CN115095079B

CN115095079B - Self-cleaning low-heat radiation energy-saving glass

Info

Publication number: CN115095079B
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: 2023-09-12
Anticipated expiration: 2042-05-20
Also published as: CN115095079A

Abstract

The utility model provides self-cleaning low-heat radiation energy-saving glass, which is characterized by comprising the following components in percentage by weight: a front functional glass layer (10), a hollow layer (20) and a rear glass layer (30); wherein the pre-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 plasmonic nanoparticles; the reflective layer (103) is used for reflecting medium-wavelength and long-wavelength infrared thermal radiation from the external and 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 room. The utility model solves the technical problems of high process complexity and high cost of the self-cleaning energy-saving glass LOW-E coating.

Description

Self-cleaning low-heat radiation energy-saving glass

Technical Field

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

Background

Curtain walls around tall buildings in cities are composed of many glasses, due to their superior lighting and construction properties. However, the glass surface is smooth, oily substances in the air are easy to combine with dust to form stains which adhere to the glass surface, and the stains are difficult to clean by flushing with water. In recent years, as building floors are continuously increased, the difficulty coefficient and the danger coefficient of cleaning glass are also increased; the falling due to the foot loss of the wiping and cleaning 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 coating: dirt is carried away by the rolling water droplets. The requirements for a self-cleaning hydrophobic surface are very high static water contact angles θ, typically θ > 150 °, and very low roll angles, i.e. minimum tilt angle θ < 10 ° required for droplet 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 uv and ir light passing through the glass without affecting the amount of visible light transmitted. They block part of solar radiation and prevent it from entering the indoor space they surround, thus keeping the indoor space at a lower temperature and reducing the use of air conditioning, so LOW-E glass is an energy-saving glass. Chinese patent No. CN204897749U discloses a laminated glass with self-cleaning outer layer and antibacterial inner layer and low thermal radiation coating, comprising: the peripheries of the two glass substrates are bonded through sealing strips, the sealing strips and the glass substrates are sealed by sealant, a hollow interlayer is formed between the two glass substrates, the outer surface of the laminated glass is coated with a layer of super-hydrophobic acid-base resistant coating, the inner surface of the laminated glass is coated with a layer of antibacterial anion transparent latex, and the surface of at least one glass substrate is plated with an Ag film. In the actual production process, ag is easily oxidized and corroded and does not resist high temperature, so that the IR transmittance (IRT) is too high, thereby affecting the energy saving effect. Industry has generally improved silver film microstructure to achieve better optical and thermal properties. Moreover, the price of Ag, as a noble metal, results in a high manufacturing cost thereof. In general, the use of Ag as a LOW-E coating for self-cleaning energy-saving glass increases the complexity and cost of the process.

Disclosure of Invention

The utility model aims to provide self-cleaning LOW-heat radiation energy-saving glass, which aims 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 is as follows:

a self-cleaning low thermal radiation energy saving glass, comprising: a front functional glass layer 10, a hollow layer 20 and a rear glass layer 30; wherein the pre-functional glass layer 10 comprises a hydrophobic layer 101, a glass matrix 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 plasmonic nanoparticles for generating plasmon resonance and heating the glass substrate layer 102; the reflecting layer 103 is used for reflecting the medium-wave and long-wave infrared heat radiation from the external and 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 the sealing strip 201; the rear glass layer 30 serves to block heat generated in the room.

Further, the plasmonic nanoparticle is made of at least one of Au, ag, al, cu, tiN, zrN materials.

Further, the plasmonic nanoparticle is made of at least one of Al, cu, tiN, zrN.

Further, the plasmonic nanoparticle may be at least one of star-shaped, spherical-shaped, shell-shaped, rod-shaped, and cup-shaped.

Further, the plasmonic nanoparticle has a size of 30 to 360nm.

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

Further, the super-hydrophobic structure is spherical in shape and has a size of 10 micrometers to 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 8mm.

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 a better low emissivity window. Meanwhile, ITO or AZO is adopted as the reflecting layer, so that the complexity and cost of adopting Ag as a LOW-E coating in the traditional technical scheme are reduced, and meanwhile, the LOW infrared radiation rate is maintained.

Drawings

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

FIG. 2 is a schematic diagram of the working principle of the self-cleaning low heat radiation energy-saving glass of the utility model;

FIG. 3 is a schematic diagram of a self-cleaning low thermal radiation energy saving glass core improvement of the present utility model;

FIG. 4 is the extinction coefficients of different sized shell-shaped inexpensive metal TiN in the self-cleaning low thermal radiation energy saving glass of the present utility model;

fig. 5 is a transmittance spectrum T obtained when shell-shaped inexpensive metal TiN in the self-cleaning low thermal radiation energy-saving glass of the present utility model is mixed as plasmonic nanoparticles (d=30, 160, 320 nm);

FIG. 6 is a schematic diagram showing the superhydrophobic performance of the self-cleaning low thermal radiation energy saving glass of the present utility model;

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

Detailed Description

For better understanding of the objects, structures and functions of the present utility model, a self-cleaning low heat radiation energy saving glass of the present utility model will be described in further detail with reference to the accompanying drawings.

The structure of the self-cleaning low-heat radiation energy-saving glass is shown in fig. 1, and comprises a front functional glass layer 10, a hollow layer 20 and a rear glass layer 30; wherein the pre-functional glass layer 10 comprises a hydrophobic layer 101, a glass matrix layer 102 and a reflective layer 103: the hydrophobic layer 101 comprises a superhydrophobic structure for hydrophobic self-cleaning; glass substrate layer 102 contains plasmonic nanoparticles for generating plasmon resonance and heating glass substrate layer 102; since plasmon resonance can enhance light absorption and enhance photothermal effects, the plasmonic nanoparticles can heat the glass substrate layer 102 to 40 degrees celsius. According to the blackbody radiation theory, the thermal window of sunlight can be moved to the middle-far infrared window.

The reflective layer 103 is for reflecting mid-wave 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 the sealing strip 201; the rear glass layer 30 serves to block heat generated in the room.

As shown in fig. 2, the working principle of the present utility model is as follows: all objects will to some extent emit 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 from the glass into the surrounding space. Low-E stands for "Low emissivity". Thus, glass with LOW-E characteristics will release less thermal energy. In summer, the front functional glass layer 10 transmits most visible light and blocks most infrared rays, so that outdoor heat is blocked from entering the room, the indoor air conditioner has better refrigerating effect, and the energy consumption is reduced. Glass matrix layer 102 contains plasmonic nanoparticles that absorb (transmit) a small portion of 380-780nm light, absorbing most of the band light where solar energy is concentrated: near infrared light and short infrared light (0.78-3 μm), heating the glass to a temperature of about 40 ℃ due to photothermal effect of the plasmon; at this time, the glass becomes a new heat source, and its thermal emission wavelength is in the far infrared (3-15 μm) according to the blackbody radiation theory. Finally, this portion of the wave (3-15 μm) is reflected by the reflection layer 103, thereby realizing "low heat emissivity". In addition, the hydrophobic layer 101 (shown in fig. 1) of the pre-functional layer provides superhydrophobic performance. When rainwater falls on the surface of glass, the hydrophobic structure of the hydrophobic layer 101 has protrusions and gaps, air in the gaps is locked, the rainwater forms point contact with only the tips of the protrusions, and the surface adhesion is weak. If dirt, dust and the like are on the glass or in the air, the dirt, the dust and the like are in point contact with the glass, the surface adhesion is weak, and the dirt, the dust and the like are easily taken away by rain, so that self-cleaning is realized.

The core improvement point of the utility model is shown in fig. 3: (1) The plasmon nano particles are added in the glass substrate layer 102, and strongly absorb and reflect infrared light and are transparent to visible light; (2) The reflective layer 103 serves to reflect mid-wave and long-wave infrared radiation emitted from the outside and the heated glass substrate layer 102. The material of the reflective layer 103 is ITO or AZO, and the thickness is 10 to 30nm. In commercial or conventional LOW-E glasses, the reflective layer contains almost all of the silver coating, either passive or active. However, its drawbacks are also apparent: 1. silver is noble metal and is expensive; 2. the reflective layer generally requires the deposition of multiple silver coatings and requires the quality of the silver coated film because the reflectivity of the silver coated film is related to the quality of deposition, thus increasing the process complexity. Transparent conductive oxides ITO and AZO can achieve high transparency (> 0.8) to visible light in the solar spectrum while maintaining a emissivity of < 0.13 in the mid-far infrared region. Meanwhile, the ITO and AZO have low requirements on the deposition process, and can be produced in large scale by adopting vacuum evaporation deposition and sol-gel. Most importantly, the electrical/optical properties of Ag thin films are largely dependent on their microstructure, whereas ITO and AZO are not, thus increasing the process tolerance. Therefore, the utility model solves the technical problems of high complexity and high cost of the self-cleaning energy-saving glass LOW-E coating process.

Alternatively, the thickness of the reflective layers ITO and AZO thin films is 10 to 30nm, and the performance of reflecting mid-far infrared heat radiation is best in this interval range.

Further, the plasmonic nanoparticle is made of a common material supporting plasmon resonance, such as Au, ag, al, cu, tiN, zrN. Still further, inexpensive metals such as Al, cu, tiN, zrN may be employed; the plasmonic nanoparticles can be optionally shaped as stars, spheres, shells, rods and cups. The plasmonic nanoparticles have a size of 30 to 360nm. Plasmonic nanoparticles can be prepared using the techniques already disclosed: such as sputter-annealing, vapor deposition, or chemical colloid synthesis. The method for adding the plasmon nano particles into the glass comprises the following steps: a thermal electric field polarization method, a rapid thermal annealing method, a plasmon heating induced nano-processing method and the like on a glass substrate.

Taking a shell-shaped cheap metal TiN as an example of the plasmon nanoparticle, the extinction coefficient thereof is shown in FIG. 4. The extinction coefficient represents the absorption and scattering of light by plasmonic nanoparticles, and it can be seen from fig. 4 that by adjusting the size of the shell-shaped TiN, extinction in near infrared light and short infrared light (0.78-3 μm) can be achieved. If a suitable plasmonic nanoparticle is placed in the glass substrate layer 102, it can absorb most of solar heat, transmit visible light, heat the glass, radiate heat in the mid-far infrared region, and reflect far infrared light by the reflective layer 103, thereby realizing "low thermal emissivity". Wherein, shell-shaped cheap metal TiN is adopted as plasmon nano particles (d=30, 160, 320 nm) to be mixed, and the concentration ratio is 1:2: in 1, the transmittance T (λ) is shown in fig. 5. The visible light transmittance VT, the infrared transmittance IRT and the solar heat gain coefficient SHGC can be obtained by the following formulas, respectively:

where T (λ) is the optical transmittance and I (λ) is the intensity of solar light at the corresponding wavelength. From the three formulas above 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, and the SHGC is 0.26.

The superhydrophobic structure of the hydrophobic layer 101 is composed of a micron-sized raised structure. The micro/nano composite coarse structure is a key element for constructing a stable super-hydrophobic interface. Superhydrophobic is defined as having a contact angle greater than 150 ° and a roll angle less than 10 °. FIG. 6 is a graph of superhydrophobic properties of a self-cleaning low thermal radiation energy efficient glass surface according to the present utility model: including contact angle diagrams and roll angle diagrams. It can be seen from fig. 6 that the contact angle of the inventive structure is 155 ° and the roll angle is 4.3 °. Fig. 7 is a scanning electron microscope image of the hydrophobic layer 101, and it can be seen from the image that the micro-scale protrusion structure is spherical and has a size of 10 micrometers to 50 micrometers. The spherical micron-sized raised structures can be produced by the following method: and (3) 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 modified super-hydrophobic silicon oxide nano particle dispersion liquid. And spraying the modified super-hydrophobic silicon oxide nanoparticle dispersion liquid on the glass substrate layer 102 by using a spray gun, and drying to obtain the hydrophobic layer 101.

By combining VT, IRT, SHGC, the contact angle and the rolling angle, the utility model solves the technical problems of high process complexity and high cost of the glass LOW-E coating while realizing self-cleaning of the glass.

Further, the hollow layer 20 is filled with argon gas. The purpose of argon is to insulate the room and minimize heat transfer through the windows. It is a colorless, odorless gas, and is harmless even if leakage occurs. Since argon is denser than air, its addition to the glazing helps to improve its overall insulation. By combining argon with the reflective layer 103, the temperature of the window glass is helped to be closer to room temperature, and the heat preservation and insulation performance of the window in winter is improved.

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

It will be understood that the utility model has been described in terms of several embodiments, and that various changes and equivalents may be made to these features and embodiments by those skilled in the art without departing from the spirit and scope of the utility model. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the utility model without departing from the essential scope thereof. Therefore, it is intended that the utility model not be limited to the particular embodiment disclosed, but that the utility model will include all embodiments falling within the scope of the appended claims.

Claims

1. A self-cleaning low thermal radiation energy saving glass, comprising: a front functional glass layer (10), a hollow layer (20) and a rear glass layer (30); wherein the pre-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 plasmonic nanoparticles for generating plasmon resonance and heating the glass substrate layer (102); the reflective layer (103) is used for reflecting medium-wavelength and long-wavelength infrared thermal radiation from the external and 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 room;

wherein the plasmonic nanoparticle is a shell-shaped TiN nanoparticle mixture of d=30, 160, 320 nm; the concentration ratio of the shell-shaped TiN nanoparticle mixture is 1:2:1, a step of; the material of the reflecting layer (103) is ITO or AZO, and the thickness is 10-30 nm.

2. The self-cleaning low thermal radiation energy saving glass according to claim 1, wherein the superhydrophobic structure is spherical in shape and has a size of 10 micrometers to 50 micrometers.

3. Self-cleaning low thermal radiation energy saving glass according to claim 2, characterized in that the hollow layer (20) is filled with argon.

4. A self-cleaning low thermal radiation energy saving glass according to any of claims 1-3, characterized in that the thickness of the hollow layer (20) is 10 to 16mm, the thickness of the glass matrix layer (102) is 4-8mm, and the thickness of the rear glass layer (30) is 4-8mm.