CN118026542A - Safe energy-saving high-boron silicon Low-E fireproof glass - Google Patents

Safe energy-saving high-boron silicon Low-E fireproof glass Download PDF

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Publication number
CN118026542A
CN118026542A CN202410185233.7A CN202410185233A CN118026542A CN 118026542 A CN118026542 A CN 118026542A CN 202410185233 A CN202410185233 A CN 202410185233A CN 118026542 A CN118026542 A CN 118026542A
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Prior art keywords
glass
parts
silicon low
energy
safe
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Pending
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CN202410185233.7A
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Inventor
尤海阳
解文旭
王亚青
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Hebei Haiyang Shunda Energy Saving Glass Co ltd
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Hebei Haiyang Shunda Energy Saving Glass Co ltd
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Priority to CN202410185233.7A priority Critical patent/CN118026542A/en
Publication of CN118026542A publication Critical patent/CN118026542A/en
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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/006—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character
    • C03C17/008—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character comprising a mixture of materials covered by two or more of the groups C03C17/02, C03C17/06, C03C17/22 and C03C17/28
    • C03C17/009—Mixtures of organic and inorganic materials, e.g. ormosils and ormocers
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B15/00—Drawing glass upwardly from the melt
    • C03B15/14—Drawing tubes, cylinders, or rods from the melt
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
    • C03C1/002—Use of waste materials, e.g. slags
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/20—Materials for coating a single layer on glass
    • C03C2217/21—Oxides
    • C03C2217/23—Mixtures
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2218/00—Methods for coating glass
    • C03C2218/10—Deposition methods
    • C03C2218/15—Deposition methods from the vapour phase
    • C03C2218/154—Deposition methods from the vapour phase by sputtering
    • C03C2218/156—Deposition methods from the vapour phase by sputtering by magnetron sputtering

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Inorganic Chemistry (AREA)
  • Composite Materials (AREA)
  • Surface Treatment Of Glass (AREA)

Abstract

The invention relates to the technical field of glass materials, and provides safe and energy-saving high-boron silicon Low-E fireproof glass which comprises a glass substrate and a coating layer on the outer surface of the glass substrate; the coating layer is formed by sputtering a solid target material onto a glass substrate through a vacuum magnetron sputtering method; the solid target comprises the following raw materials: graphene, indium triflate, and tin triflate. Through the technical scheme, the problem of poor fire resistance of Low-E glass in the prior art is solved.

Description

Safe energy-saving high-boron silicon Low-E fireproof glass
Technical Field
The invention relates to the technical field of glass materials, in particular to safe and energy-saving high-boron-silicon Low-E fireproof glass.
Background
Low-E glass, also known as Low emissivity coated glass, is coated glass with high reflectance (more than 80%) for far infrared rays with a wavelength range of 4.5-25 microns. In order to achieve the purpose of reducing radiation, the Low-E glass is required to deposit one or more layers of metal materials on the surface of the float glass in the manufacturing process so as to reflect near infrared rays in sunlight and far infrared rays in living environment, thereby reducing the absorptivity and the emissivity of the glass to the infrared rays. At present, the glass has excellent market feedback degree, and can be used for household windows, glass curtain walls of shops, office buildings and high-grade hotels and other places where the glass is required. In summer, the solar energy air conditioner can effectively prevent near infrared rays in sunlight from entering the room, avoid the rise of the indoor temperature and save the air conditioner cost; in winter, the device can prevent far infrared rays generated by indoor heating and the like from escaping outdoors, keep indoor temperature, save heating cost and bring economic compensation for users.
According to building fireproof standards, when the Low-E glass is applied to places such as household doors and windows, store doors and windows, writing building doors and windows and the like, the Low-E glass also needs to have fireproof performance so as to ensure personal and property safety, but the Low-E glass used at present has poor fireproof performance and is easy to collapse in a high-temperature environment for a long time.
Disclosure of Invention
The invention provides safe and energy-saving high-boron silicon Low-E fireproof glass, which solves the problem of poor fireproof performance of Low-E glass in the related technology.
The technical scheme of the invention is as follows:
the invention provides safe and energy-saving high-boron silicon Low-E fireproof glass, which comprises a glass substrate and a coating layer on the outer surface of the glass substrate;
The coating layer is formed by sputtering a solid target material onto a glass substrate through a vacuum magnetron sputtering method;
the solid target comprises the following raw materials: graphene, indium triflate, and tin triflate.
As a further technical scheme, the solid target comprises the following raw materials in parts by weight: 3-10 parts of graphene, 2-6 parts of indium triflate and 2-6 parts of tin triflate.
As a further technical scheme, the mass ratio of the graphene to the indium triflate to the tin triflate is 1-3:1:1.
As a further technical scheme, the mass ratio of the graphene to the indium triflate to the tin triflate is 2:1:1.
As a further technical scheme, the preparation method of the solid target material comprises the following steps: and uniformly mixing graphene, indium triflate and tin triflate to obtain the solid target.
As a further technical scheme, the glass matrix comprises the following raw materials in parts by weight: 30-35 parts of quartz sand, 10-15 parts of borax pentahydrate, 8-10 parts of boric acid, 5-8 parts of aluminum hydroxide, 40-50 parts of broken glass, 2-4 parts of sodium chloride, 0.5-1 part of indium oxide, 0.5-1 part of tin oxide, 2-4 parts of sodium silicate and 2-4 parts of magnesium silicate.
As a further technical scheme, the preparation method of the glass substrate comprises the following steps:
a1, uniformly mixing the raw materials of the glass matrix components, and melting to obtain glass melt;
a2, molding the glass melt to obtain the glass matrix.
As a further technical scheme, the melting temperature is 1400-1500 ℃, and the melting time is 6-7 h.
As a further technical scheme, A2 is that glass melt is molded, insulated and cooled to obtain a glass matrix;
as a further technical scheme, the temperature of heat preservation is 600-700 ℃, and the time of heat preservation is 50-60 min.
The invention also discloses a preparation method of the safe energy-saving high-boron silicon Low-E fireproof glass, which comprises the following steps:
s1, sputtering a solid target material onto a glass substrate by a vacuum magnetron sputtering method to obtain coated glass;
s2, cutting the coated glass, treating the four sides of the coated glass, and washing and tempering to obtain the high-boron silicon Low-E fireproof glass.
As a further technical scheme, S2 is to cut coated glass, treat four sides of the coated glass, wash the coated glass, and then sequentially perform preheating treatment, heat treatment, quenching, cooling treatment and cooling to obtain the high-boron silicon Low-E fireproof glass.
As a further technical scheme, the temperature of the preheating treatment is 500-600 ℃, and the time of the preheating treatment is 8-10 min.
As a further technical scheme, the temperature of the heat treatment is 800-850 ℃, and the time of the heat treatment is 10-15 min.
As a further technical scheme, the quenching air pressure is 25-28 kpa, and the quenching time is 40-60 s.
As a further technical scheme, the cooling treatment is to cool to 80 ℃ under the condition of wind pressure of 20-23 kpa.
The working principle and the beneficial effects of the invention are as follows:
1. According to the invention, the coating layer is added on the surface of the glass substrate, so that the fire resistance time of the Low-E glass at high temperature is improved, and the visible light transmittance of the Low-E glass is reduced, so that the Low-E glass has high fire resistance and high energy saving performance, and the problem that the Low-E glass is easy to collapse in a high-temperature environment for a long time is solved. The graphene, the indium triflate and the tin triflate are used as raw materials of the coating layer, so that the high temperature resistance and the high temperature durability of the Low-E glass can be further improved, and the visible light transmittance can be reduced.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by one of ordinary skill in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
In the following examples and comparative examples,
The specification of the quartz sand is 10-20 mm, and the Mohs hardness is 7;
The granularity of the aluminum hydroxide is 100 meshes;
the density of the graphene is 1500kg/m 3.
Example 1
A preparation method of safe and energy-saving high-boron silicon Low-E fireproof glass comprises the following steps:
S1, conveying a glass substrate into vacuum magnetron sputtering equipment, and sputtering a solid target onto the glass substrate when the vacuum degree of a vacuum environment reaches 6 multiplied by 10 -4 Pa to obtain coated glass;
s2, cutting coated glass, edging four edges of the coated glass, washing the coated glass with deionized water in a cleaning device, preheating the coated glass at 500 ℃ for 10min, heat treating the coated glass at 800 ℃ for 15min, quenching the coated glass at 25kpa under the wind pressure for 60S, cooling the coated glass at 20kpa under the wind pressure to 80 ℃, and naturally cooling the coated glass to obtain the high-boron silicon Low-E fireproof glass.
The preparation method of the glass matrix comprises the following steps:
A1, adding 30 parts of quartz sand, 10 parts of borax pentahydrate, 8 parts of boric acid, 5 parts of aluminum hydroxide, 40 parts of broken glass, 2 parts of sodium chloride, 0.5 part of indium oxide, 0.5 part of tin oxide, 2 parts of sodium silicate and 2 parts of magnesium silicate into a glass electric melting furnace, uniformly mixing, and melting for 7 hours at 1400 ℃ to obtain glass melt;
A2, drawing the glass melt into a tube by using a glass tube drawing machine, preserving heat for 60min at 600 ℃ in an annealing furnace, and naturally cooling to obtain a glass matrix.
The preparation method of the solid target comprises the following steps:
And uniformly mixing 5 parts of graphene, 5 parts of indium triflate and 5 parts of tin triflate to obtain the solid target.
Example 2
A preparation method of safe and energy-saving high-boron silicon Low-E fireproof glass comprises the following steps:
S1, conveying a glass substrate into vacuum magnetron sputtering equipment, and sputtering a solid target onto the glass substrate when the vacuum degree of a vacuum environment reaches 6 multiplied by 10 -4 Pa to obtain coated glass;
S2, cutting coated glass, edging four edges of the coated glass, washing the coated glass with deionized water in a cleaning device, preheating the coated glass at 550 ℃ for 9min, heat-treating the coated glass at 830 ℃ for 13min, quenching the coated glass at 26kpa under the air pressure for 50S, cooling the coated glass at 22kpa under the air pressure to 80 ℃, and naturally cooling the coated glass to obtain the high-boron silicon Low-E fireproof glass.
The preparation method of the glass matrix comprises the following steps:
A1, adding 32 parts of quartz sand, 13 parts of borax pentahydrate, 9 parts of boric acid, 7 parts of aluminum hydroxide, 45 parts of broken glass, 3 parts of sodium chloride, 0.8 part of indium oxide, 0.8 part of tin oxide, 3 parts of sodium silicate and 3 parts of magnesium silicate into a glass electric melting furnace, uniformly mixing, and melting for 6.5 hours at 1450 ℃ to obtain glass melt;
A2, drawing the glass melt into a tube by using a glass tube drawing machine, preserving heat for 55min at 650 ℃ in an annealing furnace, and naturally cooling to obtain a glass matrix.
The preparation method of the solid target comprises the following steps:
And uniformly mixing 5 parts of graphene, 5 parts of indium triflate and 5 parts of tin triflate to obtain the solid target.
Example 3
A preparation method of safe and energy-saving high-boron silicon Low-E fireproof glass comprises the following steps:
S1, conveying a glass substrate into vacuum magnetron sputtering equipment, and sputtering a solid target onto the glass substrate when the vacuum degree of a vacuum environment reaches 6 multiplied by 10 -4 Pa to obtain coated glass;
S2, cutting coated glass, edging four edges of the coated glass, washing the coated glass with deionized water in a cleaning device, preheating the coated glass at 600 ℃ for 8min, heat treating the coated glass at 850 ℃ for 10min, quenching the coated glass at 28kpa under the air pressure for 40S, cooling the coated glass at 23kpa under the air pressure to 80 ℃, and naturally cooling the coated glass to obtain the high-boron silicon Low-E fireproof glass.
The preparation method of the glass matrix comprises the following steps:
A1, adding 35 parts of quartz sand, 15 parts of borax pentahydrate, 10 parts of boric acid, 8 parts of aluminum hydroxide, 50 parts of broken glass, 4 parts of sodium chloride, 1 part of indium oxide, 1 part of tin oxide, 4 parts of sodium silicate and 4 parts of magnesium silicate into a glass electric melting furnace, uniformly mixing, and melting for 6 hours at 1500 ℃ to obtain glass melt;
A2, drawing the glass melt into a tube by using a glass tube drawing machine, preserving heat for 50min at 700 ℃ in an annealing furnace, and naturally cooling to obtain a glass matrix.
The preparation method of the solid target comprises the following steps:
And uniformly mixing 5 parts of graphene, 5 parts of indium triflate and 5 parts of tin triflate to obtain the solid target.
Example 4
This example differs from example 1 only in that 7.5 parts of graphene, 3.75 parts of indium triflate and 3.75 parts of tin triflate are added.
Example 5
This example differs from example 1 only in that 9 parts of graphene, 3 parts of indium triflate and 3 parts of tin triflate are added.
Example 6
This example differs from example 1 only in that 3 parts of graphene, 6 parts of indium triflate and 6 parts of tin triflate are added.
Example 7
This example differs from example 1 only in that 10 parts of graphene, 2.5 parts of indium triflate and 2.5 parts of tin triflate are added.
Comparative example 1
A preparation method of safe and energy-saving high-boron silicon Low-E fireproof glass comprises the following steps:
S1, adding 30 parts of quartz sand, 10 parts of borax pentahydrate, 8 parts of boric acid, 5 parts of aluminum hydroxide, 40 parts of broken glass, 2 parts of sodium chloride, 0.5 part of indium oxide, 0.5 part of tin oxide, 2 parts of sodium silicate and 2 parts of magnesium silicate into a glass electric melting furnace, uniformly mixing, and melting for 7 hours at 1400 ℃ to obtain glass melt;
S2, drawing a glass melt into a tube by using a glass tube drawing machine, preserving heat at 600 ℃ in an annealing furnace for 60min, and naturally cooling to obtain a glass matrix;
S3, cutting the glass substrate, edging four edges of the glass substrate, washing the glass substrate by deionized water in a cleaning device, preheating the glass substrate at 500 ℃ for 10min, heat treating the glass substrate at 800 ℃ for 15min, quenching the glass substrate at 25kpa under the wind pressure for 60S, cooling the glass substrate at 20kpa under the wind pressure to 80 ℃, and naturally cooling the glass substrate to obtain the high-boron silicon Low-E fireproof glass.
Comparative example 2
This comparative example differs from example 1 only in that no graphene was added.
Comparative example 3
This comparative example differs from example 1 only in that no indium triflate was added.
Comparative example 4
This comparative example differs from example 1 only in that no tin triflate was added.
Performance test:
The high boron silicon Low-E fireproof glass obtained in examples 1-7 and comparative examples 1-4 was subjected to the fire resistance test method for building elements part 1 according to GB/T9978.1-2008: the method in general claim was used to determine the fire resistance integrity time and the visible light transmittance according to the method in GB/T2680-2021 "determination of visible light transmittance, solar direct transmittance, solar Total transmittance, ultraviolet transmittance and related glazing parameters" for architectural glass, the test results are shown in Table 1:
table 1 results of Performance test of high borosilicate Low-E fireproof glass obtained in examples 1 to 7 and comparative examples 1 to 4
In the invention, compared with the embodiment 1, the comparative example 1 does not coat a glass substrate, the comparative example 2 does not add graphene, the comparative example 3 does not add indium triflate and the comparative example 4 does not add tin triflate, and as a result, the fire resistance integrity time in the comparative examples 1-4 is shorter than that in the embodiment 1, the visible light transmittance is higher than that in the embodiment 1, which shows that the glass substrate is coated, and the graphene, the indium triflate and the tin triflate are adopted as raw materials of a coating layer, so that the fire resistance time of Low-E glass at high temperature can be improved, and the visible light transmittance can be reduced, thereby improving the fire resistance performance and the energy saving performance of the Low-E glass.
Compared with the embodiment 1, the embodiment 4-7 changes the mass ratio of graphene, indium triflate and tin triflate, and as a result, the fire resistance integrity time in the embodiment 6-7 is shorter than that in the embodiment 1 and the embodiment 4-5, and the visible light transmittance is higher than that in the embodiment 1 and the embodiment 4-5, which means that when the mass ratio of graphene, indium triflate and tin triflate is 1-3:1:1, the fire resistance time of the Low-E glass at high temperature can be further improved, the visible light transmittance can be reduced, the Low-E glass has excellent fire resistance and energy saving performance, and the fire resistance integrity time in the embodiment 4 is longer than that in the embodiment 1 and the embodiment 5, and the visible light transmittance is lower than that in the embodiment 1 and the embodiment 5, which means that when the mass ratio of graphene, indium triflate and tin triflate is 2:1:1, the fire resistance time of the Low-E glass at high temperature can be further improved, the visible light transmittance can be reduced, and the fire resistance performance and the energy saving performance of the Low-E glass can be further improved.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the invention.

Claims (9)

1. The safe energy-saving high-boron silicon Low-E fireproof glass is characterized by comprising a glass substrate and a coating layer on the outer surface of the glass substrate;
The coating layer is formed by sputtering a solid target material onto a glass substrate through a vacuum magnetron sputtering method;
the solid target comprises the following raw materials: graphene, indium triflate, and tin triflate.
2. The safe and energy-saving high-boron silicon Low-E fireproof glass according to claim 1, wherein the solid target comprises the following raw materials in parts by weight: 3-10 parts of graphene, 2-6 parts of indium triflate and 2-6 parts of tin triflate.
3. The safe and energy-saving high-boron silicon Low-E fireproof glass disclosed by claim 1 is characterized in that the mass ratio of graphene to indium triflate to tin triflate is 1-3:1:1.
4. The safe and energy-saving high-boron silicon Low-E fireproof glass according to claim 1, wherein the preparation method of the solid target material comprises the following steps: and uniformly mixing graphene, indium triflate and tin triflate to obtain the solid target.
5. The safe and energy-saving high-boron silicon Low-E fireproof glass according to claim 1, wherein the glass substrate comprises the following raw materials in parts by weight: 30-35 parts of quartz sand, 10-15 parts of borax pentahydrate, 8-10 parts of boric acid, 5-8 parts of aluminum hydroxide, 40-50 parts of broken glass, 2-4 parts of sodium chloride, 0.5-1 part of indium oxide, 0.5-1 part of tin oxide, 2-4 parts of sodium silicate and 2-4 parts of magnesium silicate.
6. The safe and energy-saving high-boron silicon Low-E fireproof glass according to claim 1, wherein the preparation method of the glass matrix comprises the following steps:
a1, uniformly mixing the raw materials of the glass matrix components, and melting to obtain glass melt;
a2, molding the glass melt to obtain the glass matrix.
7. The method for preparing the safe and energy-saving high-boron silicon Low-E fireproof glass according to claim 1, which is characterized by comprising the following steps:
s1, sputtering a solid target material onto a glass substrate by a vacuum magnetron sputtering method to obtain coated glass;
s2, cutting the coated glass, treating the four sides of the coated glass, and washing and tempering to obtain the high-boron silicon Low-E fireproof glass.
8. The method for preparing the safe and energy-saving high-boron-silicon Low-E fireproof glass according to claim 7, wherein the step S2 is to cut the coated glass, treat four sides of the coated glass, wash the coated glass, and then sequentially perform preheating treatment, heat treatment, quenching, cooling treatment and cooling to obtain the high-boron-silicon Low-E fireproof glass.
9. The preparation method of the safe and energy-saving high-boron silicon Low-E fireproof glass according to claim 8, wherein the temperature of the heat treatment is 800-850 min, and the time of the heat treatment is 10-15 min.
CN202410185233.7A 2024-02-19 2024-02-19 Safe energy-saving high-boron silicon Low-E fireproof glass Pending CN118026542A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202410185233.7A CN118026542A (en) 2024-02-19 2024-02-19 Safe energy-saving high-boron silicon Low-E fireproof glass

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202410185233.7A CN118026542A (en) 2024-02-19 2024-02-19 Safe energy-saving high-boron silicon Low-E fireproof glass

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