CN116969674A - Float color glass and preparation method and application thereof - Google Patents

Float color glass and preparation method and application thereof Download PDF

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Publication number
CN116969674A
CN116969674A CN202311225735.XA CN202311225735A CN116969674A CN 116969674 A CN116969674 A CN 116969674A CN 202311225735 A CN202311225735 A CN 202311225735A CN 116969674 A CN116969674 A CN 116969674A
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China
Prior art keywords
glass
melting
less
cooling
color glass
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CN202311225735.XA
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Chinese (zh)
Inventor
孙立群
鲁大学
马玉聪
孟庆瑞
董淑娟
刘卫东
张欣
王贤
郭振
李彩苓
张元�
王超
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China Yaohua Glass Group Corp
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China Yaohua Glass Group Corp
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Priority to CN202311225735.XA priority Critical patent/CN116969674A/en
Publication of CN116969674A publication Critical patent/CN116969674A/en
Pending legal-status Critical Current

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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
    • C03C4/00—Compositions for glass with special properties
    • C03C4/08—Compositions for glass with special properties for glass selectively absorbing radiation of specified wave lengths
    • C03C4/085—Compositions for glass with special properties for glass selectively absorbing radiation of specified wave lengths for ultraviolet absorbing glass
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B18/00—Shaping glass in contact with the surface of a liquid
    • C03B18/02—Forming sheets
    • C03B18/20—Composition of the atmosphere above the float bath; Treating or purifying the atmosphere above the float bath
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B5/00—Melting in furnaces; Furnaces so far as specially adapted for glass manufacture
    • C03B5/16—Special features of the melting process; Auxiliary means specially adapted for glass-melting furnaces
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B5/00—Melting in furnaces; Furnaces so far as specially adapted for glass manufacture
    • C03B5/16—Special features of the melting process; Auxiliary means specially adapted for glass-melting furnaces
    • C03B5/18—Stirring devices; Homogenisation
    • C03B5/193—Stirring devices; Homogenisation using gas, e.g. bubblers
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B5/00—Melting in furnaces; Furnaces so far as specially adapted for glass manufacture
    • C03B5/16—Special features of the melting process; Auxiliary means specially adapted for glass-melting furnaces
    • C03B5/235—Heating the glass
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B5/00—Melting in furnaces; Furnaces so far as specially adapted for glass manufacture
    • C03B5/16—Special features of the melting process; Auxiliary means specially adapted for glass-melting furnaces
    • C03B5/235—Heating the glass
    • C03B5/2353—Heating the glass by combustion with pure oxygen or oxygen-enriched air, e.g. using oxy-fuel burners or oxygen lances
    • 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
    • C03C1/04—Opacifiers, e.g. fluorides or phosphates; Pigments
    • 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
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
    • C03C3/085—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal
    • C03C3/087—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal containing calcium oxide, e.g. common sheet or container glass

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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)
  • Combustion & Propulsion (AREA)
  • Glass Compositions (AREA)

Abstract

The invention provides float color glass and a preparation method and application thereof, wherein the preparation raw materials of the float color glass comprise the following components in percentage by mass: siO (SiO) 2 64%~77%，Al 2 O 3 0.4%~3%，CaO 7%~12%，MgO 1%~7%，Na 2 O 12%~16%，Fe 2 O 3 0.05 to 1 percent, 0.1 to 1 percent of colorant and 0.1 to 0.6 percent of clarifier%，NaNO 3 0.5%; the float color glass provided by the invention has the advantages of lower iron content, reasonable component collocation, better energy saving and infrared and ultraviolet resistance effects, visible light transmittance of less than 30%, total infrared (780-2500 nm) heat energy transmittance of less than 50%, ultraviolet transmittance of less than 50%, shielding coefficient of less than 0.69, and shielding coefficient of less than 0.9 of common glass, and good application prospect.

Description

Float color glass and preparation method and application thereof
Technical Field
The invention relates to the technical field of glass, in particular to float color glass and a preparation method and application thereof.
Background
Energy-saving glass is generally heat-insulating and heat-preserving, and is classified into heat-absorbing glass, heat-reflecting glass, low-emissivity glass, hollow glass, vacuum glass, common glass and the like.
The heat absorbing glass is a flat glass capable of absorbing solar energy, and the glass selectively absorbs the solar energy by utilizing metal ions in the glass and presents different colors. Some laminated glass sheets are also doped with specific metal ions, and heat absorbing laminated glass can be produced by using the sheets. The heat absorption glass can generally reduce 20% -30% of solar heat energy entering a room, and reduces air conditioning load. The heat absorbing glass has the characteristics of lower shielding coefficient, lower total solar transmittance, lower direct solar transmittance and lower direct solar reflectance, and the visible light transmittance and the color of the glass can be changed according to the composition and concentration of metal ions in the glass. The visible light reflectance, heat transfer coefficient and emissivity are not much different from those of common glass.
JP3669019B2 discloses a dark gray glass, the coloring component comprising 0.8 to 1.4% by weight of Fe 2 O 3 (total iron), feO of 0.21 wt% or less, tiO of 0.05 to 0.095 wt% 2 0.0005 to 0.015 wt% Se and 0.02 to 0.05 wt% CoO, wherein the visible light transmittance (Lta) is 20% or less, the solar radiation transmittance is 30% or less, and the ultraviolet transmittance is 10% or less based on the glass thickness of 5.0 mm.
CN200480007732.8 discloses a neutral gray glass composition for automotive vision panels having low transmission color shift characteristics, which comprises 0.30 to 0.75% by weight of Fe as the main colorant 2 O 3 (total iron), 0-15 ppm CoO and 1-15 ppm Se, wherein the glass composition is substantially free of nickel, and has a visible light transmittance (Lta) of at least 65% based on a glass thickness of 3.9mm, which is obviously unsatisfactory for privacy protection.
CN201480004129.8 discloses a dark green gray low transmission glass composition comprising 1.3 to 2 parts by weight of total Fe for 100 parts by weight of base glass 2 O 3 0.0222 to 0.0280 part by weight of CoO, 0.002 to 0.0035 part by weight of Se, and 0.01 to 0.04 part by weight of Cr 2 O 3 As a coloring component, no TiO is contained 2 The weight ratio of (CoO+Cr2O3) Se is 13-20, and the weight ratio of CoO to Cr is as follows 2 O 3 The glass has a visible Light Transmittance (LTA) of 15% or less, a solar energy transmittance (Te) of 16% or less, and an ultraviolet light transmittance (Tuv) of 3% or less, based on a glass thickness of 4mm, in a weight ratio of 1.2 to 1.8.
CN103380093B discloses a dark privacy glass, a vehicle sunroof, comprising an uncoated glass transparency with Lta in the range of more than 0% to 10% and solar factor in the range of 30% or less. The visible light transmittance ("Lta") of the glass was observed at 2 degrees using a c.i.e. illuminant aThe detector is greater than 0% and equal to or less than 15% at a glass thickness of 3.9mm and at a wavelength range of greater than 380nm to less than 780 nm. The soda lime silica matrix colorant portion includes, but is not limited to, fe 2 O 3 More than or equal to 0.95 percent; feO is more than or equal to 0.5 percent CoO is more than 0.03 percent; the redox ratio is equal to or greater than 0.5%.
CN100418912C discloses a gray privacy glass with strong ultraviolet and infrared absorption, which is a neutral color plate glass with a visible light transmittance of less than 30%, which is obtained by adding ferric oxide (Fe 2 O 3 ) Cobalt oxide (CoO), selenium (Se) and optionally nickel oxide (NiO) 2 ) The weight percentage of ferric oxide in the produced glass is 1.0-1.6%, the weight percentage of cobalt oxide is 150-200 ppm, the weight percentage of total selenium is 30-80 ppm, and the weight percentage of nickel oxide is 0-100 ppm.
CN108025954B discloses an ultraviolet-absorbing glass article suitable as a green-colored glass for vehicles (particularly, for automobiles). An ultraviolet-absorbing glass article, wherein the basic composition of glass, expressed in mass% on an oxide basis, comprises: wherein the ultraviolet-absorbing glass article having a plate thickness of 3.5mm has a visible light Transmittance (TVA) of 10% or more and 28% or less based on a standard a light source, and has a plate thickness of 3.5mm, and is produced by ISO13837: the ultraviolet transmittance (TUV 400) specified in 2008 convention a is 5% or less. 0.8% or more and less than 2.4% of Fe 2 O 3 Represented total iron, and greater than 1% and less than or equal to 5% TiO 2 Cr as a glass base composition 2 O 3 Is less than 0.04%. Se is 0.0001-0.004%. TiO (titanium dioxide) 2 0.1 to 3 percent. CoO is 0.014% -0.04%.
Most of the prior colored glass uses iron with too high content and is difficult to melt by using a common melting furnace, and certain high-end household appliance glass also needs a specific color after heat treatment, but the prior glass has the defects that the color and the performance after heat treatment do not meet the requirements of high-end household appliances on one hand, and the melting difficulty cannot meet the requirements of high-quality glass on the other hand. Therefore, how to develop a novel color glass has important significance for further application, especially application in the field of household appliances.
Disclosure of Invention
The invention aims to solve the technical problems that the existing colored glass has higher iron content and is difficult to melt in a melting furnace.
In order to solve the technical problems, the invention provides float color glass, which is characterized by comprising the following raw materials in percentage by mass:
SiO 2 64%~77%，Al 2 O 3 0.4%~3%，CaO 7%~12%，MgO 1%~7%，Na 2 O 12%~16%，Fe 2 O 3 0.05-1%, colorant 0.1-1%, clarifier 0.1-0.6%, naNO 3 0.5%。
The float color glass provided by the invention has low iron content, and has the effects of better energy saving, infrared and ultraviolet resistance by reasonably matching the components through adding the colorant, wherein the visible light transmittance is less than 30%, the total infrared (780-2500 nm) heat energy transmittance is less than 50%, the ultraviolet transmittance is less than 50%, the shielding coefficient is less than 0.69, less than 0.9 of common glass, the shielding coefficient is lower, the less sunlight is transmitted, the appearance is neutral gray, the fashion is advanced, and the atmosphere is stable.
Preferably, the clarifying agent is Na 2 SO 4 。
Preferably, the colorant comprises Fe 2 O 3 、CoO、Cr 2 O 3 、MnO 2 、Se、V 2 O 3 Or Nd 2 O, or a combination of at least two.
Cobalt is stable in coloration and is often Co in glass 2+ The cobalt present in soda lime silica glass is essentially unchanged in valence. When the glass is mixed with coloring agents such as chromium, manganese and the like for coloring, green, purple and black glass with uniform color tone can be obtained.
The color appearance of the chromium sample is green, cr 3+ There is an absorption band at 650nm and Cr6+ has a strong absorption band in the ultraviolet 365 nm.
Iron is inexpensive and there are two values in glassState of Fe 2+ And Fe (Fe) 3+ ，Fe 3+ Three weak absorption bands, fe, are respectively arranged at 380nm, 420nm and 435nm 2+ There is one absorption band at 1050nm and one absorption band at 2050nm to 2200nm, so iron can absorb both ultraviolet rays and infrared rays.
Selenium exists in glass in different valence states and exists in the state of simple substance selenium under the neutral melting condition. A pale purple color is produced which appears purer and more beautiful under oxidizing conditions.
Vanadium can form V in glass 3+ 、V 5+ In two valence states, under normal conditions, V in glass 3+ Vanadium oxides exist for making ultraviolet and infrared absorbing glasses, the glass color being between yellow and yellow-green.
The color glass provided by the invention has the color which is adjustable among gray, gray blue and gray green.
The invention also provides a preparation method of the float color glass, which comprises the following steps:
s1, mixing a preparation raw material and a colorant, and melting to obtain glass liquid;
s2, cooling the molten glass obtained in the step S1, and forming to obtain a glass sheet;
and S3, annealing and cutting the glass sheet cooled and formed in the step S2 to obtain the float color glass raw sheet, and performing heat treatment to obtain the float color glass.
In the actual preparation process, the carbon powder can be stopped by using proper sodium nitrate, and the volatile content in the silica sand needs to be controlled.
Preferably, the volatile component in the silica sand of the mixed preparation raw material in the step S1 is less than 0.3%.
Preferably, the melting in step S1 is performed in a kiln as described below.
The kiln comprises an upper structure 1, a melting part 2 and a cooling part 3, wherein the upper structure 1 and the melting part 2 are of two relatively independent upper and lower structures, the melting part 2 is connected with the cooling part 3 through a neck, the melting part 2 is provided with a 0# oxygen gun 4 and a natural gas spray gun, the bottom of the melting part 2 is provided with an electric heating device 5, and the inside of the melting part 2 is provided with a bubbler 6; a preformed hole 7 is arranged on the periphery of the melting part 2; a stirrer and an immersed water drum 8 are arranged at the joint of the channel of the melting part 2 and the cooling part 3; the cooling part 3 is provided with a hot air device 9;
the batch is melted in the melting part 2 through the full oxygen lance 4, the natural gas spray gun and the electric heating device 5 to form glass liquid, then the bubble is clarified and eliminated through the bubbler 6 and the preformed hole 7 in advance before the hot spot, the bubbles are further clarified and absorbed along with the reduction of the temperature after the hot spot reaches the neck stage, and finally the homogenization and cooling process of the glass liquid is finished at the neck position through the stirrer, the common water drum, the immersed water drum 8, the cooling part 3, the dilution wind and the hot air device 9.
The use of the complete set of special melting equipment ensures the quality of glass, and simultaneously ensures the stability of the color of the glass by controlling the chemical oxygen demand of raw materials, the melting atmosphere and the tin bath atmosphere.
In the invention, a 0# full oxygen gun is used at the front area of the melting part, and two rows of bubblers are used for introducing gas in the melting and clarifying stage.
In the invention, the 0# oxygen lance 4 is fluxing, so that the melting rate of the batch material can be enhanced. The electric heating device 5 can raise the temperature of the glass liquid at the bottom, overcome the problem of poor heat permeability of the glass liquid and accelerate the melting. The bubbler 6 can accelerate the convection circulation of the molten glass up and down and back and forth.
The temperature in the kiln is 1450-1600 ℃, for example, 1450 ℃, 1500 ℃, 1550 ℃ or 1600 ℃.
The complete equipment provided by the invention can ensure the requirement of high-quality glass, and the quality and the production efficiency of the produced glass can not meet the requirement of high-quality glass by applying other equipment.
Preferably, in step S1, the mixed raw materials and colorant are fluxing through oxygen lance 4, electric heating device 5 and bubbler 6, defoaming through preformed hole 7, and finally hot air is sprayed on cooling part 3 through stirrer and immersed water drum 8 by hot air device 9 to obtain glass liquid.
Two rows of electric heating are used at the bottom of the pool in the front zone of the melting part of the melting furnace. And a defoaming agent is used in a foam area of the melting furnace, an immersed water drum is used in a neck part of the melting furnace, hot air is used in a cooling part of the melting furnace, and the final required color is achieved after the product is subjected to heat treatment.
The cooling part 3 uses hot air to solve the problem of glass zebra angle caused by the excessively low surface temperature of the glass liquid.
Meanwhile, the invention ensures the color of glass by controlling flame atmosphere in the front region of the melting furnace, weak reducing atmosphere in the front region of the melting part 2, neutral hot spot atmosphere and oxidizing atmosphere in the clarifying part.
Preferably, the cooling temperature in step S2 is 1050 to 1200 ℃, for example, 1050 ℃, 1100 ℃, 1150 ℃, 1200 ℃, and the like.
Preferably, the molding in the step S2 is performed in a tin bath, and the hydrogen content in the tin bath is 2% -5%, for example, may be 2%, 3%, 4%, 5%, etc.
And (5) feeding the glass plate with the temperature of about 620 ℃ out of a tin bath into an annealing kiln for annealing to obtain the energy-saving float color glass raw sheet. Cutting the glass into fixed sizes, and putting the glass into a tempering furnace for secondary heat treatment to obtain the final required color.
The invention also provides application of the float color glass in household appliances.
The color glass provided by the invention has beautiful color which is neutral light gray popular at present, has certain infrared and ultraviolet resistance and energy conservation, is especially suitable for the field of household appliances, and can meet the application requirements of high-end products.
The implementation of the invention has the following beneficial effects:
the float color glass provided by the invention has low iron content, and has the advantages of better energy-saving and infrared and ultraviolet resistance effects by reasonably matching the components through adding the colorant, wherein the visible light transmittance is less than 30%, the total infrared (780-2500 nm) heat energy transmittance is less than 50%, the ultraviolet transmittance is less than 50%, the shielding coefficient is less than 0.69 and is far less than 0.9 of common glass, and the lower the shielding coefficient, the less transmitted sunlight has better energy-saving effect, the appearance of the glass is neutral gray, high-grade fashion and stable atmosphere.
Drawings
FIG. 1 is a plan view of a kiln plant for producing colored glass, 1-superstructure, 2-melting section, 3-cooling section, 4-oxygen lance, 5-electric heating device, 6-bubbler, 7-pre-orifice, 8-submerged water drum, 9-hot air device.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled 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 process of preparing the color glass, the raw material SiO is used 2 Can be composed of SiO 2 Is introduced, for example, by silica sand. Al (Al) 2 O 3 The method can be introduced from feldspar, calcium oxide from limestone, magnesium oxide from dolomite and sodium oxide from sodium carbonate, and the volatile components in sandstone are less than 0.3% in order to ensure the chemical oxygen demand of the raw materials.
The equipment diagram of the color glass produced by the invention is shown in fig. 1: comprises a superstructure 1, a melting part 2, a cooling part 3, an oxygen lance 4, an electric heating device 5, a bubbler 6, a preformed hole 7, an immersed water drum 8 and a hot air device 9.
The raw materials for preparation provided in the following examples of the present invention were prepared by the following methods to obtain shaped colored glasses.
Weighing the components according to the formula, fully mixing the components to obtain a mixture, conveying the mixture to a kiln head stock bin through a conveying mechanism, adding the mixture into a kiln melting part 2 through a feeder, and heating a combustion system arranged on the side surface of an upper structure 1 to 1450-1600 ℃ to melt molten glass: in order to accelerate the melting rate of the batch, a 0# oxygen gun 4 is needed, and a natural gas gun can be arranged at the same time to help the batch to melt; an electric heating device 5 at the bottom of the tank furnace is needed to ensure the melting quality so as to raise the temperature of the glass liquid at the bottom and overcome the problem of poor heat permeability of the glass liquid to accelerate the melting; the bubbler 6 at the hot spot is needed to be used for fluxing in order to ensure the melting quality, so that the convection circulation of the molten glass up and down and front and back is accelerated, and the temperature of the lower molten glass at the bottom can be increased; in order to ensure the clarification quality and solve the bubble problem, a defoaming agent is required to be used, and is sprayed into a foam area in the kiln from a 5# small furnace preformed hole 7 by using a special spray gun; in order to solve the problem of the glass zebra angle, a stirrer and an immersed water drum 8 are needed to be used at the neck of the melting furnace, and a hot air device 9 is used at a cooling part to solve the problem of the glass zebra angle caused by the excessively low surface temperature of glass liquid; in order to ensure the color of the glass, the flame atmosphere in the front area of the melting furnace needs to be controlled, and the weak reducing atmosphere in the front area of the melting part, the neutral hot spot atmosphere and the oxidizing atmosphere in the clarifying part need to be controlled;
and cooling the molten glass to 1050-1200 ℃ through a cooling part 3, then entering a tin bath for molding, and controlling the hydrogen content of the tin bath to be 2-5%. And cooling the formed glass plate to about 620 ℃ in a tin bath, discharging the glass plate from the tin bath, and entering an annealing kiln for annealing to obtain the energy-saving float color glass raw sheet. Cutting the glass into fixed sizes, and putting the glass into a tempering furnace for secondary heat treatment to obtain the final required color.
Example 1
The embodiment provides a colored glass, which comprises the following preparation raw materials in percentage by mass:
Al 2 O 3 1%，CaO 8.3%，MgO 4.2%，Na 2 O 14%，Na 2 SO 4 0.54%，NaNO 3 0.5%， Fe 2 O 3 0.62%, colorant: coO 330ppm, mnO 2 410ppm、Cr 2 O 3 420ppm、Se 30ppm、V 2 O 3 360ppm, the balance of SiO 2 。
Example 2
The embodiment provides a colored glass, which comprises the following preparation raw materials in percentage by mass:
Al 2 O 3 1%，CaO 8.3%，MgO 4.2%，Na 2 O 14%，Na 2 SO 4 0.54%，NaNO 3 0.5%，Fe 2 O 3 0.6%, colorant: coO 220ppm, mnO 2 350ppm、Cr 2 O 3 400ppm、Se 50 ppm、V 2 O 3 370ppm, the balance of SiO 2 。
Example 3
The embodiment provides a colored glass, which comprises the following preparation raw materials in percentage by mass:
Al 2 O 3 1%，CaO 8.3%，MgO 4.2%，Na 2 O 14%、Na 2 SO 4 0.54%，NaNO 3 0.5%，Fe 2 O 3 0.62%, colorant: coO 250ppm, mnO 2 400ppm、Cr 2 O 3 470ppm、Se 25ppm、V 2 O 3 350ppm, the balance being SiO 2 。
Example 4
The embodiment provides a colored glass, which comprises the following preparation raw materials in percentage by mass:
Al 2 O 3 2%，CaO 7%，MgO 7%，Na 2 O 12%，Na 2 SO 4 0.5%，NaNO 3 0.5%，Fe 2 O 3 0.5%, colorant: coO 310ppm, mnO 2 400ppm、Cr 2 O 3 400ppm、Se 25ppm、V 2 O 3 350ppm, the balance being SiO 2 。
Example 5
The embodiment provides a colored glass, which comprises the following preparation raw materials in percentage by mass:
Al 2 O 3 3%，CaO 12%，MgO 1%，Na 2 O 16%，Na 2 SO 4 0.1%，NaNO 3 0.5%，Fe 2 O 3 0.4%, colorant: coO 280ppm, mnO 2 350ppm、Cr 2 O 3 440ppm、Se 40ppm、V 2 O 3 330ppm, the balance of SiO 2 。
Example 6
This example differs from example 1 in that Fe in this example 2 O 3 The mass percentage of (2) is 1.2%.
Example 7
This example differs from example 1 in that Fe in this example 2 O 3 Is 0.08% by mass.
Comparative example 1
The present comparative example differs from example 1 in that the present comparative example does not include a colorant.
Comparative example 2
The difference between this comparative example and example 1 is that this comparative example does not include NaNO 3 。
Comparative example 3
The difference between this comparative example and example 1 is that this comparative example does not include a clarifying agent.
The color glasses prepared in the above examples and comparative examples were subjected to performance test, and the analytical reference standard was ISO9050:2003, the test method is to use uv-3150 ultraviolet-visible spectrophotometer to obtain data, and calculate optical parameters by converting the scan data to 3.9mm thickness using the formula, and the results are shown in table 1 below. Wherein T is visible light transmittance, and L, a, and b represent three coordinate axes of the three-dimensional color model. L is the brightness coordinate axis of the color; a is a red-green chromaticity coordinate axis, a is "+" represents red, and a is "-" represents green; b is yellow Lan Sedu coordinate axis, b is "+" represents yellow, and b is "-" represents blue. T solar (direct solar transmittance 300-2500 nm), T infrared (total solar heat transmittance 780-2500 nm), T ultraviolet (total ultraviolet transmittance 280-380 nm), and shielding coefficient (the ratio of the amount of solar radiation energy transmitted through window glass to the amount transmitted through transparent glass with the same area and 3 mm).
TABLE 1
Through comparison tests, the chromaticity coordinates of the examples 1, 2, 3, 4 and 5 are obviously changed before and after tempering; the reduction of FE2O3 in examples 4 and 5 requires an increase in the amount of other colorants, which is not cost-effective; fe in example 6 2 O 3 Is 1.2% by mass of which the color is substantially opaque to black; fe in example 7 2 O 3 When the mass percentage is 0.08%, the visible light transmittance is increased, and the color is lighter; in comparative example 1, after no colorant was added, the product was colorless and unsuitable for further use; in comparative example 2, the absence of sodium nitrate has an effect on color, mainly on change of valence of transition metal ion due to oxidation-reduction of raw materialThe quality and the color of the produced glass are affected; the addition of no mirabilite in comparative example 3 had a slight effect on the optical coefficient but the microbubbles increased much of the mass deterioration.
The experiment result shows that the colored glass provided by the invention has reasonable component collocation, has good performance after being produced in the designed complete equipment, has special color applied to household appliances, and has good application prospect.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and are not limiting; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims (10)

1. The float color glass is characterized by comprising the following raw materials in percentage by mass:
SiO 2 64%~77%，Al 2 O 3 0.4%~3%，CaO 7%~12%，MgO 1%~7%，Na 2 O 12%~16%，Fe 2 O 3 0.05-1%, colorant 0.1-1%, clarifier 0.1-0.6%, naNO 3 0.5%。
2. The float color glass of claim 1, wherein the fining agent is Na 2 SO 4 。
3. The float color glass of claim 1, wherein the colorant comprises Fe 2 O 3 、CoO、Cr 2 O 3 、MnO 2 、Se、V 2 O 3 Or Nd 2 O, or a combination of at least two.
4. A method of producing float color glass according to any one of claims 1 to 3, comprising the steps of:
s1, mixing a preparation raw material and a colorant, and melting to obtain glass liquid;
s2, cooling the molten glass obtained in the step S1, and forming to obtain a glass sheet;
and S3, annealing and cutting the glass sheet cooled and formed in the step S2 to obtain the float color glass raw sheet, and performing heat treatment to obtain the float color glass.
5. The method according to claim 4, wherein the volatile content of silica sand is less than 0.3% in the mixed raw materials in step S1.
6. The method according to claim 4, wherein the melting in step S1 is performed in a kiln;
the kiln comprises an upper structure (1), a melting part (2) and a cooling part (3), wherein the upper structure (1) and the melting part (2) are of two relatively independent upper and lower structures, the melting part (2) is connected with the cooling part (3) through a neck, the melting part (2) is provided with an oxygen gun (4), the bottom of the melting part (2) is provided with an electric heating device (5), and the inside of the melting part (2) is provided with a bubbler (6); a preformed hole (7) is arranged on the periphery of the melting part (2); a stirrer and an immersed water drum (8) are arranged at the joint of the channel of the melting part (2) and the cooling part (3); the cooling part (3) is provided with a hot air device (9);
the batch is melted in the melting part (2) through a full oxygen gun (4), a natural gas spray gun and an electric heating device (5) to form glass liquid, then the batch is clarified and bubble eliminated preliminarily through a bubbler (6) and a reserved hole (7) before a hot spot, the batch is clarified further until a neck clamping stage after the hot spot and the absorption of tiny bubbles is completed along with the reduction of temperature, and finally the homogenization and cooling process of the glass liquid is completed at the neck clamping position through a stirrer, a common water drum, an immersed water drum (8) and a cooling part (3) dilution air and hot air device (9).
7. The method according to claim 6, wherein the temperature in the kiln is 1450-1600 ℃.
8. The method according to claim 4, wherein the cooling temperature in step S2 is 1050-1200 ℃.
9. The method according to claim 4, wherein the molding in step S2 is performed in a tin bath having a hydrogen content of 2% -5%.
10. Use of float color glass according to any one of claims 1-3 in an appliance.
CN202311225735.XA 2023-09-22 2023-09-22 Float color glass and preparation method and application thereof Pending CN116969674A (en)

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