A nearly colorless high-transmission double-silver glass and a preparation process thereof

Abstract

This application relates to the field of glass, specifically disclosing a near-colorless high-transmittance double-silver glass and its preparation process. The near-colorless high-transmittance double-silver glass comprises a first dielectric layer consisting of a polypyrrole fiber layer, a TiO2 layer, and a Si3N4 layer sequentially arranged, with the polypyrrole fiber layer close to the glass substrate; a fourth protective layer is a SiAlZrN layer with a thickness of 1.3-1.5 nm; the preparation method is as follows: S1. Tempering; S2. Spraying: a polypyrrole fiber dispersion is sprayed onto the surface of the tempered glass obtained in S1 to obtain a polypyrrole fiber layer; S3. Sputtering coating. The high-transmittance double-silver glass of this application achieves a high-transmittance and low-color-difference effect, further balancing the color cast phenomenon of the glass, increasing the transmittance in the visible light band to over 72.5%, with a color cast index a* value ∈ [-2,2], b* value ∈ [-4,1], and emissivity ε ≤ 0.04.

Description

Technical Field

[0001] This application relates to the technical field of glass, and in particular to a near-colorless high-transparency double-silver glass and its preparation process. Background Technology

[0002] Double-silver coated glass is a high-performance, energy-saving glass product. It achieves a balance between excellent optical and thermal properties by depositing multiple layers of silver-containing functional films on the glass surface. The core structure of double-silver coated glass (hereinafter referred to as double-silver glass) involves depositing multiple thin films on a glass substrate, including two silver functional layers. A protective layer and a dielectric layer are sequentially arranged on both sides of each silver functional layer. The core purpose of double-silver glass is to effectively block solar heat and harmful ultraviolet rays while ensuring high light transmittance, helping consumers achieve warmth in winter and coolness in summer, energy saving, and a comfortable experience. Specifically, double-silver glass reflects most infrared rays in summer, blocking heat from entering the room, and prevents heat loss in winter, significantly reducing air conditioning and heating energy consumption. It blocks more than 99% of ultraviolet rays, protecting furniture and floors from sunburn and reducing skin damage. It also effectively reduces glare, making indoor light softer and more comfortable while maintaining good light transmittance. Most existing double-silver glass is used for car windshields and side windows, while higher quality double-silver glass is used for curtain walls and windows of office buildings, shopping malls, and residences, as well as environments such as greenhouses and museums that require precise control of light and temperature.

[0003] However, to enhance the thermal insulation performance of existing double-silvered glass, the film layer may be designed to be thicker or have higher reflectivity. This sacrifices some visible light transmittance, and an excessively thick film layer can also cause a bluish tint. Conversely, an excessively thin film layer can result in a grayish tint and reduce the thermal insulation performance of the double-silvered glass, thus affecting its energy-saving effect. Therefore, current double-silvered glass struggles to meet the comprehensive requirements of high-end buildings for high light transmittance, low color cast, and energy-saving performance, making it almost impossible to achieve a synergistic improvement in energy efficiency and aesthetics. Summary of the Invention

[0004] To address the aforementioned technical problems, this application provides a near-colorless high-transparency double-silver glass and its preparation process.

[0005] In a first aspect, this application provides a near-colorless, high-transparency double-silver glass, comprising a glass substrate, a first dielectric layer, a first protective layer, a first functional silver layer, a second dielectric layer, a second protective layer, a second functional silver layer, a third protective layer, a third dielectric layer, and a fourth protective layer, disposed sequentially.

[0006] The first dielectric layer is composed of a polypyrrole fiber layer, a TiO2 layer and a Si3N4 layer arranged sequentially, wherein the polypyrrole fiber layer is close to the glass substrate;

[0007] The fourth protective layer is a SiAlZrN layer with a thickness of 1.3-1.5 nm.

[0008] Preferably, the first protective layer, the second protective layer, and the third protective layer are all NiCr layers.

[0009] Preferably, the thickness of the first protective layer is 0.5-1.0 nm, the thickness of the second protective layer is 0.7-1.5 nm, and the thickness of the third protective layer is 0.5-1.5 nm.

[0010] Preferably, the thickness of the first dielectric layer is 8 nm, and the thickness ratio of the polypyrrole fiber layer, the TiO2 layer and the Si3N4 layer is (0.8-1.5):(1.5-3.2):(4-5).

[0011] By adopting the above technical solution, this application uses a polypyrrole fiber layer, a TiO2 layer, and a Si3N4 layer arranged sequentially as the first dielectric layer. The fibers in the polypyrrole fiber layer have good mechanical strength, which can effectively improve the overall stability of the double silver glass layer structure. More importantly, this application uses a polypyrrole fiber layer to replace conventional dielectric layers, such as Si3N4 layers, ZnSnO layers, and AZO (aluminum-doped zinc oxide) layers, which can further improve the light transmittance without affecting the growth and adhesion of the first functional silver layer. Furthermore, the TiO2 layer and the Si3N4 layer in the first dielectric layer have a significant advantage in strong bonding. At the same time, the surface of the composite layer can provide a good growth environment for the first protective layer. Therefore, the first dielectric layer and the first protective layer of this application have a tight bond, a dense internal structure, and a smooth surface, thereby effectively improving the growth quality of the first functional silver layer and thus improving the energy-saving effect of the double silver glass. Based on the improved light transmittance, this application further controls the thickness and composition of each layer, so that the overall coating thickness of the double silver glass is moderate, taking into account both energy-saving effect and high transmittance. Moreover, due to the precise design of the thickness, the double silver glass will hardly show any blue or grayish phenomena during use.

[0012] In this application, the polypyrrole fiber layer has a thickness of only 0.8-1.5 nm. According to Beer-Lambert law, the degree of light absorption by a material is proportional to its thickness. A thickness of 0.8-1.5 nm is at the sub-nanometer level, equivalent to only a few polymer chain molecular layers. Under such extreme thin-film conditions, the absorption of visible light by polypyrrole decreases exponentially, with negligible absorption loss. Furthermore, at this thickness, the polypyrrole fiber layer is not microscopically dense and opaque, but rather tends to form an extremely sparse, nano-network-like or island-like two-dimensional framework. Light can pass directly through the gaps between the fiber networks without significant blocking effects. Moreover, this application uses a polypyrrole fiber layer, a TiO2 layer, and a Si3N4 layer to form a first dielectric layer with a thickness of 8 nm. In thin-film optics, the overall transmittance of a multilayer film depends on the interference superposition of the refractive index, extinction coefficient, and physical thickness of each layer. Polypyrrole possesses a certain conjugated structure, and at sub-nanometer thicknesses, its refractive index forms a favorable gradient transition with the subsequent high-refractive-index TiO2 and medium-refractive-index Si3N4. This gradient film system design (polymer / oxide / nitride), through thin-film interference effects, can reduce light reflection at the interface between the glass substrate and the functional silver layer, thereby compensating for or even improving the overall glass transmittance. Therefore, the introduction of a polypyrrole fiber layer in this application not only does not reduce transmittance, but its surface polar groups also provide extremely abundant nucleation sites for subsequent sputtered TiO2, resulting in denser and more uniform growth of the subsequent TiO2 and Si3N4 grains. It is precisely this reduction in microscopic defects that significantly reduces light scattering loss within the dielectric layer, which is a key factor in achieving "high transmittance" in this approach.

[0013] In addition, this application utilizes a SiAlZrN layer with a thickness of 1.3-1.5 nm as the fourth protective layer. At an ultra-thin thickness of 1.3-1.5 nm, SiAlZrN has extremely low absorption rate in the visible light band, enabling the glass to have a visible light transmittance of >75%, and effectively avoiding the yellowing or bluish tint caused by traditional TiO2 or ZnO layers, achieving a colorless visual effect. At the same time, it has an atomically dense structure. Compared with traditional protective layers such as SiO2 and Ti layers, SiAlZrN has higher hardness and scratch resistance, effectively resisting physical damage, reducing the risk of microcracks in the film layer, improving product yield, and protecting the internal functional silver layer, thereby helping the functional silver layer to exert a long-term and stable energy-saving effect.

[0014] In summary, this application utilizes a polypyrrole fiber layer, a TiO2 layer, and a Si3N4 layer to form the first dielectric layer, and a SiAlZrN layer with a thickness of 1.3-1.5 nm as the fourth protective layer. Combined with the thickness and composition design of other layers, this application achieves simultaneous improvement in multiple aspects of double-silver glass, such as high light transmittance, low color deviation, and energy-saving performance. When applied to high-end buildings, it can produce a synergistic effect of improving both energy efficiency and aesthetics.

[0015] Preferably, the thickness of the second dielectric layer is 10-15 nm, and it is composed of a ZnAlO layer, a ZnSnO layer and an AZO layer arranged sequentially, wherein the thickness ratio of the ZnAlO layer, the ZnSnO layer and the AZO layer is (2-4):(3-4):(3-4), and the ZnAlO layer is close to the first functional silver layer.

[0016] By adopting the above technical solution, this application utilizes a ZnAlO layer, a ZnSnO layer, and an AZO layer to form a second dielectric layer. The ZnAlO layer, located close to the first functional silver layer, adheres firmly to the surface of the first functional silver layer, exhibiting higher process stability during the sputtering of the second dielectric layer. Both ZnSnO and AZO are high-refractive-index transparent conductive oxides with high light transmittance. The gradient refractive index structure formed by the ZnAlO, ZnSnO, and AZO layers arranged in a specified thickness ratio can create a precise optical interference network, enhancing visible light transmission while suppressing reflections in non-target wavelengths. This achieves a high-transmittance, colorless effect with high light transmittance and low color difference. Furthermore, this application controls the thickness of the second dielectric layer to 10-15 nm, further balancing the color cast of the glass and bringing the green-red axis color difference value a* and the yellow-blue axis color difference value b* closer to zero.

[0017] Preferably, the thickness of the first functional silver layer is 4.5-5 nm, and the thickness of the second functional silver layer is 11-12 nm.

[0018] Preferably, the thickness of the third dielectric layer is 20-28 nm, and it is composed of a Si3N4 layer and a ZrO layer with a thickness ratio of (15-25):(3-5), wherein the Si3N4 layer is close to the third protective layer.

[0019] By adopting the above technical solution, this application uses a Si3N4 layer and a ZrO layer with a thickness ratio of (15-25):(3-5) as the third dielectric layer. This layer is the outermost dielectric layer of the overall double silver glass. Its protective ability for the overall structure is second only to the fourth protective layer. It can effectively resist surface scratches and chemical corrosion caused by daily cleaning, wind and sand abrasion and industrial pollution, fundamentally delay the oxidation and sulfidation discoloration of the silver layer, significantly extend the service life of the functional silver layer, and improve the long-term energy-saving capability. As the main structural layer, the Si3N4 layer can form a continuous gradient refractive interface with the ZrO layer, effectively matching the optical impedance of the inner functional silver layer and the air, improving the light transmittance in the visible light band to more than 70%, while maintaining the green-red axis color difference value a* and the yellow-blue axis color difference value b* close to 0, meeting the stringent requirements of high-end buildings for energy saving and decoration.

[0020] Secondly, this application also provides a process for preparing the above-mentioned near-colorless high-transparency double-silver glass, comprising the following steps:

[0021] S1. Tempered glass;

[0022] S2. Spraying: Polypyrrole fibers are dispersed in water to obtain a polypyrrole fiber dispersion with a concentration of 2-3 wt%, and sprayed onto the surface of the tempered glass obtained in S1 under a pressure of 0.3-0.4 MPa, and dried to obtain a polypyrrole fiber layer;

[0023] S3. Sputtering coating: TiO2 layer and Si3N4 layer are sputtered sequentially on the surface of polypyrrole fiber layer to obtain first dielectric layer. Then, first protective layer, first functional silver layer, second dielectric layer, second protective layer, second functional silver layer, third protective layer, third dielectric layer and fourth protective layer are sputtered sequentially on the surface of first dielectric layer. Plasma bombardment is performed after obtaining second dielectric layer and third dielectric layer. After finishing, near-colorless high-transmittance double silver glass is obtained.

[0024] Preferably, in step S3, when sputtering to prepare the first functional silver layer, the argon flow rate is controlled to be 1200 sccm and the target power is 4.5-5.0 kW.

[0025] Preferably, in step S3, when sputtering to prepare the second functional silver layer, the argon flow rate is controlled to be 1200 sccm and the target power is 11-12 kW.

[0026] By adopting the above technical solution, this application first tempers the glass substrate to form a uniform compressive stress layer on the glass surface and a tensile stress layer inside, which improves the mechanical strength and thermal stability of the glass. After cleaning, the dirt on the glass surface is cleaned and then a film is sprayed. A uniformly dispersed polypyrrole fiber dispersion is sprayed onto the glass surface under a certain pressure. This application strictly controls the concentration of the polypyrrole fiber dispersion to 2-3 wt%, thereby promoting the formation of a polypyrrole fiber layer with uniform fiber arrangement and high film strength on the glass surface. Then, sputtering deposition is continued, and after obtaining the second and third dielectric layers, plasma bombardment is performed to obtain a near-colorless high-transmittance double-silver glass. The preparation process is smooth, and the film spraying after tempering can ensure that the polypyrrole fiber layer can exert a better stability and promote light transmission, which is convenient for industrial production and has high practicality.

[0027] In summary, this application has the following beneficial technical effects:

[0028] 1. This application utilizes a polypyrrole fiber layer, a TiO2 layer, and a Si3N4 layer to form the first dielectric layer, and a SiAlZrN layer with a thickness of 1.3-1.5nm as the fourth protective layer. In addition, the thickness and composition design of other layers are combined. In particular, by adjusting the specific composition of the second dielectric layer, the third dielectric layer, and the fourth protective layer, a high-transmittance colorless effect with high light transmittance and low color difference value is achieved, further balancing the color deviation of the glass and improving the light transmittance in the visible light band to meet the stringent requirements of high-end buildings for energy conservation and decoration.

[0029] 2. The high-transmittance double-silver glass obtained in this application has a transmittance of over 72.5% in the visible light band, and the color shift index has a* value ∈ [-2,2], b* value ∈ [-4,1], and emissivity ε ≤ 0.04;

[0030] 3. The preparation process of this application is simple to operate and has a smooth flow. The tempered spray film can ensure that the polypyrrole fiber layer can exert a better stability and promote light transmission, which is convenient for industrial production and has high practicality. Detailed Implementation

[0031] The polypyrrole fibers of this application are prepared by the following method:

[0032] The cellulose solution was extruded at a rate of 0.7 mL / min and then immersed in a sulfuric acid-sodium sulfate mixed solution at 50°C for coagulation (sulfuric acid concentration 12 wt%, sodium sulfate concentration 20 wt%, immersion time 35 min). It was then immersed in a sodium hydroxide solution at 80°C for desulfurization (sodium hydroxide concentration 1.8 wt%, immersion time 60 min), and finally immersed in a glycerol solution at 35°C for plasticization (glycerol concentration 5 wt%, immersion time 80 min). The resulting product was wound onto nylon rollers to obtain regenerated cellulose fibers. Wash and dry the fiber, and set aside for later use. Immerse the regenerated cellulose fiber in a mixed solution of 0.1M pyrrole and 0.5M sulfuric acid, controlling the amount of regenerated cellulose fiber to be 1000wt% of the amount of pyrrole. Then, sonicate for 10 minutes and let it stand at 5°C to obtain a fiber mixture. Freeze the mixed solution of 0.01M ferric chloride and 0.5M sulfuric acid until it is frozen to obtain mixed ice blocks. Then immerse the ice blocks in the above-mentioned fiber mixture that has been set aside for 10 hours. After reaction, wash, dry, and cut to a length of 5nm to obtain polypyrrole fiber.

[0033] The present application will be further described in detail below with reference to embodiments and comparative examples.

[0034] Example 1

[0035] A process for preparing near-colorless, high-transparency double-silver glass includes the following steps:

[0036] S1. Tempering: The glass slide is ultrasonically cleaned sequentially with acetone, anhydrous ethanol, and deionized water. Then, the glass slide is grounded to obtain a pre-treated glass substrate. It is then placed in a dual-chamber high-convection horizontal tempering furnace for tempering. The lower temperature is 670℃ and the upper temperature is 680℃. The tempering time is 5 minutes. The glass slide is then ultrasonically cleaned sequentially with acetone, anhydrous ethanol, and deionized water. Then, the glass slide is grounded to obtain tempered glass.

[0037] S2. Spraying: Disperse polypyrrole fibers in water, then add sodium polystyrene sulfonate at a volume of 0.3 wt% of water. After ultrasonic mixing for 10 min, a polypyrrole fiber dispersion with a concentration of 3 wt% is obtained. Mix with acetone at a volume ratio of 1:0.6 and spray onto the surface of the tempered glass obtained in S1 under a pressure of 0.4 MPa. Control the spraying speed at 1100 rpm and the single spraying time not to exceed 15 s. After drying, check the thickness and then spray and dry thoroughly until the thickness reaches 0.8 nm to obtain a polypyrrole fiber layer.

[0038] S3. Sputtering coating:

[0039] Sputtering was performed on the surface of a polypyrrole fiber layer using pure titanium as a target, while simultaneously introducing Ar and O2 at a volume ratio of 3:1. The target power was controlled at 50 kW, and the total gas flow rate was 1200 sccm. Sputtering was continued until a TiO2 layer with a thickness of 3.2 nm was obtained.

[0040] The TiO2 layer was sputtered using a pure silicon target, while Ar and N2 were introduced in a volume ratio of 1:1.2. The target power was controlled at 25 kW, and the total gas flow rate was 1200 sccm. Sputtering was continued until a Si3N4 layer with a thickness of 4 nm was obtained.

[0041] A first dielectric layer with a thickness of 8 nm is composed of a polypyrrole fiber layer, a TiO2 layer, and a Si3N4 layer.

[0042] A nickel-chromium target (nickel-chromium weight ratio of 4:1) was used to sputter the surface of the first dielectric layer while Ar was introduced. The target power was controlled at 10 kW and the total gas flow rate was 1200 sccm. Sputtering was continued until a NiCr layer with a thickness of 1 nm was obtained.

[0043] This forms a first protective layer with a thickness of 1 nm.

[0044] The surface of the first protective layer was sputtered using pure silver as a target, while Ar was introduced. The target power was controlled at 4.5 kW and the total gas flow rate at 1200 sccm. Sputtering was continued until a first functional silver layer with a thickness of 4.5 nm was obtained.

[0045] The first functional silver layer was sputtered using a zinc-aluminum target while simultaneously introducing Ar and O2 at a volume ratio of 1:1.2. The target power was controlled at 500 kW, and the total gas flow rate was 1600 sccm. Sputtering was continued until a ZnAlO layer with a thickness of 4 nm was obtained.

[0046] A zinc-tin target (zinc-tin weight ratio of 1:1) was used to sputter the ZnAlO layer surface, while Ar and O2 with a volume ratio of 1:2 were simultaneously introduced. The target power was controlled at 470 kW, the total gas flow rate was 1500 sccm, and sputtering was continued until a ZnSnO layer with a thickness of 3 nm was obtained.

[0047] An AZO target (zinc-aluminum weight ratio of 1:1) was used to sputter the ZnSnO layer surface, while Ar and O2 with a volume ratio of 1200:50 were introduced simultaneously. The target power was controlled at 15 kW, and the total gas flow rate was 1250 sccm. Sputtering was continued until an AZO layer with a thickness of 4 nm was obtained.

[0048] The ZnAlO layer, ZnSnO layer, and AZO layer constitute a second dielectric layer with a thickness of 11 nm.

[0049] The second dielectric layer was bombarded with Ne plasma at a power of 100 W, an energy of 75 eV, and a duration of 5 min, followed by Xe plasma bombardment at a frequency of 1 kHz, a pulse duty cycle of 20%, an energy of 200 eV, and a duration of 12 min.

[0050] A nickel-chromium target (nickel-chromium weight ratio of 4:1) was used to sputter the surface of the second dielectric layer while Ar was introduced. The target power was controlled at 7 kW and the total gas flow rate at 1200 sccm. Sputtering was continued until a NiCr layer with a thickness of 0.7 nm was obtained.

[0051] This forms a second protective layer with a thickness of 0.7 nm.

[0052] The surface of the second protective layer was sputtered using pure silver as a target, while Ar was introduced simultaneously. The target power was controlled at 12 kW, and the total gas flow rate was 1200 sccm. Sputtering was continued until a second functional silver layer with a thickness of 12 nm was obtained.

[0053] The second functional silver layer was sputtered onto the surface using a nickel-chromium target (nickel-chromium weight ratio of 4:1) while Ar was introduced. The target power was controlled at 5 kW and the total gas flow rate at 1200 sccm. Sputtering was continued until a NiCr layer with a thickness of 0.5 nm was obtained.

[0054] This forms a third protective layer with a thickness of 0.5 nm.

[0055] Sputtering was performed on the surface of the third protective layer using pure silicon as a target, while simultaneously introducing Ar and N2 at a volume ratio of 1:1.2. The target power was controlled at 100 kW, and the total gas flow rate was 1200 sccm. Sputtering was continued until a Si3N4 layer with a thickness of 25 nm was obtained.

[0056] Zirconia was used to target and sputter the Si3N4 layer surface while simultaneously introducing Ar and O2 at a volume ratio of 20:1. The target power was controlled at 500 kW, and the total gas flow rate was 1050 sccm. Sputtering was continued until a ZrO layer with a thickness of 3 nm was obtained.

[0057] The Si3N4 layer and the ZrO layer constitute a third dielectric layer with a thickness of 28 nm.

[0058] The third dielectric layer was bombarded with Ne plasma at a power of 100 W, an energy of 75 eV, and a duration of 5 min, followed by Xe plasma bombardment at a frequency of 1 kHz, a pulse duty cycle of 20%, an energy of 200 eV, and a duration of 12 min.

[0059] A silicon-aluminum-zirconium target (silicon-aluminum-zirconium weight ratio of 8:1:1) was used to sputter onto the surface of the third dielectric layer, while Ar and N2 were introduced in a volume ratio of 20:1. The target power was controlled at 20 kW, and the total gas flow rate was 1050 sccm. Sputtering was continued until a SiAlZrN layer with a thickness of 1.5 nm was obtained.

[0060] This forms a fourth protective layer with a thickness of 1.5 nm.

[0061] After processing, a nearly colorless, high-transparency double-silver glass is obtained.

[0062] Example 2

[0063] A process for preparing near-colorless, high-transparency double-silver glass includes the following steps:

[0064] S1. Tempering: The glass slide is ultrasonically cleaned sequentially with acetone, anhydrous ethanol, and deionized water. Then, the glass slide is grounded to obtain a pre-treated glass substrate. It is then placed in a dual-chamber high-convection horizontal tempering furnace for tempering. The lower temperature is 670℃ and the upper temperature is 680℃. The tempering time is 5 minutes. The glass slide is then ultrasonically cleaned sequentially with acetone, anhydrous ethanol, and deionized water. Then, the glass slide is grounded to obtain tempered glass.

[0065] S2. Spraying: Disperse polypyrrole fibers in water, then add sodium polystyrene sulfonate at a volume of 0.3 wt% of water. After ultrasonic mixing for 10 min, a polypyrrole fiber dispersion with a concentration of 3 wt% is obtained. Mix with acetone at a volume ratio of 1:0.6 and spray onto the surface of the tempered glass obtained in S1 under a pressure of 0.4 MPa. Control the spraying speed at 1100 rpm and the single spraying time not to exceed 15 s. After drying, check the thickness and then spray and dry thoroughly until the thickness reaches 1.5 nm to obtain a polypyrrole fiber layer.

[0066] S3. Sputtering coating:

[0067] Sputtering was performed on the surface of a polypyrrole fiber layer using pure titanium as a target, while simultaneously introducing Ar and O2 at a volume ratio of 3:1. The target power was controlled at 50 kW, and the total gas flow rate was 1200 sccm. Sputtering was continued until a TiO2 layer with a thickness of 1.5 nm was obtained.

[0068] The TiO2 layer was sputtered using a pure silicon target, while Ar and N2 were introduced in a volume ratio of 1:1.2. The target power was controlled at 25 kW, and the total gas flow rate was 1200 sccm. Sputtering was continued until a Si3N4 layer with a thickness of 5 nm was obtained.

[0069] A first dielectric layer with a thickness of 8 nm is composed of a polypyrrole fiber layer, a TiO2 layer, and a Si3N4 layer.

[0070] A nickel-chromium target (nickel-chromium weight ratio of 4:1) was used to sputter the surface of the first dielectric layer while Ar was introduced. The target power was controlled at 4 kW and the total gas flow rate at 1200 sccm. Sputtering was continued until a NiCr layer with a thickness of 0.5 nm was obtained.

[0071] This forms a first protective layer with a thickness of 0.5 nm.

[0072] Pure silver was used to sputter the surface of the first protective layer while Ar was introduced. The target power was controlled at 5 kW and the total gas flow rate was 1200 sccm, resulting in a first functional silver layer with a thickness of 5 nm.

[0073] The first functional silver layer was sputtered using a zinc-aluminum target while simultaneously introducing Ar and O2 at a volume ratio of 1:1.2. The target power was controlled at 10 kW, and the total gas flow rate was 1200 sccm. Sputtering was continued until a ZnAlO layer with a thickness of 2 nm was obtained.

[0074] A zinc-tin target (zinc-tin weight ratio of 1:1) was used to sputter the ZnAlO layer surface, while Ar and O2 with a volume ratio of 1:2 were simultaneously introduced. The target power was controlled at 470 kW, the total gas flow rate was 1200 sccm, and sputtering was continued until a ZnSnO layer with a thickness of 4 nm was obtained.

[0075] An AZO target (zinc-aluminum weight ratio of 1:1) was used to sputter the ZnSnO layer surface, while Ar and O2 with a volume ratio of 1200:50 were introduced simultaneously. The target power was controlled at 15 kW, and the total gas flow rate was 1250 sccm. Sputtering was continued until an AZO layer with a thickness of 3 nm was obtained.

[0076] The ZnAlO layer, ZnSnO layer, and AZO layer constitute a second dielectric layer with a thickness of 9 nm.

[0077] The second dielectric layer was bombarded with Ne plasma at a power of 100 W, an energy of 75 eV, and a duration of 5 min, followed by Xe plasma bombardment at a frequency of 1 kHz, a pulse duty cycle of 20%, an energy of 200 eV, and a duration of 12 min.

[0078] A nickel-chromium target (nickel-chromium weight ratio of 4:1) was used to sputter the surface of the second dielectric layer while Ar was introduced. The target power was controlled at 5 kW and the total gas flow rate at 1200 sccm. Sputtering was continued until a NiCr layer with a thickness of 1.5 nm was obtained.

[0079] This forms a second protective layer with a thickness of 1.5 nm.

[0080] The surface of the second protective layer was sputtered using pure silver as a target, while Ar was introduced simultaneously. The target power was controlled at 11 kW, and the total gas flow rate was 1200 sccm. Sputtering was continued until a second functional silver layer with a thickness of 11 nm was obtained.

[0081] The second functional silver layer was sputtered onto the surface using a nickel-chromium target (nickel-chromium weight ratio of 4:1) while Ar was introduced. The target power was controlled at 5 kW and the total gas flow rate at 1200 sccm. Sputtering was continued until a NiCr layer with a thickness of 1.5 nm was obtained.

[0082] This forms a third protective layer with a thickness of 1.5 nm.

[0083] Sputtering was performed on the surface of the third protective layer using pure silicon, while simultaneously introducing Ar and N2 at a volume ratio of 1:1.2. The target power was controlled at 60 kW, and the total gas flow rate was 1200 sccm. Sputtering was continued until a Si3N4 layer with a thickness of 15 nm was obtained.

[0084] Zirconia was used to target and sputter the Si3N4 layer surface while simultaneously introducing Ar and O2 at a volume ratio of 20:1. The target power was controlled at 500 kW and the total gas flow rate at 1200 sccm. Sputtering was continued until a ZrO layer with a thickness of 5 nm was obtained.

[0085] The Si3N4 layer and the ZrO layer constitute a third dielectric layer with a thickness of 20 nm.

[0086] The third dielectric layer was bombarded with Ne plasma at a power of 100 W, an energy of 75 eV, and a duration of 5 min, followed by Xe plasma bombardment at a frequency of 1 kHz, a pulse duty cycle of 20%, an energy of 200 eV, and a duration of 12 min.

[0087] A silicon-aluminum-zirconium target (silicon-aluminum-zirconium weight ratio of 8:1:1) was used to sputter onto the surface of the third dielectric layer, while Ar and N2 were introduced in a volume ratio of 20:1. The target power was controlled at 20 kW, the total gas flow rate was 1050 sccm, and sputtering was continued until a SiAlZrN layer with a thickness of 1.3 nm was obtained.

[0088] This forms a fourth protective layer with a thickness of 1.3 nm.

[0089] After processing, a nearly colorless, high-transparency double-silver glass is obtained.

[0090] Example 3.1

[0091] The preparation process of a near-colorless high-transparency double silver glass differs from that of Example 1 in that: in S3, while the sputtering process parameters such as target power, gas introduction parameters, and gas type remain unchanged, only the sputtering time is adjusted to adjust the layer thickness, resulting in a first protective layer with a thickness of 1.5 nm, a second protective layer with a thickness of 2.0 nm, and a third protective layer with a thickness of 2.0 nm. The rest is the same as in Example 1.

[0092] Example 3.2

[0093] The preparation process of a near-colorless high-transparency double silver glass differs from that of Example 1 in that: in S3, while the sputtering process parameters such as target power, gas introduction parameters, and gas type remain unchanged, only the sputtering time is adjusted to adjust the layer thickness, resulting in a first protective layer with a thickness of 0.3 nm, a second protective layer with a thickness of 0.5 nm, and a third protective layer with a thickness of 0.4 nm. The rest is the same as in Example 1.

[0094] Example 4.1

[0095] The preparation process of a near-colorless high-transmittance double silver glass differs from that of Example 1 in that: in S3, the sputtering order of the AZO layer and the ZnAlO layer in the second dielectric layer is changed to obtain a second dielectric layer composed of an AZO layer, a ZnSnO layer and a ZnAlO layer in sequence; the rest is the same as in Example 1.

[0096] Example 4.2

[0097] The preparation process of a near-colorless high-transparency double silver glass differs from that of Example 1 in that: in S3, the sputtering order of the ZnSnO layer and the ZnAlO layer in the second dielectric layer is changed to obtain a second dielectric layer composed of ZnSnO layer, ZnAlO layer and AZO layer in sequence; the rest is the same as in Example 1.

[0098] Example 5

[0099] The preparation process of a near-colorless high-transparency double silver glass differs from that of Example 1 in that: in S3, the sputtering order of the Si3N4 layer and the ZrO layer in the third dielectric layer is changed to obtain a third dielectric layer with the ZrO layer close to the third protective layer. The rest is the same as in Example 1.

[0100] Comparative Example 1

[0101] The difference from Example 1 is that in S3, the sputtering order of the TiO2 layer and the Si3N4 layer in the first dielectric layer is changed to obtain a first dielectric layer composed of a polypyrrole fiber layer, a Si3N4 layer and a TiO2 layer in sequence. The rest is the same as in Example 1.

[0102] Comparative Example 2.1

[0103] The difference from Example 1 is that S2 is removed. In S3, pure titanium is first used to target the tempered glass surface for sputtering, while Ar and N2 with a volume ratio of 1:1.2 are introduced. The target power is controlled at 25 kW and the total gas flow rate is 1200 sccm. Sputtering is continued until a Si3N4 layer with a thickness of 0.8 nm is obtained. The Si3N4 layer, TiO2 layer and Si3N4 layer constitute the first dielectric layer with a thickness of 0.8 nm. The rest is the same as in Example 1.

[0104] Comparative Example 2.2

[0105] The difference from Example 1 is that S2 is removed. In S3, a zinc-tin target (zinc-tin weight ratio of 1:1) is first used to sputter the tempered glass surface, while Ar and O2 with a volume ratio of 1:2 are introduced. The target power is controlled at 470 kW and the total gas flow rate is 1200 sccm. Sputtering continues until a ZnSnO layer with a thickness of 0.8 nm is obtained. The ZnSnO layer, TiO2 layer and Si3N4 layer constitute the first dielectric layer with a thickness of 8 nm. The rest is the same as in Example 1.

[0106] Comparative Example 2.3

[0107] The difference from Example 1 is that S2 is removed. In S3, a zinc-aluminum target (zinc-aluminum weight ratio of 1:1) is first used to sputter the tempered glass surface, while Ar and O2 with a volume ratio of 1:2 are introduced. The target power is controlled at 475 kW and the total gas flow rate is 1200 sccm. Sputtering continues until an AZO layer with a thickness of 0.8 nm is obtained. The AZO layer, TiO2 layer and Si3N4 layer constitute the first dielectric layer with a thickness of 8 nm. The rest is the same as in Example 1.

[0108] Comparative Example 3.1

[0109] The difference from Example 1 is that pure titanium was used to target the surface of the third dielectric layer bombarded by plasma for sputtering, while Ar and O2 with a volume ratio of 3:1 were introduced. The target power was controlled at 15 kW and the total gas flow rate was 1200 sccm. Sputtering was continued until a TiO2 layer with a thickness of 1.5 nm was obtained as the fourth protective layer. All other aspects were the same as in Example 1.

[0110] Comparative Example 3.2

[0111] The difference from Example 1 is that pure zinc was used to target the surface of the third dielectric layer bombarded by plasma for sputtering, while Ar and O2 with a volume ratio of 4:1 were introduced, the target power was controlled at 40 kW, the total gas flow rate was 1200 sccm, and sputtering was continued until a ZnO layer with a thickness of 1.5 nm was obtained as the fourth protective layer. All other aspects were the same as in Example 1.

[0112] The light transmittance (%), a* value, b* value, and heat transfer coefficient K value (W / (m²)) of the high-transmittance double-silver glass obtained in the test examples and comparative examples were evaluated. 2 ·K), and record the results in Table 1, where:

[0113] 1. Light transmittance, measured in accordance with ISO 9050-2003 "Architectural glass - Determination of light transmittance, direct sunlight, total solar transmittance and ultraviolet transmittance and related gloss coefficients";

[0114] 2. Emissivity ε, determined with reference to the records in ISO 9050-2003 "Coated glass - Part 2: Low emissivity coated glass";

[0115] 3. The a* and b* values ​​shall be determined in accordance with the records in GB / T 2680-2021 "Determination of Visible Light Transmittance, Direct Solar Transmittance, Total Solar Transmittance, Ultraviolet Transmittance and Related Parameters of Window Glass in Architectural Glass".

[0116] Table 1 Performance Test Table

[0117]

[0118] According to the data in Table 1, the high-transmittance double-silver glass in Examples 1-2 has a transmittance of 74.8-75.3% in the visible light band, a* value ∈ [-2,2], b* value ∈ [-4,1], and emissivity ε≤0.04. It can be seen that this application uses a polypyrrole fiber layer, a TiO2 layer, and a Si3N4 layer to form the first dielectric layer, and uses a SiAlZrN layer with a thickness of 1.3-1.5nm as the fourth protective layer. With the thickness and composition design of other layers, the double-silver glass achieves simultaneous improvement in multiple aspects such as high transmittance, low color deviation, and energy-saving performance. When applied to high-end buildings, it can achieve a dual improvement in energy-saving effect and decorative effect.

[0119] In Examples 3.1-3.2, the thicknesses of the first, second, and third protective layers were adjusted. The results showed that the transmittance and color deviation of the high-transmittance double-silver glass were unbalanced, and the emissivity increased. It can be seen that a moderate thickness design can provide a good balance for the transmittance, color deviation, and emissivity of the high-transmittance double-silver glass.

[0120] In Examples 4.1-4.2, this application adjusted the arrangement order in the second dielectric layer. The results showed that the color shift was significantly severe. It can be seen that the gradient refractive index structure formed by the ZnAlO layer, ZnSnO layer and AZO layer arranged in the specified thickness ratio can form a precise optical interference network, enhance visible light transmission, and suppress reflection of non-target bands, achieving a high-transmittance and colorless effect with high transmittance and low color difference value. At the same time, this application controlled the thickness of the second dielectric layer to 10-15nm, which can further balance the color shift phenomenon of the glass, making the data of the green-red axis color difference value a* and the yellow-blue axis color difference value b* closer to 0.

[0121] In Example 5, the arrangement order of the third dielectric layer was adjusted. The results showed that the transmittance and color shift of the high-transmittance double silver glass were unbalanced, and the emissivity increased. It can be seen that the Si3N4 layer, as the main structural layer, can form a continuous gradient refractive interface with the ZrO layer, effectively matching the optical impedance of the inner functional silver layer and air. In the visible light band, the light transmittance is increased to more than 70%, while maintaining the green-red axis color difference value a* and the yellow-blue axis color difference value b* close to 0, which meets the stringent requirements of high-end buildings for energy saving and decoration.

[0122] In Comparative Example 1, the arrangement order of the first dielectric layer was adjusted. In Comparative Examples 2.1-2.3, the polypyrrole fiber layer was replaced with Si3N4 layer, ZnSnO layer and AZO layer respectively. The results showed that the transmittance and color deviation of the high-transmittance double silver glass were unbalanced and the emissivity increased. It can be seen that the fibers in the polypyrrole fiber layer have good mechanical strength, which improves the overall stability of the layer structure of the double silver glass. More importantly, this application uses the polypyrrole fiber layer to replace the conventional dielectric layer, such as Si3N4 layer, ZnSnO layer and AZO (aluminum-doped zinc oxide) layer, which can further improve the transmittance without affecting the growth and adhesion of the first functional silver layer.

[0123] In Comparative Examples 3.1-3.2, this application replaced the SiAlZrN layer with a TiO2 layer and a ZnO layer, respectively. The results showed that the transmittance and color deviation of the high-transmittance double-silver glass were unbalanced, and the emissivity increased. It can be seen that SiAlZrN has extremely low absorption rate in the visible light band, which can effectively maintain the visible light transmittance of the glass >75%, while avoiding the yellowing and bluish phenomena caused by traditional TiO2 or ZnO layers, achieving a colorless visual effect. At the same time, it has an atomically dense structure, which can effectively block the corrosion of the functional silver layer by water vapor, oxygen and sulfides. Compared with traditional protective layers such as SiO2 and Ti layers, SiAlZrN has higher hardness and scratch resistance, which can effectively resist physical damage, reduce the risk of micro-cracks in the film layer, improve product yield, protect the internal functional silver layer, and enable the functional silver layer to exert a long-term and stable energy-saving effect.

[0124] The embodiments described in this specific implementation are preferred embodiments of this application and are not intended to limit the scope of protection of this application. Therefore, all equivalent changes made in accordance with the structure, shape and principle of this application should be covered within the scope of protection of this application.

Claims

1. A near-colorless, high-transparency double-silver glass, comprising a glass substrate, a first dielectric layer, a first protective layer, a first functional silver layer, a second dielectric layer, a second protective layer, a second functional silver layer, a third protective layer, a third dielectric layer, and a fourth protective layer, arranged sequentially, characterized in that, The first dielectric layer is composed of a polypyrrole fiber layer, a TiO2 layer and a Si3N4 layer arranged sequentially, wherein the polypyrrole fiber layer is close to the glass substrate; The fourth protective layer is a SiAlZrN layer with a thickness of 1.3-1.5 nm.

2. The near-colorless, high-transparency double-silver glass according to claim 1, characterized in that, The first protective layer, the second protective layer, and the third protective layer are all NiCr layers.

3. The near-colorless, high-transparency double-silver glass according to claim 2, characterized in that, The thickness of the first protective layer is 0.5-1.0 nm, the thickness of the second protective layer is 0.7-1.5 nm, and the thickness of the third protective layer is 0.5-1.5 nm.

4. The near-colorless, high-transparency double-silver glass according to claim 1, characterized in that, The thickness of the first dielectric layer is 8 nm, and the thickness ratio of the polypyrrole fiber layer, TiO2 layer and Si3N4 layer is (0.8-1.5):(1.5-3.2):(4-5).

5. The near-colorless, high-transparency double-silver glass according to claim 1, characterized in that, The second dielectric layer has a thickness of 10-15 nm and is composed of a ZnAlO layer, a ZnSnO layer and an AZO layer arranged sequentially, wherein the thickness ratio of the ZnAlO layer, the ZnSnO layer and the AZO layer is (2-4):(3-4):(3-4), and the ZnAlO layer is close to the first functional silver layer.

6. The near-colorless, high-transparency double-silver glass according to claim 1, characterized in that, The thickness of the first functional silver layer is 4.5-5 nm, and the thickness of the second functional silver layer is 11-12 nm.

7. The near-colorless, high-transparency double-silver glass according to claim 1, characterized in that, The thickness of the third dielectric layer is 20-28 nm, and it is composed of a Si3N4 layer and a ZrO layer with a thickness ratio of (15-25):(3-5), wherein the Si3N4 layer is close to the third protective layer.

8. A process for preparing near-colorless high-transparency double-silver glass according to any one of claims 1-7, characterized in that, Includes the following steps: S1. Tempered glass; S2. Spraying: Polypyrrole fibers are dispersed in water to obtain a polypyrrole fiber dispersion with a concentration of 2-3 wt%, and sprayed onto the surface of the tempered glass obtained in S1 under a pressure of 0.3-0.4 MPa, and dried to obtain a polypyrrole fiber layer; S3. Sputtering coating: TiO2 layer and Si3N4 layer are sputtered sequentially on the surface of polypyrrole fiber layer to obtain first dielectric layer. Then, first protective layer, first functional silver layer, second dielectric layer, second protective layer, second functional silver layer, third protective layer, third dielectric layer and fourth protective layer are sputtered sequentially on the surface of first dielectric layer. Plasma bombardment is performed after obtaining second dielectric layer and third dielectric layer. After finishing, near-colorless high-transmittance double silver glass is obtained.

9. The preparation process of a near-colorless high-transparency double-silver glass according to claim 8, characterized in that, In step S3, when sputtering to prepare the first functional silver layer, the argon flow rate is controlled at 1200 sccm and the target power is 4.5-5.0 kW.

10. The preparation process of a near-colorless high-transparency double-silver glass according to claim 8, characterized in that, In step S3, when sputtering to prepare the second functional silver layer, the argon flow rate is controlled at 1200 sccm and the target power is 11-12 kW.

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