RU2696742C1 - Blue glass and a method for production thereof - Google Patents

Abstract

FIELD: manufacturing technology.

SUBSTANCE: invention relates to blue glass. Blue glass contains the following components, wt%: SiO₂ – 65.0–75.0; Al₂O₃ – 0.9–5.0; CaO – 7.0–10.0; MgO – 3.0–5.0; K₂O – 0.3–0.6; Na₂O – 13.0–20.0; SO₃ – 0.2–0.4; Fe₂O₃ (total iron) – 0.65–0.95; FeO – 0.15–0.33; CoO – 0.003–0.03; Se – 0–0.011; Redox glass is within 0.23–0.35. Following components are introduced into the mixture for producing blue glass, kg/1 t of glass mass: iron oxide – crocus 2.5–4.5, iron powder 2.5–4.5, sodium nitrate NaNO₃ 3.5–5.0, sodium sulphate 5.0–8.0, where NaNO₃+NaCI+Na₂SO₄=11.0–13.0; Na₂SO₄:(NaNO₃+NaCI)=1:(0.7–1.3). Glass has a thickness of – 5 mm dominant wavelength (λ_DW,) in range of 480–489 nm, purity of color (C) – 7.0–12.0, optical and energy parameters, respectively, within the limits of, %: LTA – 30–70; TSUV – 29–41; TSIR – 20–33; TSET – 27–48.

EFFECT: obtaining blue sheet glass with lighting and power parameters, which provide improved comfort inside glazed spaces.

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Description

1. The technical field

The alleged invention relates to the glass industry, to the composition of the blue sheet glass, tinted in bulk, for land vehicles and construction.

2. The level of technology

Various compositions of blue glasses with different light transmission and absorption in the infrared and ultraviolet spectral ranges are known from the prior art as applied mainly to the float method for their preparation. For dyeing the glass blue, dyes are used that create corresponding dye centers in the glass caused by absorption bands in the wavelength range of the solar spectrum of 380-2500 nm. As the main dyes, mainly iron oxides (Fe ₂ O ₃ , FeO), cobalt (CoO) are patented. When using individual dyes, it is difficult to obtain blue glass with predetermined lighting characteristics. Therefore, to modify the primary color, additional coloring components are used that correct the optical properties of the glass by shifting the absorption bands in some parts of its spectrum. As additional dyes, oxides are used: CuO, Nd ₂ O ₃ , Cr ₂ O ₃ , TiO ₂ , WO ₃ , V ₂ O ₅ , CeO ₂ , NiO and others in various combinations.

The multicomponent composition of the dyes used complicates the technology for producing blue glasses with good reproducibility of the given optical, lighting and energy characteristics of the glass, especially when using dyes with variable valency, such as oxides of manganese, copper, chromium, etc. The spectral properties of glass containing several coloring components are the result of complex interactions between them and depend mainly on its redox coefficient (Redox) and on the presence of other compounds.

Therefore, in the specific claimed variants of the compositions of blue glass and methods for their preparation, it is required to find the appropriate ratio between the main and additional coloring components to obtain glass with desired properties. In addition, it is necessary to take into account the influence of some components of the basic (main) composition of glass and the redox conditions of glass melting on its characteristics. To regulate Redox, oxidizing agents, for example, sodium sulfate, sodium nitrate and reducing agents, such as carbon, and others, and, if necessary, special methods for their input in the process of glass melting, are used.

As a rule, to obtain blue glasses with different light transmission and various lighting and energy characteristics, basic compositions and their own set of dyes and substances that regulate redox cooking conditions are declared.

So, in US patent 4792536, IPC CO3C 3/087, obtaining blue glass with high light transmission (not less than 65%) is carried out only due to the high content of FeO - up to 40% with a total content of iron oxide of less than 0.65%. Preservation of reducing conditions during the glass melting process is achieved by additional supply of iron-containing, carbon-containing materials using special devices. Glass has a dominant wavelength of 486-489 nm, a color purity of 8-14%, transmission in the infrared region of more than 15%. The main disadvantage of the proposed method is the technologically difficult implementation of maintaining the reducing conditions in the furnace throughout the entire process of glass melting.

In the patent of the Russian Federation 2329959, IPC CO3C 3/087, SOZS 4/02, to obtain dark-colored float glass of a blue-green shade with a light transmission, preferably 20-50%, the glass contains the following coloring substances: Fe ₂ O ₃ (total iron) 1.2-1.85%, FeO 0.4-0.52%, CoO 0.002-0.013%, Cr ₂ O ₃ 0.0005-0.0295%, V ₂ O ₅ O 0-0.095%, Se 0 - 0-0014% (weight). In addition, it additionally contains one of the oxides of titanium, cerium, manganese. Glass has a dominant wavelength in the range of 480-520 nm, color purity more than 9% and Redox less than 0.35 with a thickness of 4 mm. The disadvantage of this invention is the multicomponent used dyes, which complicates the technological process of manufacturing glass with good reproducibility of the given lighting, optical and energy characteristics of the glass. In particular, Cr ₂ O ₃ is a high-intensity dye, its removal from glass is carried out with great difficulty and complicates technological transitions with a change in color. In addition, Cr ₂ O ₃ together with FeO reduce the thermal transparency of the glass melt.

Closest to the alleged invention is blue tinted glass according to the patent of the Russian Federation 2214975, IPC SOZS Z / 087, SOZS 4/02. This patent claims a blue glass composition, based on the base composition, wt. %:

SiO ₂ - 66-75 Na ₂ O - 10-20 Cao - 5-15 MgO - 0-5 Al ₂ O ₃ - 0-5 K ₂ O - 0-5

and dyes taken in the following amounts:

Fe ₂ O ₃ (total iron) 1-2 wt. % FeO 0.15-0.65 wt. % Coo 90-250 ppm TiO ₂ 0-0.9 wt. % MnO2 - up to 39 ppm

The glass has a light transmittance (LTA) of 35 to 60%, the total solar ultraviolet radiation (TSUV) transmittance is less than 35%, the total solar infrared transmittance (TSIR) is less than or equal to 25%, and the total solar transmittance is (TSET) - less than or equal to 40% for glass with a thickness of 4.06 mm. Glass is characterized by a dominant wavelength from 480-489 nm and a color purity of at least 8%. Redox is 0.15-0.40, preferably 0.20-0.35. The disadvantage of the claimed invention is the use of dyes that impede the technological process of manufacturing glass with good reproducibility of the specified parameters. So the oxidizing properties of MnO ₂ can reduce the degree of reduction of iron and thereby reduce the selectivity of the glass, giving it a purple tint. The high content of total iron in the glass (more than 1%) makes it difficult to control the degree of reduction of iron oxide with its high total content in the glass mass, reduces the thermal transparency of the glass mass, and thereby complicates the process of glass melting.

3. Disclosure of the invention.

The technical task of the alleged invention is to obtain blue glass for transport and construction based on the basic compositions of sheet glass with a limited set of dyes and directional regulation of the method for its production.

The technical result of the proposed invention is to obtain blue sheet glass of various saturations, with a wide range of light transmission with lighting and energy parameters, providing improved comfort inside glazed spaces.

The essence of the alleged invention is that blue glass containing the following components, wt. %:

SiO ₂ - 65.0-75.0 Al ₂ O ₃ - 0.9-5.0 CaO - 7.0-10.0 MgO - 3.0-5.0 K ₂ O - 0.3-0.6 Na ₂ O - 13.0-20.0 SO ₃ - 0.2-0.4 Fe ₂ O ₃ (total iron) - 0.65-0.95 FeO - 0.15-0.33 Soo - 0.003-0.03 Se - 0-0.011,

and having a dominant wavelength (λ _DW ,) of 5 mm thickness within the range of 480-489 nm, color purity (H) of 7.0-12.0, optical and energy parameters, respectively, in the range of (%): LTA - 30-70; TSUV - 29-41; TSIR - 20-33, TSET 27-48, and Redox glass in the range 0.23-0.35 obtained by cooking the mixture with subsequent production by introducing iron oxide - crocus, metallic iron powder (RV), sodium sulfate, nitrate into the mixture sodium, sodium chloride in the following amounts and ratios, kg / 1 ton of glass melt:

Iron Oxide - Crocus - 2.5-4.5 Pancreas - 2.5-4.5 Sodium nitrate NaNO ₃ - 3.5-5.0 Sodium Chloride NaCI - 0.5-2.5 Sodium Sulfate Na ₂ SO ₄ - 5.0-8.0,

moreover, NaNO ₃ + NaCI + Na ₂ SO ₄ = 11.0-13.0;

Na ₂ SO ₄ : (NaNO ₃ + NaCI) = 1: (0.7-1.3).

Iron metal powder in certain embodiments of the invention is introduced into the mixture in the form of a heterogeneous mechanically activated mixture (SiO ₂ + RV) with a particle size distribution of 20-25 μm. In a mechanically activated mixture (SiO ₂ + RV), the oxidation of metallic iron powder is slowed down by driving it into the voids of SiO ₂ crystals (RF patent 2330820, IPC СО3С 3/087).

NaCl is introduced into the mixture through table salt and / or through impurities of alkali-containing components.

In addition, in addition to adjusting the coloring components, an additional regulation of Redox glass is carried out by introducing NaNO ₃ , NaCI, Na ₂ SO ₄ into the glass mixture in various quantities and ratios. Decomposed by heating NaNO ₃ creates oxidizing conditions in the molten glass and thereby prevents the reduction of sulfate to sulfide sulfur. It also creates conditions for reducing the concentration of yellow color centers (amber chromophore), formed due to the four coordinated ions of ferric iron, in which one of the oxygen ions is replaced by a sulfide sulfur ion. Upon decomposition of the oxygen-free compound NaCI, the formed Na ⁺ ions compete for oxygen ions, thereby preventing the oxidation of iron to Fe ₂ O ₃ .

The use of iron oxides - Fe ₂ O ₃ , FeO, cobalt -CoO as the main dyes for the production of blue glasses is known in the practice of glassmaking of special glasses: Kotsik I, Nebrzhensky I, Fanderlik I. Glass staining. M .: Stroyizdat, 1983. S. 42-140.

Both iron oxides are present in the glass:

- Fe ₂ O ₃ has a strong absorption in the UV region and gives the glass a yellow color;

- FeO causes strong absorption in the solar infrared region in combination with high light transmission and gives the glass a blue color. CoO gives the glass a blue color, reducing its light transmission, and practically does not absorb ultraviolet and infrared radiation.

The industrial production of blue sheet glass with specified optical and energy indicators is in each case the result of a search for the ratio of FeO / Fe ₂ O ₃ content by selecting oxidizing and reducing ingredients of the mixture and, if necessary, introducing corrective additives of other dyes and modifiers. In certain embodiments of the invention, in order to further adjust certain parts of the optical spectrum and improve the cooking properties of the glass melt, insignificant amounts (wt.%) Of ZnO - 0-1.0 and B ₂ O ₃ - 0-2.0 are introduced into the base glass composition. ZnO in the composition of glass contributes to the suppression of yellow staining centers in the presence of sulfur and under reducing synthesis conditions. In ₂ About ₃ improves the cooking properties of glass.

The use of these dyes and the regulation of Redox in accordance with the alleged invention allows to obtain glass with a given optical and energy characteristics and the dominant wavelength.

Thus, the production of glass with increased light transmission and specified lighting and energy characteristics is regulated by a combination of the following parameters: increasing the degree of reduction of Fe2O3 to FeO, reducing the CoO content, the ratio of FeO / CoO in the glass within the claimed composition and, accordingly, the formation of blue color centers, as well as by increasing Redox glass and by using partially or fully iron powder as an iron-containing material, or, in some embodiments of the method, heterogeneous mechanodispersed mixture (SiO ₂ + RV), with a particle size distribution of 20-25 microns; reducing the MgO content and adjusting the MgO / FeO ratios in the glass. The presence of MgO ion in the glass due to the proximity of the ionic radii of Mg ⁺² -Fe ⁺² and metal-oxygen bonds leads to a decrease in the ratio of FeO / Fe ₂ O ₃ in the glass (. The effect of glass composition on the thermodynamics of the Fe ²⁺ (Fe ³⁺ equilibrium and the iron diffusivity in Na2O / MgO / CaO / Al2O3 / SiO2 melts. Russel Christian, Wiedenroth Achim. Chem. Geol. 2004.213, No. 1-3, pp. 125-135).

Obtaining glasses with lower light transmission and the specified lighting and energy characteristics in accordance with the proposed invention is carried out by increasing the content of Fe ₂ O ₃ , CoO, FeO in the glass and introducing Se at a ratio of Se / CoO in the range of 0.45-0.50. Se enhances the absorption of glass in the solar infrared region.

Glasses, in accordance with the alleged invention, are produced by sheet glass production technologies, mainly by the float method.

The implementation of the invention.

The alleged invention was tested on several glass compositions under the conditions of the institute's existing facilities.

In the examples, the compositions and properties of the synthesized glasses with different light transmission and various optical, lighting and energy characteristics are given (values are given for glasses 5 mm thick).

The light transmittance (LTA) in the wavelength range of 380-780 nm was measured using a standard light source "A" of the International Commission on Lighting (CIE) at a viewing angle of 2 ° Obs according to the standard ASTM E308 -90 / CLE. Calculation of color parameters in the values of the dominant wavelength (λ _d , nm) and color purity (H),%, was performed in accordance with ASTM E 308.

Determination of transmittance of total solar ultraviolet radiation (TSUV) in the wavelength range 300-380 nm, transmittance of total solar infrared radiation (TSIR) in the wavelength range 780-2500 nm, and transmittance of total solar energy (TSET) in the wavelength range from 300 to 2500 nm conducted according to EN410-2014 “Glass and glass products. Methods for determining optical characteristics. Determination of light and solar characteristics. ”

Example 1

Blue glass containing the following components, wt. %:

SiO ₂ 71.44; Al ₂ O ₃ - 1.4; CaO - 9.0; MgO - 3.0; K ₂ O - 0.43; Na ₂ O - 14.5; SO ₃ 0.23; Fe ₂ O ₃ (total iron) - 0.65; FeO - 0.15; CoO - 0.0032; Se - 0. The glass obtained by melting the mixture with subsequent development has a dominant wavelength (λ _DW ,), 5 nm thick, 485 nm, color purity (H,%) - 7.3, optical and energy parameters,%: LTA - 70; TSUV - 41; TSI - 33; TSET - 4 and Redox - 0.23.

Redox - 0.23 is achieved by introducing iron-crocus oxide, metallic iron powder (RV), as well as sodium sulfate, sodium nitrate, sodium chloride in the mixture in the following amount and ratio, kg / per 1 ton of glass melt:

Iron oxide crocus - 2.7; Pancreas - 1.5; Heterogeneous mechanically activated mixture (SiO ₂ + RV) with a granulometry of 20-25 microns. - 1.3; Sodium Nitrate -NaNO ₃ - 4.0; Sodium Chloride - NaCI - 2.5; Sodium Sulfate-Na ₂ SO ₄ - 5.0;

ΣNaNO ₃ + NaCI + Na ₂ SO ₄ = 11.5;

Na ₂ SO _4: (NaNO ₃ + NaCI) = 1 / 1.3.

The traditional raw materials are used in the batch preparation technology: quartz sand, chalk, dolomite, soda ash, feldspar concentrate. Glass is brewed in an industrial glass melting furnace and is produced by the float method.

Example 2

Blue glass containing the following components, wt. %:

SiO ₂ - 66.9; Al ₂ O ₃ - 5.0; CaO - 8.8; MgO - 3.2; K ₂ O - 0.6; Na ₂ O - 15.2; SO ₃ - 0.3; Fe ₂ O ₃ (total iron) - 0.77; FeO 0.22; CoO - 0.016; Se is 0.0053. Glass obtained by melting a mixture with subsequent production has a dominant wavelength (λ _DW ,) of 486 nm to a thickness of 5 mm, a color purity (H,%) of 8, optical and energy parameters,%: LTA - 50; TSUV - 39; TSIR - 30, TSET - 40 and Redox - 0.29.

Redox - 0.29 is achieved by introducing into the mixture of iron oxide - crocus, metallic iron powder (RV), sodium sulfate, sodium nitrate and sodium chloride in the following quantity and ratio, kg / per 1 ton of glass melt:

Iron Oxide - Crocus - 3.0; Pancreas - 3.6; Sodium nitrate-NaNO ₃ - 3.5; Sodium Chloride -NaCI - 2.2; Sodium Sulfate - Na ₂ SO ₄ - 6.5;

ΣNaNO ₃ + NaCI + Na ₂ SO ₄ = 12.2

Na ₂ SO ₄ / (NaNO ₃ + NaCI) = 1 / 0.9.

The traditional raw materials are used in the batch preparation technology: quartz sand, chalk, dolomite, soda ash, feldspar concentrate. Glass is brewed in pilot industrial conditions on a gas-fired furnace of periodic action and is produced on a metal plate in the form of disks.

Example 3

Dark blue glass containing the following components, wt. %:

SiO ₂ 69.43; Al ₂ O ₃ - 2.7; CaO - 8.2; MgO - 4.0; K ₂ O - 0.42; Na ₂ O - 14.9; SO ₃ 0.35; Fe ₂ O ₃ (total iron) - 0.85; FeO 0.28; CoO - 0.020; Se is 0.0065.

Additionally, in order to intensify the glass melting process, the glass contains a component B ₂ O ₃ - 2.0 wt. %

Glass obtained by melting the mixture with subsequent production has a dominant wavelength (λ _DW ,) of 483 nm to a thickness of 5 mm, color purity (H,%) of 9, LTA,% of 36; TSUV,% - 32; TSIR,% - 26.5; TSET,% - 33. Redox - 0.33.

Redox - 0.33 is achieved by introducing into the mixture of iron oxide - crocus, metallic iron powder (RV), sodium sulfate, sodium nitrate, and sodium chloride in the following quantity and ratio, kg / per 1 ton of glass melt:

Iron Oxide - Crocus - 3.4; Pancreas - 4.0; Sodium Nitrate - NaNO ₃ - 5.0; Sodium Chloride -NaCI - 0.5; Sodium Sulfate -Na ₂ SO ₄ - 7.5;

ΣNaNO ₃ + NaCI + Na ₂ SO ₄ = 13.0;

Na ₂ SO ₄ : (NaNO ₃ + NaCI) = 1 / 0.7.

The raw material preparation technology uses traditional raw materials: quartz sand, chalk, dolomite, calcined technical soda, feldspar concentrate and borax. Glass is boiled in an industrial glass melting furnace and a float is produced.

Example 4

Dark blue glass containing the following components, wt. %:

SiO ₂ - 70.23; Al ₂ O ₃ - 0.95; CaO - 7.2; MgO - 5.0; K ₂ O - 0.35; Na ₂ O - 15.9; SO ₃ 0.37; Fe ₂ O ₃ - 0.95; FeO - 0.33; CoO - 0.024; Se is 0.011.

in addition, for color purity, the glass contains a ZnO component of 1.0 wt. %

Glass obtained by melting the mixture with subsequent production has a dominant wavelength (5 mm) (λ _DW ), nm — 484 mm, color purity (H,%) —12, LTA,% —30; TSUV,% - 29.6; TSIR,% - 22; TSET,% - 27. Redox - 0.35.

Redox - 0.33 is achieved by introducing into the mixture of iron oxide - crocus, metallic iron powder (RV), sodium sulfate, sodium nitrate and sodium chloride, kg / per 1 ton of glass melt:

Iron oxide crocus - 4.0; Pancreas - 3.0; Heterogeneous mechanically activated a mixture (SiO ₂ + RV) with a particle size distribution of 20-25 microns. - 1.5; Sodium Nitrate -NaNO ₃ - 3.5; Sodium Chloride-NaCI - 1.5 Sodium Sulfate - Na ₂ SO ₄ - 8.0;

ΣNaNO ₃ + NaCI + Na ₂ SO ₄ = 13.0;

Na ₂ SO ₄ / (NaNO ₃ + NaCI) = 1 / 0.7.

The traditional raw materials are used in the batch preparation technology: quartz sand, chalk, dolomite, soda ash, feldspar concentrate. Glass is brewed in pilot industrial conditions on a gas-fired furnace of periodic action and is produced on a metal plate in the form of disks.

Claims (9)

1. Blue glass containing the following components, wt. %: SiO ₂  65.0-75.0 Al ₂ O ₃  0.9-5.0 CaO 7.0-10.0 MgO  3.0-5.0 K ₂ O  0.3-0.6 Na ₂ O  13.0-20.0 SO ₃  0.2-0.4 Fe ₂ O ₃ (total iron)   0.65-0.95 FeO  0.15-0.33 Soo  0.003-0.03 Se  0-0.011, and having a dominant wavelength (λ _DW ,) of 5 mm thickness within the range of 480-489 nm, color purity (H) of 7.0-12.0, optical and energy parameters, respectively, in the range,%: LTA - 30-70; TSUV - 29-41; TSIR - 20-33; TSET - 27-48, and Redox glass in the range 0.23-0.35, obtained by cooking the mixture with subsequent development, characterized in that iron oxide is introduced into the mixture - crocus, metallic iron powder (RV), sodium sulfate, sodium nitrate , sodium chloride in the following quantity and ratio, kg / 1 ton of glass melt: Iron Oxide - Crocus  2.5-4.5 Pancreas  2.5-4.5 Sodium nitrate NaNO ₃  3,5-5,0 Sodium Chloride NaCI  0.5-2.5 Sodium Sulfate Na ₂ SO ₄  5.0-8.0; moreover, NaNO ₃ + NaCI + Na ₂ SO ₄ = 11.0-13.0; Na ₂ SO ₄ : (NaNO ₃ + NaCI) = 1: (0.7-1.3). 2. Glass according to claim 1, characterized in that insignificant amounts of B ₂ O ₃ , ZnO, in the amount, wt. %: ZnO - 0-1.0 and B ₂ O ₃ - 0-2.0. 3. The glass according to claim 1, characterized in that the metallic iron powder in individual embodiments is introduced into the charge in the form of a heterogeneous mechanically activated mixture (SiO ₂ + RV) with a particle size distribution of 20-25 microns. 4. The glass according to claim 1, characterized in that NaCI is introduced into the mixture through sodium chloride and / or through impurities of alkali-containing components.