subsequent coating. The method for plasma cleaning the surface of the hard substrate 30 comprises the steps of: placing the hard substrate 30 in a coating chamber of a radio frequency magnetron sputtering coating machine, and evacuating to a vacuum of 1.0×10 ^-3 Pa to 250~ A flow rate of 600 sccm was passed through the coating chamber to an argon gas having a purity of 99.999%, and a bias of -300 to -800 V was applied to the hard substrate 30, and the surface of the hard substrate 30 was plasma-cleaned for 10 to 15 minutes.

S3: A bonding layer 20 is formed on the hard substrate 30.

The bonding layer 20 is a Zr layer. In this embodiment, the bonding layer 20 is prepared by the following steps: after the plasma cleaning of the hard substrate 30, the power supply of the zirconium target installed in the coating chamber of the magnetron sputtering coating machine is turned on, and the power is set to 150~ 200W, apply a bias voltage of -100~-250V to the hard substrate 30, adjust the flow rate of argon gas to 100~200sccm, heat the coating chamber to 150~300 °C (ie, the sputtering temperature is 150~300 °C), and deposit the bonding layer 20 . The time for depositing the bonding layer 20 is 5 to 10 minutes.

S4: forming a gradient film layer 11 on the bonding layer 20.

The gradient film layer 11 is a ZrBN layer. When the gradient film layer 11 is prepared, the number of N atoms and B atoms in the gradient film layer 11 is adjusted by adjusting the flow rate of the nitrogen gas and the power of the boron target according to the deposition time with nitrogen as the reaction gas. The gradient changes from a direction close to the hard substrate 30 to away from the hard substrate 30. In this embodiment, the preparation of the gradient film layer 11 includes the following steps: after forming the bonding layer 20, a nitrogen gas having a purity of 99.999% is introduced into the coating chamber at a flow rate of 5 to 25 sccm, and the zirconium target and the boron target are simultaneously turned on. The power source is set to have a power of 150 to 200 W for the zirconium target and 100 to 200 W for the boron target, and a gradient film layer 11 is deposited. In the process of depositing the gradient film layer 11, the flow rate of the nitrogen gas is increased by 5 to 25 sccm and the power of the boron target is increased by 20 to 40 W for every 15 minutes of deposition. The time for depositing the gradient film layer 11 is 45 to 90 minutes. .

The bias voltage and the current of the zirconium target and the boron target are turned off, and the argon gas and the nitrogen gas are stopped. After the gradient film layer 11 is cooled, air is introduced into the coating chamber, the coating chamber door is opened, and the plating layer 20 is removed and plated. The hard substrate 30 of the gradient film layer 11.

It is to be understood that the method of preparing the covering member 40 may further include plating a color layer 13 on the surface of the gradient film layer 11 to enhance the aesthetics of the covering member 40.

The preparation method of the above-mentioned covering member 40 is made by increasing the flow rate of the nitrogen gas and the power of the boron target during the deposition process, so that the number of N atoms and B atoms in the gradient film layer 11 is close to the hard matrix 30 to be far from the hard material. The direction of the substrate 30 increases in a gradient, and the content of the N atom and the B atom in the junction with the bonding layer 20 is relatively low. The gradient film layer 11 mainly exhibits a metal phase of Zr and has thermal expansion similar to that of the hard substrate 30 and the bonding layer 20. The coefficient, and thus the internal stress at the interface, is small, so that the bonding force between the gradient film layer 11 and the bonding layer 20 is enhanced. The gradient film layer 11 has a high content of N atoms and B atoms, and the gradient film layer 11 mainly exhibits a BN phase, a ZrB ₂ phase and a ZrN phase, thereby avoiding coating toughness and wear resistance caused by a single ZrB ₂ phase being brittle. The disadvantage of poor performance, and the BN phase and ZrB ₂ phase have the advantages of high hardness and high corrosion resistance, which significantly improves the hardness and corrosion resistance of the gradient film layer.

In addition, since the internal stress at the interface between the gradient film layer 11 and the bonding layer 20 is small, it is difficult to form a crack when the hard substrate 30 is deformed by force, and it is difficult to expand even if a crack is formed, thereby greatly improving the toughness of the gradient film layer 11. The improvement of the hardness and toughness of the gradient film layer 11 and the enhancement of the bonding force between the gradient film layer 11 and the bonding layer 20 can significantly improve the wear resistance of the coating layer 10.

In summary, the present invention complies with the requirements of the invention patent and submits a patent application according to law. but The above description is only the preferred embodiment of the present invention, and equivalent modifications or variations made by those skilled in the art will be included in the following claims.

10‧‧‧ Coating

11‧‧‧ Gradient film

13‧‧‧ color layer

20‧‧‧bonding layer

30‧‧‧hard substrate

40‧‧‧Cladding

Claims (9)

A coating formed on a surface of a hard substrate, the coating comprising a gradient film layer, wherein the gradient film layer is a ZrBN layer, and the number of N atoms and B atoms in the gradient film layer is close to The hard matrix increases in a gradient away from the hard substrate, and the coating further includes a color layer formed on the gradient film layer. The coating of claim 1, wherein the gradient film layer has a thickness of 0.5 to 2 μm. A coated member comprising a hard substrate and a coating formed on the hard substrate, the coating comprising a gradient film layer formed on the hard substrate, wherein the gradient film layer is a ZrBN layer, The number of N atoms and B atoms in the gradient film layer increases in a gradient from the hard matrix to a direction away from the hard matrix, and the coating further includes a color layer formed on the gradient film layer. The covering member according to claim 3, wherein the gradient film layer has a thickness of 0.5 to 2 μm. The covering member according to claim 3, wherein the covering member further comprises a bonding layer formed between the hard substrate and the coating layer, the bonding layer being a Zr layer having a thickness of 100 to 200 nm. A method for preparing a coated member, comprising the steps of: providing a hard substrate; magnetron sputtering a gradient film layer on the surface of the hard substrate, the gradient film layer being a ZrBN layer, and the N and B atoms in the gradient film layer The amount of the content increases in a gradient from the hard substrate to a direction away from the hard substrate; a color layer is plated on the surface of the gradient film layer. The method for preparing a coated member according to claim 6, wherein when the gradient film layer is magnetron-sputtered, a zirconium target and a boron target are used as targets, and nitrogen is used as a reactive gas, and the initial flow of the nitrogen is used. The amount is 5~25sccm, the flow rate of the nitrogen gas is increased by 5~25sccm every 15min, and the initial power of the boron target is 100~200W. The flow rate of the nitrogen gas is increased by 20~40W every 15min. The method for preparing a coated member according to claim 6, wherein the method for preparing the coated member further comprises the step of magnetron sputtering a bonding layer on the hard substrate before forming the gradient film layer, the bonding layer being a Zr layer. The method for preparing a coated member according to claim 8, wherein the process parameter for forming the bonding layer is: using a zirconium target as a target, setting a power of the zirconium target to 150 to 200 W, and applying a bias voltage to the hard substrate It is -100~-250V, the flow rate of argon gas is 100~200sccm, the sputtering temperature is 150~300°C, and the sputtering time is 5~10min.