CN115095079A

CN115095079A - Self-cleaning low-heat-radiation energy-saving glass

Info

Publication number: CN115095079A
Application number: CN202210547195.6A
Authority: CN
Inventors: 陈洪根; 李泽刚; 黄小辉; 简杨; 宋扬; 李武滔; 陈华良; 肖达; 吴映江; 张龙; 付烨; 杜浪; 姜山; 李聪; 肖啸; 黄林清; 周祥; 蒋美琴; 张晓敏; 罗添禄
Original assignee: Chengdu Institute Of Product Quality Supervision And Inspection; SICHUAN INSTITUTE PRODUCT QUALITY SUPERVISION INSPECTION AND RESEARCH
Current assignee: Chengdu Institute Of Product Quality Supervision And Inspection; SICHUAN INSTITUTE PRODUCT QUALITY SUPERVISION INSPECTION AND RESEARCH
Priority date: 2022-05-20
Filing date: 2022-05-20
Publication date: 2022-09-23
Anticipated expiration: 2042-05-20
Also published as: CN115095079B

Abstract

The invention provides self-cleaning low-heat radiation energy-saving glass which is characterized by comprising the following components: a front functional glass layer (10), a hollow layer (20) and a rear glass layer (30); the front functional glass layer (10) comprises a hydrophobic layer (101), a glass substrate layer (102) and a reflecting layer (103); the hydrophobic layer (101) comprises a superhydrophobic structure for hydrophobic self-cleaning; the glass matrix layer (102) contains plasmonic nanoparticles; the reflecting layer (103) is used for reflecting medium-wave and long-wave infrared heat radiation from the outside and the heated glass substrate layer (102); the hollow layer (20) is filled with gas, and the front functional glass layer (10) and the rear glass layer (30) are bonded through a sealing strip (201); the rear glass layer (30) is used for blocking heat generated in the chamber. The invention solves the technical problems of high complexity and high cost of the LOW-E coating process of the self-cleaning energy-saving glass.

Description

Self-cleaning low-heat-radiation energy-saving glass

Technical Field

The invention belongs to the field of multifunctional glass, and particularly relates to self-cleaning low-heat-radiation energy-saving glass used on buildings.

Background

Curtain walls around tall buildings in cities are composed of a lot of glass because of its superior lighting and architectural properties. However, the surface of the glass is smooth, oily substances in the air are easily combined with dust to form stains which are adhered to the surface of the glass, and the stains are difficult to remove by water. In recent years, along with the increasing floors of buildings, the difficulty coefficient and the danger coefficient of glass cleaning are increased; the case of falling due to the insufficient cleaning of the glass occurs every year; at the same time, cleaning the glass requires a large maintenance cost. To solve this problem, self-cleaning glass can be used as a high-rise glass curtain wall. Self-cleaning glass is self-cleaning mainly by hydrophobic coatings: dirt is carried away by the rolling water droplets. The requirements for self-cleaning hydrophobic surfaces are a very high static water contact angle theta, typically theta > 150 deg., and a very low roll angle, i.e. a minimum tilt angle theta < 10 deg. required for a drop to roll off. However, such self-cleaning glass generally does not have an energy saving function. LOW-E glass, i.e., LOW emissivity glass, minimizes the amount of ultraviolet and infrared light passing through the glass without affecting the amount of visible light transmitted. They block part of the solar radiation and prevent it from entering the indoor space they surround, thereby keeping the indoor space at a lower temperature and reducing the use of air conditioners, so the LOW-E glass is an energy saving glass. Chinese utility model patent CN204897749U discloses an outer automatically cleaning, inlayer antibiotic low heat radiation coated laminated glass, include: the periphery of the two glass substrates are bonded through the sealing strips, the sealing strips and the glass substrates are sealed through the sealing glue, a hollow interlayer is formed between the two glass substrates, a super-hydrophobic acid-base resistant coating is coated on the surface of the outer layer of the laminated glass, an antibacterial negative ion transparent latex layer is coated on the surface of the inner layer of the laminated glass, and an Ag film layer is plated on the surface of at least one of the glass substrates. In the actual production process, Ag is easily oxidized and corroded and is not high temperature resistant, so that the infrared transmittance (IRT) of Ag is too high, thereby affecting the energy-saving effect. Industry has generally improved the microstructure of silver films to achieve better optical and thermal properties. Moreover, the price of Ag as a noble metal leads to higher manufacturing costs. In general, the use of Ag as the LOW-E coating of self-cleaning energy-saving glass increases the complexity and cost of the process.

Disclosure of Invention

The invention aims to provide self-cleaning LOW-heat-radiation energy-saving glass to solve the technical problems of high complexity and high cost of a LOW-E coating process of the self-cleaning energy-saving glass.

In order to solve the technical problems, the specific technical scheme of the self-cleaning low-heat radiation energy-saving glass provided by the invention is as follows:

a self-cleaning low-heat radiation energy-saving glass is characterized by comprising: the front functional glass layer 10, the hollow layer 20 and the rear glass layer 30; the front functional glass layer 10 comprises a hydrophobic layer 101, a glass substrate layer 102 and a reflecting layer 103; the hydrophobic layer 101 comprises a super-hydrophobic structure for hydrophobic self-cleaning; the glass substrate layer 102 contains plasmon nanoparticles for generating plasmon resonance and heating the glass substrate layer 102; the reflective layer 103 is used for reflecting medium-wave and long-wave infrared heat radiation from the outside and the heated glass matrix layer 102; the hollow layer 20 is filled with gas, and the front functional glass layer 10 and the rear glass layer 30 are bonded through a sealing strip 201; the rear glass layer 30 serves to block heat generated in the chamber.

Furthermore, the material of the plasmon nanoparticles is at least one of Au, Ag, Al, Cu, TiN and ZrN.

Furthermore, the material of the plasmon nanoparticles is at least one of Al, Cu, TiN and ZrN.

Further, the plasmonic nanoparticle may be optionally shaped in at least one of a star shape, a sphere shape, a shell shape, a rod shape, and a cup shape.

Further, the size of the plasmonic nanoparticles is 30 to 360 nm.

Further, the material of the reflective layer 103 is ITO or AZO, and the thickness is 10 to 30 nm.

Further, the shape of the super-hydrophobic structure is spherical, and the size of the super-hydrophobic structure is 10-50 micrometers.

Further, the hollow layer 20 is filled with argon gas.

Further, the thickness of the hollow layer 20 is 10 to 16mm, the thickness of the glass substrate layer 102 is 4 to 8mm, and the thickness of the rear glass layer 30 is 4 to 8 mm.

The self-cleaning low-heat-radiation energy-saving glass has the following advantages: with plasmonic nanoparticles, plasmonic nanoparticles of different shapes and materials are used to create better low emissivity windows. Meanwhile, ITO or AZO is adopted as a reflecting layer, so that the complexity and cost of adopting Ag as a LOW-E coating in the traditional technical scheme are reduced, and LOW infrared radiance is maintained.

Drawings

FIG. 1 is a schematic view of the self-cleaning low-heat radiation energy-saving glass structure of the present invention;

FIG. 2 is a schematic view of the working principle of the self-cleaning low-thermal-radiation energy-saving glass of the present invention;

FIG. 3 is a schematic diagram of a modified self-cleaning low-heat radiation energy-saving glass core of the present invention;

FIG. 4 is an extinction coefficient of shell-shaped cheap metal TiN with different sizes in the self-cleaning low-heat radiation energy-saving glass of the invention;

FIG. 5 is a transmittance spectrum T obtained when the shell-shaped cheap metal TiN is mixed as plasmon nanoparticles (d =30, 160, 320 nm) in the self-cleaning low-heat radiation energy-saving glass of the invention;

FIG. 6 is a schematic diagram of the super-hydrophobic property of the self-cleaning low-heat radiation energy-saving glass of the present invention;

fig. 7 is a scanning electron microscope image of the hydrophobic layer 101 of the self-cleaning low-heat radiation energy-saving glass of the present invention.

Detailed Description

In order to better understand the purpose, structure and function of the present invention, the following will describe a self-cleaning low-heat radiation energy-saving glass in further detail with reference to the attached drawings.

The structure of the self-cleaning low-heat radiation energy-saving glass is shown in figure 1 and comprises a front functional glass layer 10, a hollow layer 20 and a rear glass layer 30; the front functional glass layer 10 includes a hydrophobic layer 101, a glass substrate layer 102, and a reflective layer 103: the hydrophobic layer 101 comprises a super-hydrophobic structure for hydrophobic self-cleaning; the glass substrate layer 102 contains plasmon nanoparticles for generating plasmon resonance and heating the glass substrate layer 102; the plasmon resonance can enhance light absorption and photo-thermal effect, so the plasmon nanoparticles can heat the glass substrate layer 102 to 40 ℃. According to the blackbody radiation theory, the thermal window of the sunlight can be moved to the middle and far infrared windows.

The reflective layer 103 is for reflecting medium and long-wave infrared heat radiation emitted from the outside and the heated glass substrate layer 102; the hollow layer 20 is filled with gas, and the front functional glass layer 10 and the rear glass layer 30 are bonded through a sealing strip 201; the rear glass layer 30 serves to block heat generated in the chamber.

As shown in fig. 2, the working principle of the present invention is as follows: all objects to some extent give off thermal energy in the form of radiant heat. Glass is a natural insulator, which means that it is a good heat absorber. It absorbs thermal energy from the sun and then gradually releases it from the glass into the surrounding space. LOW-E stands for "LOW emissivity". Therefore, glass with LOW-E characteristics will release less thermal energy. In summer, the front functional glass layer 10 penetrates most visible light and blocks most infrared rays, so that outdoor heat is prevented from entering the room, the indoor air conditioner has a better refrigeration effect, and energy consumption is reduced. The glass matrix layer 102 contains plasmon nanoparticles, which absorb (transmit) a small portion of light at 380-780nm, and absorb most of light in a band where solar energy is concentrated: near infrared light and short infrared light (0.78-3 μm), and the glass is heated to raise the temperature of the glass to about 40 ℃ due to the photothermal action of the plasmon polariton; at this time, the glass becomes a new heat source, and its heat emission wavelength is in far infrared (3-15 μm) according to the blackbody radiation theory. This part of the wave (3-15 μm) is finally reflected by the reflective layer 103, thus achieving a "low emissivity". Furthermore, the hydrophobic layer 101 (shown in fig. 1) of the front functional layer provides superhydrophobic performance. When rainwater falls on the surface of the glass, the hydrophobic structure of the hydrophobic layer 101 has projections and gaps, air in the gaps is locked, the rainwater makes point contact only with the tips of the projections, and the surface adhesion is weak. If dirt and dust exist on the glass or in the air, the dirt and dust also form point contact with the glass, the surface adhesion is weak, and the dirt and dust can be easily taken away by rain, so that self-cleaning is realized.

The core improvement point of the invention is shown in fig. 3: (1) adding plasmon nanoparticles into the glass substrate layer 102, wherein the plasmon nanoparticles strongly absorb and reflect infrared light and are transparent to visible light; (2) the reflective layer 103 serves to reflect medium and long wavelength infrared radiation emitted from the outside and the heated glass substrate layer 102. The material of the reflecting layer 103 is ITO or AZO, and the thickness is 10 to 30 nm. In commercial or conventional LOW-E glass, the reflective layer contains almost all silver coating, whether passive or active. However, its disadvantages are also evident: 1. silver is a precious metal and is expensive; 2. the reflective layer generally requires the deposition of a multi-layered silver coating and requires the quality of the silver coating film, since the transflective ratio of the silver coating film depends on the deposition quality, thereby increasing the process complexity. The transparent conductive oxides ITO and AZO can realize high transparency (> 0.8) of visible light in the solar spectrum, and simultaneously maintain the radiance of less than 0.13 in the middle and far infrared region. Meanwhile, the ITO and AZO have low requirements on deposition processes, such as vacuum evaporation deposition and sol-gel mass production. Most importantly, the electrical/optical properties of the Ag film depend on its microstructure to a large extent, whereas ITO and AZO are not, so ITO and AZO increase the fault tolerance of the process. Therefore, the invention solves the technical problems of high complexity and high cost of the LOW-E coating process of the self-cleaning energy-saving glass.

Optionally, the thickness of the ITO and AZO thin films of the reflecting layer is 10 to 30nm, and the performance of reflecting middle-far infrared radiation is best in the range of the interval.

Further, the material of the plasmon nanoparticles is common material supporting plasmon resonance, such as Au, Ag, Al, Cu, TiN, ZrN. Further, inexpensive metals such as Al, Cu, TiN, ZrN; the plasmonic nanoparticles may be optionally shaped as stars, spheres, shells, rods and cups. The size of the plasmonic nanoparticles is 30 to 360 nm. Plasmonic nanoparticles can be prepared using already disclosed techniques: such as sputter-annealing, vapor deposition, or chemical colloid synthesis. The method for adding the plasmon nanoparticles to the glass comprises the following steps: thermal field polarization of glass, rapid thermal annealing, and nano-machining on a glass substrate induced by plasmon heating.

Taking a shell-shaped cheap metal TiN as the plasmon nano-particle as an example, the extinction coefficient is shown in FIG. 4. The extinction coefficient represents absorption and scattering of light by the plasmonic nanoparticles, and as can be seen from fig. 4, by adjusting the size of the shell-shaped TiN, its extinction in near-infrared light and short-infrared light (0.78-3 μm) can be achieved. If proper plasmon nanoparticles are placed in the glass substrate layer 102, most of the solar heat can be absorbed, visible light is transmitted, the glass is heated, the glass radiates heat in the middle and far infrared regions, and the reflecting layer 103 reflects far infrared light, so that the low thermal radiance is realized. Wherein, a shell-shaped cheap metal TiN is adopted as a plasmon nano particle (d =30, 160, 320 nm) to be mixed, and the concentration ratio is 1: 2: the transmittance T (λ) obtained when 1 is used is shown in fig. 5. The visible light transmittance VT, the infrared transmittance IRT and the solar heat gain coefficient SHGC can be respectively obtained by the following formulas:

where T (λ) is the optical transmittance, and I (λ) is the intensity of sunlight at the corresponding wavelength. From the above three equations and T (λ) of FIG. 5: the visible light transmittance VT is 0.74, the infrared transmittance IRT is 0.125, and the solar heat gain coefficient SHGC is 0.24; the VT of the common single-interlayer LOW-E glass is 0.75, the IRT is 0.2 to 0.2, and the SHGC is 0.26.

The superhydrophobic structure of the hydrophobic layer 101 is composed of a micro-scale protrusion structure. The micro/nano composite rough structure is the key element for constructing the stable super-hydrophobic interface. Superhydrophobicity is defined as a contact angle greater than 150 ° and a sliding angle less than 10 °. FIG. 6 is a super-hydrophobic property diagram of the surface of the self-cleaning low-heat radiation energy-saving glass of the present invention: including contact angle plots and rolling angle plots. From fig. 6, it can be seen that the contact angle and the rolling angle of the structure of the present invention are 155 ° and 4.3 °. Fig. 7 is a scanning electron microscope image of the hydrophobic layer 101, and it can be seen that the micro-scale raised structures are spherical and have a size of 10 to 50 micrometers. The spherical micron-scale convex structure can be prepared by the following method: preparing silicon oxide nano particles by using a Stober method, coupling the silicon oxide nano particles with 1H, 2H, 3H, 4H-perfluoroalkyl triethoxysilane, and finally obtaining the modified super-hydrophobic silicon oxide nano particle dispersion liquid. Spraying the modified super-hydrophobic silica nanoparticle dispersion liquid on the glass substrate layer 102 by using a spray gun, and drying to obtain the hydrophobic layer 101.

By combining the VT, IRT, SHGC, contact angle and rolling angle, the self-cleaning glass disclosed by the invention can realize self-cleaning of glass and solve the technical problems of high complexity and high cost of a LOW-E coating process of the glass.

Further, the hollow layer 20 is filled with argon gas. The argon gas serves to insulate the room from heat and to minimize heat transfer through the windows. It is a colorless, odorless gas that is harmless even if leaked. Since argon is denser than air, its addition to a glazing contributes to its overall insulation. By combining argon with the reflective layer 103, the temperature of the window glass will be assisted to be closer to room temperature, and the thermal insulation performance of the window in winter can be improved.

The thickness of the hollow layer 20 has a direct influence on the heat transmittance. The heat transmittance refers to a ratio of energy transmitted in a heat ray projected to the surface of an object to total energy projected to the surface. The thickness of the glass substrate layer 102 can be 4-8mm, and the thickness of the rear glass layer 30 can be 4-8 mm. In particular, when the thickness of the glass substrate layer 102 is 8mm and the thickness of the rear glass layer 30 is 8mm, the thickness of the hollow layers 20 is 10 to 16mm, and their thermal transmittance IRT is as follows: 35% for 10mm, 24% for 11mm, 16% for 12mm, 7% for 13mm, 1% for 14 mm, 1.1% for 15mm, 0.9% for 16 mm.

It is to be understood that the present invention has been described with reference to certain embodiments and that various changes in form and details may be made therein by those skilled in the art without departing from the spirit and scope of the invention. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the invention without departing from the essential scope thereof. Therefore, it is intended that the invention not be limited to the particular embodiment disclosed, but that the invention will include all embodiments falling within the scope of the appended claims.

Claims

1. A self-cleaning low-heat radiation energy-saving glass is characterized by comprising: a front functional glass layer (10), a hollow layer (20) and a rear glass layer (30); the front functional glass layer (10) comprises a hydrophobic layer (101), a glass substrate layer (102) and a reflecting layer (103); the hydrophobic layer (101) comprises a superhydrophobic structure for hydrophobic self-cleaning; the glass substrate layer (102) contains plasmon nanoparticles for generating plasmon resonance and heating the glass substrate layer (102); the reflecting layer (103) is used for reflecting medium-wave and long-wave infrared heat radiation from the outside and the heated glass substrate layer (102); the hollow layer (20) is filled with gas, and the front functional glass layer (10) and the rear glass layer (30) are bonded through a sealing strip (201); the rear glass layer (30) is used for blocking heat generated in the chamber.

2. The self-cleaning low-heat radiation energy-saving glass according to claim 1, wherein the material of the plasmonic nanoparticles is at least one of Au, Ag, Al, Cu, TiN and ZrN.

3. The self-cleaning low-heat radiation energy-saving glass according to claim 2, wherein the material of the plasmonic nanoparticles is at least one of Al, Cu, TiN and ZrN.

4. The self-cleaning low thermal radiation energy saving glass according to claim 3, characterized in that the shape of the plasmonic nanoparticles is at least one of star, sphere, shell, rod and cup.

5. The self-cleaning low thermal radiation energy saving glass according to claim 4, characterized in that the size of the plasmonic nanoparticles is 30 to 360 nm.

6. The self-cleaning low heat radiation energy saving glass according to claim 1, characterized in that the material of the reflecting layer (103) is ITO or AZO with a thickness of 10 to 30 nm.

7. The self-cleaning low heat radiation energy saving glass according to claim 6, wherein the super-hydrophobic structure is spherical in shape and has a size of 10 to 50 micrometers.

8. The self-cleaning low heat radiation energy saving glass according to claim 7, characterized in that the hollow layer (20) is filled with argon gas.

9. The self-cleaning low heat radiation energy saving glass according to any one of claims 1 to 8, wherein the thickness of the hollow layer (20) is 10 to 16mm, the thickness of the glass matrix layer (102) is 4 to 8mm, and the thickness of the rear glass layer (30) is 4 to 8 mm.