Interface coupling method based on multi-level nano-coating superposition on glass substrate

Abstract

The present invention provides a method for superimposing an interface coupling of a multi-level nano-coating on a glass substrate, firstly preparing LaMgAl 11 O 19 Target material and transition metal element Cr target material; cleaning glass substrate; sputtering LaMgAl alternately on the target position of magnetron sputtering instrument 11 O 19 and transition metal element Cr target to a glass substrate at a temperature of 200-300°C; the resulting laminate is a glass substrate / LaMgAl 11 O 19 / Transition metal element Cr target / LaMgAl 11 O 19 / Transition metal element Cr target / LaMgAl 11 O 19 ; The molecular formula is Cr‑LaMgAl 11 O 19 doping material; then prepare the nano coating, the single-stage nano coating TiNx / TiO2, X = 0.8-2.0, by N times superposition, N ≥ 4, to obtain a multi-stage nano coating; for X-LaMgAl 11 O 19 Multi-level nano-coating sprayed on the glass substrate interface of doped materials; achieving X-LaMgAl 11 O 19 The doping material is externally coupled with the multi-level nano coating. The invention significantly improves the bonding strength, weather resistance, color aging resistance and impact resistance of the multi-level superimposed coating on the glass substrate.

Description

Technical Field

[0001] The present invention belongs to the technical field of household appliance glass panels, and in particular relates to a method for superimposing an interface of a multi-level nano-coating on a glass substrate. Background Art

[0002] Currently, home appliances such as refrigerators, freezers, and air conditioners often use glass panels with various patterns for surface decoration. Refrigerators, in particular, are known for their elegant and aesthetically pleasing appearance. Existing glass panels typically use screen printing, digital inkjet printing, or full-body lamination to create patterns.

[0003] Before screen printing, glass panels need to be coated with a thermal barrier coating. Cr coatings offer excellent corrosion resistance, a high melting point, and superior mechanical strength and wear resistance. They also possess excellent chemical inertness, high-temperature oxidation resistance, and substrate adhesion. Currently, a variety of methods are available for depositing metallic Cr coatings. Magnetron sputtering, with its low energy consumption, controllable deposition rate, and excellent process repeatability, is a relatively mature coating preparation technology. Cr coatings prepared by magnetron sputtering typically exhibit a columnar crystal growth morphology. The continuous grain boundaries of these columnar crystals are defects that can easily cause cracking and flaking of the coating under external forces. Therefore, the continued growth of columnar crystals is detrimental to improving the performance of the metallic Cr coating. Summary of the Invention

[0004] In view of the problems existing in the existing technical solutions, the present invention aims to provide a method for superimposing an interface coupling of a multi-level nano-coating on a glass substrate.

[0005] To achieve the above objectives, the present invention provides the following technical solutions:

[0006] The method for superimposing an interface coupling of a multi-level nano-coating on a glass substrate includes the following steps:

[0007] Step 1: Preparation of LaMgAl 11 O 19 Target materials and transition metal element X targets;

[0008] Step 2: Cleaning the glass base substrate;

[0009] Step 3: LaMgAl 11 O 19 The target material and the transition metal element X target material are respectively mounted on the target position of the magnetron sputtering instrument; the glass substrate is subjected to high temperature pretreatment to obtain a pretreated high temperature glass substrate; and the high temperature glass substrate substrate is fixed on the stage;

[0010] Step 4: Evacuate the sputtering environment and sputter LaMgAl alternately under the conditions of Ar gas flow rate of 50 sccm and sputtering pressure of 0.8 Pa. 11 O 19 and transition metal element X target on a glass substrate at a temperature of 200-300°C. The two targets are deposited alternately to obtain a laminate of glass substrate / LaMgAl 11 O 19 / Transition Metal Element X Target / LaMgAl 11 O 19 / Transition Metal Element X Target / LaMgAl 11 O 19 ; A total of 2 doped layers, and then annealed in an annealing furnace with Ar gas protection environment, and finally obtained the molecular formula X-LaMgAl 11 O 19 doping materials;

[0011] Step 5: Preparation of nanocoating:

[0012] Single-stage nanocoating is TiNx / TiO2, X=0.8-2.0;

[0013] The thickness of the TiNx film in the single-stage nano coating, where X=0.8-2.0, is 10-15 nm; the thickness of the TiO2 film in the single-stage nano layer is 15-20 nm; the above single-stage nano coating is stacked N times to obtain a multi-stage nano coating, where N≥4;

[0014] Step 6: Use atmospheric plasma spraying technology to load multi-level nano coating materials into the powder feeder, compile a computer spraying program, and start and stop the plasma spray gun and powder feeder by the spraying program to spray the multi-level nano coating on the glass substrate interface; achieve X-LaMgAl 11 O 19 Coupling of external doping materials and multi-level nanocoating.

[0015] Furthermore, the transition metal element target X is Cr2S3.

[0016] Furthermore, the X-LaMgAl in step 4 11 O 19 The specific structure of the doping material is: 200nm X-doped LaMgAl is grown on the first substrate 11 O 19 Buffer layer, doping concentration is 10 20 cm -3 On the second substrate, 800nm ​​X-doped LaMgAl is grown. 11 O 19 Buffer layer, doping concentration is 10 20 cm-3 Magnitude.

[0017] Furthermore, the TiNx preparation process in step 5 is as follows: ammonia, carbon monoxide, and tetrakis(diethyl)titanium amine are used as reaction gas sources; the heater is set to 250°C, the purge temperature is 100°C / 80°C, the hot trap temperature is 500°C, and the pump tube temperature is 120°C; the process pressure is 0.15 torr, ammonia and carbon monoxide are injected at a ratio of 1:8 for 0.04s, and the purge time is 50s; the injection time of tetrakis(diethyl)titanium amine is 0.05-0.1s, and the purge time is 40s; the film thickness increases by 0.1-0.2nm each cycle, and this process is repeated multiple times until the thickness of the titanium nitride film reaches the design standard.

[0018] Furthermore, in step 6, the spraying current is 550-650 A, the argon flow rate is 44-48 SLPM, the hydrogen flow rate is 7-9 SLPM, the spraying distance is 90-110 mm, and the spray gun moving speed is 900-1100 mm / s.

[0019] Furthermore, the purity of the Ar gas in step 4 is greater than 99.99% by volume.

[0020] The present invention further discloses a multi-level nano-coating glass substrate, which is prepared by adopting the above-mentioned interface coupling method.

[0021] Compared with the prior art, the present invention has the following advantages: the present invention deposits metal Cr-LaMgAl with nano-multilevel structure on a clean glass substrate by magnetron sputtering deposition method. 11 O 19 Coating, nano-hierarchical structure of metal Cr-LaMgAl 11 O 19 The coating has a columnar crystal morphology, the columnar crystal size is stable in the nanocrystalline range, and the columnar crystal surface is a carambola-like structure with multi-level micro-nano scales. A single-level nano-coating is sprayed on the surface of the columnar crystal through N times of superimposed TiNx / TiO2 layers, X=0.8-2.0; finally, a stable glass-based multi-level superimposed coating is formed, which improves the bonding strength, weather resistance, color aging resistance and impact resistance of existing glass-based coatings by more than 20%. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] The present invention will be further described below with reference to the accompanying drawings.

[0023] Figure 1 It is a schematic flow chart of the preparation method of the present invention;

[0024] Figure 2 The metal Cr-LaMgAl prepared by the present invention 11 O 19SEM surface photograph of the coating;

[0025] Figure 3 The metal Cr-LaMgAl prepared by the present invention 11 O 19 SEM cross-sectional photograph of the coating;

[0026] Figure 4 The metal Cr-LaMgAl prepared by the present invention 11 O 19 High-magnification SEM cross-sectional image of the coating. DETAILED DESCRIPTION

[0027] The following will clearly and completely describe the technical solutions in the embodiments of the present invention in conjunction with the accompanying drawings. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of the present invention.

[0028] The experimental target materials, auxiliary materials and reagent parameters used in the embodiments of the present invention are shown in Table 1:

[0029] Table 1

[0030]

[0031]

[0032] The specifications of the experimental instruments and equipment used in the embodiments of the present invention are shown in Table 2:

[0033] Table 2

[0034] Instrument name Specifications Manufacturer Magnetron sputtering FU-10SP Zhengzhou Ketan Instrument Equipment Co., Ltd. Ultrasonic cleaner KQ-250E Kunshan Ultrasonic Instrument Co., Ltd. electronic balance BSA124S-CW Sydocs Scientific Instruments Co., Ltd. Vacuum tube is annealing furnace GSL-1100X Shanghai Institute of Optics and Fine Mechanics

[0035] Example 1

[0036] like Figures 1-4 As shown, this embodiment provides a method for superimposing an interface coupling of a multi-level nano-coating on a glass substrate, comprising the following steps:

[0037] Step 1: Preparation of LaMgAl 11 O 19 Target material and transition metal element Cr2S3 target material.

[0038] Step 2: Clean the glass base substrate.

[0039] Step 3: LaMgAl 11 O 19The target material and the transition metal element X target material are respectively installed on the target position of the magnetron sputtering instrument; the glass substrate is subjected to high-temperature pretreatment to obtain a pretreated high-temperature glass substrate; and the high-temperature glass substrate substrate is fixed on the stage.

[0040] Step 4: Evacuate the sputtering environment and sputter LaMgAl alternately under the conditions of Ar gas flow rate of 50 sccm and sputtering pressure of 0.8 Pa. 11 O 19 and transition metal element X target on a glass substrate at a temperature of 200-300°C. The two targets are deposited alternately to obtain a laminate of glass substrate / LaMgAl 11 O 19 / Transition metal element Cr2S3 target / LaMgAl 11 O 19 / Transition metal element Cr2S3 target / LaMgAl 11 O 19 ; A total of 2 doped layers, and then annealed in an annealing furnace in an Ar gas protection environment, and finally obtained a molecular formula of Cr-LaMgAl 11 O 19 Doping material.

[0041] Step 5: Preparation of nanocoating: The single-stage nanocoating is TiN / TiO2; the TiN in the single-stage nanocoating has a film thickness of 10-15nm; the thickness of the TiO2 film in the single-stage nanolayer is 15-20nm; the above single-stage nanocoating is stacked 4 times to obtain a multi-stage nanocoating.

[0042] Step 6: Use atmospheric plasma spraying technology to load multi-level nano coating materials into the powder feeder, compile a computer spraying program, and start and stop the plasma spray gun and powder feeder by the spraying program to spray the multi-level nano coating on the glass substrate interface; achieve Cr-LaMgAl 11 O 19 Coupling of external doping materials and multi-level nanocoating.

[0043] The Cr-LaMgAl in step 4 11 O 19 The specific structure of the doping material is: 200nm X-doped LaMgAl is grown on the first substrate 11 O 19 Buffer layer, doping concentration is 10 20 cm -3 On the second substrate, 800nm ​​X-doped LaMgAl is grown. 11 O 19 Buffer layer, doping concentration is 10 20 cm -3 Magnitude.

[0044] The TiN preparation process in step 5 is as follows: ammonia, carbon monoxide, and tetradiethylammonium titanium are used as reaction gas sources; the heater is set to 250°C, the purge temperature is 100°C, the hot trap temperature is 500°C, and the pump tube temperature is 120°C; the process pressure is 0.15 torr, ammonia and carbon monoxide are injected at a ratio of 1:8 for 0.04s and 50s, and the purge time is 0.1s and 40s for tetradiethylammonium titanium; the film thickness increases by 0.2nm each cycle, and this process is repeated multiple times until the titanium nitride film thickness reaches the design standard.

[0045] In step 6, the spraying current is 550 A, the argon flow rate is 44 SLPM, the hydrogen flow rate is 7 SLPM, the spraying distance is 90 mm, and the spray gun moving speed is 900 mm / s.

[0046] The purity of the Ar gas in step 4 is greater than 99.99% by volume.

[0047] Example 2

[0048] like Figures 1-4 As shown, this embodiment provides a method for superimposing an interface coupling of a multi-level nano-coating on a glass substrate, comprising the following steps:

[0049] Step 1: Preparation of LaMgAl 11 O 19 Target material and transition metal element Cr2S3 target material.

[0050] Step 2: Clean the glass base substrate.

[0051] Step 3: LaMgAl 11 O 19 The target material and the transition metal element Cr2S3 target material are respectively installed on the target position of the magnetron sputtering instrument; the glass substrate is subjected to high-temperature pretreatment to obtain a pretreated high-temperature glass substrate; and the high-temperature glass substrate substrate is fixed on the stage.

[0052] Step 4: Evacuate the sputtering environment and sputter LaMgAl alternately under the conditions of Ar gas flow rate of 50 sccm and sputtering pressure of 0.8 Pa. 11 O 19 and transition metal element X target on a glass substrate at a temperature of 200-300°C. The two targets are deposited alternately to obtain a laminate of glass substrate / LaMgAl 11 O 19 / Transition metal element Cr2S3 target / LaMgAl 11 O 19 / Transition metal element Cr2S3 target / LaMgAl 11 O 19; A total of 2 doped layers, and then annealed in an annealing furnace with Ar gas protection environment, and finally obtained the molecular formula X-LaMgAl 11 O 19 Doping material.

[0053] Step 5: Preparation of nano coating, the single-stage nano coating is TiN2 / TiO2; the TiN2 in the single-stage nano coating has a film thickness of 10-15nm; the TiO2 film thickness in the single-stage nano layer is 15-20nm; the above single-stage nano coating is stacked 8 times to obtain a multi-stage nano coating.

[0054] Step 6: Use atmospheric plasma spraying technology to load multi-level nano coating materials into the powder feeder, compile a computer spraying program, and start and stop the plasma spray gun and powder feeder by the spraying program to spray the multi-level nano coating on the glass substrate interface; achieve Cr-LaMgAl 11 O 19 Coupling of external doping materials and multi-level nanocoating.

[0055] The Cr-LaMgAl in step 4 11 O 19 The specific structure of the doping material is: 200nm X-doped LaMgAl is grown on the first substrate 11 O 19 Buffer layer, doping concentration is 10 20 cm -3 On the second substrate, 800nm ​​X-doped LaMgAl is grown. 11 O 19 Buffer layer, doping concentration is 10 20 cm -3 Magnitude.

[0056] The TiN2 preparation process in step 5 is: ammonia, carbon monoxide, and tetradiethylammonium titanium are used as reaction gas sources; the heater is set to 250°C, the purge temperature is 80°C, the hot trap temperature is 500°C, and the pump tube temperature is 120°C; the process pressure is 0.15 torr, ammonia and carbon monoxide are injected at a ratio of 1:8 for 0.04s and 50s respectively; the injection time of tetradiethylammonium titanium is 0.1s and 40s respectively; the film thickness increases by 0.2nm each cycle, and this process is repeated multiple times until the thickness of the titanium nitride film reaches the design standard.

[0057] In step 6, the spraying current is 650 A, the argon flow rate is 48 SLPM, the hydrogen flow rate is 9 SLPM, the spraying distance is 110 mm, and the spray gun moving speed is 1100 mm / s.

[0058] Example 3

[0059] This embodiment provides a multi-level nano-coated glass substrate, which is prepared by the interface coupling method of the above embodiment. The metal Cr-LaMgAl with a nano-multi-level structure is deposited on a clean glass substrate by magnetron sputtering deposition. 11 O 19 Coating, nano-hierarchical structure of metal Cr-LaMgAl 11 O 19 The coating has a columnar crystal morphology, the columnar crystal size is stable in the nanocrystalline range, and the columnar crystal surface is a carambola-like structure with multi-level micro-nano scales. A single-level nano-coating is sprayed on the surface of the columnar crystal through N times of superimposed TiNx / TiO2 layers, X=0.8-2.0; finally, a stable glass-based multi-level superimposed coating is formed, which improves the bonding strength, weather resistance, color aging resistance and impact resistance of existing glass-based coatings by more than 20%.

[0060] The above content is merely an example of the structure of the present invention. Those skilled in the art may make various modifications or additions to the described specific embodiments or replace them in a similar manner. As long as they do not deviate from the structure of the present invention or exceed the scope defined by the claims, they should all fall within the scope of protection of the present invention.

Claims

1. A multi-level nano-coating superposition interface coupling method based on a glass substrate, characterized in that: The following steps are involved: Step 1: Preparation of LaMgAl 11 O 19 Target materials and transition metal element X targets; Step 2: Cleaning the glass base substrate; Step 3: LaMgAl 11 O 19 The target material and the transition metal element X target material are respectively mounted on the target position of the magnetron sputtering instrument; the glass substrate is subjected to high temperature pretreatment to obtain a pretreated high temperature glass substrate; and the high temperature glass substrate substrate is fixed on the stage; Step 4: Evacuate the sputtering environment and sputter LaMgAl alternately under the conditions of Ar gas flow rate of 50 sccm and sputtering pressure of 0.8 Pa. 11 O 19 and transition metal element X target on a glass substrate at a temperature of 200-300°C. The two targets are deposited alternately to obtain a laminate of glass substrate / LaMgAl 11 O 19 / Transition Metal Element X Target / LaMgAl 11 O 19 / Transition Metal Element X Target / LaMgAl 11 O 19 ; A total of 2 doped layers, and then annealed in an annealing furnace with Ar gas protection environment, and finally obtained the molecular formula X-LaMgAl 11 O 19 doping materials; Step 5: Preparation of nanocoating: Single-stage nanocoating is TiNx / TiO2, X=0.8-2.0; The thickness of the TiNx film in the single-stage nano coating, where X=0.8-2.0, is 10-15 nm; the thickness of the TiO2 film in the single-stage nano layer is 15-20 nm; the above single-stage nano coating is stacked N times to obtain a multi-stage nano coating, where N≥4; Step 6: Using atmospheric plasma spraying technology, load the multi-stage nano coating material into the powder feeder, compile a computer spraying program, and start and stop the plasma spray gun and powder feeder according to the spraying program to spray the multi-stage nano coating on the glass substrate interface; Realizing X-LaMgAl 11 O 19 Coupling of external doping materials and multi-level nanocoating.

2. The method for superimposing interface coupling of multi-level nano-coatings on a glass substrate according to claim 1, characterized in that: The transition metal element target material X is Cr2S3.

3. The method for superimposing interface coupling of multi-level nano-coatings on a glass substrate according to claim 1, characterized in that: X-LaMgAl in step 4 11 O 19 The specific structure of the doping material is: 200nm X-doped LaMgAl is grown on the first substrate 11 O 19 Buffer layer, doping concentration is 10 20 cm -3 On the second substrate, 800nm ​​X-doped LaMgAl is grown. 11 O 19 Buffer layer, doping concentration is 10 20 cm -3 Magnitude.

4. The method for superimposing interface coupling of multi-level nano-coatings on a glass substrate according to claim 1, characterized in that: The TiNx preparation process in step 5 is as follows: ammonia, carbon monoxide, and tetrakis(diethyl)titanium amine are used as reaction gas sources; the heater is set to 250°C, the purge temperature is 100°C / 80°C, the hot trap temperature is 500°C, and the pump tube temperature is 120°C; the process pressure is 0.15 torr, ammonia and carbon monoxide are injected at a ratio of 1:8 for 0.04s and 50s respectively; the injection time of tetrakis(diethyl)titanium amine is 0.05-0.1s and 40s respectively; the film thickness increases by 0.1-0.2nm each time, and this process is repeated multiple times until the thickness of the titanium nitride film reaches the design standard.

5. The method for superimposing interface coupling of multi-level nano-coatings on a glass substrate according to claim 1, characterized in that: In step 6, the spraying current is 550-650A, the argon flow rate is 44-48SLPM, the hydrogen flow rate is 7-9SLPM, the spraying distance is 90-110mm, and the spray gun moving speed is 900-1100mm / s.

6. The method for superimposing interface coupling of multi-level nano-coatings on a glass substrate according to claim 1, characterized in that: The purity of the Ar gas in step 4 is greater than 99.99% by volume.

7. A multi-level nano-coated glass substrate, characterized in that: The multi-level nano-coated glass substrate is prepared by the interface coupling method according to any one of claims 1 to 6.

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