A monolithic heat-insulating and fireproof glass composite coating and its preparation method

Abstract

The present invention relates to the technical field of glass manufacturing, and specifically discloses a single-piece heat-insulating and fire-proof glass composite coating and a preparation method thereof, which sequentially include: a base layer, a functional layer 1, a functional layer 2, and a protective layer. The base layer is a SiO2-Al2O3 composite film, the functional layer 1 is a TiN-Ag-TiN sandwich structure, the functional layer 2 includes a composite material layer and a hydrogen-doped diamond-like carbon layer, and the protective layer is a ZrO2 nanocrystal coating. The present invention deposits the composite coating on the surface of a single-piece glass by chemical vapor deposition. By optimizing the coating composition, film layer structure, and coating process, while ensuring the visible light transmittance, the fire-proof, heat-insulating, and impact-resistant properties of the glass are significantly improved, enabling the single-piece fire-proof glass to meet the national standards for Class A fire-proof glass and being applicable to fields such as building fire protection and safety protection, with broad application prospects.

Description

Technical Field

[0001] The present invention relates to the technical field of glass manufacturing, and particularly relates to a single-piece heat-insulating and fire-proof glass composite coating and a preparation method thereof. Background Art

[0002] Float glass is mainly divided into two major types, ordinary float glass and ultra-clear float glass, according to its composition and properties. Ordinary float glass belongs to the sodium-calcium-silicate glass system. In its main chemical components, the proportion of SiO2 is about 70%-75%, the proportion of Na2O is about 12%-16%, the proportion of CaO is about 8%-12%, and it also contains a small amount of components such as MgO and Al2O3. Different from this, ultra-clear float glass, as high-quality float glass, has an extremely low iron content. The relevant national standards strictly limit its iron content to usually not exceed 0.015%. With excellent properties such as high light transmittance and low absorption rate, ultra-clear float glass is widely used in high-end buildings, photovoltaics and other fields. Various float glasses in the market have different functions corresponding to different application requirements, providing rich directions for the research and development of float glass. Traditional float glass has the problem of insufficient fire-proof and heat-insulating performance, and most of them can only meet the use requirements of ordinary glass or reach the Class C fire-proof standard. However, the demand for glass with higher fire-proof and heat-insulating performance, especially reaching the national standard of Class A fire-proof glass, is increasing in the fields of architecture, transportation, etc. Although the existing technology improves the performance of glass through coating technology, it often faces problems such as poor bonding force between the film layer and the substrate, unsatisfactory heat-insulating effect, complex preparation process and high cost, and it is difficult to achieve large-scale production and meet the high-performance requirements.

[0003] The patent with the application number CN201811218608.6 provides a single-piece fireproof glass and its preparation method. This fireproof glass is composed of the following raw materials in parts by weight: 50 - 70 parts of silica sol, 10 - 20 parts of silicon dioxide, 4 - 10 parts of calcium oxide, 5 - 12 parts of gypsum crystals, 3 - 9 parts of silica powder, 4 - 10 parts of nano-aluminum oxide powder, 2 - 4 parts of hydroxymethyl cellulose, 5 - 10 parts of boron oxide, 10 - 20 parts of attapulgite, and 2 - 4 parts of a fire retardant. The fire retardant is composed of the following raw materials in mass percentages: 30% of sodium dodecyl sulfate, 20% of resin, 20% of sodium silicate, and 30% of lithium dihydrogen phosphate aerogel. This single-piece fireproof glass has a variety of outstanding properties. It not only has excellent fireproof, heat-insulating, and compressive properties, but also has the characteristics of low expansion coefficient, not easy to burst, good safety performance, and long service life. However, the fire retardant contains organic substances such as sodium dodecyl sulfate, which will decompose or volatilize at high temperatures and cannot play a flame-retardant role during a fire, affecting the long-term stability and fireproof performance of the glass. The patent with the application number CN201711234873.9 provides a heat-insulating composite fireproof glass and its preparation method. This composite fireproof glass is composed of two single-piece glasses bonded by an adhesive. The single-piece glass includes the following raw materials in parts by weight: 60 - 90 parts of silicon dioxide, 1 - 15 parts of aluminum oxide, 1 - 15 parts of sodium oxide, 1 - 15 parts of calcium oxide, 0.01 - 10 parts of germanium dioxide, 0.1 - 10 parts of potassium oxide, 0.2 - 10 parts of sodium chloride, 0.1 - 10 parts of zirconium dioxide, 20 - 80 parts of magnesium chloride, 5 - 40 parts of potassium chloride, 0.3 - 10 parts of an organic phosphorus flame retardant, 1 - 10 parts of ferrous sulfate, 1 - 25 parts of gadolinium oxide, 1 - 25 parts of lithium oxide, and 1 - 30 parts of cerium dioxide. The raw materials are made into a mixture, and through high-temperature forming, annealing, cooling, and physical tempering treatments, the single-piece glass is obtained. The composite fireproof glass of this invention shows excellent fireproof performance in a high-temperature environment or a fire, significantly extends the fire resistance time, and has a good heat-insulating effect. However, the raw materials of this heat-insulating composite fireproof glass are diverse, including relatively uncommon and expensive raw materials such as germanium dioxide, which will lead to a high raw material procurement cost and thus increase the product cost.

[0004] Therefore, developing a method to enable the fireproof and heat-insulating performance of single-piece fireproof glass to reach Class A standards has great practical significance. Summary of the Invention

[0005] To solve the above problems, the present invention provides a single-piece heat-insulating fireproof glass composite coating and its preparation method. By using chemical vapor deposition to deposit a multifunctional composite coating on a glass substrate, and combining the film layer structure and coating process, the single-piece fireproof glass meets the national standards of Class A fireproof glass, while ensuring the film layer quality, adhesion, and uniformity, and is suitable for large-scale production.

[0006] The technical solution adopted by the present invention to achieve the above object is as follows:

[0007] A single-piece heat-insulating and fire-proof glass composite coating, which successively includes: a base layer, a functional layer 1, a functional layer 2, and a protective layer;

[0008] Among them, the base layer is a SiO2-Al2O3 composite film, the functional layer 1 is a TiN-Ag-TiN sandwich structure, the functional layer 2 includes a composite material layer and a hydrogen-doped diamond-like carbon layer, and the protective layer is a ZrO2 nanocrystal coating;

[0009] Among them, the preparation method of the composite material used in the composite material layer is as follows:

[0010] Step S1: Ball-mill titanium carbide, zinc borate anhydrous and absolute ethanol in an inert atmosphere for 4-6 h, and then dry at a temperature of 60-80 °C for 12-24 h to obtain a mixture;

[0011] Step S2: Heat the mixture obtained in step S1 in an inert atmosphere at a heating rate of 5-10 °C / min to 500-600 °C, then hold for reaction for 2-3 h, and naturally cool to room temperature to obtain a composite material;

[0012] Further, the mass ratio of titanium carbide to zinc borate anhydrous in step S1 is 10:1-3.

[0013] The present invention also provides a preparation method of a single-piece heat-insulating and fire-proof glass composite coating, including the following steps:

[0014] (1) Base layer deposition: Deposit a SiO2-Al2O3 composite film on the surface of the pretreated glass substrate by chemical vapor deposition, which is the base layer;

[0015] SiO2 has a low thermal conductivity, can effectively block the transfer of heat, and improve the heat insulation performance of the glass. Al2O3 has a high melting point and excellent thermal stability, and can maintain structural integrity at high temperatures. The addition of Al2O3 further enhances the thermal stability of the glass and reduces the expansion coefficient, which enables the SiO2-Al2O3 composite film to effectively improve the fire and heat insulation performance of the glass. The addition of SiO2 also helps to stabilize the glass network, while the introduction of Al2O3 further improves the crack resistance of the glass. Therefore, the combination of SiO2 and Al2O3 not only improves the thermal stability of the glass, but also enhances the mechanical properties.

[0016] (2) Functional layer 1 deposition: Deposit the first layer of TiN, Ag layer, and the second layer of TiN on the surface of the base layer in sequence, which is the functional layer 1;

[0017] The functional layer 1 is a sandwich structure composed of the first layer of TiN, Ag layer, and the second layer of TiN. Among them, TiN has a low thermal conductivity, a high melting point, and excellent thermal stability, which can effectively block the transfer of heat and maintain the structural integrity of the glass at high temperatures. Therefore, the first layer of TiN can improve the heat resistance and fireproof performance of the glass. The Ag layer mainly plays the roles of heat insulation and reflection in the single-piece heat-insulating refractory glass. Ag has a high reflectivity and can effectively reflect infrared and ultraviolet rays, thereby reducing the transfer of heat. At the same time, the Ag layer can also further reduce the thermal permeability of the glass by absorbing part of the infrared radiation. The function of the second layer of TiN is similar to that of the first layer, but it can also enhance the adhesion and durability of the overall coating. The TiN layer can form a stable chemical bond with the Ag layer to prevent the Ag layer from peeling off or oxidizing during high-temperature or long-term use. In addition, the second layer of TiN can further improve the overall hardness and wear resistance of the coating. The design of the TiN-Ag-TiN sandwich structure can achieve the synergistic effect of multiple functions. The three-layer structure cooperates with each other to provide a comprehensive performance improvement in terms of the heat insulation, fire resistance, and mechanical properties of the glass.

[0018] (3) Deposition of the functional layer 2: Deposit a composite material layer and a hydrogen-doped diamond-like carbon layer on the surface of the functional layer 1 in sequence, which is the functional layer 2;

[0019] The composite material layer is deposited from titanium carbide modified by zinc borate. Zinc borate has a heat-insulating and fire-resistant effect. B2O3 generated by its decomposition at high temperatures can form a protective barrier to reduce heat transfer, playing a heat-insulating role. At the same time, it can lower the temperature inside the combustible material, thereby delaying the burning speed of the material and improving its fire-resistant performance. Titanium carbide has a low thermal conductivity, which helps reduce the transfer of heat from high-temperature areas to low-temperature areas. The high hardness and strength of titanium carbide can also improve the overall mechanical properties of the glass. Therefore, the composite material layer deposited with zinc borate-modified titanium carbide as the raw material can more effectively enhance the fireproof and heat-insulating performance and mechanical properties of a single-piece heat-insulating and fireproof glass. Moreover, the composite material layer can also improve the adhesion between the hydrogenated diamond-like carbon layer and functional layer 1, ensuring that the hydrogenated diamond-like carbon layer can fully exert its performance-enhancing effect. The hydrogenated diamond-like carbon layer is prepared by a gradient hydrogen doping process. This carbon layer consists of three diamond-like carbon layers with different hydrogen contents. First, the diamond-like carbon coating has a low thermal conductivity, which can effectively block the transfer of heat. The diamond-like carbon layer also has excellent high-temperature resistance and chemical stability, which can provide additional protection during a fire. In addition, the high-strength and hardness characteristics of the diamond-like carbon layer can significantly improve the mechanical properties of the glass. However, as an amorphous carbon material, the surface of the diamond-like carbon layer may have a certain roughness or non-uniformity, which will lead to an increase in light absorption or reflection. Therefore, hydrogen elements are introduced to reduce the negative impact on the visible light transmittance. By introducing hydrogen elements, the absorption and scattering of light by the film layer can be reduced by changing the microstructure and defect state distribution of the diamond-like carbon layer. However, during the post-annealing treatment of the glass, hydrogen elements are prone to escape, which will weaken the improvement effect on the visible light transmittance. Therefore, in the present invention, through the gradient hydrogen doping process, the hydrogen content on the surface layer of the diamond-like carbon layer is low, while the hydrogen content in the inner layer is high. This structure can effectively reduce the escape of hydrogen during the annealing process. Moreover, the hydrogen content gradually decreases from the inner layer to the outer layer, forming a gradient structure, which can gradually release internal stress, reduce the internal stress of the diamond-like carbon layer, and improve the adhesion and stability of the coating. The synergistic use of the composite material layer and the hydrogenated diamond-like carbon layer can significantly enhance the comprehensive performance of a single-piece heat-insulating and fireproof glass by improving the fire-resistant performance, heat-insulating performance, and mechanical strength.

[0020] The TiN-Ag-TiN sandwich structure can effectively reflect infrared radiation and reduce heat transfer due to its high reflectivity and low thermal conductivity. At the same time, zinc borate-modified titanium carbide decomposes endothermically at high temperatures and forms a dense protective barrier, further blocking the inward diffusion of heat. The hydrogen-doped diamond-like carbon layer significantly reduces the heat conduction efficiency through its low thermal conductivity. Functional layer 1 and functional layer 2 act together through synergistic effects, working together from multiple aspects such as reflection, blocking, and reducing conduction. This multi-level and multi-mechanism synergistic effect forms a more comprehensive and efficient fire and heat insulation barrier, not only significantly improving the fire and heat insulation performance of the glass but also enhancing its overall stability and durability.

[0021] (4)Deposition of the protective layer: Deposit a ZrO2 protective layer on the surface of functional layer 2 to obtain a single-piece heat-insulating and fire-proof glass composite coating.

[0022] The protective layer is a ZrO2 nanocrystalline coating. The ZrO2 nanocrystalline coating has excellent heat insulation performance. Its low thermal conductivity and high reflectivity enable it to effectively block heat transfer. ZrO2 also has a high melting point, which allows the ZrO2 nanocrystalline coating to exhibit good stability in high-temperature environments. Therefore, using the ZrO2 nanocrystalline coating as the protective layer can ensure the stability of the film layer of the glass in a fire environment.

[0023] In a high-temperature environment, zinc borate in the zinc borate-modified titanium carbide composite material layer in functional layer 2 decomposes endothermically and generates a barrier layer, and titanium carbide blocks heat due to its high melting point; the hydrogen-doped diamond-like carbon layer reduces heat conduction by its low thermal conductivity; the ZrO2 nanocrystalline coating also has low thermal conductivity, can continue to block heat transfer, and can also reduce thermal radiation by scattering and absorbing specific light. The three work together synergistically from different mechanisms such as heat conduction and thermal radiation, greatly enhancing the fire and heat insulation performance of the glass. In addition, the two-layer structure of functional layer 2 and the ZrO2 nanocrystalline coating have a synergistic effect, significantly improving the impact resistance of the glass. The two-layer structure of functional layer 2 has high hardness and strength, providing basic impact resistance support for the glass and initially reducing the overall impact on the glass; the ZrO2 nanocrystalline coating can form a uniform protective layer on the surface of the glass. When the glass is impacted, this protective layer can effectively disperse stress, avoid stress concentration, and stress dispersion can reduce the local stress on the glass surface, thereby reducing the generation and expansion of cracks. The high-strength structure of functional layer 2 combined with the stress dispersion effect of the ZrO2 nanocrystalline coating complement each other and jointly build an efficient impact resistance system, comprehensively improving the impact resistance of the glass and ensuring that the glass can better maintain its integrity when subjected to external impacts.

[0024] Furthermore, the thickness of the base layer described in step (1) is 40 - 60 nm.

[0025] Further, the thickness of the first layer of TiN in step (2) is 40 - 60 nm, the thickness of the Ag layer is 5 - 10 nm, and the thickness of the second layer of TiN is 40 - 60 nm.

[0026] Further, the thickness of the composite material layer in step (3) is 40 - 50 nm.

[0027] Further, the hydrogen-doped diamond-like carbon layer in step (3) adopts a gradient hydrogen doping process, uses methane as the carbon source and hydrogen as the hydrogen source, and is prepared by chemical vapor deposition. The hydrogen-doped diamond-like carbon layer includes a high-hydrogen-content layer in the initial stage, a medium-hydrogen-content layer in the middle stage, and a low-hydrogen-content layer in the final stage.

[0028] Further, in the gradient hydrogen doping process, the flow ratio of methane gas to hydrogen gas in the initial stage is 1:8 - 10, forming a high-hydrogen-content layer with a thickness of 20 - 30 nm; the flow ratio of methane gas to hydrogen gas in the middle stage is 1:5 - 7, forming a medium-hydrogen-content layer with a thickness of 50 - 60 nm; the flow ratio of methane gas to hydrogen gas in the final stage is 1:2 - 4, forming a low-hydrogen-content layer with a thickness of 20 - 30 nm.

[0029] Further, the thickness of the protective layer in step (4) is 20 - 30 nm.

[0030] The present invention has the following beneficial effects:

[0031] The present invention uses chemical vapor deposition to sequentially deposit a base layer composed of a SiO2 - Al2O3 composite film, a functional layer 1 composed of a TiN - Ag - TiN sandwich structure, a functional layer 2 composed of a composite material layer and a hydrogen-doped diamond-like carbon layer, and a protective layer composed of a ZrO2 nanocrystalline coating on the surface of a single-piece float glass. The various film layers cooperate with each other to form an integral whole. The base layer, as the bottom film, has good adhesion to the glass substrate, can firmly adhere to the glass surface, provides stable support for the functional layer 1, and also provides a stable substrate for other functional layers, enhancing the mechanical strength and thermal stability of the overall structure; the functional layer 1, as the intermediate layer, significantly improves the heat insulation and fireproof performance of the glass, while enhancing the mechanical strength, providing multiple protections for the glass; the functional layer 2, as another intermediate layer, through the synergistic use of the composite material layer and the hydrogen-doped diamond-like carbon layer, significantly improves the fire resistance, heat insulation, visible light transmittance and mechanical strength of the glass, providing comprehensive performance improvement for the glass; the protective layer, as the outermost layer, can protect other functional layers from high temperature and mechanical damage, ensuring the overall stability of the glass in a fire environment. The composite use of multiple film layers realizes the efficient synergistic effect between the film layers. This synergistic effect not only significantly improves the fire resistance and heat insulation performance of the single-piece glass, enabling it to successfully meet the standards of Class A fireproof glass, but also optimizes the comprehensive performance such as the visible light transmittance and mechanical properties of the single-piece heat-insulating and fireproof glass.

[0032] By optimizing the composition of the composite coating and combining the adjustment of the coating process and the film layer structure, the three work synergistically to significantly improve the fire resistance, heat insulation, visible light transmittance and compressive strength of the single-piece heat-insulating and fire-proof glass. Specific Embodiments

[0033] The technical solutions in the embodiments of the present application will be clearly and completely described below in conjunction with the embodiments of the present application. Obviously, the described embodiments are only a part of the embodiments of the present application, rather than all the embodiments. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present application without creative efforts shall fall within the protection scope of the present application.

[0034] The raw materials used in the following embodiments are all ordinary commercially available products. The neutral cleaning agent is an industrial glass cleaning agent purchased from Dongguan Hill Metal Materials Co., Ltd., with a neutral pH value; the titanium carbide has a particle size of 3000 mesh and an active ingredient content of 99.9%, and is purchased from Hebei Ruihuang Metal Materials Co., Ltd.

[0035] Example 1

[0036] A composite coating for a single-piece heat-insulating and fire-proof glass sequentially includes: a base layer, a functional layer 1, a functional layer 2, and a protective layer;

[0037] Among them, the base layer is a SiO2-Al2O3 composite film, the functional layer 1 is a TiN-Ag-TiN sandwich structure, the functional layer 2 includes a composite material layer and a hydrogen-doped diamond-like carbon layer, and the protective layer is a ZrO2 nanocrystal coating;

[0038] The preparation method of the composite material used in the composite material layer is as follows:

[0039] Step S1: Ball-mill titanium carbide, zinc borate anhydrous and absolute ethanol in a nitrogen atmosphere for 4 h, where the ball-to-material ratio during ball-milling is 10:1, the rotation speed is 400 r / min, zirconia balls are selected, the diameter of the small balls is 1 mm, the diameter of the medium balls is 2.5 mm, the diameter of the large balls is 5 mm, and the ratio of large, medium and small balls is 3:3:2. Then vacuum dry at 60 °C for 24 h to obtain a mixture, where the mass ratio of titanium carbide to zinc borate anhydrous is 10:1, and the mass of absolute ethanol is the same as the total mass of titanium carbide and zinc borate anhydrous;

[0040] Step S2: Heat the mixture obtained in Step S1 in a nitrogen atmosphere at a heating rate of 5 °C / min to 500 °C, then hold for 3 h, and naturally cool to room temperature to obtain the composite material;

[0041] The present invention also provides a preparation method for a composite coating of a single-piece heat-insulating and fire-proof glass, including the following steps:

[0042] (1)Pretreatment of glass substrate: The single-piece float glass substrate was ultrasonically treated successively with deionized water and a neutral cleaning agent. The ultrasonic frequency was 40 kHz, and the ultrasonic time was 20 min. Then it was rinsed 3 times with deionized water, dried in an oven at 120 °C for 40 min, and then under the condition of a pressure of 1×10 -3 Pa, a mixed gas with a gas flow rate of 50 sccm was introduced according to a volume ratio of Ar / O2 = 4:1. The plasma cleaning power was set to 300 W, and plasma cleaning was carried out for 15 min. Finally, under the condition of a pressure of 1×10 -3 Pa, H2O vapor with a gas flow rate of 30 sccm was introduced, and plasma was generated by a radio frequency power supply for surface hydroxylation treatment. The frequency was 13.56 MHz, and the treatment time was 10 min;

[0043] (2)Deposition of the base layer: The pressure in the chamber was pumped down to 1 Pa, Ar gas was introduced, the gas flow rate was adjusted to 200 sccm, and an SiO2 - Al target was selected. Under the conditions of a power of 300 W and a substrate temperature of 500 °C, an SiO2 - Al2O3 composite film was deposited on the surface of the pretreated glass substrate by radio frequency sputtering, which was the base layer, and the thickness of the base layer was 40 nm;

[0044] (3)Preparation of functional layer 1: First, under the pressure condition of 5×10 -4 Pa, a Ti target was selected, a mixed gas of N2 / Ar = 1:3 was introduced, the total gas flow rate was 200 sccm, the power was set to 150 W, and the first layer of TiN was deposited on the surface of the base layer by DC sputtering. The thickness of the first layer of TiN was 40 nm; Under the pressure condition of 2×10 -3 mbar, an Ag target was selected, argon gas with a gas flow rate of 100 sccm was introduced, the power was set to 100 W, and an Ag layer was deposited on the surface of the first layer of TiN by DC sputtering. The thickness of the Ag layer was 5 nm; Under the pressure condition of 5×10 -4 Pa, a Ti target was selected, a mixed gas of N2 / Ar = 1:3 was introduced, the total gas flow rate was 200 sccm, the power was set to 150 W, and the second layer of TiN was deposited on the surface of the Ag layer by DC sputtering. The thickness of the second layer of TiN was 40 nm, and functional layer 1 was thus prepared;

[0045] (4)Deposition of functional layer 2: First, under the condition of 5×10 -4Under the pressure condition of Pa, using the composite material as the target, setting the power to 300 W and the argon flow rate to 100 sccm, deposit the composite material layer on the surface of functional layer 1 by DC sputtering, and the thickness of the composite material layer is 40 nm; then introduce argon with a gas flow rate of 100 sccm and deposit the hydrogen-doped diamond-like carbon layer on the surface of the composite material layer by plasma-enhanced chemical vapor deposition method. Among them, in the initial stage, introduce a mixed gas of CH4 / H2 = 1:8 with a gas flow rate of 100 sccm to obtain a 20-nm high-hydrogen-content layer, in the middle stage, introduce a mixed gas of CH4 / H2 = 1:5 with a gas flow rate of 100 sccm to obtain a 50-nm medium-hydrogen-content layer, and in the final stage, introduce a mixed gas of CH4 / H2 = 1:2 with a gas flow rate of 100 sccm to obtain a 20-nm low-hydrogen-content layer, and functional layer 2 is then prepared;

[0046] (5)Growth of protective layer: Under the pressure condition of 5×10 -4 Pa, select the Zr target, introduce a mixed gas of O2 / Ar = 1:3, the total gas flow rate is 100 sccm, set the RF sputtering power to 600 W, keep the substrate temperature at 200 °C and deposit the ZrO2 nanocrystalline coating of the protective layer, and the thickness of the protective layer is 20 nm.

[0047] Example 2

[0048] A single-piece heat-insulating and fire-proof glass composite coating, successively including: a base layer, a functional layer 1, a functional layer 2, and a protective layer;

[0049] Among them, the base layer is a SiO2-Al2O3 composite film, the functional layer 1 is a TiN-Ag-TiN sandwich structure, the functional layer 2 includes a composite material layer and a hydrogen-doped diamond-like carbon layer, and the protective layer is a ZrO2 nanocrystalline coating;

[0050] Among them, the preparation method of the composite material used for the composite material layer is as follows:

[0051] Step S1: Ball-mill titanium carbide, zinc borate anhydrous and absolute ethanol in a nitrogen atmosphere for 6 h. Among them, the ball-to-material ratio during ball-milling is 10:1, the rotation speed is 400 r / min, select zirconia balls, the diameter of small balls is 1 mm, the diameter of medium balls is 2.5 mm, the diameter of large balls is 5 mm, and the ratio of large, medium and small balls is 3:3:2. Then vacuum-dry at 80 °C for 12 h to obtain a mixture, where the mass ratio of titanium carbide to zinc borate anhydrous is 10:3, and the mass of absolute ethanol is the same as the total mass of titanium carbide and zinc borate anhydrous;

[0052] Step S2: Heat the mixture obtained in Step S1 in a nitrogen atmosphere at a heating rate of 10 °C / min to 600 °C, then hold the temperature for reaction for 2 h, and naturally cool to room temperature to obtain the composite material;

[0053] The present invention also provides a method for preparing a single-piece heat-insulating and fireproof glass composite coating, comprising the following steps:

[0054] (1) Pretreatment of the glass substrate: Ultrasonically treat the single-piece float glass substrate successively with deionized water and a neutral cleaning agent, with an ultrasonic frequency of 40 kHz and an ultrasonic time of 20 min, then rinse it 3 times with deionized water, and then dry it in an oven at 120 °C for 40 min. Then, under the condition of a pressure of 1×10 -3 Pa, introduce a mixed gas with a gas flow rate of 50 sccm according to a volume ratio of Ar / O2 = 4:1, set the plasma cleaning power to 300 W, perform plasma cleaning for 15 min, and finally, under the condition of a pressure of 1×10 -3 Pa, introduce H2O vapor with a gas flow rate of 30 sccm, and use a radio frequency power supply to generate plasma for surface hydroxylation treatment, with a frequency of 13.56 MHz and a treatment time of 10 min;

[0055] (2) Deposition of the base layer: Pump the pressure in the chamber to 1 Pa, introduce Ar gas, adjust the gas flow rate to 200 sccm, select a SiO2-Al target, and deposit a SiO2-Al2O3 composite film on the surface of the pretreated glass substrate by ion beam sputtering under the conditions of a power of 300 W and a substrate temperature of 500 °C, which is the base layer, and the thickness of the base layer is 60 nm;

[0056] (3) Preparation of functional layer 1: First, under the pressure condition of 5×10 -4 Pa, select a Ti target, introduce a mixed gas of N2 / Ar = 1:3, with a total gas flow rate of 200 sccm, set the power to 150 W, and deposit the first layer of TiN on the surface of the base layer by DC sputtering, and the thickness of the first layer of TiN is 60 nm; Under the pressure condition of 2×10 -3 mbar, select an Ag target, introduce argon gas with a gas flow rate of 100 sccm, set the power to 100 W, and deposit an Ag layer on the surface of the first layer of TiN by DC sputtering, and the thickness of the Ag layer is 10 nm; Under the pressure condition of 5×10 -4 Pa, select a Ti target, introduce a mixed gas of N2 / Ar = 1:3, with a total gas flow rate of 200 sccm, set the power to 150 W, and deposit the second layer of TiN on the surface of the Ag layer by DC sputtering, and the thickness of the second layer of TiN is 60 nm, and the preparation of functional layer 1 is completed;

[0057] (4) Deposition of functional layer 2: First, under the condition of 5×10 -4Under the pressure condition of Pa, using the composite material as the target, setting the power to 300 W and the argon flow rate to 100 sccm, deposit the composite material layer on the surface of functional layer 1 by DC sputtering, and the thickness of the composite material layer is 50 nm; then introduce argon with a gas flow rate of 100 sccm and deposit the hydrogen-doped diamond-like carbon layer on the surface of the composite material layer by plasma-enhanced chemical vapor deposition method. Among them, in the initial stage, introduce a mixed gas of CH4 / H2 = 1:10 with a gas flow rate of 100 sccm to obtain a 30-nm high-hydrogen-content layer, in the middle stage, introduce a mixed gas of CH4 / H2 = 1:7 with a gas flow rate of 100 sccm to obtain a 60-nm medium-hydrogen-content layer, and in the final stage, introduce a mixed gas of CH4 / H2 = 1:4 with a gas flow rate of 100 sccm to obtain a 30-nm low-hydrogen-content layer, and functional layer 2 is then prepared;

[0058] (5)Growth of the protective layer: Under the pressure condition of 5×10 -4 Pa, select the Zr target, introduce a mixed gas of O2 / Ar = 1:3, the total gas flow rate is 100 sccm, set the RF sputtering power to 600 W, and keep the substrate temperature at 200 °C to deposit the ZrO2 nanocrystalline coating of the protective layer, and the thickness of the protective layer is 30 nm.

[0059] Example 3

[0060] A single-piece heat-insulating and fire-proof glass composite coating, successively including: a base layer, functional layer 1, functional layer 2, and a protective layer;

[0061] Among them, the base layer is a SiO2-Al2O3 composite film, functional layer 1 is a TiN-Ag-TiN sandwich structure, functional layer 2 includes a composite material layer and a hydrogen-doped diamond-like carbon layer, and the protective layer is a ZrO2 nanocrystalline coating;

[0062] Among them, the preparation method of the composite material used in the composite material layer is as follows:

[0063] Step S1: Ball-mill titanium carbide, zinc borate anhydrous and absolute ethanol in a nitrogen atmosphere for 5 h. Among them, the ball-to-material ratio during ball-milling is 10:2, the rotation speed is 400 r / min, select zirconia balls, the diameter of the small balls is 1 mm, the diameter of the medium balls is 2.5 mm, the diameter of the large balls is 5 mm, and the ratio of large, medium and small balls is 3:3:2. Then vacuum-dry at 70 °C for 20 h to obtain a mixture, where the mass ratio of titanium carbide to zinc borate anhydrous is 10:1, and the mass of absolute ethanol is the same as the total mass of titanium carbide and zinc borate anhydrous;

[0064] Step S2: Heat the mixture obtained in Step S1 in a nitrogen atmosphere at a heating rate of 8 °C / min to 550 °C, then hold for reaction for 2.5 h, and naturally cool to room temperature to obtain the composite material;

[0065] The present invention also provides a preparation method for a single-piece heat-insulating and fireproof glass composite coating, comprising the following steps:

[0066] (1) Pretreatment of the glass substrate: Ultrasonically treat the single-piece float glass substrate successively with deionized water and a neutral cleaning agent, with an ultrasonic frequency of 40 kHz and an ultrasonic time of 20 min, then rinse with deionized water 3 times, and then dry in an oven at 120 °C for 40 min. Then, under the condition of a pressure of 1×10 -3 Pa, introduce a mixed gas with a gas flow rate of 50 sccm according to a volume ratio of Ar / O2 = 4:1, set the plasma cleaning power to 300 W, and perform plasma cleaning for 15 min. Finally, under the condition of a pressure of 1×10 -3 Pa, introduce H2O vapor with a gas flow rate of 30 sccm, and use a radio frequency power supply to generate plasma for surface hydroxylation treatment, with a frequency of 13.56 MHz and a treatment time of 10 min;

[0067] (2) Deposition of the base layer: Pump the pressure in the chamber down to 0.01 MPa, introduce Ar gas and reduce the pressure to 0.4 - 0.6 MPa. A part of the Ar gas enters a reactor filled with tetraethoxysilane, with a gas flow rate of 400 sccm and a reactor temperature of 50 °C; a part of the Ar gas enters a reactor filled with Al2O3 powder, with a gas flow rate of 400 sccm and a reactor temperature of 130 °C; a part of the Ar gas is used as a dilution gas and is mixed and diluted with the two gas streams flowing out of the reactors of tetraethoxysilane and Al2O3 powder, with a gas flow rate of 400 sccm. Perform chemical vapor deposition of a SiO2 - Al2O3 composite film under the condition of a substrate temperature of 600 °C, which is the base layer, and the thickness of the base layer is 50 nm;

[0068] (3) Preparation of functional layer 1: First, evacuate the reaction chamber to -0.02 MPa. Under the condition of a reaction chamber temperature of 600 °C, introduce TiCl4 gas with a gas flow rate of 300 sccm, NH3 gas with a gas flow rate of 150 sccm, and N2 gas with a gas flow rate of 900 sccm. Deposit the first layer of TiN on the surface of the base layer by chemical vapor deposition, and the thickness of the first layer of TiN is 50 nm; Then deposit the Ag layer. Evacuate the evaporation chamber to 2.5×10 -4After reaching [[Pa]], increase the current until the silver solid in the evaporation boat completely melts. Adjust the current so that the evaporation rate stabilizes at 0.1 Å / S. Then adjust the rotation speed of the sample stage to 20 r / min and thermally evaporate the Ag layer on the surface of the first TiN layer. The thickness of the Ag layer is 8 nm. Then proceed with the deposition of the second TiN layer. Evacuate the reaction chamber to -0.02 MPa, and under the condition that the reaction chamber temperature is 600 °C, introduce TiCl4 gas with a gas flow rate of 300 sccm, NH3 gas with a gas flow rate of 150 sccm, and N2 gas with a gas flow rate of 900 sccm. Deposit the second TiN layer on the Ag layer surface through chemical vapor deposition. The thickness of the second TiN layer is 50 nm, and the functional layer 1 is thus prepared.

[0069] (4)Deposition of functional layer 2: First, under the pressure condition of 5×10 -4 Pa, use the composite material as the target, set the power to 300 W, and the argon gas flow rate to 100 sccm. Deposit the composite material layer on the surface of functional layer 1 through DC sputtering. The thickness of the composite material layer is 45 nm. Then, introduce argon gas with a gas flow rate of 100 sccm and deposit a hydrogen-doped diamond-like carbon layer on the composite material surface using plasma-enhanced chemical vapor deposition. Among them, in the initial stage, introduce a mixed gas of CH4 / H2 = 1:9 with a gas flow rate of 100 sccm to obtain a 25-nm high-hydrogen-content layer. In the middle stage, introduce a mixed gas of CH4 / H2 = 1:6 with a gas flow rate of 100 sccm to obtain a 55-nm medium-hydrogen-content layer. In the final stage, introduce a mixed gas of CH4 / H2 = 1:3 with a gas flow rate of 100 sccm to obtain a 25-nm low-hydrogen-content layer. The functional layer 2 is thus prepared.

[0070] (5)Growth of the protective layer: Pump the chamber pressure to 0.01 Pa, introduce carrier gas N2 gas with a gas flow rate of 80 sccm and precursor ZrCl(tmhd)3, where tmhd = 2,2,6,6-tetramethyl-3,5-heptanedionate. The gas flow ratio of the precursor to the carrier gas is 1:2. At 130 °C, deposit a protective layer of ZrO2 nanocrystalline coating on the surface of functional layer 2 through chemical vapor deposition. The thickness of the protective layer is 25 nm.

[0071] Comparative Example 1

[0072] A monolithic heat-insulating and fire-proof glass composite coating, successively including: a base layer, a functional layer 1, a functional layer 2, and a protective layer;

[0073] Among them, the base layer is a SiO2 - Al2O3 composite film, the functional layer 1 is a TiN - Ag - TiN sandwich structure, the functional layer 2 includes a titanium carbide layer and a hydrogen-doped diamond-like carbon layer, and the protective layer is a ZrO2 nanocrystalline coating;

[0074] The present invention also provides a method for preparing a single-piece heat-insulating and fireproof glass composite coating, comprising the following steps:

[0075] (1) Pretreatment of the glass substrate: Ultrasonically treat the single-piece float glass substrate successively with deionized water and a neutral cleaning agent, with an ultrasonic frequency of 40 kHz and an ultrasonic time of 20 min, then rinse it 3 times with deionized water, and then dry it in an oven at 120 °C for 40 min. Then, under the condition of a pressure of 1×10 -3 Pa, introduce a mixed gas with a gas flow rate of 50 sccm according to a volume ratio of Ar / O2 = 4:1, set the plasma cleaning power to 300 W, and perform plasma cleaning for 15 min. Finally, under the condition of a pressure of 1×10 -3 Pa, introduce H2O vapor with a gas flow rate of 30 sccm, and use a radio frequency power supply to generate plasma for surface hydroxylation treatment, with a frequency of 13.56 MHz and a treatment time of 10 min;

[0076] (2) Deposition of the base layer: Pump the pressure in the chamber to 1 Pa, introduce Ar gas, adjust the gas flow rate to 200 sccm, select a SiO2-Al target, and deposit a SiO2-Al2O3 composite film on the surface of the pretreated glass substrate by radio frequency sputtering under the conditions of a power of 300 W and a substrate temperature of 500 °C, which is the base layer, and the thickness of the base layer is 60 nm;

[0077] (3) Preparation of functional layer 1: First, under the pressure condition of 5×10 -4 Pa, select a Ti target, introduce a mixed gas of N2 / Ar = 1:3, with a total gas flow rate of 200 sccm, set the power to 150 W, and deposit the first layer of TiN on the surface of the base layer by DC sputtering, and the thickness of the first layer of TiN is 60 nm; Under the pressure condition of 2×10 -3 mbar, select an Ag target, introduce argon with a gas flow rate of 100 sccm, set the power to 100 W, and deposit an Ag layer on the surface of the first layer of TiN by DC sputtering, and the thickness of the Ag layer is 10 nm; Under the pressure condition of 5×10 -4 Pa, select a Ti target, introduce a mixed gas of N2 / Ar = 1:3, with a total gas flow rate of 200 sccm, set the power to 150 W, and deposit the second layer of TiN on the surface of the Ag layer by DC sputtering, and the thickness of the second layer of TiN is 60 nm, and functional layer 1 is thus prepared;

[0078] (4) Deposition of functional layer 2: First, under the condition of 5×10 -4Under the pressure condition of Pa, using titanium carbide as the target, setting the power to 800 W, the argon gas flow rate to 40 sccm, a titanium carbide layer is deposited on the surface of functional layer 1 by DC sputtering, and the thickness of the titanium carbide layer is 50 nm; then argon gas with a gas flow rate of 40 sccm is introduced, and a hydrogen-doped diamond-like carbon layer is deposited on the surface of the composite material by plasma-enhanced chemical vapor deposition. Among them, a mixed gas of CH4 / H2 = 1:10 with a gas flow rate of 100 sccm is introduced in the initial stage to obtain a 30-nm high-hydrogen-content layer, a mixed gas of CH4 / H2 = 1:7 with a gas flow rate of 100 sccm is introduced in the middle stage to obtain a 60-nm medium-hydrogen-content layer, and a mixed gas of CH4 / H2 = 1:4 with a gas flow rate of 100 sccm is introduced in the final stage to obtain a 30-nm low-hydrogen-content layer, and functional layer 2 is thus prepared;

[0079] (5)Growth of the protective layer: Under the pressure condition of 5×10 -4 Pa, select a Zr target, introduce a mixed gas of O2 / Ar = 1:3, the total gas flow rate is 80 sccm, set the RF sputtering power to 600 W, and keep the substrate temperature at 200 °C to deposit a protective layer of ZrO2 nanocrystalline coating, and the thickness of the protective layer is 30 nm.

[0080] Comparative Example 2

[0081] A monolithic heat-insulating and fire-proof glass composite coating, which successively includes: a base layer, functional layer 1, functional layer 2, and a protective layer;

[0082] Among them, the base layer is a SiO2-Al2O3 composite film, functional layer 1 is a TiN-Ag-TiN sandwich structure, functional layer 2 includes a composite material layer and a diamond-like carbon layer, and the protective layer is a ZrO2 nanocrystalline coating;

[0083] Among them, the preparation method of the composite material used in the composite material layer is as follows:

[0084] Step S1: Ball-mill titanium carbide, zinc borate anhydrous, and absolute ethanol in a nitrogen atmosphere for 6 h. Among them, the ball-to-material ratio during ball-milling is 10:1, the rotation speed is 400 r / min, zirconia balls are selected, the diameter of the small balls is 1 mm, the diameter of the medium balls is 2.5 mm, the diameter of the large balls is 5 mm, and the ratio of large, medium, and small balls is 3:3:2. Then vacuum-dry at 80 °C for 12 h to obtain a mixture, where the mass ratio of titanium carbide to zinc borate anhydrous is 10:3, and the mass of absolute ethanol is the same as the total mass of titanium carbide and zinc borate anhydrous;

[0085] Step S2: Heat the mixture obtained in Step S1 in a nitrogen atmosphere at a heating rate of 10 °C / min to 600 °C, then hold for 2 h, and naturally cool to room temperature to obtain the composite material;

[0086] The present invention also provides a method for preparing a single-piece heat-insulating and fireproof glass composite coating, comprising the following steps:

[0087] (1) Pretreatment of the glass substrate: The single-piece float glass substrate is ultrasonically treated successively with deionized water and a neutral cleaning agent. The ultrasonic frequency is 40 kHz, and the ultrasonic time is 20 min. Then it is rinsed 3 times with deionized water, dried in an oven at 120 °C for 40 min, and then under the condition of a pressure of 1×10 -3 Pa, a mixed gas with a gas flow rate of 50 sccm is introduced according to a volume ratio of Ar / O2 = 4:1. The plasma cleaning power is set to 300 W, and plasma cleaning is carried out for 15 min. Finally, under the condition of a pressure of 1×10 -3 Pa, H2O vapor with a gas flow rate of 30 sccm is introduced, and plasma is generated by a radio frequency power supply for surface hydroxylation treatment. The frequency is 13.56 MHz, and the treatment time is 10 min;

[0088] (2) Deposition of the base layer: The pressure in the chamber is pumped to 1 Pa, Ar gas is introduced, the gas flow rate is adjusted to 200 sccm, an SiO2-Al target is selected, and an SiO2-Al2O3 composite film is deposited on the surface of the pretreated glass substrate by radio frequency sputtering under the conditions of a power of 300 W and a substrate temperature of 500 °C, which is the base layer. The thickness of the base layer is 60 nm;

[0089] (3) Preparation of functional layer 1: First, under the pressure condition of 5×10 -4 Pa, a Ti target is selected, a mixed gas of N2 / Ar = 1:3 is introduced, the total gas flow rate is 200 sccm, the power is set to 150 W, and the first layer of TiN is deposited on the surface of the base layer by DC sputtering. The thickness of the first layer of TiN is 60 nm; Under the pressure condition of 2×10 -3 mbar, an Ag target is selected, argon with a gas flow rate of 100 sccm is introduced, the power is set to 100 W, and an Ag layer is deposited on the surface of the first layer of TiN by DC sputtering. The thickness of the Ag layer is 10 nm; Under the pressure condition of 5×10 -4 Pa, a Ti target is selected, a mixed gas of N2 / Ar = 1:3 is introduced, the total gas flow rate is 200 sccm, the power is set to 150 W, and the second layer of TiN is deposited on the surface of the Ag layer by DC sputtering. The thickness of the second layer of TiN is 60 nm, and functional layer 1 is thus prepared;

[0090] (4) Deposition of functional layer 2: First, under the pressure condition of 5×10 -4Under the pressure condition of Pa, using the composite material as the target, setting the power to 300 W, the argon gas flow rate to 100 sccm, depositing a composite material layer on the surface of functional layer 1 by DC sputtering, and the thickness of the composite material layer is 50 nm; then introducing argon gas with a gas flow rate of 40 sccm and using plasma enhanced chemical vapor deposition method to deposit a diamond-like carbon layer on the surface of the composite material layer, where a mixed gas of CH4 / H2 = 1:7 with a gas flow rate of 50 sccm is introduced to obtain a 100-nm diamond-like carbon layer, and then functional layer 2 is prepared;

[0091] (5)Growth of protective layer: Under the pressure condition of 5×10 -4 Pa, select a Zr target, introduce a mixed gas of O2 / Ar = 1:3, the total gas flow rate is 80 sccm, set the RF sputtering power to 600 W, and keep the substrate temperature at 200 °C to deposit a ZrO2 nanocrystalline coating for the protective layer, and the thickness of the protective layer is 30 nm.

[0092] Comparative Example 3

[0093] A single-piece heat-insulating and fire-proof glass composite coating, successively including: a base layer, functional layer 1, functional layer 2, and a protective layer;

[0094] Among them, the base layer is a SiO2-Al2O3 composite film, functional layer 1 is a TiN-Ag-TiN sandwich structure, functional layer 2 includes a titanium carbide layer and a diamond-like carbon layer, and the protective layer is a ZrO2 nanocrystalline coating;

[0095] The present invention also provides a preparation method of a single-piece heat-insulating and fire-proof glass composite coating, including the following steps:

[0096] (1)Pretreatment of glass substrate: Ultrasonically treat a single-piece float glass substrate successively with deionized water and a neutral cleaning agent, the ultrasonic frequency is 40 kHz, the ultrasonic time is 20 min, then rinse with deionized water 3 times, and then dry in an oven at 120 °C for 40 min, and then under the condition of a pressure of 1×10 -3 Pa, introduce a mixed gas with a gas flow rate of 50 sccm according to the volume ratio of Ar / O2 = 4:1, set the plasma cleaning power to 300 W, perform plasma cleaning for 15 min, and finally under the condition of a pressure of 1×10 -3 Pa, introduce H2O vapor with a gas flow rate of 30 sccm, and use a radio frequency power supply to generate plasma for surface hydroxylation treatment, the frequency is 13.56 MHz, and the treatment time is 10 min;

[0097] (2)Deposition of base layer: Pump the pressure in the chamber to 5×10 -4Pa, introduce Ar gas, adjust the gas flow rate to 80 sccm, select the SiO2-Al target, and deposit the SiO2-Al2O3 composite film on the surface of the pretreated glass substrate by radio frequency sputtering under the conditions of a power of 800 W and a substrate temperature of 200 °C, which is the base layer, and the thickness of the base layer is 60 nm;

[0098] (3)Preparation of functional layer 1: First, under a pressure condition of 5×10 -4 Pa, select the Ti target, introduce a mixed gas of N2 / Ar = 1:3, the total gas flow rate is 200 sccm, set the power to 150 W, and deposit the first layer of TiN on the surface of the base layer by DC sputtering, and the thickness of the first layer of TiN is 60 nm; Under a pressure condition of 2×10 -3 mbar, select the Ag target, introduce argon gas with a gas flow rate of 100 sccm, set the power to 100 W, and deposit the Ag layer on the surface of the first layer of TiN layer by DC sputtering, and the thickness of the Ag layer is 10 nm; Under a pressure condition of 5×10 -4 Pa, select the Ti target, introduce a mixed gas of N2 / Ar = 1:3, the total gas flow rate is 200 sccm, set the power to 150 W, and deposit the second layer of TiN on the surface of the Ag layer by DC sputtering, and the thickness of the second layer of TiN is 60 nm, and the preparation of functional layer 1 is completed;

[0099] (4)Deposition of functional layer 2: First, under a pressure condition of 5×10 -4 Pa, use titanium carbide as the target, set the power to 800 W, and the argon gas flow rate is 40 sccm, and deposit the titanium carbide layer on the surface of functional layer 1 by DC sputtering, and the thickness of the titanium carbide layer is 50 nm; Then introduce argon gas with a gas flow rate of 40 sccm and use plasma enhanced chemical vapor deposition to deposit a diamond-like carbon layer on the surface of the composite material layer, and introduce a mixed gas of CH4 / H2 = 1:7 with a gas flow rate of 50 sccm to obtain a 100-nm diamond-like carbon layer, and the preparation of functional layer 2 is completed;

[0100] (5)Growth of the protective layer: Under a pressure condition of 5×10 -4 Pa, select the Zr target, introduce a mixed gas of O2 / Ar = 1:3, the total gas flow rate is 80 sccm, set the radio frequency sputtering power to 600 W, and keep the substrate temperature at 200 °C to deposit the protective layer ZrO2 nanocrystalline coating, and the thickness of the protective layer is 30 nm.

[0101] The single-piece float glass with the composite coatings prepared in Examples 1-3 or Comparative Examples 1-3 on its surface was post-treated to obtain single-piece heat-insulating and fire-proof glass, and performance tests were carried out. The post-treatment process includes rapid thermal annealing treatment and edge laser etching. In the rapid thermal annealing treatment process, the single-piece float glass with the composite coatings prepared in Examples 1-3 or Comparative Examples 1-3 was transferred to a rapid thermal annealing furnace, and N2 gas was introduced as a protective atmosphere with a gas flow rate of 200 sccm. The temperature in the furnace was raised to 600 °C at a heating rate of 10 °C / min, held for 30 s, and then cooled to room temperature at a cooling rate of 5 °C / s. In the edge laser etching process, ultraviolet laser with a wavelength of 355 nm and a pulse width of 15 ns was used to etch the glass edge. The glass was fixed on a high-precision motion platform, and the repetition frequency of the laser was set to 20 kHz and the scanning speed was 100 mm / s.

[0102] Fire resistance performance: The fire resistance test was carried out in accordance with the standard of GB / T 12315-2006 "Fire Resistance Test Method for Glazed Elements" as mentioned in GB 15763.1-2009 "Safety Glazing for Building - Part 1: Fire Resistant Glazing". The size of the single-piece float glass was 3000 mm × 3000 mm, and the experiment was selected to be carried out in a vertical furnace. Visible light transmittance: It was inspected in accordance with the method specified in 3.1 of GB / T 2680-1994 "Building Glass - Determination of Visible Light Transmittance, Solar Direct Transmittance, Total Solar Energy Transmittance, Ultraviolet Transmittance and Related Glazing Parameters" as mentioned in GB 15763.1-2009 "Safety Glazing for Building - Part 1: Fire Resistant Glazing". Impact resistance performance: It was inspected in accordance with the method specified in 6.5 of GB 15763.2-2005 "Safety Glazing for Building - Part 2: Tempered Glass" as mentioned in GB 15763.1-2009 "Safety Glazing for Building - Part 1: Fire Resistant Glazing". Fragment state: It was inspected in accordance with the method specified in 6.6 of GB 15763.2-2005 "Safety Glazing for Building - Part 2: Tempered Glass" as mentioned in GB 15763.1-2009 "Safety Glazing for Building - Part 1: Fire Resistant Glazing".

[0103] The specific test data can be seen from Table 1.

[0104] Table 1 Performance Test Results

[0105]

[0106] As can be seen from Table 1, the single-piece heat-insulating and fireproof glass with the composite coatings prepared in Examples 1-3 has excellent fire-resistant and heat-insulating properties compared to the glass obtained in Comparative Examples 1-4. This is because the composite coatings prepared in Examples 1-3 of the present invention enable the single-piece fireproof glass to form a stable barrier layer at high temperatures, effectively blocking heat transfer, delaying the softening and cracking of the glass. Moreover, the single-piece fireproof glass obtained from Examples 1-3 and Comparative Examples 1-3 all meet the standards of Class A heat-insulating fireproof glass, indicating that the coating process and film layer structure used in the present invention can also improve the fireproof and heat-insulating properties of the glass. The single-piece heat-insulating and fireproof glass with the composite coatings prepared in Examples 1-3 has better visible light transmittance than the glass obtained in Comparative Examples 2-3. This is because gradient hydrogen doping can offset the adverse effects of diamond-like carbon and titanium carbide on the light transmittance of the glass, indicating that the composite coatings, coating process, and film layer structure prepared in the present invention can still provide good light transmittance while maintaining the fireproof performance, meeting the requirements of building lighting. The impact resistance is also one of the important indicators of fireproof glass. According to Table 1, the single-piece heat-insulating and fireproof glass prepared with the composite coatings of the examples and comparative examples all show excellent performance in impact resistance. However, in the fragment state test, the single-piece heat-insulating and fireproof glass prepared with the composite coatings of Examples 1-3 has more fragments, indicating that the internal stress distribution of the glass is relatively uniform. The more fragments there are, the more effectively the glass can convert the impact energy into the kinetic energy of the fragments during the cracking process, reducing the harm to surrounding objects and personnel.

[0107] Although the embodiments of the present application have been shown and described, it will be understood by those of ordinary skill in the art that various changes, modifications, substitutions, and variations can be made to these embodiments without departing from the principles and spirit of the present application. The scope of the present application is defined by the appended claims and their equivalents.

Claims

1. A monolithic heat-insulating and fireproof glass composite coating, characterized in that, Including in order: Base layer, functional layer 1, functional layer 2, protective layer; The base layer is a SiO2-Al2O3 composite film; the functional layer 1 is a TiN-Ag-TiN sandwich structure; the functional layer 2 includes a composite material layer and a hydrogen-doped diamond-like carbon layer; the protective layer is a ZrO2 nanocrystalline coating; The preparation method of the composite material used in the composite material layer is as follows: Step S1, ball-milling titanium carbide, anhydrous zinc borate and anhydrous ethanol under an inert atmosphere for 4-6 hours, and then drying at a temperature of 60-80° C. for 12-24 hours to obtain a mixture; Step S2, heating the mixture obtained in step S1 to 500-600°C at a heating rate of 5-10°C / min under an inert atmosphere, then keeping the temperature for reaction for 2-3 hours, and naturally cooling to room temperature to obtain a composite material.

2. The single-piece heat-insulating and fireproof glass composite coating according to claim 1, characterized in that The mass ratio of titanium carbide to anhydrous zinc borate in step S1 is 10:1-3.

3. The preparation method of the monolithic heat-insulating and fireproof glass composite coating according to any one of claims 1-2, characterized in that, The following steps are involved: (1) Base layer deposition: A SiO2-Al2O3 composite film is deposited on the surface of the pretreated glass substrate by vapor deposition, which is the base layer; (2) Deposition of functional layer 1: The first layer of TiN, the Ag layer, and the second layer of TiN are sequentially deposited on the surface of the base layer, which is functional layer 1; (3) Deposition of functional layer 2: a composite material layer and a hydrogen-doped diamond-like carbon layer are sequentially deposited on the surface of functional layer 1 to form functional layer 2; (4) Deposition of protective layer: A ZrO2 protective layer is deposited on the surface of the functional layer 2 to obtain a single-piece heat-insulating and fire-resistant glass composite coating.

4. The preparation method of the single-piece heat-insulating and fireproof glass composite coating according to claim 3, characterized in that, The thickness of the base layer in step (1) is 40-60 nm.

5. The preparation method of the monolithic heat-insulating and fire-proof glass composite coating according to claim 3, characterized in that, In step (2), the thickness of the first TiN layer is 40-60 nm, the thickness of the Ag layer is 5-10 nm, and the thickness of the second TiN layer is 40-60 nm.

6. The preparation method of the monolithic heat-insulating and fireproof glass composite coating according to claim 3, characterized in that The thickness of the composite material layer in step (3) is 40-50 nm.

7. The preparation method of the single-piece heat-insulating and fire-proof glass composite coating according to claim 3, wherein, The hydrogen-doped diamond-like carbon layer in step (3) is prepared by a gradient hydrogen doping process using methane as a carbon source and hydrogen as a hydrogen source using a vapor deposition method. The hydrogen-doped diamond-like carbon layer includes a high hydrogen content layer in an initial stage, a medium hydrogen content layer in an intermediate stage, and a low hydrogen content layer in a final stage.

8. The preparation method of the single-piece heat-insulating and fireproof glass composite coating according to claim 7, characterized in that, The gradient hydrogen doping process is as follows: in the initial stage, the flow ratio of methane gas to hydrogen is 1:8-10, forming a high hydrogen content layer of 20-30nm; in the middle stage, the flow ratio of methane gas to hydrogen is 1:5-7, forming a medium hydrogen content layer of 50-60nm; in the final stage, the flow ratio of methane gas to hydrogen is 1:2-4, forming a low hydrogen content layer of 20-30nm.

9. The preparation method of the single-piece heat-insulating and fire-proof glass composite coating according to claim 3, wherein, The thickness of the protective layer in step (4) is 20-30 nm.

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