CN107032621B - Green glass ceramics and preparation method and application thereof - Google Patents

Green glass ceramics and preparation method and application thereof Download PDF

Info

Publication number
CN107032621B
CN107032621B CN201611096281.0A CN201611096281A CN107032621B CN 107032621 B CN107032621 B CN 107032621B CN 201611096281 A CN201611096281 A CN 201611096281A CN 107032621 B CN107032621 B CN 107032621B
Authority
CN
China
Prior art keywords
glass
green
raw materials
glass ceramics
ceramics
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201611096281.0A
Other languages
Chinese (zh)
Other versions
CN107032621A (en
Inventor
程金树
袁坚
范亚伟
骞少阳
信彩丽
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Glass Technology Research Institute Of Shahe City Of Hebei Province
Wuhan University of Technology WUT
Original Assignee
Glass Technology Research Institute Of Shahe City Of Hebei Province
Wuhan University of Technology WUT
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Glass Technology Research Institute Of Shahe City Of Hebei Province, Wuhan University of Technology WUT filed Critical Glass Technology Research Institute Of Shahe City Of Hebei Province
Priority to CN201611096281.0A priority Critical patent/CN107032621B/en
Publication of CN107032621A publication Critical patent/CN107032621A/en
Application granted granted Critical
Publication of CN107032621B publication Critical patent/CN107032621B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

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
    • C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
    • C03C10/0009—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing silica as main constituent
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B32/00—Thermal after-treatment of glass products not provided for in groups C03B19/00, C03B25/00 - C03B31/00 or C03B37/00, e.g. crystallisation, eliminating gas inclusions or other impurities; Hot-pressing vitrified, non-porous, shaped glass products
    • C03B32/02—Thermal crystallisation, e.g. for crystallising glass bodies into glass-ceramic articles
    • 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
    • C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
    • C03C1/04—Opacifiers, e.g. fluorides or phosphates; Pigments
    • C03C1/06—Opacifiers, e.g. fluorides or phosphates; Pigments to produce non-uniformly pigmented, e.g. speckled, marbled, or veined 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
    • C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
    • 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

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)
  • Ceramic Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Vascular Medicine (AREA)
  • Glass Compositions (AREA)

Abstract

A green glass ceramic belongs to the technical field of glass ceramic, and comprises the following raw materials in percentage by weight: SiO 2246‑56％，Al2O316‑24％，CaO 4.8‑10.6％，MgO 5.5‑13.5％，Na2O and/or K2O 7‑14％，ZnO 0.2‑1.8％，TiO2Or TiO2+ZrO23‑8％，Cr2O30.1-1.5% of CuO and 0-1.5% of CuO. The invention also discloses a preparation method and application of the green glass ceramics, and the green glass ceramics do not contain fluoride, have soft color and luster, are similar to natural green granite in color, and have better physical and chemical properties than the natural granite.

Description

Green glass ceramics and preparation method and application thereof
Technical Field
The invention belongs to the technical field of microcrystalline glass, and relates to green microcrystalline glass, in particular to green microcrystalline glass, a preparation method and application thereof.
Background
The microcrystalline glass is also called as microcrystalline jade or ceramic glass, has the dual characteristics of glass and ceramic, is one kind of novel microcrystalline material, and is a composite solid material which is obtained by controlling crystallization of basic glass or other materials in a heating process and contains a large number of microcrystals and glass bodies. The microcrystalline glass has the advantages of compact structure, clear texture, no water absorption, no fading, corrosion resistance, pollution resistance, no radioactivity, smoothness, brightness and much better decoration effect than natural stone, can recycle byproducts such as industrial slag, waste steel slag or tailings and the like, is favorable for ecological environment protection, becomes an excellent green environment-friendly building material, and has wide development prospect in the field of buildings.
The building glass ceramics as the decorative material has the characteristics of designable color and soft color, and the color glass ceramics in the market are mainly sintered, but have the defects of high porosity, high energy consumption and low yield. The microcrystalline glass suitable for other industrial production has relatively single color, and the defects of high melting furnace material changing cost and low efficiency exist when the colored microcrystalline glass is produced. Thus, the above-mentioned problems in producing colored glass ceramics have yet to be solved.
Disclosure of Invention
The invention provides green glass ceramics and a preparation method and application thereof, which aim at the problems, do not contain fluoride, are suitable for various forming methods, can be directly formed and prepared into green glass ceramics products, and can also be prepared into glass ceramics pigment frits which are used for preparing green glass ceramics with similar expansion coefficients or similar systems by a material channel coloring mode.
The technical scheme adopted by the invention for realizing the purpose is as follows:
the green glass ceramics comprises the following raw materials in percentage by weight: SiO 2246-56％，Al2O316-24％，CaO 4.8-10.6％，MgO 5.5-13.5％，Na2O and/or K2O 7-14％，ZnO 0.2-1.8％，TiO2Or TiO2+ZrO23-8％，Cr2O30.1-1.5％，CuO 0-1.5％。
The green glass ceramics comprises the following raw materials in percentage by weight: SiO 2247％，Al2O316％，CaO6.7％，MgO 7.5％，Na2O and/or K2O 13％，ZnO 1.8％，TiO2Or TiO2+ZrO27.5％，Cr2O30.5％。
The green glass ceramics comprises the following raw materials in percentage by weight: SiO 2250％，Al2O317.7％，CaO 7.2％，MgO 9.2％，Na2O and/or K2O 7.8％，ZnO 1.3％，TiO2Or TiO2+ZrO23.8％，Cr2O31.5％，CuO 1.5％。
The green glass ceramics comprises the following raw materials in percentage by weight: SiO 2251％，Al2O321％，CaO6％，MgO 9％，Na2O and/or K2O 8.3％，ZnO 1.1％，TiO2Or TiO2+ZrO23％，Cr2O30.6％。
The green glass ceramics comprises the following raw materials in percentage by weight: SiO 2253％，Al2O318％，CaO5.8％，MgO 8.2％，Na2O and/or K2O 7.5％，ZnO 1％，TiO2Or TiO2+ZrO25.3％，Cr2O31.2％。
A preparation method of green glass ceramics comprises the following steps:
A. preparing raw materials: weighing the raw materials SiO by weight percentage246-56％，Al2O316-24％，CaO4.8-10.6％，MgO 5.5-13.5％，Na2O and/or K2O 7-14％，ZnO 0.2-1.8％，TiO2Or TiO2+ZrO23-8％，Cr2O30.1-1.5% of CuO and 0-1.5% of CuO, and uniformly mixing to obtain a batch;
B. preparing base glass: melting the batch mixture obtained in the step A at the temperature of 1500-;
C. preparation of green glass ceramics: and C, carrying out nucleation, crystallization and annealing treatment on the base glass obtained in the step B, cutting and polishing to obtain the green glass ceramics.
In the step C, the nucleation temperature is 700-.
The application of green glass ceramics in glass ceramics with the same system or similar thermal expansion coefficient comprises the following steps:
a. preparing raw materials: weighing the raw materials SiO by weight percentage246-56％，Al2O316-24％，CaO4.8-10.6％，MgO 5.5-13.5％，Na2O and/or K2O 7-14％，ZnO 0.2-1.8％，TiO2Or TiO2+ZrO23-8％，Cr2O30.1-1.5% of CuO and 0-1.5% of CuO, and uniformly mixing to obtain a batch;
b. preparation of green microcrystalline glass frit: b, melting the batch mixture obtained in the step a at the temperature of 1500-;
c. preparing the microcrystalline glass imitating natural green granite: and c, adding the green glass-ceramic frits obtained in the step b into a glass-ceramic system without a colorant or a glass-ceramic belt matched with the expansion coefficient of the green glass-ceramic frits in a way of coloring the material channel, controlling the temperature of the glass-ceramic liquid in the material channel to be 1200-0 ℃, and carrying out molding, crystallization, annealing and cutting on the glass belt to obtain the natural-simulated green granite glass-ceramic.
In the step c, the crystallization temperature is 870-.
The invention has the beneficial effects that:
1) the green glass ceramics provided by the invention does not contain fluoride, is uniform in coloring, soft in color and luster, bright in color and superior to natural granite in physical and chemical properties.
2) The invention provides a production method of green glass ceramics, which is used for producing Cr when the glass ceramics are used as body-colored glass ceramics2O3Not only can play the role of a coloring agent, but also can be mixed with TiO2And ZrO2Composite crystal nucleus agent capable of effectively promoting CaO-MgO-A12O3-SiO2The system glass starts to crystallize at a lower temperature and forms microcrystalline glass taking diopside as a main crystal phase; meanwhile, the material channel can be colored according to the requirement, the traditional step of changing the material in the kiln when producing the colored glass ceramics is omitted, and the multi-color in one kiln is realized.
3) Through long-term creative research, the invention summarizes that the ratio of calcium to magnesium in the raw materials is controlled to be 0.4-1.9, and aims to control the crystallization amount, ensure the glass to have glossiness and improve the brightness value of the glass, namely the ratio of calcium to magnesium is controlled to be capable of improving L value.
The main crystalline phase of the invention is aluminum diopside, SiO2、Al2O3The oxide forms a glass network as a network, and simultaneously participates in the formation of a main crystal phase. The chemical stability of the microcrystalline glass is improved. CaO, MgO, Na2O、K2The O is used as a network exo-oxide, not only reduces the melting temperature of a glass system, but also plays a role in breaking bonds, and is beneficial to the precipitation of crystals. ZnO can improve the thermal stability of the system and reduce the brittleness of the glass ceramics. TiO 22Or TiO2+ZrO2The crystal nucleating agent is used for promoting the nucleation and crystallization of the system, the titanium oxide is used as a main crystal nucleating agent and can be used as the crystal nucleating agent alone or together with the zirconium oxide, but the zirconium oxide cannot be used as the crystal nucleating agent alone, and the zirconium oxide is used as the crystal nucleating agent to help to refine grains, so that the grains are more uniform, the improvement on the mechanical strength is beneficial, but the melting temperature is excessively increased.
The melting temperature control in the invention is to melt the raw materials into a uniform glass body, and then the nucleation and crystallization are controlled to influence the content of a crystal phase, thereby improving the performance of the glass.
Detailed Description
The present invention will be further described with reference to the following specific examples. The same system described in the following examples refers to a microcrystalline glass system without adding a colorant, and the microcrystalline glass strip with the similar expansion coefficient refers to a microcrystalline glass strip with the expansion coefficient matched with that of a green microcrystalline glass frit, namely, a pigment part and a base glass part need to adapt to the expansion coefficient, otherwise, the defects such as cracking and the like can be caused in the cooling process.
Example 1
The green glass ceramics comprises the following raw materials in percentage by weight: SiO 2248.5％；Al2O320％；CaO6.5％；MgO7％；Na2O8.5％；K2O3.3％；ZnO0.2％；TiO23.4％；ZrO22.5％；Cr2O30.1％。
The preparation of the green microcrystalline glass comprises the following steps:
A. preparing raw materials: weighing the raw materials according to the weight percentage, and uniformly mixing to obtain a batch;
B. preparing base glass: melting the batch mixture obtained in the step A at 1530 ℃, and cooling the liquid obtained by melting to 770-860 ℃ to form to obtain base glass;
C. preparation of green glass ceramics: and C, carrying out nucleation at the temperature of 710-.
The application of the green glass ceramics in the glass ceramics imitating natural green granite comprises the following steps:
a. preparing raw materials: weighing the raw materials of the green glass ceramics according to the weight percentage, and uniformly mixing to obtain a batch;
b. preparation of green microcrystalline glass frit: b, melting the batch mixture obtained in the step a at 1530 ℃, and quenching the liquid obtained by melting with water to obtain a green glass ceramic frit;
c. preparing the microcrystalline glass imitating natural green granite: and c, adding the green glass ceramics frits obtained in the step b into the glass ceramics belt of the same system or similar expansion coefficient in a material channel coloring mode, molding the glass belt at the temperature of 1220 ℃, crystallizing at 875-885 ℃ for 15-25min, annealing at 810-850 ℃ and cutting to obtain the natural-simulated green granite glass ceramics.
Example 2
The green glass ceramics comprises the following raw materials in percentage by weight: SiO 2249％；Al2O318.5％；CaO 7％；MgO 8.5％；Na2O 6％；K2O 4.5％；ZnO 0.5％；TiO23％；ZrO22％；Cr2O31％。
The preparation of the green microcrystalline glass comprises the following steps:
A. preparing raw materials: weighing the raw materials according to the weight percentage, and uniformly mixing to obtain a batch;
B. preparing base glass: melting the batch mixture obtained in the step A at 1525 ℃, cooling the liquid obtained by melting to 780-850 ℃, and forming to obtain base glass;
C. preparation of green glass ceramics: and C, carrying out 720-730 ℃ nucleation for 18-20min, 880-887 ℃ crystallization for 18-20min and 820-840 ℃ annealing treatment on the base glass obtained in the step B, cutting and polishing to obtain the green glass ceramics.
The application of the green glass ceramics in the glass ceramics imitating natural green granite comprises the following steps:
a. preparing raw materials: weighing the raw materials of the green glass ceramics according to the weight percentage, and uniformly mixing to obtain a batch;
b. preparation of green microcrystalline glass frit: b, melting the batch mixture obtained in the step a at 1525 ℃, and performing water quenching on the liquid obtained by melting to obtain a green glass ceramic frit;
c. preparing the microcrystalline glass imitating natural green granite: and c, adding the green glass ceramics frits obtained in the step b into the glass ceramics belt of the same system or similar expansion coefficient in a material channel coloring mode, and carrying out molding, 880-887 ℃ crystallization for 18-20min, 820-840 ℃ annealing and cutting on the glass belt at the temperature of 1210 ℃ to obtain the natural green granite-like glass ceramics.
Example 3
The green glass ceramics comprises the following raw materials in percentage by weight: SiO 2254.5％；Al2O317％；CaO 5.25％；MgO 6.5％；Na2O 5.5％；K2O 3％；ZnO 1.5％；TiO24％；ZrO22.5％；CuO0.1％；Cr2O30.15％。
The preparation of the green microcrystalline glass comprises the following steps:
A. preparing raw materials: weighing the raw materials according to the weight percentage, and uniformly mixing to obtain a batch;
B. preparing base glass: melting the batch mixture obtained in the step A at 1550 ℃, cooling the liquid obtained by melting to 780-840 ℃, and forming to obtain base glass;
C. preparation of green glass ceramics: and C, carrying out nucleation at the temperature of 720-750 ℃ for 10-20min, crystallization at the temperature of 873-875 ℃ for 10-20min and annealing at the temperature of 815-835 ℃, cutting and polishing to obtain the green glass ceramics.
The application of the green glass ceramics in the glass ceramics imitating natural green granite comprises the following steps:
a. preparing raw materials: weighing the raw materials of the green glass ceramics according to the weight percentage, and uniformly mixing to obtain a batch;
b. preparation of green microcrystalline glass frit: b, melting the batch mixture obtained in the step a at 1550 ℃, and quenching the liquid obtained by melting with water to obtain a green glass ceramic frit;
c. preparing the microcrystalline glass imitating natural green granite: and c, adding the green glass ceramics frits obtained in the step b into the glass ceramics belt of the same system or similar expansion coefficient in a material channel coloring mode, and carrying out molding, crystallization at 873-875 ℃ for 10-20min, annealing at 815-835 ℃ and cutting on the glass belt at 1280 ℃ to obtain the natural green granite-like glass ceramics.
Example 4
The green glass ceramics comprises the following raw materials in percentage by weight: SiO 2252％；Al2O316.5％；CaO 9％；MgO 7.5％；Na2O 4.2％；K2O 4.1％；ZnO 1.2％；TiO22.5％；ZrO21％；CuO21.2％；Cr2O30.8％。
The preparation of the green microcrystalline glass comprises the following steps:
A. preparing raw materials: weighing the raw materials according to the weight percentage, and uniformly mixing to obtain a batch;
B. preparing base glass: melting the batch materials obtained in the step A at 1535 ℃, and cooling and molding the liquid obtained by melting to obtain base glass;
C. preparation of green glass ceramics: and C, carrying out nucleation, crystallization and annealing treatment on the base glass obtained in the step B, cutting and polishing to obtain the green glass ceramics.
The application of the green glass ceramics in the glass ceramics imitating natural green granite comprises the following steps:
a. preparing raw materials: weighing the raw materials of the green glass ceramics according to the weight percentage, and uniformly mixing to obtain a batch;
b. preparation of green microcrystalline glass frit: b, melting the batch mixture obtained in the step a at 1535 ℃, and performing water quenching on the liquid obtained by melting to obtain a green glass ceramic frit;
c. preparing the microcrystalline glass imitating natural green granite: and c, adding the green microcrystalline glass frit obtained in the step b into a microcrystalline glass belt of the same system or similar expansion coefficient in a material channel coloring mode, and carrying out molding, crystallization, annealing and cutting on the glass belt at the temperature of 1250 ℃ to obtain the natural green granite-like microcrystalline glass.
Example 5
The green glass ceramics comprises the following raw materials in percentage by weight: SiO 2246.5％；Al2O322％；CaO 8％；MgO 5.5％；Na2O 5％；K2O 5.8％；ZnO 0.4％；TiO24％；CuO21.4％；Cr2O31.4％。
The preparation of the green microcrystalline glass comprises the following steps:
A. preparing raw materials: weighing the raw materials according to the weight percentage, and uniformly mixing to obtain a batch;
B. preparing base glass: b, melting the batch mixture obtained in the step A at 1540 ℃, and cooling and forming the liquid obtained by melting to obtain base glass;
C. preparation of green glass ceramics: and C, carrying out nucleation, crystallization and annealing treatment on the base glass obtained in the step B, cutting and polishing to obtain the green glass ceramics.
The application of the green glass ceramics in the glass ceramics imitating natural green granite comprises the following steps:
a. preparing raw materials: weighing the raw materials of the green glass ceramics according to the weight percentage, and uniformly mixing to obtain a batch;
b. preparation of green microcrystalline glass frit: b, melting the batch mixture obtained in the step a at 1540 ℃, and performing water quenching on the liquid obtained by melting to obtain a green glass ceramic frit;
c. preparing the microcrystalline glass imitating natural green granite: and c, adding the green microcrystalline glass frit obtained in the step b into a microcrystalline glass belt of the same system or similar expansion coefficient in a material channel coloring mode, and carrying out molding, crystallization, annealing and cutting on the glass belt at the temperature of 1260 ℃ to obtain the natural green granite-like microcrystalline glass.
Example 6
The green glass ceramics comprises the following raw materials in percentage by weight: SiO 2247％，Al2O316％，CaO4.8％，MgO 12％，Na2O 10.4％，ZnO 1.8％，TiO23％，ZrO24.5％，Cr2O30.5％。
The preparation of the green microcrystalline glass comprises the following steps:
A. preparing raw materials: weighing the raw materials according to the weight percentage, and uniformly mixing to obtain a batch;
B. preparing base glass: b, melting the batch mixture obtained in the step A at 1540 ℃, and cooling and forming the liquid obtained by melting to obtain base glass;
C. preparation of green glass ceramics: and C, carrying out nucleation, crystallization and annealing treatment on the base glass obtained in the step B, cutting and polishing to obtain the green glass ceramics.
The application of the green glass ceramics in the glass ceramics imitating natural green granite comprises the following steps:
a. preparing raw materials: weighing the raw materials of the green glass ceramics according to the weight percentage, and uniformly mixing to obtain a batch;
b. preparation of green microcrystalline glass frit: b, melting the batch mixture obtained in the step a at 1540 ℃, and performing water quenching on the liquid obtained by melting to obtain a green glass ceramic frit;
c. preparing the microcrystalline glass imitating natural green granite: and c, adding the green microcrystalline glass frit obtained in the step b into a microcrystalline glass belt of the same system or similar expansion coefficient in a material channel coloring mode, and carrying out molding, crystallization, annealing and cutting on the glass belt at the temperature of 1242 ℃ to obtain the natural green granite-like microcrystalline glass.
Example 7
The green glass ceramics comprises the following raw materials in percentage by weight: SiO 2250％，Al2O317.7％，CaO 5.5％，MgO 11％，K2O 7.7％，ZnO 1.3％，TiO23％，ZrO20.8％，Cr2O31.5％，CuO 1.5％。
The preparation of the green microcrystalline glass comprises the following steps:
A. preparing raw materials: weighing the raw materials according to the weight percentage, and uniformly mixing to obtain a batch;
B. preparing base glass: melting the batch mixture obtained in the step A at 1553 ℃, and cooling and forming the liquid obtained by melting to obtain base glass;
C. preparation of green glass ceramics: and C, carrying out nucleation, crystallization and annealing treatment on the base glass obtained in the step B, cutting and polishing to obtain the green glass ceramics.
The application of the green glass ceramics in the glass ceramics imitating natural green granite comprises the following steps:
a. preparing raw materials: weighing the raw materials of the green glass ceramics according to the weight percentage, and uniformly mixing to obtain a batch;
b. preparation of green microcrystalline glass frit: b, melting the batch materials obtained in the step a at 1553 ℃, and performing water quenching on the liquid obtained by melting to obtain a green glass ceramic frit;
c. preparing the microcrystalline glass imitating natural green granite: and c, adding the green microcrystalline glass frit obtained in the step b into a microcrystalline glass belt of the same system or similar expansion coefficient in a material channel coloring mode, and carrying out molding, crystallization, annealing and cutting on the glass belt at the temperature of 1256 ℃ to obtain the natural green granite-like microcrystalline glass.
Example 8
The green glass ceramics comprises the following raw materials in percentage by weight: SiO 2251％，Al2O321％，CaO5.4％，MgO 9％，Na2O4％，K2O 4.9％，ZnO 1.1％，TiO23％，Cr2O30.6％。
The preparation of the green microcrystalline glass comprises the following steps:
A. preparing raw materials: weighing the raw materials according to the weight percentage, and uniformly mixing to obtain a batch;
B. preparing base glass: b, melting the batch mixture obtained in the step A at 1567 ℃, and cooling and forming the liquid obtained by melting to obtain base glass;
C. preparation of green glass ceramics: and C, carrying out nucleation, crystallization and annealing treatment on the base glass obtained in the step B, cutting and polishing to obtain the green glass ceramics.
The application of the green glass ceramics in the glass ceramics imitating natural green granite comprises the following steps:
a. preparing raw materials: weighing the raw materials of the green glass ceramics according to the weight percentage, and uniformly mixing to obtain a batch;
b. preparation of green microcrystalline glass frit: b, melting the batch materials obtained in the step a at 1567 ℃, and quenching the liquid obtained by melting with water to obtain a green glass ceramic frit;
c. preparing the microcrystalline glass imitating natural green granite: and c, adding the green microcrystalline glass frit obtained in the step b into a microcrystalline glass belt of the same system or similar expansion coefficient in a material channel coloring mode, and carrying out molding, crystallization, annealing and cutting on the glass belt at the temperature of 1272 ℃ to obtain the natural green granite-like microcrystalline glass.
Example 9
The green glass ceramics comprises the following raw materials in percentage by weight: SiO 2252％，Al2O318％，CaO6.3％，MgO 9％，Na2O 7.2％，ZnO 1％，TiO25.3％，Cr2O31.2％。
The preparation of the green microcrystalline glass comprises the following steps:
A. preparing raw materials: weighing the raw materials according to the weight percentage, and uniformly mixing to obtain a batch;
B. preparing base glass: melting the batch mixture obtained in the step A at 1524 ℃, and cooling and molding the liquid obtained by melting to obtain base glass;
C. preparation of green glass ceramics: and C, carrying out nucleation, crystallization and annealing treatment on the base glass obtained in the step B, cutting and polishing to obtain the green glass ceramics.
The application of the green glass ceramics in the glass ceramics imitating natural green granite comprises the following steps:
a. preparing raw materials: weighing the raw materials of the green glass ceramics according to the weight percentage, and uniformly mixing to obtain a batch;
b. preparation of green microcrystalline glass frit: b, melting the batch mixture obtained in the step a at 1524 ℃, and performing water quenching on the liquid obtained by melting to obtain a green glass ceramic frit;
c. preparing the microcrystalline glass imitating natural green granite: and c, adding the green microcrystalline glass frit obtained in the step b into a microcrystalline glass belt of the same system or similar expansion coefficient in a material channel coloring mode, and carrying out molding, crystallization, annealing and cutting on the glass belt at the temperature of 1233 ℃ to obtain the natural green granite-like microcrystalline glass.
Example 10
The green glass ceramics comprises the following raw materials in percentage by weight: SiO 2255％，Al2O317.5％，CaO 5％，MgO 8.3％，K2O 8％，ZnO 0.7％，TiO22.5％，ZrO22％，Cr2O30.7％，CuO0.3％。
The preparation of the green microcrystalline glass comprises the following steps:
A. preparing raw materials: weighing the raw materials according to the weight percentage, and uniformly mixing to obtain a batch;
B. preparing base glass: melting the batch obtained in the step A at 1546 ℃, and cooling and molding the liquid obtained by melting to obtain base glass;
C. preparation of green glass ceramics: and C, carrying out nucleation, crystallization and annealing treatment on the base glass obtained in the step B, cutting and polishing to obtain the green glass ceramics.
The application of the green glass ceramics in the glass ceramics imitating natural green granite comprises the following steps:
a. preparing raw materials: weighing the raw materials of the green glass ceramics according to the weight percentage, and uniformly mixing to obtain a batch;
b. preparation of green microcrystalline glass frit: b, melting the batch materials obtained in the step a at 1546 ℃, and performing water quenching on the liquid obtained by melting to obtain a green glass ceramic frit;
c. preparing the microcrystalline glass imitating natural green granite: and c, adding the green microcrystalline glass frit obtained in the step b into a microcrystalline glass belt of the same system or similar expansion coefficient in a material channel coloring mode, and carrying out molding, crystallization, annealing and cutting on the glass belt at the temperature of 1241 ℃ to obtain the natural green granite-like microcrystalline glass.
Example 11
The green glass ceramics comprises the following raw materials in percentage by weight: SiO 2254.8％，Al2O319％，CaO 4.8％，MgO 9％，Na2O5％，K2O 2％，ZnO 0.3％，TiO23.2％，，Cr2O31.1％，CuO0.8％。
The preparation of the green microcrystalline glass comprises the following steps:
A. preparing raw materials: weighing the raw materials according to the weight percentage, and uniformly mixing to obtain a batch;
B. preparing base glass: melting the batch obtained in the step A at 1548 ℃, and cooling and molding the liquid obtained by melting to obtain base glass;
C. preparation of green glass ceramics: and C, carrying out nucleation, crystallization and annealing treatment on the base glass obtained in the step B, cutting and polishing to obtain the green glass ceramics.
The application of the green glass ceramics in the glass ceramics imitating natural green granite comprises the following steps:
a. preparing raw materials: weighing the raw materials of the green glass ceramics according to the weight percentage, and uniformly mixing to obtain a batch;
b. preparation of green microcrystalline glass frit: b, melting the batch materials obtained in the step a at 1548 ℃, and performing water quenching on the liquid obtained by melting to obtain a green glass ceramic frit;
c. preparing the microcrystalline glass imitating natural green granite: and c, adding the green microcrystalline glass frit obtained in the step b into a microcrystalline glass belt of the same system or similar expansion coefficient in a material channel coloring mode, and carrying out molding, crystallization, annealing and cutting on the glass belt at the temperature of 1269 ℃ to obtain the natural green granite-like microcrystalline glass.
Comparative example 1
Microcrystalline glasses, differing by, for example, B in addition to colorants2O3And/or P2O5And/or Co2O3And/or Ni2O3And the like.
Comparative example 2
Green glass ceramics, comprising a colorant, except for the fact that it also comprises, for example, B2O3And/or P2O5And/or Co2O3And/or Ni2O3And the like.
The performance parameters of the green glass ceramics and the simulated natural green granite glass ceramics are as follows:
Figure BDA0001169553750000151

Claims (3)

1. the green glass ceramics are characterized by comprising the following raw materials in percentage by weight: SiO 2248.5-54.5％，Al2O317-20％，CaO 5.25-7％，MgO 6.5-8.5％，Na2O 5.5-8.5％，K2O 3-4.5％，ZnO0.2-1.5％，TiO23-4％，ZrO22-2.5％，Cr2O30.1-1% of CuO and 0-1.5% of green glass ceramics, which is prepared by the following method comprising the following steps:
A. preparing raw materials: weighing the raw materials SiO by weight percentage248.5-54.5％，Al2O317-20％，CaO5.25-7％，MgO 6.5-8.5％，Na2O 5.5-8.5％，K2O 3-4.5％，ZnO 0.2-1.5％，TiO23-4％，ZrO22-2.5％，Cr2O30.1-1% of CuO and 0-1.5% of CuO, and uniformly mixing to obtain a batch;
B. preparing base glass: melting the batch mixture obtained in the step A at the temperature of 1500-;
C. preparation of green glass ceramics: b, carrying out nucleation, crystallization and annealing treatment on the base glass obtained in the step B, cutting and polishing to obtain green glass ceramics; in the step C, the nucleation temperature is 700-.
2. The application of the green glass ceramics in the natural-green granite imitation glass ceramics is characterized by comprising the following steps:
a. preparing raw materials: weighing the raw materials SiO by weight percentage248.5-54.5％，Al2O317-20％，CaO5.25-7％，MgO 6.5-8.5％，Na2O 5.5-8.5％，K2O 3-4.5％，ZnO 0.2-1.5％，TiO23-4％，ZrO22-2.5％，Cr2O30.1-1% of CuO, 0-1.5% of CuO and mixingMixing uniformly to obtain a batch;
b. preparation of green microcrystalline glass frit: b, melting the batch mixture obtained in the step a at the temperature of 1500-;
c. preparing the microcrystalline glass imitating natural green granite: and c, adding the green glass-ceramic frits obtained in the step b into a glass-ceramic system without a colorant or a glass-ceramic belt matched with the expansion coefficient of the green glass-ceramic frits in a way of coloring the material channel, controlling the temperature of the glass-ceramic liquid in the material channel to be 1200-1280 ℃, and carrying out molding, crystallization, annealing and cutting on the glass belt to obtain the natural-simulated green granite glass-ceramic.
3. The application of the green glass-ceramic in the natural-green granite imitation glass-ceramic according to claim 2, wherein in step c, the crystallization temperature is 870-.
CN201611096281.0A 2016-12-02 2016-12-02 Green glass ceramics and preparation method and application thereof Active CN107032621B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201611096281.0A CN107032621B (en) 2016-12-02 2016-12-02 Green glass ceramics and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201611096281.0A CN107032621B (en) 2016-12-02 2016-12-02 Green glass ceramics and preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN107032621A CN107032621A (en) 2017-08-11
CN107032621B true CN107032621B (en) 2020-08-04

Family

ID=59530903

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201611096281.0A Active CN107032621B (en) 2016-12-02 2016-12-02 Green glass ceramics and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN107032621B (en)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110002733A (en) * 2018-01-05 2019-07-12 南昌欧菲光学技术有限公司 The production method of the intensifying method and devitrified glass cover board of devitrified glass
CN109809696A (en) * 2018-12-19 2019-05-28 温州市康尔微晶器皿有限公司 A kind of magnalium silicon spinel devitrified glass
CN110937812A (en) * 2019-12-13 2020-03-31 中郡庄艺(泉州)新材料有限公司 Dark green microcrystalline glass and preparation method thereof
CN110981472B (en) * 2019-12-30 2022-06-07 江西赛瓷材料有限公司 High-strength green zirconia ceramic powder and preparation method and application thereof
CN111635132A (en) * 2020-06-15 2020-09-08 山东三汇玻璃有限公司 Green glass product
CN112745027A (en) * 2021-01-19 2021-05-04 广西中炀新材料科技有限公司 Jade-like microcrystalline glass and preparation method thereof

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1126181A (en) * 1994-09-28 1996-07-10 李天伶 Prodn. of crystal stone decorative material by utilizing tailing grit
US6825139B2 (en) * 2001-01-08 2004-11-30 Glasscerax Ltd. Poly-crystalline compositions
CN101759368B (en) * 2010-03-18 2011-08-03 凤县三联建材有限责任公司 Green glass-ceramic plate made from lead-zinc smelting slag and manufacturing method thereof
CN103553341B (en) * 2013-10-22 2016-06-29 河北省沙河玻璃技术研究院 A kind of floride-free granite mine slag microcrystalline glass and production method thereof

Also Published As

Publication number Publication date
CN107032621A (en) 2017-08-11

Similar Documents

Publication Publication Date Title
CN107032621B (en) Green glass ceramics and preparation method and application thereof
CN111453995A (en) Microcrystalline glass mainly containing spinel and preparation method thereof
CN102060571A (en) Green glaze for daily porcelain
CN102491641B (en) Wear-resistant crystallized glass plate and preparation method thereof
CN101265027A (en) Formulation of imperforate micro-spar sheet material and manufacturing method thereof
CN110092579A (en) A kind of starry sky glaze glaze, starry sky glaze pottery and preparation method thereof
CN105948514A (en) Method for manufacturing colorful transparent colored glass ceramics with high degree of crystallinity by adopting fusing-cooling method for crystallization
CN107572826B (en) A kind of microcrystalline jade ornament materials and preparation method thereof based on graphene
CN103663967B (en) A kind of preparation method of Jade-like microcrystalline glass
CN102557455A (en) Sky blue glass ceramic fusion block and preparation method thereof
CN106746618A (en) A kind of ecru devitrified glass and its preparation method and application
CN105541113A (en) A fully-glazed frit and a preparing method thereof
CN101412576A (en) Technological process of thin type nucleated glass wall surface decorative plate
CN105060721A (en) High-strength wall tile for building
CN104649579B (en) Energy saving high devitrified glass and preparation method
CN103588394B (en) A kind of White fluoride-free calendering devitrified glass and production method thereof
CN103739202B (en) A kind of devitrified glass and production method thereof
CN102795778A (en) Formula of microcrystalline plate and process for producing microcrystalline plate by using diopside
CN102531694A (en) Glass ceramics frit and preparation method thereof
CN103232162A (en) Method for preparing compound microcrystalline glass based on raw material of iron tailings
CN103482874B (en) Utilize the method for cullet low-firing crystallizing glass sheet material
CN102557456A (en) Light-coffee microcrystalline glass fusion cake and preparation method thereof
CN110104948A (en) It is the heat-resistant opal glass and preparation method thereof of raw material preparation using recessed soil
CN106746677A (en) A kind of purplish-red glass-ceramic and its preparation method and application
CN111439932B (en) Jade-like microcrystalline glass and preparation method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant