CN107032621A - A kind of green glass-ceramic and its preparation method and application - Google Patents

A kind of green glass-ceramic and its preparation method and application Download PDF

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Publication number
CN107032621A
CN107032621A CN201611096281.0A CN201611096281A CN107032621A CN 107032621 A CN107032621 A CN 107032621A CN 201611096281 A CN201611096281 A CN 201611096281A CN 107032621 A CN107032621 A CN 107032621A
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glass
green
ceramic
tio
raw
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CN107032621B (en
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程金树
袁坚
范亚伟
骞少阳
信彩丽
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Hebei shahe glass technology research institute
Wuhan University of Technology WUT
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Hebei shahe glass technology research institute
Wuhan University of Technology WUT
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    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL 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
    • C03C10/00Devitrified 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
    • C03C10/0009Devitrified 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
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03BMANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B32/00Thermal 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
    • C03B32/02Thermal crystallisation, e.g. for crystallising glass bodies into glass-ceramic articles
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL 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
    • C03C1/00Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
    • C03C1/04Opacifiers, e.g. fluorides or phosphates; Pigments
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL 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
    • C03C1/00Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
    • C03C1/04Opacifiers, e.g. fluorides or phosphates; Pigments
    • C03C1/06Opacifiers, e.g. fluorides or phosphates; Pigments to produce non-uniformly pigmented, e.g. speckled, marbled, or veined products
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL 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
    • C03C10/00Devitrified 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
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL 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
    • C03C4/00Compositions for glass with special properties
    • C03C4/02Compositions for glass with special properties for coloured glass

Abstract

A kind of green glass-ceramic, belongs to the technical field of devitrified glass, by weight percentage, including following raw material:SiO246 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 invention also discloses the preparation method and application of green glass-ceramic, green glass-ceramic of the present invention not fluoride, color and luster is soft, and color is close with natural green granite, and physicochemical property is better than natural granite.

Description

A kind of green glass-ceramic and its preparation method and application
Technical field
The invention belongs to the technical field of devitrified glass, it is related to a kind of green devitrified glass, and in particular to a kind of green Devitrified glass and its preparation method and application, green glass-ceramic of the present invention not fluoride, color and luster is soft, color and natural green Dyeing defect hilllock petrofacies are near, and physicochemical property is better than natural granite.
Background technology
Devitrified glass is also known as microcrystalline jade or glass-ceramic, and the double grading with glass and ceramics, is Novel microcrystalline material One kind of material, it is contained in one kind obtained from crystallization is controlled in heating process by parent glass or other materials The composite solid material of a large amount of microcrystals and vitreum.Structure of Glass Ceramic is fine and close, clean mark, does not absorb water, colour-fast, corrosion resistant Erosion, anti-pollution, "dead", bright and clean, the decorative effect compared with lithotome are more advantageous, and can by industrial slag, The byproduct such as steel slag or mine tailing is recycled, and is conducive to ecological environmental protection, as a kind of excellent green structural material, Building field has vast potential for future development.
Building microcrystalline glass as a big feature of ornament materials be color can design, color and luster it is soft, in the market Colour devitrified glass haves the shortcomings that porosity height, high energy consumption based on sintering process, but, yielded poorly.And suitable for other works Then color is relatively single for the devitrified glass of industry production, and during production color microcrystalline glass, there are melting furnaces and reloads that cost is high, efficiency is low Shortcoming.Thus, have to be solved to the above mentioned problem for producing color microcrystalline glass.
The content of the invention
The present invention is in view of the above-mentioned problems, propose a kind of green glass-ceramic and preparation method and application, it is not fluorine-containing Compound, it is adapted to various forming methods, straight forming and green glass-ceramic product can be prepared, can also be prepared into devitrified glass colorant Frit, is used to prepare the close coefficient of expansion or with system green glass-ceramic by way of material road is coloured.
The present invention is to realize that the technical scheme that its purpose is used is:
A kind of green glass-ceramic, by weight percentage, including following raw material:SiO246-56%, Al2O3 16- 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%.
A kind of green glass-ceramic, by weight percentage, including following raw material:SiO247%, Al2O316%, CaO 6.7%, MgO 7.5%, Na2O and/or K2O 13%, ZnO 1.8%, TiO2Or TiO2+ZrO27.5%, Cr2O30.5%.
A kind of green glass-ceramic, by weight percentage, including following raw material:SiO250%, 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%.
A kind of green glass-ceramic, by weight percentage, including following raw material:SiO251%, Al2O321%, CaO 6%, MgO 9%, Na2O and/or K2O 8.3%, ZnO 1.1%, TiO2Or TiO2+ZrO23%, Cr2O30.6%.
A kind of green glass-ceramic, by weight percentage, including following raw material:SiO253%, Al2O318%, CaO 5.8%, MgO 8.2%, Na2O and/or K2O 7.5%, ZnO 1%, TiO2Or TiO2+ZrO25.3%, Cr2O31.2%.
A kind of preparation method of green glass-ceramic, comprises the following steps:
A, preparation raw material:Raw material, SiO are weighed by following percentage by weights246-56%, 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+ZrO2 3- 8%, Cr2O30.1-1.5%, CuO 0-1.5%, are well mixed, obtain batch;
B, parent glass preparation:The batch that step A is obtained is founded under the conditions of 1500-1550 DEG C, will be molten The liquid being made obtains parent glass after being cooled to 760-870 DEG C, being molded;
C, green glass-ceramic preparation:The parent glass that step B is obtained is cut after coring, crystallization, annealing Cut, polish, obtain green glass-ceramic.
In step C, nucleation temperature is 700-750 DEG C, and nucleation time is 10-30min, and crystallization temperature is 870-950 DEG C, brilliant Change time 10-30min, annealing temperature is 800-860 DEG C.
A kind of application of green glass-ceramic in the devitrified glass of same system or close thermal coefficient of expansion, including following step Suddenly:
A, preparation raw material:Raw material, SiO are weighed by following percentage by weights246-56%, 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+ZrO2 3- 8%, Cr2O30.1-1.5%, CuO 0-1.5%, are well mixed, obtain batch;
B, Green microcrystalline glass fusion cake preparation:The batch that step a is obtained is melted under the conditions of 1500-1550 DEG C System, will found obtained liquid through water quenching, obtains Green microcrystalline glass fusion cake;
C, imitative natural green granite devitrified glass preparation:The Green microcrystalline glass fusion cake that step b is obtained is with material road The mode of coloring be added to the devitrified glass system that is not added with colouring agent or with Green microcrystalline glass fusion cake matched expansion coefficient In devitrified glass band, control temperature of the devitrified glass liquid in material road for 1200-1280 DEG C of glass tape through shaping, crystallization, annealing And cutting, obtain imitative natural green granite devitrified glass.
In step c, crystallization temperature is 870-950 DEG C, crystallization time 10-30min, and annealing temperature is 800-860 DEG C.
The beneficial effects of the invention are as follows:
1) a kind of green glass-ceramic for providing of the present invention, not fluoride, uniform coloring, color and luster is soft, bright-colored, Physicochemical property is better than natural granite.
2) a kind of green glass-ceramic production method that the present invention is provided, during as mass colouring devitrified glass, Cr2O3Both Play colouring agent effect, and energy and TiO2And ZrO2The Composite Nucleation Agents of composition, Composite Nucleation Agents can be effectively facilitated CaO-MgO- A12O3-SiO2System glass starts crystallization at a lower temperature, and forms the devitrified glass using diopside as principal crystalline phase;Simultaneously Material road coloring can be also carried out as needed, and the step of kiln reloads when saving traditional mode of production color microcrystalline glass realizes that a kiln is more Color.
3) present invention passes through long-term creative research, and it is 0.4-1.9 to summarize to calcium and magnesium ratio in raw material is controlled, it is therefore an objective to controlled Crystallization amount processed, makes glass glossy, improves the brightness value of glass, that is, controls calcium and magnesium ratio, can put forward high l value.
The principal crystalline phase of the present invention is aluminium diopside, SiO2、Al2O3Effect, be used as Network former oxide, formed glass Glass network, simultaneously participates in the formation of principal crystalline phase.Improve the chemical stability of devitrified glass.CaO、MgO、Na2O、K2O is used as net Network modifier oxides, in addition to the glass melting temperature of reduction glass system, also act as scission of link effect, are conducive to the precipitation of crystal.ZnO can The thermal stability of raising system, reduces devitrified glass fragility.TiO2Or TiO2+ZrO2It is used as Nucleating Agent, the analysis of promotion system nucleation Crystalline substance, titanium oxide, can be separately as Nucleating Agent as main Nucleating Agent, can also be with zirconium oxide collectively as Nucleating Agent, still Zirconium oxide can not be separately as Nucleating Agent, and zirconium oxide contributes to crystal grain thinning as Nucleating Agent, makes crystal grain more uniform, for machine The raising of tool intensity is beneficial to, but excessively can also increase fusion temperature.
Glass melting temperature control is in order to raw material is melting into uniform vitreum, then by coring, crystallization in the present invention Control, influences the content of crystalline phase, and then improve the performance of glass.
Embodiment
With reference to specific embodiment, the invention will be further described.Consubstantiality system described in following embodiments refers to The devitrified glass system of colouring agent is not added with, close coefficient of expansion devitrified glass band refers to the Green microcrystalline glass fusion cake coefficient of expansion The devitrified glass band matched, i.e. colorant part need the coefficient of expansion to adapt to Base Glass Portion, otherwise meeting in cooling procedure Cause the defects such as cracking.
Embodiment 1
A kind of green glass-ceramic, by weight percentage, including following raw material:SiO248.5%;Al2O320%; CaO6.5%;MgO7%;Na2O8.5%;K2O3.3%;ZnO0.2%;TiO23.4%;ZrO22.5%;Cr2O30.1%.
The preparation of green glass-ceramic, comprises the steps:
A, preparation raw material:Raw material is weighed by above-mentioned percentage by weight, is well mixed, obtains batch;
B, parent glass preparation:The batch that step A is obtained is founded under the conditions of 1530 DEG C, is obtained founding Liquid through be cooled to 770-860 DEG C, shaping after, obtain parent glass;
C, green glass-ceramic preparation:The parent glass that step B is obtained through 710-740 DEG C of coring 15-25min, After 875-885 DEG C of crystallization 15-25min, 810-850 DEG C annealing, cutting, polishing obtain green glass-ceramic.
A kind of application of green glass-ceramic in imitative natural green granite devitrified glass, comprises the following steps:
A, preparation raw material:The raw material of green glass-ceramic is weighed by above-mentioned percentage by weight, is well mixed, is coordinated Material;
B, Green microcrystalline glass fusion cake preparation:The batch that step a is obtained is founded under the conditions of 1530 DEG C, will Obtained liquid is founded through water quenching, Green microcrystalline glass fusion cake is obtained;
C, imitative natural green granite devitrified glass preparation:The Green microcrystalline glass fusion cake that step b is obtained is with material road The mode of coloring is added in the devitrified glass band of same system or the close coefficient of expansion, temperature be 1220 DEG C of glass tapes through shaping, 875-885 DEG C of crystallization 15-25min, 810-850 DEG C annealing and cutting, obtain imitative natural green granite devitrified glass.
Embodiment 2
A kind of green glass-ceramic, by weight percentage, including following raw material:SiO249%;Al2O318.5%; CaO 7%;MgO 8.5%;Na2O 6%;K2O 4.5%;ZnO 0.5%;TiO23%;ZrO22%;Cr2O31%.
The preparation of green glass-ceramic, comprises the steps:
A, preparation raw material:Raw material is weighed by above-mentioned percentage by weight, is well mixed, obtains batch;
B, parent glass preparation:The batch that step A is obtained is founded under the conditions of 1525 DEG C, is obtained founding Liquid through be cooled to 780-850 DEG C, shaping after, obtain parent glass;
C, green glass-ceramic preparation:The parent glass that step B is obtained through 720-730 DEG C of coring 18-20min, After 880-887 DEG C of crystallization 18-20min, 820-840 DEG C annealing, cutting, polishing obtain green glass-ceramic.
A kind of application of green glass-ceramic in imitative natural green granite devitrified glass, comprises the following steps:
A, preparation raw material:The raw material of green glass-ceramic is weighed by above-mentioned percentage by weight, is well mixed, is coordinated Material;
B, Green microcrystalline glass fusion cake preparation:The batch that step a is obtained is founded under the conditions of 1525 DEG C, will Obtained liquid is founded through water quenching, Green microcrystalline glass fusion cake is obtained;
C, imitative natural green granite devitrified glass preparation:The Green microcrystalline glass fusion cake that step b is obtained is with material road The mode of coloring is added in the devitrified glass band of same system or the close coefficient of expansion, temperature be 1210 DEG C of glass tapes through shaping, 880-887 DEG C of crystallization 18-20min, 820-840 DEG C annealing and cutting, obtain imitative natural green granite devitrified glass.
Embodiment 3
A kind of green glass-ceramic, by weight percentage, including following raw material:SiO254.5%;Al2O317%; CaO 5.25%;MgO 6.5%;Na2O 5.5%;K2O 3%;ZnO 1.5%;TiO24%;ZrO22.5%;CuO 0.1%;Cr2O30.15%.
The preparation of green glass-ceramic, comprises the steps:
A, preparation raw material:Raw material is weighed by above-mentioned percentage by weight, is well mixed, obtains batch;
B, parent glass preparation:The batch that step A is obtained is founded under the conditions of 1550 DEG C, is obtained founding Liquid through be cooled to 780-840 DEG C, shaping after, obtain parent glass;
C, green glass-ceramic preparation:The parent glass that step B is obtained through 720-750 DEG C of coring 10-20min, After 873-875 DEG C of crystallization 10-20min, 815-835 DEG C annealing, cutting, polishing obtain green glass-ceramic.
A kind of application of green glass-ceramic in imitative natural green granite devitrified glass, comprises the following steps:
A, preparation raw material:The raw material of green glass-ceramic is weighed by above-mentioned percentage by weight, is well mixed, is coordinated Material;
B, Green microcrystalline glass fusion cake preparation:The batch that step a is obtained is founded under the conditions of 1550 DEG C, will Obtained liquid is founded through water quenching, Green microcrystalline glass fusion cake is obtained;
C, imitative natural green granite devitrified glass preparation:The Green microcrystalline glass fusion cake that step b is obtained is with material road The mode of coloring is added in the devitrified glass band of same system or the close coefficient of expansion, temperature be 1280 DEG C of glass tapes through shaping, 873-875 DEG C of crystallization 10-20min, 815-835 DEG C annealing and cutting, obtain imitative natural green granite devitrified glass.
Embodiment 4
A kind of green glass-ceramic, by weight percentage, including following raw material:SiO252%;Al2O316.5%; CaO 9%;MgO 7.5%;Na2O 4.2%;K2O 4.1%;ZnO 1.2%;TiO22.5%;ZrO21%;CuO2 1.2%;Cr2O30.8%.
The preparation of green glass-ceramic, comprises the steps:
A, preparation raw material:Raw material is weighed by above-mentioned percentage by weight, is well mixed, obtains batch;
B, parent glass preparation:The batch that step A is obtained is founded under the conditions of 1535 DEG C, is obtained founding Liquid through cooling, shaping after, obtain parent glass;
C, green glass-ceramic preparation:The parent glass that step B is obtained is cut after coring, crystallization, annealing Cut, polish, obtain green glass-ceramic.
A kind of application of green glass-ceramic in imitative natural green granite devitrified glass, comprises the following steps:
A, preparation raw material:The raw material of green glass-ceramic is weighed by above-mentioned percentage by weight, is well mixed, is coordinated Material;
B, Green microcrystalline glass fusion cake preparation:The batch that step a is obtained is founded under the conditions of 1535 DEG C, will Obtained liquid is founded through water quenching, Green microcrystalline glass fusion cake is obtained;
C, imitative natural green granite devitrified glass preparation:The Green microcrystalline glass fusion cake that step b is obtained is with material road The mode of coloring is added in the devitrified glass band of same system or the close coefficient of expansion, temperature be 1250 DEG C of glass tapes through shaping, Crystallization, annealing and cutting, obtain imitative natural green granite devitrified glass.
Embodiment 5
A kind of green glass-ceramic, by weight percentage, including following raw material:SiO246.5%;Al2O322%; CaO 8%;MgO 5.5%;Na2O 5%;K2O 5.8%;ZnO 0.4%;TiO24%;CuO21.4%;Cr2O31.4%.
The preparation of green glass-ceramic, comprises the steps:
A, preparation raw material:Raw material is weighed by above-mentioned percentage by weight, is well mixed, obtains batch;
B, parent glass preparation:The batch that step A is obtained is founded under the conditions of 1540 DEG C, is obtained founding Liquid through cooling, shaping after, obtain parent glass;
C, green glass-ceramic preparation:The parent glass that step B is obtained is cut after coring, crystallization, annealing Cut, polish, obtain green glass-ceramic.
A kind of application of green glass-ceramic in imitative natural green granite devitrified glass, comprises the following steps:
A, preparation raw material:The raw material of green glass-ceramic is weighed by above-mentioned percentage by weight, is well mixed, is coordinated Material;
B, Green microcrystalline glass fusion cake preparation:The batch that step a is obtained is founded under the conditions of 1540 DEG C, will Obtained liquid is founded through water quenching, Green microcrystalline glass fusion cake is obtained;
C, imitative natural green granite devitrified glass preparation:The Green microcrystalline glass fusion cake that step b is obtained is with material road The mode of coloring is added in the devitrified glass band of same system or the close coefficient of expansion, temperature be 1260 DEG C of glass tapes through shaping, Crystallization, annealing and cutting, obtain imitative natural green granite devitrified glass.
Embodiment 6
A kind of green glass-ceramic, by weight percentage, including following raw material:SiO247%, Al2O316%, CaO 4.8%, MgO 12%, Na2O 10.4%, ZnO 1.8%, TiO23%, ZrO24.5%, Cr2O30.5%.
The preparation of green glass-ceramic, comprises the steps:
A, preparation raw material:Raw material is weighed by above-mentioned percentage by weight, is well mixed, obtains batch;
B, parent glass preparation:The batch that step A is obtained is founded under the conditions of 1540 DEG C, is obtained founding Liquid through cooling, shaping after, obtain parent glass;
C, green glass-ceramic preparation:The parent glass that step B is obtained is cut after coring, crystallization, annealing Cut, polish, obtain green glass-ceramic.
A kind of application of green glass-ceramic in imitative natural green granite devitrified glass, comprises the following steps:
A, preparation raw material:The raw material of green glass-ceramic is weighed by above-mentioned percentage by weight, is well mixed, is coordinated Material;
B, Green microcrystalline glass fusion cake preparation:The batch that step a is obtained is founded under the conditions of 1540 DEG C, will Obtained liquid is founded through water quenching, Green microcrystalline glass fusion cake is obtained;
C, imitative natural green granite devitrified glass preparation:The Green microcrystalline glass fusion cake that step b is obtained is with material road The mode of coloring is added in the devitrified glass band of same system or the close coefficient of expansion, temperature be 1242 DEG C of glass tapes through shaping, Crystallization, annealing and cutting, obtain imitative natural green granite devitrified glass.
Embodiment 7
A kind of green glass-ceramic, by weight percentage, including following raw material:SiO250%, Al2O317.7%, CaO 5.5%, MgO 11%, K2O 7.7%, ZnO 1.3%, TiO23%, ZrO20.8%, Cr2O31.5%, CuO 1.5%.
The preparation of green glass-ceramic, comprises the steps:
A, preparation raw material:Raw material is weighed by above-mentioned percentage by weight, is well mixed, obtains batch;
B, parent glass preparation:The batch that step A is obtained is founded under the conditions of 1553 DEG C, is obtained founding Liquid through cooling, shaping after, obtain parent glass;
C, green glass-ceramic preparation:The parent glass that step B is obtained is cut after coring, crystallization, annealing Cut, polish, obtain green glass-ceramic.
A kind of application of green glass-ceramic in imitative natural green granite devitrified glass, comprises the following steps:
A, preparation raw material:The raw material of green glass-ceramic is weighed by above-mentioned percentage by weight, is well mixed, is coordinated Material;
B, Green microcrystalline glass fusion cake preparation:The batch that step a is obtained is founded under the conditions of 1553 DEG C, will Obtained liquid is founded through water quenching, Green microcrystalline glass fusion cake is obtained;
C, imitative natural green granite devitrified glass preparation:The Green microcrystalline glass fusion cake that step b is obtained is with material road The mode of coloring is added in the devitrified glass band of same system or the close coefficient of expansion, temperature be 1256 DEG C of glass tapes through shaping, Crystallization, annealing and cutting, obtain imitative natural green granite devitrified glass.
Embodiment 8
A kind of green glass-ceramic, by weight percentage, including following raw material:SiO251%, Al2O321%, CaO 5.4%, MgO 9%, Na2O4%, K2O 4.9%, ZnO 1.1%, TiO23%, Cr2O30.6%.
The preparation of green glass-ceramic, comprises the steps:
A, preparation raw material:Raw material is weighed by above-mentioned percentage by weight, is well mixed, obtains batch;
B, parent glass preparation:The batch that step A is obtained is founded under the conditions of 1567 DEG C, is obtained founding Liquid through cooling, shaping after, obtain parent glass;
C, green glass-ceramic preparation:The parent glass that step B is obtained is cut after coring, crystallization, annealing Cut, polish, obtain green glass-ceramic.
A kind of application of green glass-ceramic in imitative natural green granite devitrified glass, comprises the following steps:
A, preparation raw material:The raw material of green glass-ceramic is weighed by above-mentioned percentage by weight, is well mixed, is coordinated Material;
B, Green microcrystalline glass fusion cake preparation:The batch that step a is obtained is founded under the conditions of 1567 DEG C, will Obtained liquid is founded through water quenching, Green microcrystalline glass fusion cake is obtained;
C, imitative natural green granite devitrified glass preparation:The Green microcrystalline glass fusion cake that step b is obtained is with material road The mode of coloring is added in the devitrified glass band of same system or the close coefficient of expansion, temperature be 1272 DEG C of glass tapes through shaping, Crystallization, annealing and cutting, obtain imitative natural green granite devitrified glass.
Embodiment 9
A kind of green glass-ceramic, by weight percentage, including following raw material:SiO252%, Al2O318%, CaO 6.3%, MgO 9%, Na2O 7.2%, ZnO 1%, TiO25.3%, Cr2O31.2%.
The preparation of green glass-ceramic, comprises the steps:
A, preparation raw material:Raw material is weighed by above-mentioned percentage by weight, is well mixed, obtains batch;
B, parent glass preparation:The batch that step A is obtained is founded under the conditions of 1524 DEG C, is obtained founding Liquid through cooling, shaping after, obtain parent glass;
C, green glass-ceramic preparation:The parent glass that step B is obtained is cut after coring, crystallization, annealing Cut, polish, obtain green glass-ceramic.
A kind of application of green glass-ceramic in imitative natural green granite devitrified glass, comprises the following steps:
A, preparation raw material:The raw material of green glass-ceramic is weighed by above-mentioned percentage by weight, is well mixed, is coordinated Material;
B, Green microcrystalline glass fusion cake preparation:The batch that step a is obtained is founded under the conditions of 1524 DEG C, will Obtained liquid is founded through water quenching, Green microcrystalline glass fusion cake is obtained;
C, imitative natural green granite devitrified glass preparation:The Green microcrystalline glass fusion cake that step b is obtained is with material road The mode of coloring is added in the devitrified glass band of same system or the close coefficient of expansion, temperature be 1233 DEG C of glass tapes through shaping, Crystallization, annealing and cutting, obtain imitative natural green granite devitrified glass.
Embodiment 10
A kind of green glass-ceramic, by weight percentage, including following raw material:SiO255%, Al2O317.5%, CaO 5%, MgO 8.3%, K2O 8%, ZnO 0.7%, TiO22.5%, ZrO22%, Cr2O30.7%, CuO0.3%.
The preparation of green glass-ceramic, comprises the steps:
A, preparation raw material:Raw material is weighed by above-mentioned percentage by weight, is well mixed, obtains batch;
B, parent glass preparation:The batch that step A is obtained is founded under the conditions of 1546 DEG C, is obtained founding Liquid through cooling, shaping after, obtain parent glass;
C, green glass-ceramic preparation:The parent glass that step B is obtained is cut after coring, crystallization, annealing Cut, polish, obtain green glass-ceramic.
A kind of application of green glass-ceramic in imitative natural green granite devitrified glass, comprises the following steps:
A, preparation raw material:The raw material of green glass-ceramic is weighed by above-mentioned percentage by weight, is well mixed, is coordinated Material;
B, Green microcrystalline glass fusion cake preparation:The batch that step a is obtained is founded under the conditions of 1546 DEG C, will Obtained liquid is founded through water quenching, Green microcrystalline glass fusion cake is obtained;
C, imitative natural green granite devitrified glass preparation:The Green microcrystalline glass fusion cake that step b is obtained is with material road The mode of coloring is added in the devitrified glass band of same system or the close coefficient of expansion, temperature be 1241 DEG C of glass tapes through shaping, Crystallization, annealing and cutting, obtain imitative natural green granite devitrified glass.
Embodiment 11
A kind of green glass-ceramic, by weight percentage, including following raw material:SiO254.8%, Al2O319%, CaO 4.8%, MgO 9%, Na2O5%, K2O 2%, ZnO 0.3%, TiO23.2%, Cr2O31.1%, CuO0.8%.
The preparation of green glass-ceramic, comprises the steps:
A, preparation raw material:Raw material is weighed by above-mentioned percentage by weight, is well mixed, obtains batch;
B, parent glass preparation:The batch that step A is obtained is founded under the conditions of 1548 DEG C, is obtained founding Liquid through cooling, shaping after, obtain parent glass;
C, green glass-ceramic preparation:The parent glass that step B is obtained is cut after coring, crystallization, annealing Cut, polish, obtain green glass-ceramic.
A kind of application of green glass-ceramic in imitative natural green granite devitrified glass, comprises the following steps:
A, preparation raw material:The raw material of green glass-ceramic is weighed by above-mentioned percentage by weight, is well mixed, is coordinated Material;
B, Green microcrystalline glass fusion cake preparation:The batch that step a is obtained is founded under the conditions of 1548 DEG C, will Obtained liquid is founded through water quenching, Green microcrystalline glass fusion cake is obtained;
C, imitative natural green granite devitrified glass preparation:The Green microcrystalline glass fusion cake that step b is obtained is with material road The mode of coloring is added in the devitrified glass band of same system or the close coefficient of expansion, temperature be 1269 DEG C of glass tapes through shaping, Crystallization, annealing and cutting, obtain imitative natural green granite devitrified glass.
Comparative example 1
Devitrified glass, in addition to colouring agent is different, difference also includes such as B2O3And/or P2O5And/or Co2O3And/or Ni2O3Etc. other components.
Comparative example 2
Green glass-ceramic, comprising colouring agent, difference also includes such as B2O3And/or P2O5And/or Co2O3And/or Ni2O3Etc. other components.
The performance parameter of green glass-ceramic of the present invention, imitative natural green granite devitrified glass, it is as follows:

Claims (9)

1. a kind of green glass-ceramic, it is characterised in that by weight percentage, including following raw material:SiO246-56%, 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%.
2. a kind of green glass-ceramic according to claim 1, it is characterised in that by weight percentage, including it is following Raw material:SiO247%, Al2O316%, CaO 6.7%, MgO 7.5%, Na2O and/or K2O 13%, ZnO 1.8%, TiO2 Or TiO2+ZrO27.5%, Cr2O30.5%.
3. a kind of green glass-ceramic according to claim 1, it is characterised in that by weight percentage, including it is following Raw material:SiO250%, 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%.
4. a kind of green glass-ceramic according to claim 1, it is characterised in that by weight percentage, including it is following Raw material:SiO251%, Al2O321%, CaO 6%, MgO 9%, Na2O and/or K2O 8.3%, ZnO 1.1%, TiO2Or TiO2+ZrO23%, Cr2O30.6%.
5. a kind of green glass-ceramic according to claim 1, it is characterised in that by weight percentage, including it is following Raw material:SiO253%, Al2O318%, CaO 5.8%, MgO 8.2%, Na2O and/or K2O 7.5%, ZnO 1%, TiO2Or TiO2+ZrO25.3%, Cr2O31.2%.
6. a kind of preparation method of green glass-ceramic, it is characterised in that comprise the following steps:
A, preparation raw material:Raw material, SiO are weighed by following percentage by weights246-56%, 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%, are well mixed, obtain batch;
B, parent glass preparation:The batch that step A is obtained is founded under the conditions of 1500-1550 DEG C, will be melted into To liquid through be cooled to 760-870 DEG C, shaping after, obtain parent glass;
C, green glass-ceramic preparation:The parent glass that step B is obtained cuts, beaten after coring, crystallization, annealing Mill, obtains green glass-ceramic.
7. the preparation method of a kind of green glass-ceramic according to claim 6, it is characterised in that in step C, coring temperature Spend for 700-750 DEG C, nucleation time is 10-30min, crystallization temperature is 870-950 DEG C, crystallization time 10-30min, annealing temperature Spend for 800-860 DEG C.
8. application of a kind of green glass-ceramic in imitative natural green granite devitrified glass, it is characterised in that including following Step:
A, preparation raw material:Raw material, SiO are weighed by following percentage by weights246-56%, 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%, are well mixed, obtain batch;
B, Green microcrystalline glass fusion cake preparation:The batch that step a is obtained is founded under the conditions of 1500-1550 DEG C, Obtained liquid will be founded through water quenching, Green microcrystalline glass fusion cake is obtained;
C, imitative natural green granite devitrified glass preparation:The obtained Green microcrystalline glass fusion cakes of step b are coloured with material road Mode be added to the devitrified glass system that is not added with colouring agent or the crystallite with Green microcrystalline glass fusion cake matched expansion coefficient In glass tape, control temperature of the devitrified glass liquid in material road for 1200-1280 DEG C of glass tape through shaping, crystallization, anneal and cut Cut out, obtain imitative natural green granite devitrified glass.
9. a kind of application of the green glass-ceramic according to claim 8 in imitative natural green granite devitrified glass, Characterized in that, in step c, crystallization temperature is 870-950 DEG C, crystallization time 10-30min, annealing temperature is 800-860 DEG C.
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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
CN110981472A (en) * 2019-12-30 2020-04-10 江西赛瓷材料有限公司 High-strength green zirconia ceramic powder and preparation method and application thereof

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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
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