CN111606561A - Red glass and preparation method thereof - Google Patents
Red glass and preparation method thereof Download PDFInfo
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- CN111606561A CN111606561A CN202010544732.2A CN202010544732A CN111606561A CN 111606561 A CN111606561 A CN 111606561A CN 202010544732 A CN202010544732 A CN 202010544732A CN 111606561 A CN111606561 A CN 111606561A
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- 239000011521 glass Substances 0.000 title claims abstract description 268
- 238000002360 preparation method Methods 0.000 title abstract description 13
- 238000004519 manufacturing process Methods 0.000 claims abstract description 30
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000010949 copper Substances 0.000 claims abstract description 13
- 229910052802 copper Inorganic materials 0.000 claims abstract description 13
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000003086 colorant Substances 0.000 claims abstract description 7
- 229910052718 tin Inorganic materials 0.000 claims abstract description 7
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims abstract description 5
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 claims abstract description 5
- 239000000463 material Substances 0.000 claims description 71
- 238000003756 stirring Methods 0.000 claims description 56
- 239000007788 liquid Substances 0.000 claims description 54
- 239000002245 particle Substances 0.000 claims description 52
- 238000004040 coloring Methods 0.000 claims description 37
- 238000010438 heat treatment Methods 0.000 claims description 28
- 238000001816 cooling Methods 0.000 claims description 23
- 239000006060 molten glass Substances 0.000 claims description 20
- 238000000137 annealing Methods 0.000 claims description 19
- 238000000227 grinding Methods 0.000 claims description 13
- 229940108928 copper Drugs 0.000 claims description 12
- 239000000446 fuel Substances 0.000 claims description 10
- 238000000465 moulding Methods 0.000 claims description 10
- 238000002844 melting Methods 0.000 claims description 9
- 230000008018 melting Effects 0.000 claims description 9
- 239000002893 slag Substances 0.000 claims description 9
- 239000002994 raw material Substances 0.000 claims description 7
- 238000002485 combustion reaction Methods 0.000 claims description 6
- 239000012856 weighed raw material Substances 0.000 claims description 6
- 238000005303 weighing Methods 0.000 claims description 6
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 4
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 claims description 4
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 claims description 4
- 239000005751 Copper oxide Substances 0.000 claims description 3
- 229910000431 copper oxide Inorganic materials 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 229940116318 copper carbonate Drugs 0.000 claims description 2
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 2
- 229960000355 copper sulfate Drugs 0.000 claims description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 2
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 claims description 2
- 229960004643 cupric oxide Drugs 0.000 claims description 2
- 229940112669 cuprous oxide Drugs 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 12
- 229910052793 cadmium Inorganic materials 0.000 description 13
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 13
- 239000000156 glass melt Substances 0.000 description 12
- 239000011133 lead Substances 0.000 description 12
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 11
- 229910052804 chromium Inorganic materials 0.000 description 11
- 239000011651 chromium Substances 0.000 description 11
- 229910001385 heavy metal Inorganic materials 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- 239000007789 gas Substances 0.000 description 9
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- 239000003638 chemical reducing agent Substances 0.000 description 7
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 5
- 229910001431 copper ion Inorganic materials 0.000 description 5
- 239000003034 coal gas Substances 0.000 description 4
- 238000005520 cutting process Methods 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000000295 fuel oil Substances 0.000 description 4
- 239000003345 natural gas Substances 0.000 description 4
- 239000000049 pigment Substances 0.000 description 4
- 238000002834 transmittance Methods 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 229910052593 corundum Inorganic materials 0.000 description 3
- 229910001845 yogo sapphire Inorganic materials 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 208000027418 Wounds and injury Diseases 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 238000004134 energy conservation Methods 0.000 description 2
- 208000014674 injury Diseases 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000001054 red pigment Substances 0.000 description 2
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 1
- CJOBVZJTOIVNNF-UHFFFAOYSA-N cadmium sulfide Chemical compound [Cd]=S CJOBVZJTOIVNNF-UHFFFAOYSA-N 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- 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
- C03C4/02—Compositions for glass with special properties for coloured glass
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B25/00—Annealing glass products
-
- 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
- C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
- C03C3/091—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium
- C03C3/093—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium containing zinc or zirconium
Landscapes
- 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)
- Glass Compositions (AREA)
Abstract
The invention discloses red glass which comprises the following components in percentage by mass: 70.1-81% SiO2、0.5‑22％Al2O3、0.01‑18.5％Na2O、0‑13％CaO、0.001‑4％Si、0.001‑2％Sr、0.001‑2％Sn、0‑5％Li2O、0‑3％ZnO、0‑15％BaO、0‑16％B2O3、0‑5％K2O, 0-8% MgO and 0.1-5% copper-containing colorant. The red glass and the preparation method thereof have the advantages of short conversion time, high production efficiency and uniform color.
Description
Technical Field
The invention relates to the technical field of glass products, in particular to red glass and a preparation method thereof.
Background
In the prior art, the red coloring of the glass without introducing lead, chromium and cadmium has become a particularly difficult challenge for technicians in the glass industry. It is conventional practice to use one or more of iron, lead, chromium oxide or cadmium sulphide to introduce the red colour, however, iron oxide often has undesirable side effects. Moreover, lead, chromium and cadmium are heavy metals, which are increasingly monitored by environmental protection departments and are prohibited from being used.
The glass material channel coloring technology for providing copper red glass by reducing copper by a reducing agent is produced, but because glass liquid in the whole furnace needs to be replaced when red material color adding and color changing are carried out in a glass tank furnace, time is wasted, production efficiency is reduced, and high-quality red glass cannot be obtained due to too many factors influenced by the structure of the furnace.
With the development of the technology, the color selection of the channel coloring technology is found to be very rich, the flexibility is high, the color change time is short, the color can not fade, the pigments are uniformly mixed, the color and the production quality of the glass are stable, and the energy conservation and the low consumption are realized. However, the red glass production technology for obtaining stable color and quality of red glass by the material channel coloring of the red glass pigment always has technical barriers and does not break through.
Disclosure of Invention
The invention aims to provide red glass and a preparation method thereof, and solves the problems that the existing red glass contains heavy metals of lead, chromium and cadmium, pollutes the environment, is low in production efficiency, and is uneven in glass color and unstable in production quality.
In order to achieve the purpose, the invention provides red glass which comprises the following components in percentage by mass: 70.1-81% SiO2、0.5-22％Al2O3、0.01-18.5％Na2O、0-13％CaO、0.001-4％Si、0.001-2％Sr、0.001-2％Sn、0-5％Li2O、0-3％ZnO、0-15％BaO、0-16％B2O3、0-5％K2O, 0-8% MgO and 0.1-5% copper-containing colorant.
Preferably, the copper-containing colorant is one or a mixture of copper oxide, copper carbonate, cuprous oxide and copper sulfate.
A preparation method of red glass comprises the following steps:
s1, preparing a glass preform, glass slag or a formed glass product: weighing raw materials according to the component ratio, putting the weighed raw materials into a glass pool furnace for heating and melting, wherein the melting temperature is 1450-;
s2, annealing heat treatment: annealing the glass preform obtained in the step S1 at the temperature of 400-700 ℃, wherein the annealing time is 1-4 hours, and obtaining a red glass blank;
s3, grinding: grinding the red glass blank obtained in the step S2 or the glass slag obtained in the step S1 by direct flow cooling, and grinding the red glass blank into particles of 2-5 mm;
s4, coloring the material channel: heating the molten colorless or light-colored glass liquid flowing into the material channel at the heating temperature of not higher than 1400 ℃, and then adding the glass particles treated in the step S3 into the high-temperature glass liquid;
s5, stirring: stirring the high-temperature glass liquid in the material channel by adopting a stirrer, wherein the stirring frequency of the stirrer is 10-20 revolutions per minute;
s6, cooling, homogenizing and molding: and cooling, homogenizing and molding the molten glass processed in the step S5 to obtain red glass.
Preferably, in the step S3, the red glass blank is ground into 3mm particles.
Preferably, in the step S4, the addition amount of the glass particles is 4 to 60% of the glass liquid amount.
Preferably, in step S4, the addition amount of the glass particles is 5% of the discharge amount.
Preferably, in step S5, the material channel is provided with a plurality of stirring areas for stirring the high-temperature molten glass, the number of the stirrers, the rotation direction of the stirrers, and the shape of the stirrers in each stirring area are not completely the same, and the stirring frequency of the stirrers is 13 revolutions per minute.
Preferably, in step S1, the glass melting furnace is a gas, oil, oxy-fuel combustion, all-electric furnace, or electric-assisted furnace.
Therefore, the red glass and the preparation method thereof have the following beneficial effects:
(1) the raw materials are added with a reducing agent and a copper-containing coloring agent, copper ions in the glass are reduced into metal copper particles under the action of the reducing agent after annealing heat treatment, and the glass is red after clustering.
2Cu++Sn2+→2Cu+Sn4+
(2) Grinding the reduced glass to be used as a concentrated red pigment, coloring the colorless or light-colored glass in a material channel, and stirring the glass liquid in the material channel by a stirrer in the coloring process to obtain the red glass with uniform color.
(3) The invention mixes and colors the glass particles and the colorless or light-colored glass liquid in the material channel, does not need to replace the glass liquid in the whole furnace, and has short conversion time and high production efficiency.
(4) The silica, alkali metal oxide, alkaline earth metal oxide, tin oxide and copper oxide glass frit compositions and the red glass bodies prepared therefrom of the present invention are useful as red pigments for obtaining high quality red glass by way of frit coloring, and can be used for producing various red glass products.
The technical solution of the present invention is further described in detail by the following examples.
Detailed Description
The embodiments of the present invention will be further explained below.
Example one
The red glass comprises the following components in percentage by mass: 70.1% SiO2、1.5％Al2O3、12.5％Na2O、12％CaO、0.1％Si、0.1％Sr、0.9％Sn、0.1％Li2O、0.5％K2O、0.5％MgO、1.7％CuO。
The preparation method of the red glass comprises the following steps:
s1, preparing glass preform and glass slag or forming glass product
Weighing the raw materials according to the component ratio, putting the weighed raw materials into a glass tank furnace for heating at the temperature of about 1500 ℃ (which can be adjusted according to actual conditions), melting at high temperature to form a glass melt, and cooling and molding the glass melt to form a glass preform. Or directly cooling and molding various glass products, and directly obtaining red glass products through annealing heat treatment.
The glass tank furnace is a gas (including gas fuel such as coal gas, natural gas and the like), fuel oil, oxy-fuel combustion, an all-electric furnace, an electric-assisted furnace and other glass tank furnaces.
S2 annealing heat treatment
The glass preform obtained in step S1 was annealed at a temperature of about 500 ℃ for about 1.5 hours to obtain a red glass blank. During annealing, copper ions are reduced by the reducing agent to metallic copper particles or clusters together to show a red color. The red glass material can be obtained without using heavy metals such as cadmium, lead and chromium in the glass tank furnace.
S3, grinding
And (4) grinding the red glass blank obtained in the step S2 or the glass slag obtained in the step S1 by direct flow cooling, and grinding the red glass blank into particles of 3 mm.
S4 coloring material channel
And (3) heating the molten colorless or light-colored glass liquid flowing into the material channel at the temperature of about 1300 ℃, and then adding the glass particles treated in the step S3 into the high-temperature glass liquid, wherein the addition amount of the glass particles is 5% of the discharge amount. The red glass particles added to the surface of the molten glass at high temperature are melted by the high temperature. The size of the material channel is determined according to the discharge amount of the kiln and the amount of the coloring blank required by the product. The method for coloring the material channel realizes the compatibility and the conversion of colorless or light-colored glass frit and red glass frit, does not need to replace glass liquid in the whole furnace, has short conversion time and flexible material replacement production, and improves the production efficiency.
S5, stirring
And stirring the high-temperature molten glass by using a stirrer in the material channel, wherein the stirring frequency of the stirrer is 13 revolutions per minute. The material channel is internally provided with a plurality of stirring areas for stirring the high-temperature molten glass, the number of the stirrers arranged in each stirring area, the rotating direction of the stirrers and the shapes of the stirrers are not completely the same, and the number of the stirring areas and the number, the rotating direction and the shapes of the stirrers in each stirring area are determined according to the discharge amount of the coloring material channel. After stirring, the color of the glass liquid reaches the best mixing homogeneity effect.
Red glass particles are added into the coloring material channel, and because the density of the red glass particles is less than that of the glass liquid and the granularity of the red glass particles is smaller, the red glass particles float on the surface of the glass liquid after being thrown into the surface of the glass liquid; the glass liquid in the material channel has vertical height difference, the mixing effect of the red glass particles and the glass liquid is improved through stirring, and the vertical height difference of the glass liquid is eliminated.
S6, cooling and homogenizing
The molten glass processed in step S5 is cooled and homogenized to obtain red glass. The time required for cooling and homogenizing the glass melt after colouring varies according to the product to be produced.
Through detection, the ring-cutting uniformity of the glass is more than or equal to C level, and the light transmittance of the glass at 650 nm is stable.
Example two
The red glass comprises the following components in percentage by mass: SiO 2272％、Al2O32.2％、Na2O 12％、CaO 8.5％、Si 0.1％、Sr 0.05％、Sn 1.7％、Li2O 0.25％、BaO 0.1％、K2O 2％、MgO 0.5％、Cu2O 0.6％。
The preparation method of the red glass comprises the following steps:
s1, preparing glass preform and glass slag or forming glass product
Weighing the raw materials according to the component ratio, putting the weighed raw materials into a glass tank furnace for heating at the temperature of about 1520 ℃, melting at high temperature to form a glass melt, and cooling and forming the glass melt to form a glass preform. Or directly cooling and molding various glass products, and directly obtaining red glass products through annealing heat treatment.
The glass tank furnace is a gas (including gas fuel such as coal gas, natural gas and the like), fuel oil, oxy-fuel combustion, an all-electric furnace, an electric-assisted furnace and other glass tank furnaces.
S2 annealing heat treatment
The glass preform obtained in step S1 was annealed at a temperature of about 400 ℃ for about 2 hours to obtain a red glass blank. During annealing, copper ions are reduced by the reducing agent to metallic copper particles or clusters together to show a red color. The red glass material can be obtained without using heavy metals such as cadmium, lead and chromium in the glass tank furnace.
S3, grinding
The red glass material obtained in step S2 was ground, and the red glass material was ground into 3mm particles.
S4 coloring material channel
And (3) heating the molten colorless or light-colored glass liquid flowing into the material channel at the heating temperature of not higher than 1300 ℃, and then adding the glass particles treated in the step S3 into the high-temperature glass liquid, wherein the addition amount of the glass particles is 5% of the discharge amount. The red glass particles added to the surface of the molten glass at high temperature are melted by the high temperature. The size of the material channel is determined according to the discharge amount of the kiln and the amount of the coloring blank required by the product. The method for coloring the material channel realizes the compatibility and the conversion of colorless or light-colored glass frit and red glass frit, does not need to replace glass liquid in the whole furnace, has short conversion time and flexible material replacement production, and improves the production efficiency.
S5, stirring
And stirring the high-temperature molten glass by using a stirrer in the material channel, wherein the stirring frequency of the stirrer is 13 revolutions per minute. The material channel is internally provided with a plurality of stirring areas for stirring the high-temperature molten glass, the number of the stirrers arranged in each stirring area, the rotating direction of the stirrers and the shapes of the stirrers are not completely the same, and the number of the stirring areas and the number, the rotating direction and the shapes of the stirrers in each stirring area are determined according to the discharge amount of the coloring material channel. After stirring, the color of the glass liquid reaches the best mixing homogeneity effect.
Red glass particles are added into the coloring material channel, and because the density of the red glass particles is less than that of the glass liquid and the granularity of the red glass particles is smaller, the red glass particles float on the surface of the glass liquid after being thrown into the surface of the glass liquid; the glass liquid in the material channel has vertical height difference, the mixing effect of the red glass particles and the glass liquid is improved through stirring, and the vertical height difference of the glass liquid is eliminated.
S6, cooling and homogenizing
The molten glass processed in step S5 is cooled and homogenized to obtain red glass. The time required for cooling and homogenizing the glass melt after colouring varies according to the product to be produced.
Through detection, the ring-cutting uniformity of the glass is more than or equal to C level, and the light transmittance of the glass at 650 nm is stable.
EXAMPLE III
The red glass comprises the following components in percentage by mass: SiO 2257％、Al2O320％、B2O38％、Na2O 0.5％、CaO 5％、Si 0.1％、Sr 0.1％、Sn 0.7％、MgO 8％、CuO0.6％。
The preparation method of the red glass comprises the following steps:
s1, preparing glass preform and glass slag or forming glass product
Weighing the raw materials according to the component ratio, putting the weighed raw materials into a glass tank furnace for heating at about 1580 ℃, melting at high temperature to form a glass melt, and cooling and forming the glass melt to form a glass preform. Or directly cooling and molding various glass products, and directly obtaining red glass products through annealing heat treatment.
The glass tank furnace is a gas (including gas fuel such as coal gas, natural gas and the like), fuel oil, oxy-fuel combustion, an all-electric furnace, an electric-assisted furnace and other glass tank furnaces.
S2 annealing heat treatment
The glass preform obtained in step S1 was annealed at a temperature of about 650 ℃ for about 1.5 hours to obtain a red glass blank. During annealing, copper ions are reduced by the reducing agent to metallic copper particles or clusters together to show a red color. The red glass material can be obtained without using heavy metals such as cadmium, lead and chromium in the glass tank furnace.
S3, grinding
The red glass material obtained in step S2 was ground, and the red glass material was ground into 3mm particles.
S4 coloring material channel
And (3) heating the molten colorless or light-colored glass liquid flowing into the material channel at the heating temperature of not higher than 1300 ℃, and then adding the glass particles treated in the step S3 into the high-temperature glass liquid, wherein the addition amount of the glass particles is 5% of the discharge amount. The red glass particles added to the surface of the molten glass at high temperature are melted by the high temperature. The size of the material channel is determined according to the discharge amount of the kiln and the amount of the coloring blank required by the product. The method for coloring the material channel realizes the compatibility and the conversion of colorless or light-colored glass frit and red glass frit, does not need to replace glass liquid in the whole furnace, has short conversion time and flexible material replacement production, and improves the production efficiency.
S5, stirring
And stirring the high-temperature molten glass by using a stirrer in the material channel, wherein the stirring frequency of the stirrer is 13 revolutions per minute. The material channel is internally provided with a plurality of stirring areas for stirring the high-temperature molten glass, the number of the stirrers arranged in each stirring area, the rotating direction of the stirrers and the shapes of the stirrers are not completely the same, and the number of the stirring areas and the number, the rotating direction and the shapes of the stirrers in each stirring area are determined according to the discharge amount of the coloring material channel. After stirring, the color of the glass liquid reaches the best mixing homogeneity effect.
Red glass particles are added into the coloring material channel, and because the density of the red glass particles is less than that of the glass liquid and the granularity of the red glass particles is smaller, the red glass particles float on the surface of the glass liquid after being thrown into the surface of the glass liquid; the glass liquid in the material channel has vertical height difference, the mixing effect of the red glass particles and the glass liquid is improved through stirring, and the vertical height difference of the glass liquid is eliminated.
S6, cooling and homogenizing
The molten glass processed in step S5 is cooled and homogenized to obtain red glass. The time required for cooling and homogenizing the glass melt after colouring varies according to the product to be produced.
Through detection, the ring-cutting uniformity of the glass is more than or equal to C level, and the light transmittance of the glass at 650 nm is stable.
Example four
The red glass comprises the following components in percentage by mass: SiO 2278.5％、Al2O32％、Na2O 5％、B2O312.5％、Si 0.1％、Sr 0.1％、Sn 1％、Cu2O 0.8％。
The preparation method of the red glass comprises the following steps:
s1, preparing glass preform and glass slag or forming glass product
Weighing the raw materials according to the component ratio, putting the weighed raw materials into a glass tank furnace for heating at the temperature of about 1620 ℃, melting at high temperature to form a glass melt, and cooling and molding the glass melt to form a glass preform. Or directly cooling and molding various glass products, and directly obtaining red glass products through annealing heat treatment.
The glass tank furnace is a gas (including gas fuel such as coal gas, natural gas and the like), fuel oil, oxy-fuel combustion, an all-electric furnace, an electric-assisted furnace and other glass tank furnaces.
S2 annealing heat treatment
The glass preform obtained in step S1 was annealed at a temperature of about 650 ℃ for about 2 hours to obtain a red glass blank. During annealing, copper ions are reduced by the reducing agent to metallic copper particles or clusters together to show a red color. The red glass material can be obtained without using heavy metals such as cadmium, lead and chromium in the glass tank furnace.
S3, grinding
The red glass material obtained in step S2 was ground, and the red glass material was ground into 3mm particles.
S4 coloring material channel
And (3) heating the molten colorless or light-colored glass liquid flowing into the material channel at the heating temperature of not higher than 1300 ℃, and then adding the glass particles treated in the step S3 into the high-temperature glass liquid, wherein the addition amount of the glass particles is 5% of the discharge amount. The red glass particles added to the surface of the molten glass at high temperature are melted by the high temperature. The size of the material channel is determined according to the discharge amount of the kiln and the amount of the coloring blank required by the product. The method for coloring the material channel realizes the compatibility and the conversion of colorless or light-colored glass frit and red glass frit, does not need to replace glass liquid in the whole furnace, has short conversion time and flexible material replacement production, and improves the production efficiency.
S5, stirring
And stirring the high-temperature molten glass by using a stirrer in the material channel, wherein the stirring frequency of the stirrer is 13 revolutions per minute. The material channel is internally provided with a plurality of stirring areas for stirring the high-temperature molten glass, the number of the stirrers arranged in each stirring area, the rotating direction of the stirrers and the shapes of the stirrers are not completely the same, and the number of the stirring areas and the number, the rotating direction and the shapes of the stirrers in each stirring area are determined according to the discharge amount of the coloring material channel. After stirring, the color of the glass liquid reaches the best mixing homogeneity effect.
Red glass particles are added into the coloring material channel, and because the density of the red glass particles is less than that of the glass liquid and the granularity of the red glass particles is smaller, the red glass particles float on the surface of the glass liquid after being thrown into the surface of the glass liquid; the glass liquid in the material channel has vertical height difference, the mixing effect of the red glass particles and the glass liquid is improved through stirring, and the vertical height difference of the glass liquid is eliminated.
S6, cooling and homogenizing
The molten glass processed in step S5 is cooled and homogenized to obtain red glass. The time required for cooling and homogenizing the glass melt after colouring varies according to the product to be produced.
Through detection, the ring-cutting uniformity of the glass is more than or equal to C level, and the light transmittance of the glass at 650 nm is stable.
By adopting the method, glass products such as glassware, glass bottle and can, plate glass, glass tube, glass rod, glass block, artistic glass product and the like can be produced by pressing, blowing, drawing, overflowing, floating, centrifuging, casting and other production modes, and the produced red glass product has the advantages of uniform color, fastness, short time for color change, high production efficiency, energy conservation and low consumption.
The red glass and the preparation method thereof are realized by material path coloring, and compared with the traditional method for producing the red glass by coloring cadmium, lead and chromium or continuously producing the red glass by coloring in a tank furnace, the red glass and the preparation method thereof have prominent innovativeness and breakthroughs:
1. can thoroughly solve the problems that the prior red glass product contains heavy metals of cadmium, lead and chromium to pollute the environment and can cause personal injury when being used as a packaging container to contain food. Since the prior red glass is produced by introducing heavy metals of cadmium, lead and chromium into red, the production of the red glass by using the pigment without cadmium instead of the pigment containing cadmium has been a great problem of the glass industry for a long time. The red glass does not contain heavy metals such as cadmium, lead and chromium, can ensure food safety when being used for food packaging, avoids the seepage of the heavy metals, and does not cause any personal injury, so the red glass is safer and more environment-friendly to use, belongs to a green environment-friendly product, and has very wide market prospect.
2. The glass liquid in the whole furnace is required to be replaced when the glass is added and changed in color in the glass tank furnace in the traditional method, various defects such as time waste and reduction of production efficiency are avoided, compatibility and conversion of producing transparent, colorless or light-colored glass materials and producing red glass materials are achieved, conversion time is short, material changing production is flexible, production loss is greatly reduced, and production efficiency is greatly improved.
3. The red glass products are produced in a way of material channel coloring, and the multistage forced stirring and the accurate temperature control process are adopted, so that the temperature of the glass liquid and the material color are uniform, the material color of the products is uniform and stable, and the products cannot fade, and the stable production of various red glass products is realized.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that modifications can be made by those skilled in the art without departing from the principle of the present invention, and these modifications should also be construed as the protection scope of the present invention.
Claims (8)
1. The red glass is characterized by comprising the following components in percentage by mass: 70.1-81% SiO2、0.5-22％Al2O3、0.01-18.5％Na2O、0-13％CaO、0.001-4％Si、0.001-2％Sr、0.001-2％Sn、0-5％Li2O、0-3％ZnO、0-15％BaO、0-16％B2O3、0-5％K2O, 0-8% MgO and 0.1-5% copper-containing colorant.
2. A red glass according to claim 1, wherein: the copper-containing colorant is one or a mixture of copper oxide, copper carbonate, cuprous oxide and copper sulfate.
3. A method of making red glass according to any of claims 1-2, comprising the steps of:
s1, preparing a glass preform, glass slag or a formed glass product: weighing raw materials according to the component ratio, putting the weighed raw materials into a glass pool furnace for heating and melting, wherein the melting temperature is 1450-;
s2, annealing heat treatment: annealing the glass preform obtained in the step S1 at the temperature of 400-700 ℃, wherein the annealing time is 1-4 hours, and obtaining a red glass blank;
s3, grinding: grinding the red glass blank obtained in the step S2 or the glass slag obtained in the step S1 by direct flow cooling, and grinding the red glass blank into particles of 2-5 mm;
s4, coloring the material channel: heating the molten colorless or light-colored glass liquid flowing into the material channel at the heating temperature of not higher than 1400 ℃, and then adding the glass particles treated in the step S3 into the high-temperature glass liquid;
s5, stirring: stirring the high-temperature glass liquid in the material channel by adopting a stirrer, wherein the stirring frequency of the stirrer is 10-20 revolutions per minute;
s6, cooling, homogenizing and molding: and cooling, homogenizing and molding the molten glass processed in the step S5 to obtain red glass.
4. A method for producing red glass according to claim 3, wherein: in the step S3, the red glass blank is ground into 3mm particles.
5. A method for producing red glass according to claim 3, wherein: in the step S4, the addition amount of the glass particles is 4 to 60% of the amount of the glass liquid.
6. A method for producing red glass according to claim 3, wherein: in step S4, the addition amount of the glass particles is 5% of the discharge amount.
7. A method for producing red glass according to claim 3, wherein: in the step S5, a plurality of stirring areas are provided in the material channel to stir the high-temperature molten glass, the number of the stirrers provided in each stirring area, the rotation direction of the stirrers and the shape of the stirrers are not completely the same, and the stirring frequency of the stirrers is 13 revolutions per minute.
8. A method for producing red glass according to claim 3, wherein: in the step S1, the glass tank furnace is a gas, oil, oxy-fuel combustion, all-electric furnace, or electric-assisted furnace.
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| JPH09268027A (en) * | 1996-04-04 | 1997-10-14 | T & D Ceratec:Kk | Red glass composition |
| CN101279819A (en) * | 2008-04-30 | 2008-10-08 | 陕西科技大学 | A kind of preparation method of red glass |
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Application publication date: 20200901 |