TWI496903B - 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, toughness and wear resistance, and it is difficult to meet the needs of modern industry.

In view of this, there is provided a coated member using a coating having good hardness, toughness and abrasion resistance.

Further, a method of preparing the above-mentioned covering member is also provided.

A covering member comprising a base body, a bonding layer formed on the base body, and a coating layer formed on the bonding layer, the bonding layer being a ZrY layer, the coating layer comprising a nano composite layer, the nano composite layer comprising The complex ZrN layer and the complex ZrYN layer, the complex ZrN layer and the complex ZrYN layer are alternately arranged.

A method for preparing a coated member, comprising the steps of: providing a substrate; magnetron sputtering a bonding layer on a surface of the substrate, the bonding layer is a ZrY layer; and magnetron sputtering a nano composite layer on the surface of the bonding layer, the nano layer The m composite layer includes a complex ZrN layer and a complex ZrYN layer, and the complex ZrN layer and the complex ZrYN layer are alternately arranged.

When forming the ZrYN layer, the N atom preferentially forms ZrN grains with the Zr atoms, and the Y atoms are segregated in an independent form on the grain boundaries to form a Y phase, which can inhibit the growth of the ZrN grains, thereby making the ZrYN layer The particle size of the ZrN grains is maintained at the nanometer level, and the nano-sized ZrN grains can effectively improve the hardness and toughness of the nanocomposite layer. More importantly, due to the difference in shear modulus between the nanoscale nitride ZrN and ZrYN, the dislocation motion between each ZrN layer and each ZrYN layer alternately deposited stops at the interface of the two layers. The plug product of the bit error can cause a hardening phenomenon and suppress deformation of the film layer, so that the hardness and toughness of the nanocomposite layer are further significantly improved. The covering member is provided with a ZrY bonding layer between the substrate and the nano composite layer, which can effectively improve the bonding force between the coating and the substrate. The increase in hardness and toughness of the coating and the enhanced bonding between the coating and the substrate can significantly improve the wear resistance of the coating.

10‧‧‧ base

20‧‧‧bonding layer

31‧‧‧ nano composite layer

311‧‧‧ZrN layer

313‧‧‧ZrYN layer

33‧‧‧ color layer

40‧‧‧Cladding

1 is a cross-sectional view of a coating according to a preferred embodiment of the present invention; and FIG. 2 is a cross-sectional view of a covering 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 30 according to a preferred embodiment of the present invention includes a nanocomposite layer 31. The nanocomposite layer 31 includes a complex zirconium nitride (ZrN) layer 311 and a complex zirconium nitride zirconium (ZrYN) layer 313, and the complex ZrN layer 311 and the complex ZrYN layer 313 are alternately arranged. The complex ZrN layer 311 and the complex ZrYN layer 313 are formed by a magnetron sputtering method. The number of layers of the complex ZrN layer 311 and the complex ZrYN layer 313 is 20 to 50 layers, respectively.

Each ZrN layer 311 has a thickness of 10 to 20 nm, and each ZrYN layer 313 has a thickness of 10 to 20 nm. The total thickness of the coating layer 30 is 1 to 4 μm.

It will be appreciated that the coating 30 may also include a color layer 33 plated on the surface of the nanocomposite layer 31 to enhance the aesthetics of the coating 30.

Referring to FIG. 2, a covering member 40 according to a preferred embodiment of the present invention includes a base 10, a bonding layer 20 formed on the substrate 10, and the coating layer 30 formed on the bonding layer 20. The material of the base 10 may be high speed steel, hard alloy, stainless steel or the like. The covering member 40 can be various types of cutting tools, precision measuring tools, molds, 3C electronic product casings, and various architectural decorative parts.

The bonding layer 20 is a zirconium-germanium (ZrY) layer having a thickness of 0.05 to 0.2 μm. The bonding layer 20 is formed by magnetron sputtering deposition. The chemical stability and thermal expansion coefficient of the bonding layer 20 is between the substrate 10 and the coating layer 30, so that the bonding force between the coating layer 30 and the substrate 10 can be effectively improved. The coating 30 directly bonded to the substrate 11 is a ZrN layer 311.

The preparation method of the covering member 40 mainly includes the following steps:

The base body 10 is provided, and the material of the base body 10 can be high speed steel, hard alloy, metal ceramic Porcelain and sintered diamonds. The substrate 10 is placed in an ultrasonic cleaner containing an ethanol and/or acetone solution for vibration cleaning to remove impurities, oil stains, and the like on the surface of the substrate 10. After cleaning, dry and set aside.

The surface of the substrate 10 subjected to the above treatment is subjected to plasma cleaning to further remove the oil stain on the surface of the substrate 10, and to improve the bonding force between the surface of the substrate 10 and the subsequent coating. The specific operation and process parameters of the plasma cleaning are: fixing the substrate 10 to the workpiece holder of the coating chamber of the magnetron sputtering coating machine, and vacuuming the coating chamber to a vacuum of 8.0×10 ^-3 Pa to 300~ A flow rate of 600 sccm (standard state ML/min) was introduced into 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 substrate 10, and the surface of the substrate 10 was plasma-cleaned for 3 times. ~10min.

After the substrate 10 is subjected to plasma cleaning, a bonding layer 20 is formed on the substrate 10. The bonding layer 20 is a ZrY layer. The specific operation method and process parameters for forming the bonding layer 20 are as follows: adjusting the flow rate of the argon gas (working gas) to 150 to 300 sccm, and heating the coating chamber to 150 to 300 ° C (ie, the sputtering temperature is 150 to 300 ° C). The revolution speed of the workpiece holder is 1.0 to 3.0 rpm (revolution per minute); the power supply of the zirconium target and the zirconium-niobium alloy target respectively mounted on both sides of the coating chamber is opened, and the zirconium target and zirconium are disposed. The current of the tantalum alloy target is 20 to 100 A; a bonding layer of 20 is deposited by applying a bias of -100 to -300 V on the substrate 10. The time for depositing the bonding layer 20 is 5 to 15 minutes. The mass percentage of Zr in the zirconium-niobium alloy target is 70-90%.

After the bonding layer 20 is formed, a nanocomposite layer 31 is formed on the bonding layer 20. The nanocomposite layer 31 is formed by alternately depositing a plurality of ZrN layers 311 and a plurality of ZrYN layers 313. The specific operation method and process parameters for forming the nanocomposite layer 31 are as follows: nitrogen gas having a flow rate of 10 to 200 sccm and having a purity of 99.999% is introduced into the coating chamber to deposit the nanocomposite layer 31. When the nanocomposite layer 31 is deposited, it is alternately opened and installed separately in the office. The zirconium-niobium alloy target and the zirconium target of the magnetron sputtering coating machine are used to alternately deposit a plurality of ZrN layers 311 and a plurality of ZrYN layers 313 on the bonding layer 20. The time for depositing the nanocomposite layer 31 is 60 to 120 min.

The negative bias voltage, the zirconium-niobium alloy target and the zirconium target power source are turned off, and the argon gas and the nitrogen gas are stopped. After the nano-composite layer 31 is cooled, air is introduced into the coating film, the coating chamber door is opened, and the plating is combined and removed. The layer 20 and the substrate 10 of the nanocomposite layer 31.

It is to be understood that the method of preparing the covering member 40 may further include plating the color layer 33 on the surface of the nanocomposite layer 31 to enhance the aesthetics of the covering member 40.

When the ZrYN layer 313 is formed, since Y and Zr cannot form a solid solution, and Y is not easily reacted with nitrogen, the N atom in the nitrogen preferentially forms ZrN grains with the Zr atom during the deposition process, and the Y atom is segregated in an independent form. A Y phase is formed on the grain boundary, which can suppress the growth of ZrN crystal grains, thereby maintaining the particle size of the ZrN crystal grains in the ZrYN layer 313 at the nanometer level, and the nano-sized ZrN crystal grains can remarkably improve the Nai The hardness and toughness of the rice composite layer 31. More importantly, due to the difference in shear modulus between the nanoscale nitride ZrN and ZrYN, the dislocation motion between each ZrN layer 311 and each ZrYN layer 313 alternately deposited is at the interface of the two layers. On the other hand, the plugging of the bit error can cause a hardening phenomenon and suppress deformation of the film layer, so that the hardness and toughness of the nanocomposite layer 31 are further remarkably improved.

The covering member 40 is provided with a ZrY bonding layer 20 between the substrate 10 and the nanocomposite layer 31. Since the chemical stability and the coefficient of thermal expansion of the bonding layer 20 are between the substrate 10 and the nanocomposite layer 31, The bonding force between the nanocomposite layer 31 and the substrate 10 is effectively improved. The improvement in hardness and toughness of the nanocomposite layer 31 and the enhancement of the bonding force between the nanocomposite layer 31 and the substrate 10 can remarkably improve the wear resistance of the coating layer 30.

In addition, during the abrasion process of the coating layer 30, the surface layer Y of the coating layer 30 may be combined with elements such as O and S outside the film layer to form a film layer containing a corresponding oxide or/and sulfide, and the film layer is dense. Moreover, the hardness is high, and the covering member 40 is better protected during the working process, and the hardness and wear resistance of the covering member 40 are indirectly improved.

In summary, the present invention complies with the requirements of the invention patent and submits a patent application according to law. 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 covered by the following claims.

10‧‧‧ base

20‧‧‧bonding layer

31‧‧‧ nano composite layer

311‧‧‧ZrN layer

313‧‧‧ZrYN layer

33‧‧‧ color layer

40‧‧‧Cladding

Claims (6)

A covering member comprising a base body, a bonding layer formed on a surface of the base body, and a coating layer formed on the bonding layer, the coating layer comprising a nano composite layer, wherein the bonding layer is a ZrY layer, The nanocomposite layer includes a complex ZrN layer and a complex ZrYN layer, and the complex ZrN layer and the complex ZrYN layer are alternately arranged. The covering member according to claim 1, wherein the bonding layer is a ZrY layer having a thickness of 0.05 to 0.2 μm. A method for preparing a coated member, comprising the steps of: providing a substrate; magnetron sputtering a bonding layer on a surface of the substrate, the bonding layer is a ZrY layer; and magnetron sputtering a nano composite layer on the surface of the bonding layer, the nano layer The m composite layer includes a complex ZrN layer and a complex ZrYN layer, and the complex ZrN layer and the complex ZrYN layer are alternately arranged. The method for preparing a coated article according to claim 3, wherein the step of magnetron sputtering the bonding layer is performed by using a zirconium target and a zirconium-niobium alloy target as a target, and the zirconium target and zirconium are disposed. The current of the bismuth alloy target is 20~100A, the working gas is argon gas, the flow rate is 150~300sccm, the bias voltage of -100~-300V is applied to the substrate, the sputtering temperature is 150~300 °C, and the sputtering time is 5~15min. The method for preparing a coated article according to claim 3, wherein the step of magnetron sputtering the nanocomposite layer is performed in the following manner: a zirconium target and a zirconium-niobium alloy target are alternately opened targets, and nitrogen is used. For the reactive gas, the flow rate is 10 to 200 sccm, and the sputtering time is 60 to 120 min. The method for preparing a coated article according to claim 3, wherein the zirconium alloy target has a mass percentage of Zr of 70 to 90%.