Rare earth element doped silver film low-radiation suspended film energy-saving hollow glass and preparation method thereof

Abstract

The invention provides rare earth element doped silver film low-radiation suspended film energy-saving hollow glass and a preparation method thereof, and relates to the technical field of energy-saving windows. The preparation method comprises the following steps: (1) sequentially plating a first dielectric layer, a seed crystal layer, an infrared reflection functional layer, a middle protection layer, a second dielectric layer and an air surface protection layer on the surface of a flexible high-transmittance polymer material film through magnetron sputtering to prepare a flexible low-radiation film; the infrared reflection functional layer adopts a co-sputtering method to prepare rare earth element doped silver; and (2) the flexible low-radiation film in the step (1) is hung between the two pieces of glass through a steel bar and an adhesive, and the energy-saving outer window of the two-glass two-cavity structure is formed. The magnetron sputtering silver film low-radiation suspended film fireproof hollow glass based on rare earth element doping has excellent heat insulation performance, visible light transmittance and infrared light reflection performance, has good weather resistance and oxidation resistance, and is suitable for various places with high building energy saving and comfort requirements.

Description

Technical Field

[0001] The invention relates to the field of energy-saving windows, and in particular to a rare earth element-doped silver film low-radiation suspended film energy-saving insulating glass and a preparation method thereof. Background Art

[0002] LOW-E (low-emissivity) glass reduces heat transfer through its special coating, reduces indoor heat loss in winter, and reduces outdoor heat entry in summer, thereby reducing the heating and cooling needs of buildings. This not only reduces the operating costs of buildings, but also helps reduce energy consumption, thereby reducing greenhouse gas emissions, which has positive significance for environmental protection.

[0003] In addition to LOW-E glass, magnetron sputtering of low-emissivity films on the surface of flexible polymer materials and then constructing suspended film energy-saving insulating glass is also a development trend today. This technology is also based on the control of infrared radiation, and a uniform and dense silver film is formed on the surface of the material through magnetron sputtering technology. However, the transmittance of metallic silver in the visible light region is low. In order to effectively reflect infrared radiation, thicker silver films or multi-layer silver films are usually required. This thicker silver film will result in lower visible light transmittance, thereby reducing indoor comfort. In addition, metallic silver is easily oxidized in the air, which will further reduce the visible light transmittance and also reduce the infrared reflectivity.

[0004] The plasma resonance frequency of the silver film is closely related to its electron density. By doping with rare earth elements such as cerium (Ce), lanthanum (La) or yttrium (Y), the electron density of the silver film can be controlled, thereby adjusting its plasma resonance frequency. Specifically, since rare earth elements generally have a higher electron density, doping with rare earth elements can increase the electron density of the silver film, causing its plasma resonance frequency to move toward the long wavelength direction, thereby improving the transmittance of the silver film in the visible light range while increasing its reflection of infrared light. In addition, the electronic structure of rare earth elements can also interact with the electronic structure of the silver film, and this interaction can also affect its chemical stability in the air. Summary of the invention

[0005] In view of this, the present invention proposes a rare earth element doped silver film low-radiation suspended film energy-saving hollow glass and a preparation method thereof. The doping technology of the present invention optimizes the plasma resonance frequency and electronic structure of metallic silver, significantly improves the light transmittance of the silver film in the visible light range, and enhances its reflection performance to infrared light; not only optimizes the optical properties of the silver film, but also significantly enhances its weather resistance and oxidation resistance, and effectively prolongs its service life; the present invention suspends a flexible low-radiation film between two pieces of glass to form an energy-saving exterior window with a "two-glass two-cavity" structure, thereby effectively enhancing the thermal insulation performance of the glass and improving the quietness of the living environment.

[0006] The technical solution of the present invention is achieved in this way:

[0007] A method for preparing a rare earth element doped silver film low-radiation suspended film energy-saving insulating glass comprises the following steps:

[0008] (1) A first dielectric layer, a seed layer, an infrared reflection functional layer, an intermediate protective layer, a second dielectric layer and an air surface protective layer are sequentially magnetron sputtered on the surface of a flexible high-transmittance polymer material film to obtain a flexible low-radiation film; this flexible low-radiation film not only has excellent thermal insulation performance, but also can effectively reflect infrared radiation, while improving visible light transmittance, ensuring sufficient indoor light and improving living comfort.

[0009] (2) The flexible low-emissivity film of step (1) is suspended between two sheets of glass by steel bars and adhesive to form an energy-saving exterior window with a two-glass two-cavity structure. This structural design not only enhances the thermal insulation performance of the glass, but also effectively isolates external noise and improves the quietness of the living environment.

[0010] Furthermore, the infrared reflection functional layer is prepared by co-sputtering rare earth element-doped silver, wherein the rare earth element is at least one of Ce, La or Y, and a rare earth metal alloy target is used for two or more rare earth elements. In the magnetron sputtering coating process, the present invention adjusts the plasma resonance frequency and electronic structure of the silver film by doping rare earth elements such as cerium (Ce), lanthanum (La) or yttrium (Y), thereby improving the transmittance of the silver film in the visible light range and the reflection of infrared light, and improving its stability in the air.

[0011] Furthermore, the total amount of rare earth doping is controlled at 1-15%wt, and the thickness of the infrared reflection functional layer is 3-35nm.

[0012] Furthermore, the total amount of rare earth doping is controlled at 6-12%wt.

[0013] Furthermore, in step (1), the sputtering power is 90-150 W, the sputtering atmosphere is Ar gas, and the Ar gas flow rate is 50-70 sccm.

[0014] Furthermore, the first dielectric layer and the second dielectric layer are a conductive layer selected from the group consisting of indium oxide, ITO, and FTO, and have a thickness of 5 to 60 nm, preferably 15 to 40 nm.

[0015] Furthermore, the seed layer is one of ZnO, Ti, Cu and Pt, and has a thickness of 2 to 20 nm, preferably 3 to 8 nm.

[0016] Furthermore, the intermediate protective layer is Ti, NiCr, Au or Ni, and has a thickness of 2 to 20 nm, preferably 3 to 10 nm.

[0017] Furthermore, the air surface protection layer is made of silicon nitride, silicon oxide, etc., and has a thickness of 5 to 30 nm, preferably 5 to 15 nm.

[0018] Furthermore, in step (1), the flexible high-transmittance polymer material is one of PVB, EVA, and PET.

[0019] Furthermore, in step (2), the glass is transparent glass, and the hollow glass is composed of two pieces of glass and a flexible suspension film, and the thickness of each cavity is 2 to 15 mm, preferably 3 to 10 mm.

[0020] A method for preparing rare earth element doped silver film low-radiation suspended film energy-saving insulating glass is prepared by any preparation method described in the present invention.

[0021] Compared with the prior art, the present invention has the following beneficial effects:

[0022] (1) The present invention provides a method for preparing a rare earth element doped magnetron sputtered silver film low-radiation suspended film fireproof insulating glass, which has excellent thermal insulation performance, visible light transmittance and infrared light reflection performance, and has good weather resistance and oxidation resistance, and is suitable for various places with high requirements for building energy saving and comfort.

[0023] (2) The present invention adjusts the plasma resonance frequency and electronic structure of the silver film by doping rare earth elements such as cerium (Ce), lanthanum (La) or yttrium (Y), thereby increasing the transmittance of the silver film in the visible light range and the reflection of infrared light, and improving its stability in the air. The introduction of rare earth elements not only optimizes the optical properties of the silver film, but also enhances its weather resistance and oxidation resistance, thereby extending its service life.

[0024] (3) The present invention suspends a flexible low-radiation film between two sheets of glass by means of steel bars and adhesives, thereby forming an energy-saving exterior window with a "two-glass, two-cavity" structure. This structural design not only enhances the thermal insulation performance of the glass, but also effectively isolates external noise, thereby improving the quietness of the living environment. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] Figure 1 It is the magnetron sputtering low-radiation film system structure of the present invention; in the figure, 1-thin film, 201 first dielectric layer, 202 seed layer, 203 infrared reflection functional layer, 204 intermediate protection layer, 205 second dielectric layer, 206 air surface protection layer.

[0026] Figure 2 This is a schematic diagram of the suspended film high-transmittance energy-saving insulating glass structure. DETAILED DESCRIPTION

[0027] In order to better understand the technical content of the present invention, specific embodiments are provided below to further illustrate the present invention.

[0028] Unless otherwise specified, the experimental methods used in the embodiments of the present invention are all conventional methods.

[0029] Unless otherwise specified, the materials, reagents, etc. used in the embodiments of the present invention can be obtained from commercial sources.

[0030] Table 1 Chinese meaning of English

[0031] Serial number English or abbreviation Chinese 1 PVB Polyvinyl butyral 2 EVA Ethylene-vinyl acetate copolymer 3 PET Polyethylene terephthalate

[0032] A method for preparing a rare earth element doped silver film low-radiation suspended film energy-saving insulating glass comprises the following steps:

[0033] (1) A first dielectric layer 201, a seed layer 202, an infrared reflection functional layer 203, an intermediate protective layer 204, a second dielectric layer 205 and an air surface protective layer 206 are sequentially magnetron sputtered on the surface of a flexible high-transmittance polymer material film 1 to obtain a flexible low-radiation film ( Figure 1 ); This flexible low-emissivity film not only has excellent thermal insulation properties, but also can effectively reflect infrared radiation, while increasing visible light transmittance, ensuring sufficient indoor light and improving living comfort.

[0034] (2) The flexible low-emissivity film prepared in step (1) is suspended between two sheets of glass through steel bars and adhesive to form an energy-saving exterior window with a two-glass two-cavity structure ( Figure 2 ). This structural design not only enhances the thermal insulation performance of the glass, but also effectively isolates external noise and improves the quietness of the living environment.

[0035] Furthermore, the infrared reflection functional layer is prepared by co-sputtering rare earth element-doped silver, wherein the rare earth element is at least one of Ce, La or Y, and a rare earth metal alloy target is used for two or more rare earth elements. In the magnetron sputtering coating process, the present invention adjusts the plasma resonance frequency and electronic structure of the silver film by doping rare earth elements such as cerium (Ce), lanthanum (La) or yttrium (Y), thereby improving the transmittance of the silver film in the visible light range and the reflection of infrared light, and improving its stability in the air.

[0036] Furthermore, in step (1), the sputtering power is 90-150 W, the sputtering atmosphere is Ar gas, and the Ar gas flow rate is 50-70 sccm.

[0037] Furthermore, the first dielectric layer and the second dielectric layer are a conductive layer selected from the group consisting of indium oxide, ITO, and FTO, and have a thickness of 5 to 60 nm, preferably 15 to 40 nm.

[0038] The seed layer is one of ZnO, Ti, Cu and Pt, and has a thickness of 2 to 20 nm, preferably 3 to 8 nm.

[0039] The total amount of rare earth doping is controlled at 1-15%wt, and the single layer thickness of the infrared reflection functional layer is 3-35nm.

[0040] The intermediate protective layer is Ti, NiCr, Au or Ni, and has a thickness of 2 to 20 nm, preferably 3 to 10 nm.

[0041] The air surface protection layer is made of silicon nitride, silicon oxide, etc., and has a thickness of 5 to 30 nm, preferably 5 to 15 nm.

[0042] The flexible high-transmittance polymer material is PVB, EVA, or PET.

[0043] The glass is transparent glass, a hollow glass composed of two sheets of glass and a flexible suspension film, and the thickness of each cavity is 2 to 15 mm, preferably 3 to 10 mm.

[0044] Example

[0045] Preparation method of rare earth element doped silver film low-radiation suspended film energy-saving insulating glass

[0046] The flexible suspension film (flexible high-transmittance polymer material film) used in the present invention is a 50 μm thick PET film, on which the first dielectric layer (indium oxide), seed layer (Ti), infrared reflection functional layer (silver doped with Ce, La or Y rare earth elements), protective layer (NiCr), second dielectric layer (indium oxide) and air surface protective layer (silicon nitride) are sequentially plated on one side of the surface by magnetron sputtering at room temperature. The magnetron sputtering coating target used in the embodiment of the present invention was purchased from Qijin New Materials Co., Ltd. The magnetron sputtering coating conditions are shown in Table 2.

[0047] Then two pieces of 5mm thick ordinary float glass are constructed into a single-film two-cavity insulating glass through polyurethane glue, a stainless steel strip with a thickness of 8mm and a width of 8.5mm, and a flexible low-e film.

[0048] Table 2.

[0049]

[0050] The suspended film insulating glass of the present invention is mainly tested for performance by the following methods: the molar ratio of rare earth / silver in the film system is determined by ICS-AES; the visible light transmittance of the insulating glass in the embodiment is measured by Lambda950 spectrophotometer; and the K value is measured according to GB 10294-88 and GB / T 2680-94.

[0051] According to the magnetron sputtering coating conditions in Table 2, flexible low-emissivity films with different silver layer compositions were prepared (Table 3), and the light transmittance and heat transfer coefficient K values ​​of the single-film two-cavity insulating glass were constructed, as shown in Table 3. In order to compare the effects of different silver layer compositions on the stability of the film, the coated flexible low-emissivity films were exposed to air at room temperature for 48 hours, and then the insulating glass was constructed to test the light transmittance and heat transfer coefficient K values.

[0052] Table 3.

[0053]

[0054] Note: The element ratios in the infrared reflection functional layer composition in Table 3 are atomic ratios.

[0055] The results show that the stability of pure silver film in the air is poor and it is easy to oxidize, resulting in decreased light transmittance and thermal insulation performance. By introducing a certain amount of rare earth elements to optimize the plasma resonance frequency and electronic structure of metallic silver, not only the light transmittance of the silver film in the visible light range is improved, but also its stability in the air is enhanced and its service life is extended. The rare earth element doped silver film low-radiation suspended film energy-saving insulating glass of the present invention shows excellent performance in visible light transmittance, heat transfer coefficient K value, weather resistance and oxidation resistance, which is better than traditional pure silver film and is suitable for various places with high requirements for building energy saving and comfort.

[0056] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention should be included in the protection scope of the present invention.

Claims

1. A method for preparing a rare earth element doped silver film low-radiation suspended film energy-saving insulating glass, characterized in that: The following steps are involved: (1) magnetron sputtering is performed on the surface of a flexible high-transmittance polymer material film in sequence to form a first dielectric layer, a seed layer, an infrared reflection functional layer, an intermediate protective layer, a second dielectric layer and an air surface protective layer to obtain a flexible low-radiation film; the infrared reflection functional layer is prepared by a co-sputtering method with silver doped with rare earth elements; (2) Suspending the flexible low-emissivity film of step (1) between two sheets of glass to form an energy-saving exterior window with a two-glass two-cavity structure.

2. The method for preparing a rare earth element doped silver film low-emissivity suspended film energy-saving insulating glass according to claim 1, characterized in that: The rare earth element is one, two or three of Ce, La or Y.

3. The method for preparing a rare earth element doped silver film low-radiation suspended film energy-saving insulating glass according to claim 1 or 2, characterized in that: The total amount of rare earth doping is controlled at 1-15%wt.

4. The method for preparing a rare earth element doped silver film low-emissivity suspended film energy-saving insulating glass according to claim 1 or 2, characterized in that: The infrared reflection functional layer has a thickness of 3 to 35 nm.

5. The method for preparing a rare earth element doped silver film low-emissivity suspended film energy-saving insulating glass according to claim 1, characterized in that: In step (1), the sputtering power is 90-150 W, the sputtering atmosphere is Ar gas, and the Ar gas flow rate is 50-70 sccm.

6. The method for preparing a rare earth element doped silver film low-emissivity suspended film energy-saving insulating glass according to claim 1, characterized in that: The first dielectric layer and the second dielectric layer are a conductive layer selected from indium oxide, ITO, and FTO, and have a thickness of 5 to 60 nm; the seed layer is a conductive layer selected from ZnO, Ti, Cu, and Pt, and has a thickness of 2 to 20 nm.

7. The method for preparing a rare earth element doped silver film low-emissivity suspended film energy-saving insulating glass according to claim 1, characterized in that: The intermediate protection layer is Ti, NiCr, Au or Ni, with a thickness of 2 to 20 nm; the air surface protection layer is silicon nitride, silicon oxide, etc., with a thickness of 5 to 30 nm.

8. The method for preparing a rare earth element doped silver film low-emissivity suspended film energy-saving insulating glass according to claim 1, characterized in that: In step (1), the flexible high-transmittance polymer material is one of PVB, EVA and PET.

9. The method for preparing a rare earth element doped silver film low-emissivity suspended film energy-saving insulating glass according to claim 1, characterized in that: Step (2), the glass is transparent glass, a hollow glass composed of two pieces of glass and a flexible suspended film, and the thickness of each cavity is 2 to 15 mm.

10. A rare earth element doped silver film low-emissivity suspended film energy-saving insulating glass, characterized in that: Prepared by the preparation method according to any one of claims 1 to 9.

Images