CN112458417A - Growth process of multi-element layered hardened coating - Google Patents

Abstract

The invention belongs to the technical field of PVD magnetron sputtering, and discloses a growth process of a multi-element layered hardened coating. The growth process of the multi-element layered hard coating comprises the following steps: (1) completing liquid cleaning of the base material on an automatic cleaning line; (2) placing the substrate in a magnetron sputtering coating machine for pre-vacuumizing; (3) glow cleaning is carried out in a magnetron sputtering coating machine; (4) performing film deposition in a magnetron sputtering film plating machine, wherein the film deposition comprises deposition of a hard layer, and three or more than three targets are used in the deposition of the hard layer to obtain a multilayer structure formed by stacking carbides or nitrides of ternary or more than ternary metals as a single-layer structure; (5) and (6) cooling and discharging. According to the process, nitrides or carbides of different materials are sequentially deposited in a layered manner in the film layer deposition process to form layered stacks of the different materials, so that the hardening effect is achieved, the coarsening growth of the surface appearance is inhibited, and a coating with the protection and decoration effects is formed on the surface of a base material.

Description

Growth process of multi-element layered hardened coating

Technical Field

The invention relates to the technical field of PVD magnetron sputtering, in particular to a growth process of a multi-element layered hardened coating.

Background

Physical Vapor Deposition (PVD) coating techniques are used in many surface treatments and thin film material preparation, such as hard coatings on mold surfaces, protective coatings on various component surfaces, surface modification coatings, conductive and light-transmitting coatings, and the like.

The traditional decorative PVD technique is a conventional surface decorative treatment technique for the surface of stainless steel products and ceramic surfaces. Due to the pursuit of glossiness and color effect, the coating has various colors and high glossiness, but the thickness of the film layer is thin, the components are often deviated from the standard stoichiometric ratio, the film layer has defects on the mechanical property, namely the daily use protection of the coated product, the phenomenon of film layer abrasion is often generated, and the appearance life of the product is reduced. At present, the common mode of increasing the hardness is to coat a single metal nitride or carbide film layer with larger thickness and optimize the protective performance of the film layer, but the film layer inevitably causes coarsening of the surface of the film layer due to the consistency of continuous growth of the film layer in the growth process, thereby reducing the glossiness of the film layer and having poorer integral decorative effect.

Disclosure of Invention

The invention aims to overcome the defects of the background technology and provide a growth process of a multi-element layered hard coating, which adopts the steps of liquid cleaning PVD, glow cleaning, film layer deposition and the like, nitrides or carbides of different materials are sequentially deposited in a layered manner in the film layer deposition process to form layered stacks of different materials, the structure is utilized to achieve the hardening effect and inhibit the coarsening growth of the surface appearance, and a coating with high glossiness, good decoration, excellent hardness and both protection and decoration effects can be formed on the surface of a base material.

In order to achieve the purpose of the invention, the growth process of the multielement layer-by-layer hard coating comprises the following steps:

(1) completing liquid cleaning of the base material on an automatic cleaning line;

(2) placing the substrate in a magnetron sputtering coating machine for pre-vacuumizing;

(3) glow cleaning is carried out in a magnetron sputtering coating machine;

(4) performing film deposition in a magnetron sputtering film plating machine, wherein the film deposition comprises deposition of a hard layer, and three or more than three targets are used in the deposition of the hard layer to obtain a multilayer structure formed by stacking carbides or nitrides of ternary or more than ternary metals as a single-layer structure;

(5) and (6) cooling and discharging.

Further, the three or more target materials of the hard layer are selected from one or more of a chromium target, a titanium target, a tungsten target, a silicon target, an aluminum target or an alloy target. Those skilled in the art will appreciate that these targets are merely exemplary and that the targets described herein are not limited to these.

Preferably, in some embodiments of the present invention, the hard layer is formed by using nitrogen as a reactive gas, the three or more target materials are a silicon target, a chromium target and a titanium target, and the three single-layer structures of silicon nitride, chromium nitride and titanium nitride are sequentially deposited to form a multi-layer structure.

Preferably, in some embodiments of the present invention, the hard layer is formed by using a hydrocarbon gas as a reaction gas, the three or more target materials are a silicon target, a chromium target and a titanium target, and the three single-layer structures of silicon carbide, chromium carbide and titanium carbide are sequentially deposited to form a multi-layer structure.

Preferably, in some embodiments of the present invention, the hard layer is formed by using nitrogen as a reactive gas, the three or more target materials are a tungsten target, a chromium target and a titanium target, and the three single-layer structures of tungsten nitride, chromium nitride and titanium nitride are sequentially deposited to form a multi-layer structure.

Preferably, in some embodiments of the present invention, the hard layer is formed by using a hydrocarbon gas as a reaction gas, the three or more target materials are a tungsten target, a chromium target and a titanium target, and the three single-layer structures of tungsten carbide, chromium carbide and titanium carbide are sequentially deposited to form a multi-layer structure.

Preferably, in some embodiments of the present invention, the hard layer is formed by using nitrogen as a reactive gas, the three or more target materials are an aluminum target, a chromium target and a titanium target, and the three single-layer structures of aluminum nitride, chromium nitride and titanium nitride are sequentially deposited to form a multi-layer structure.

Preferably, in some embodiments of the present invention, the hard layer is formed by using a hydrocarbon gas as a reaction gas, the three or more target materials are an aluminum target, a chromium target and a titanium target, and the three single-layer structures of aluminum carbide, chromium carbide and titanium carbide are sequentially deposited to form a multi-layer structure.

Further, the parameters of the film deposition are as follows:

bottom layer: the deposition time is 10 minutes, the vacuum degree is 0.3Pa, argon is adopted as gas, the volume flow of argon is 400sccm, the bias voltage is 100V, the duty ratio is 50%, a single target material (Cr or Ti) is adopted, and the current is 10-20A;

hardening layer: the time is 60 minutes, the vacuum degree is 0.32Pa, argon is adopted as sputtering gas, the flow is 400sccm, nitrogen or hydrocarbon gas is adopted as reaction gas, the flow is 100 sccm-300 sccm, three or more target materials are adopted, and the current is 10A-50A;

color layer: the time is about 30 minutes, the vacuum degree is 0.4Pa, the sputtering gas is argon, the flow is 400sccm, the target material adopts a single target material, and the current is 15-30A.

The reaction gas and the flow in the color layer are determined by nitrogen, hydrocarbon gas or oxygen according to the needed color.

Further, the single target material of the color layer is a titanium target, a chromium target or a tungsten target.

Compared with the prior art, the invention has the following advantages:

(1) the growth process of the multi-element layered hard coating is mainly characterized in that three or more different target materials are placed in a furnace, nitrides or carbides of different materials are sequentially deposited in a layered manner in the process of depositing a film layer to form layered stacks of different materials, and the structure is utilized to achieve the hardening effect and inhibit the coarsening growth of the surface appearance;

(2) the film material obtained by the process has excellent mechanical properties, the hardness of the film material reaches over 1200Hv, and the film material has lower roughness and higher glossiness, and is an excellent hardened structure film in the field of decorative coating.

Detailed Description

In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention. It is to be understood that the following description is only illustrative of the present invention and is not to be construed as limiting the present invention.

The terms "comprises," "comprising," "includes," "including," "has," "having," "contains," "containing," or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a composition, process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus.

Furthermore, the description below of the terms "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above are not necessarily for the same embodiment or example. Further, the technical features of the embodiments of the present invention may be combined with each other as long as they do not conflict with each other.

Example 1

A multi-element layered hard coating growth process comprises the following steps:

(1) completing liquid cleaning of the stainless steel substrate on an automatic cleaning line;

(2) placing the substrate in a magnetron sputtering coating machine for pre-vacuumizing;

(3) glow cleaning is carried out in a magnetron sputtering coating machine;

(4) performing film layer deposition in a magnetron sputtering film plating machine, wherein the film layer deposition comprises a deposition hardening layer to obtain a multilayer structure formed by stacking carbides or nitrides of ternary or more metals as a single-layer structure;

(5) cooling and discharging;

wherein the parameters of the film deposition are as follows:

bottom layer: the deposition time is 10 minutes, the vacuum degree is 0.3Pa, argon is adopted as gas, the volume flow of the argon is 400sccm, the bias voltage is 100V, the duty ratio is 50%, a single target Cr is adopted, and the current is 15A;

hardening layer: the time is 60 minutes, the vacuum degree is 0.3Pa, argon is adopted as sputtering gas, the flow rate is 400sccm, the reaction gas is nitrogen, and the flow rate is 250 sccm. Three target materials, namely a silicon target, a chromium target and a titanium target are adopted, and the currents of the three target materials are respectively 15A,15A and 20A;

color layer: the time is about 30 minutes, the vacuum degree is 0.4Pa, the sputtering gas is argon, the reaction gas is acetylene, the flow is 400sccm, the target material adopts a single Cr target material, and the current is 15A.

The reaction gas of the hard layer is nitrogen, the three or more target materials are a silicon target, a chromium target and a titanium target, and three single-layer structures of silicon nitride, chromium nitride and titanium nitride are deposited in sequence to form a multi-layer structure.

The color layer is a Cr-C ultra-black coating. The film obtained by the structure has high glossiness, surface average roughness below 10nm and overall hardness above 1200Hv, and can pass a 96H vibration abrasion test.

Example 2

A multi-element layered hard coating growth process comprises the following steps:

(1) the titanium alloy base material is subjected to liquid cleaning on an automatic cleaning line;

(2) placing the substrate in a magnetron sputtering coating machine for pre-vacuumizing;

(3) glow cleaning is carried out in a magnetron sputtering coating machine;

(4) performing film layer deposition in a magnetron sputtering film plating machine, wherein the film layer deposition comprises a deposition hardening layer to obtain a multilayer structure formed by stacking carbides or nitrides of ternary or more metals as a single-layer structure;

(5) cooling and discharging;

wherein the parameters of the film deposition are as follows:

bottom layer: the deposition time is 10 minutes, the vacuum degree is 0.3Pa, argon is adopted as gas, the volume flow of the argon is 400sccm, the bias voltage is 100V, the duty ratio is 50%, a single target Cr is adopted, and the current is 15A;

hardening layer: the time is 60 minutes, the vacuum degree is 0.32Pa, the sputtering gas adopts argon gas, the flow is 400sccm, the reaction gas adopts acetylene gas, the flow is 300sccm, a silicon target, a chromium target and a titanium target are adopted, and the currents are respectively 15A,15A and 20A;

color layer: the time is about 30 minutes, the vacuum degree is 0.4Pa, the sputtering gas is argon, the reaction gas is acetylene, the flow is 400sccm, the target material adopts a single Ti target material, and the current is 20A.

The reaction gas of the hard layer is acetylene gas, the three or more target materials are a silicon target, a chromium target and a titanium target, and three single-layer structures of silicon carbide, chromium carbide and titanium carbide are sequentially deposited to form a multi-layer structure.

The Ti-C ultra-black film layer of the color layer has high glossiness, the surface average roughness is below 10nm, the overall hardness is above 1200Hv, and the Ti-C ultra-black film layer can pass a 96H vibration abrasion test.

Example 3

A multi-element layered hard coating growth process comprises the following steps:

(1) the method comprises the following steps of (1) finishing liquid cleaning on a zirconia ceramic substrate on an automatic cleaning line;

(2) placing the substrate in a magnetron sputtering coating machine for pre-vacuumizing;

(3) glow cleaning is carried out in a magnetron sputtering coating machine;

(4) performing film layer deposition in a magnetron sputtering film plating machine, wherein the film layer deposition comprises a deposition hardening layer to obtain a multilayer structure formed by stacking carbides or nitrides of ternary or more metals as a single-layer structure;

(5) cooling and discharging;

wherein the parameters of the film deposition are as follows:

bottom layer: the deposition time is 10 minutes, the vacuum degree is 0.3Pa, argon is adopted as gas, the volume flow of the argon is 400sccm, the bias voltage is 100V, the duty ratio is 50%, a single target Cr is adopted, and the current is 15A;

hardening layer: the time is 60 minutes, the vacuum degree is 0.32Pa, argon is adopted as sputtering gas, the flow is 400sccm, nitrogen is adopted as reaction gas, the flow is 400sccm, three targets of a tungsten target, a chromium target and a titanium target are adopted, and the current is respectively 15A,15A and 20A;

color layer: the time is about 30 minutes, the vacuum degree is 0.4Pa, the sputtering gas is argon, the flow rate is 400sccm, the reaction gas is acetylene, the flow rate is 150sccm, the target material adopts a single tungsten target material, and the current is 15A.

The reaction gas of the hard layer is nitrogen, the three or more than three target materials are a tungsten target, a chromium target and a titanium target, and a multilayer structure is formed by sequentially depositing three single-layer structures of tungsten nitride, chromium nitride and titanium nitride.

And the tungsten carbide ultra-black film layer of the color layer. The film obtained by the structure has high glossiness, surface average roughness below 10nm and overall hardness above 1200Hv, and can pass a 96H vibration abrasion test.

Example 4

A multi-element layered hard coating growth process comprises the following steps:

(1) the aluminum alloy substrate is subjected to liquid cleaning on an automatic cleaning line;

(2) placing the substrate in a magnetron sputtering coating machine for pre-vacuumizing;

(3) glow cleaning is carried out in a magnetron sputtering coating machine;

(4) performing film layer deposition in a magnetron sputtering film plating machine, wherein the film layer deposition comprises a deposition hardening layer to obtain a multilayer structure formed by stacking carbides or nitrides of ternary or more metals as a single-layer structure;

(5) cooling and discharging;

wherein the parameters of the film deposition are as follows:

bottom layer: the deposition time is 10 minutes, the vacuum degree is 0.3Pa, argon is adopted as gas, the volume flow of the argon is 400sccm, the bias voltage is 100V, the duty ratio is 50%, a single target Cr is adopted, and the current is 15A;

hardening layer: the time is 60 minutes, the vacuum degree is 0.32Pa, argon is adopted as sputtering gas, the flow is 400sccm, acetylene is adopted as reaction gas, the flow is 300sccm, three targets of a tungsten target, a chromium target and a titanium target are adopted, and the current is respectively 15A,15A and 20A;

color layer: the time is about 30 minutes, the vacuum degree is 0.4Pa, the sputtering gas is argon, the flow rate is 400sccm, the reaction gas is acetylene, the flow rate is 150sccm, the target material adopts a single tungsten target material, and the current is 15A.

The reaction gas of the hard layer is nitrogen, the three or more than three target materials are a tungsten target, a chromium target and a titanium target, and three single-layer structures of tungsten carbide, chromium carbide and titanium carbide are sequentially deposited to form a multi-layer structure.

And the tungsten carbide ultra-black film layer of the color layer. The film obtained by the structure has high glossiness, surface average roughness below 10nm and overall hardness above 1200Hv, and can pass a 96H vibration abrasion test.

Example 5

A multi-element layered hard coating growth process comprises the following steps:

(1) liquid metal base materials are cleaned in a liquid state on an automatic cleaning line;

(2) placing the substrate in a magnetron sputtering coating machine for pre-vacuumizing;

(3) glow cleaning is carried out in a magnetron sputtering coating machine;

(4) performing film layer deposition in a magnetron sputtering film plating machine, wherein the film layer deposition comprises a deposition hardening layer to obtain a multilayer structure formed by stacking carbides or nitrides of ternary or more metals as a single-layer structure;

(5) cooling and discharging;

wherein the parameters of the film deposition are as follows:

bottom layer: the deposition time is 10 minutes, the vacuum degree is 0.3Pa, argon is adopted as gas, the volume flow of the argon is 400sccm, the bias voltage is 100V, the duty ratio is 50%, a single target Cr is adopted, and the current is 15A;

hardening layer: the time is 60 minutes, the vacuum degree is 0.32Pa, argon is adopted as sputtering gas, the flow is 400sccm, nitrogen is adopted as reaction gas, the flow is 500sccm, three targets of an aluminum target, a chromium target and a titanium target are adopted, and the currents are respectively 20A,15A and 20A;

color layer: the time is about 30 minutes, the vacuum degree is 0.4Pa, the sputtering gas is argon, the reaction gas is nitrogen, the flow is 200sccm, the target material adopts a single Cr target material, and the current is 15A.

The reaction gas of the hard layer is nitrogen, the three or more than three target materials are an aluminum target, a chromium target and a titanium target, and three single-layer structures of aluminum nitride, chromium nitride and titanium nitride are sequentially deposited to form a multi-layer structure.

The CrN silver film layer of the color layer. The film obtained by the structure has high glossiness, surface average roughness below 10nm and overall hardness above 1200Hv, and can pass a 96H vibration abrasion test.

Example 6

A multi-element layered hard coating growth process comprises the following steps:

(1) completing liquid cleaning of the glass substrate on an automatic cleaning line;

(2) placing the substrate in a magnetron sputtering coating machine for pre-vacuumizing;

(3) glow cleaning is carried out in a magnetron sputtering coating machine;

(4) performing film layer deposition in a magnetron sputtering film plating machine, wherein the film layer deposition comprises a deposition hardening layer to obtain a multilayer structure formed by stacking carbides or nitrides of ternary or more metals as a single-layer structure;

(5) cooling and discharging;

wherein the parameters of the film deposition are as follows:

bottom layer: the deposition time is 10 minutes, the vacuum degree is 0.3Pa, argon is adopted as gas, the volume flow of the argon is 400sccm, the bias voltage is 100V, the duty ratio is 50%, a single target Cr is adopted, and the current is 15A;

hardening layer: the time is 60 minutes, the vacuum degree is 0.32Pa, argon is adopted as sputtering gas, the flow is 400sccm, acetylene is adopted as reaction gas, the flow is 300sccm, three targets of an aluminum target, a chromium target and a titanium target are adopted, and the currents are respectively 20A,15A and 20A;

color layer: the time is about 30 minutes, the vacuum degree is 0.4Pa, the sputtering gas is argon, the reaction gas is nitrogen, the flow is 300sccm, the target material adopts a single Ti target material, and the current is 20A.

The three targets are an aluminum target, a chromium target and a titanium target, and three single-layer structures of aluminum carbide, chromium carbide and titanium carbide are sequentially deposited to form a multi-layer structure.

And the TiN gold film layer of the color layer. The film obtained by the structure has high glossiness, surface average roughness below 10nm and overall hardness above 1200Hv, and can pass a 96H vibration abrasion test.

It will be understood by those skilled in the art that the foregoing is only exemplary of the present invention, and is not intended to limit the invention, which is intended to cover any variations, equivalents, or improvements therein, which fall within the spirit and scope of the invention.

Claims (10)

1. The growth process of the multi-element layered hard coating is characterized by comprising the following steps:

(1) completing liquid cleaning of the base material on an automatic cleaning line;

(2) placing the substrate in a magnetron sputtering coating machine for pre-vacuumizing;

(3) glow cleaning is carried out in a magnetron sputtering coating machine;

(4) performing film deposition in a magnetron sputtering film plating machine, wherein the film deposition comprises deposition of a hard layer, and three or more than three targets are used in the deposition of the hard layer to obtain a multilayer structure formed by stacking carbides or nitrides of ternary or more than ternary metals as a single-layer structure;

(5) and (6) cooling and discharging.

2. The process of claim 1, wherein the three or more target materials of the hard layer are selected from one or more of a chromium target, a titanium target, a tungsten target, a silicon target, an aluminum target, or an alloy target.

3. The process according to claim 1, wherein the hard layer is formed by using nitrogen as a reactive gas, the three or more target materials are a silicon target, a chromium target and a titanium target, and the three single-layer structures of silicon nitride, chromium nitride and titanium nitride are sequentially deposited to form a multi-layer structure.

4. The process according to claim 1, wherein the hard layer is formed by using hydrocarbon gas as a reactive gas, the three or more target materials are a silicon target, a chromium target and a titanium target, and the three single-layer structures of silicon carbide, chromium carbide and titanium carbide are sequentially deposited to form a multi-layer structure.

5. The process according to claim 1, wherein the hard layer is formed by using nitrogen as a reactive gas, the three or more target materials are a tungsten target, a chromium target and a titanium target, and the three single-layer structures of tungsten nitride, chromium nitride and titanium nitride are sequentially deposited to form a multi-layer structure.

6. The process according to claim 1, wherein the hard layer is formed by using hydrocarbon gas as a reactive gas, the three or more target materials are tungsten target, chromium target and titanium target, and the three single-layer structures of tungsten carbide, chromium carbide and titanium carbide are deposited in sequence to form a multi-layer structure.

7. The process according to claim 1, wherein the hard layer is formed by using nitrogen as a reactive gas, the three or more target materials are an aluminum target, a chromium target and a titanium target, and the three single-layer structures of aluminum nitride, chromium nitride and titanium nitride are sequentially deposited to form a multi-layer structure.

8. The process according to claim 1, wherein the hard layer is formed by using hydrocarbon gas as a reactive gas, the three or more target materials are an aluminum target, a chromium target and a titanium target, and the three single-layer structures of aluminum carbide, chromium carbide and titanium carbide are sequentially deposited to form a multi-layer structure.

9. The process of claim 1, wherein the parameters of the film deposition are as follows:

bottom layer: the deposition time is 10 minutes, the vacuum degree is 0.3Pa, argon is adopted as gas, the volume flow of argon is 400sccm, the bias voltage is 100V, the duty ratio is 50%, a single target material (Cr or Ti) is adopted, and the current is 10-20A;

hardening layer: the time is 60 minutes, the vacuum degree is 0.32Pa, argon is adopted as sputtering gas, the flow is 400sccm, nitrogen or hydrocarbon gas is adopted as reaction gas, the flow is 100 sccm-300 sccm, three or more target materials are adopted, and the current is 10A-50A;

color layer: the time is about 30 minutes, the vacuum degree is 0.4Pa, the sputtering gas is argon, the flow is 400sccm, the target material adopts a single target material, and the current is 15-30A.

10. The process of claim 1, wherein the single target material of the color layer is a titanium target, a chromium target or a tungsten target.