CN111072276A - Lithium-aluminum-silicon microcrystalline glass containing composite clarifying agent and preparation method thereof - Google Patents
Lithium-aluminum-silicon microcrystalline glass containing composite clarifying agent and preparation method thereof Download PDFInfo
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- CN111072276A CN111072276A CN201911359374.1A CN201911359374A CN111072276A CN 111072276 A CN111072276 A CN 111072276A CN 201911359374 A CN201911359374 A CN 201911359374A CN 111072276 A CN111072276 A CN 111072276A
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
- C03C1/004—Refining agents
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B25/00—Annealing glass products
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B5/00—Melting in furnaces; Furnaces so far as specially adapted for glass manufacture
- C03B5/16—Special features of the melting process; Auxiliary means specially adapted for glass-melting furnaces
- C03B5/225—Refining
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- 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
- C03C10/0018—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 SiO2, Al2O3 and monovalent metal oxide as main constituents
- C03C10/0027—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 SiO2, Al2O3 and monovalent metal oxide as main constituents containing SiO2, Al2O3, Li2O as main constituents
Abstract
The invention discloses a lithium aluminum silicon glass ceramic containing a composite clarifying agent, which comprises the following raw materials in parts by weight: 0.2 to 0.7 percent of BaO, 0.2 to 0.4 percent of SrO and 0.4 to 0.7 percent of SnO2And 0 to 0.3 percent of carbon. The invention also provides a preparation method of the lithium aluminum silicon glass ceramics containing the composite clarifying agent, which comprises the following steps: mixing and grinding the raw materials consisting of the main material and the clarifying agent, melting and clarifying, molding the obtained glass liquid, annealing the obtained plate-shaped glass, and nucleating and crystallizing to obtain the lithium-aluminum-silicon microcrystalline glass containing the composite clarifying agent. The invention has good clarification effect and is greenAnd is environment-friendly.
Description
Technical Field
The invention relates to a production method of lithium aluminum silicon glass ceramics, in particular to a production method of environment-friendly lithium aluminum silicon glass ceramics containing a composite clarifying agent.
Background
Li2O-Al2O3-SiO2The (lithium aluminum silicon) system microcrystalline glass is one of the systems which are the earliest, the deepest and the most widely used in the microcrystalline glass, and is Li2O、Al2O3、SiO2The microcrystalline glass system composed of basic glass components is mainly characterized in that the thermal expansibility can be adjusted in a large range, and a zero expansion coefficient can be obtained, so that the microcrystalline glass system has good thermal shock resistance, and is widely used in the fields of manufacturing electric appliance matching panels, cookers, tableware, heating appliances for laboratories, high-temperature electric light source glass, high-temperature heat exchangers, quartz glass substitutes, high-temperature windows, astronomical telescopes, radar radomes, liquid crystal displays and the like.
In the melting stage of the lithium aluminum silicon system glass, a large amount of bubbles are generated due to various physical and chemical reactions of carbonate decomposition, high-temperature volatilization of volatile substances and the like of a glass batch, but the bubbles are not easy to discharge under the influence of the properties of the batch and melting conditions, and the bubbles remained in the glass after molding can form defects, so that the mechanical property and the optical property of the glass are influenced. One or more fining agents are typically added to the glass batch materials to release gases that accelerate bubble removal and fining during the glass melting process. The conventional lithium aluminum silicon glass ceramics use arsenic trioxide and/or antimony trioxide as a clarifying agent, the clarifying effect is good, but the toxicity of the arsenic trioxide and the antimony trioxide has great influence on the environment. The use of the clarifier is forbidden at home and abroad, and arsenic trioxide and antimony trioxide are gradually restricted to be used as clarifiers for producing glass ceramic panels in various countries around the world. The european union, read No. 1907/2006, limits the arsenic and antimony content of glass products. Therefore, novel clarifiers capable of replacing toxic and harmful clarifiers such as arsenic trioxide and antimony trioxide are researched and developed at home and abroad.
As a clarifier for replacing arsenic trioxide and antimony trioxide in lithium aluminosilicate glass ceramics, arsenic-free and antimony-free lithium aluminosilicate glass ceramics and a preparation method thereof are disclosed in patents of publication numbers CN107667076A, CN109594674A, CN106517775A, CN104609733A, CN104609733A, CN103058524A, CN109020191A and the like. In the above patent publications, tin oxide is mainly used as a clarifier for lithium aluminosilicate glass or other glass systems, and cerium oxide, sodium carbonate, calcium fluoride, ammonium dihydrogen phosphate, sodium chloride, ammonium chloride, sodium sulfate, barium sulfate, and sodium nitrate may be used alone or in combination as a clarifier. It should be noted, however, that tin oxide is a preferred non-toxic glass ceramic fining agent, but its fining effect is not very good when used alone. Cerium oxide is an expensive rare earth compound, has a certain clarifying effect, but increases the raw material cost. Ammonium salt, halogen salt, nitrate and sulfate are used as clarifying agents, the clarifying effect on the lithium-aluminum-silicon microcrystalline glass is general, and high-temperature decomposed SO2、SO3、NO2、F-、Cl-When the volatile components are clarified, the emission of the volatile components can cause great harm to the environment and is not suitable for the development requirement of future clarifying agents. Therefore, it is important to develop a new type of non-toxic and harmless clarifier.
Disclosure of Invention
The invention mainly solves the technical problem of providing the lithium aluminum silicon glass ceramics containing the composite clarifying agent and the preparation method thereof.
In order to solve the technical problems, the invention provides lithium aluminum silicon glass ceramics containing a composite clarifying agent, which comprises the following raw materials in parts by weight: BaO (barium oxide) 0.2-0.7%, SrO (strontium oxide) 0.2-0.4% and SnO 0.4-0.7%2(tin oxide) and 0% to 0.3% of carbon (carbon powder).
The preferred scheme is as follows: the clarifying agent comprises the following components in parts by weight: BaO (barium oxide) 0.2-0.7%, SrO (strontium oxide) 0.2-0.4% and SnO 0.4-0.7%2(tin oxide) and 0.1 to 0.3% of carbon (carbon powder).
The further preferred scheme is as follows: the clarifying agent comprises the following components in parts by weight: BaO 0.2%, SrO0.4%, SnO20.5% and carbon (carbon powder) 0.3%.
The improvement of the lithium-aluminum-silicon glass ceramics containing the composite clarifying agent of the invention comprises the following steps: the main materials of the lithium aluminum silicon glass ceramics comprise the following components by weight:
SiO2(silica) 70%, Li23.8% of O (lithium oxide) and Al2O316% of (aluminum oxide), 1.0% of MgO (magnesium oxide), 1.3% of ZnO (zinc oxide), and TiO2(titanium oxide) 2.0%, ZrO2(zirconia) 1.5%, P2O51.0 percent of (phosphorus pentoxide) and (K)2O+Na2O) (potassium oxide and sodium oxide) 2.0%.
The improvement of the lithium-aluminum-silicon glass ceramics containing the composite clarifying agent of the invention comprises the following steps: (K)2O+Na2In O), K2O account for (K)2O+Na2O) 40 to 60% by weight.
The invention also provides a preparation method of the lithium aluminum silicon glass ceramic containing the composite clarifying agent, which comprises the following steps:
1) mixing and grinding the raw materials (the components with the weight content as described above) consisting of the main material and the clarifying agent (grinding the raw materials to a 100-mesh sieve) to obtain a uniform mixed material;
the step can adopt a mechanical ball milling mode;
2) melting and clarifying the mixture at 1600-1650 ℃ for 10-15 hours to obtain molten glass (low-viscosity and fully-clarified molten glass);
3. carrying out forming treatment on the molten glass to obtain plate-shaped glass;
4) annealing the plate-shaped glass at the annealing temperature of 500-550 ℃ for 1 +/-0.2 hours;
this step 4) can be carried out in an annealing furnace;
5) nucleating the annealed plate-shaped glass obtained in the step 4) for 1-2 hours at 600-800 ℃, then heating to 800-950 ℃, performing heat preservation crystallization treatment for 2-4 hours, and finally cooling to room temperature; the lithium-aluminum-silicon glass-ceramic containing the composite clarifying agent is obtained.
As an improvement of the preparation method of the invention: the forming treatment in the step 3) is compression forming or calendaring forming.
Specifically, in the invention, the raw materials of the lithium aluminosilicate glass ceramics comprise the following components in percentage by weight:
SiO2(silica) 70%, Li23.8% of O (lithium oxide) and Al2O316% of (aluminum oxide), 1.0% of MgO (magnesium oxide), 1.3% of ZnO (zinc oxide), and TiO2(titanium oxide) 2.0%, ZrO2(zirconia) 1.5%, P2O5(phosphorus pentoxide) 1.0%, K2O+Na22.0 percent of O (potassium oxide and sodium oxide), 0.2 to 0.7 percent of BaO (barium oxide), 0.2 to 0.4 percent of SrO (strontium oxide), SnO20.4 to 0.7 percent of (tin oxide) and 0 to 0.3 percent of carbon powder.
Wherein, SiO2、Li2O、Al2O3Is the basic glass component of lithium-aluminum-silicon glass system, MgO, ZnO and K2O、Na2O is fluxing agent, TiO2、ZrO2、P2O5Is a composite crystal nucleus agent of BaO, SrO and SnO2And carbon powder is a composite clarifying agent.
The invention has the following technical advantages:
1) BaO, SrO and SnO are used in the invention2And carbon powder (the dosage of the carbon powder can also be 0) as a composite clarifying agent, BaO, SrO and SnO2The glass is a variable valence oxide clarifier, namely low-temperature oxidation and high-temperature reduction, and is firstly combined with oxygen at low temperature to form a high valence oxide in the glass melting and heating process, when the temperature is raised to the decomposition temperature of the high valence oxide, the high valence oxide is decomposed again, oxygen is released into glass liquid, when the temperature exceeds the oxygen saturation solubility in the glass liquid, the oxygen is separated out and enters air bubbles, and the volume of the air bubbles is increased, so that the clarification effect is achieved. The three kinds of variable valence oxides are cooperated with each other,the effect of the clarifying agent is fully exerted, and the optimal clarifying effect is realized. The carbon powder is mainly used as a reducing agent and plays a role in adjusting the oxidation-reduction atmosphere during high-temperature clarification.
2) The invention adopts the nontoxic composite clarifying agent to replace the traditional arsenic trioxide and antimony trioxide and also replace the clarifying agents such as vanadium oxide, cerium oxide and the like which are newly developed at present.
The invention can produce and prepare the non-toxic, harmless and environment-friendly lithium aluminum silicon glass ceramic panel, the main crystal phase of the panel is β -quartz solid solution (shown in figure 1), the grain size is about 100nm (shown in figure 2), and the thermal expansion coefficient is 0-1.2 multiplied by 10-6The bending strength is 110-150 MPa, each technical index meets the requirement of QB/T4831-2015, and the content of arsenic and antimony meets the requirement of REACH regulation No. 1907/2006 of European Union.
In conclusion, the composite clarifying agent disclosed by the invention achieves the clarifying effect of the clarifying agents such as arsenic trioxide, antimony trioxide, vanadium oxide, cerium oxide and the like, and is green and environment-friendly; can be used for preparing products such as electromagnetic oven panels, daily kitchenware or tableware, heating appliances for laboratories and the like.
Drawings
The following describes embodiments of the present invention in further detail with reference to the accompanying drawings.
FIG. 1 is an XRD (X-ray diffraction) pattern of lithium-aluminum-silicon glass containing a composite clarifying agent after crystallization at different temperatures;
FIG. 2 is an SEM photograph of the microstructure of the lithium aluminosilicate glass containing the composite clarifying agent after crystallization at 950 ℃.
FIG. 3 is an SEM photograph of the microstructure of lithium aluminosilicate glass containing the composite clarifying agent after crystallization at 850 ℃.
FIG. 4 is an SEM photograph of the microstructure of the lithium aluminosilicate glass containing the composite clarifier after crystallization at 900 ℃.
FIG. 5 is an SEM photograph of the microstructure of the lithium aluminosilicate glass containing the composite clarifier after crystallization at 1050 ℃.
Detailed Description
The invention will be further described with reference to specific examples, but the scope of the invention is not limited thereto:
example 1-1:the lithium-aluminum-silicon glass ceramic containing the composite clarifying agent comprises the following raw materials in parts by weight: SiO 2270％、Li2O 3.8％、Al2O316％、MgO 1.0％、ZnO 1.3％、TiO22.0％、ZrO21.5％、P2O51.0％、K2O+Na2O2.0% (i.e., K)2O1.0％、Na2O 1.0％)、BaO 0.2％、SrO 0.4％、SnO20.5 percent and 0.3 percent of carbon powder.
The preparation method comprises the following steps:
1) mixing and grinding the raw materials (the ingredients with the weight content) in a mechanical ball milling mode (grinding to a 100-mesh sieve) to prepare a uniform mixture;
2) melting and clarifying the mixture at 1600-1650 ℃ for 13-15 hours to obtain molten glass (low-viscosity and fully-clarified molten glass);
3. carrying out hydraulic calendering on the glass to obtain plate-shaped glass; the thickness of the plate-shaped glass is about 5-6 mm;
4) conveying the formed plate-shaped glass to an annealing furnace for annealing at the annealing temperature of 500-550 ℃ for 1 hour;
5) nucleating the annealed plate-shaped glass obtained in the step 4) for 1 hour at 650 ℃, then heating to 950 ℃, carrying out heat preservation crystallization treatment for 4 hours, and finally naturally cooling to room temperature; the lithium-aluminum-silicon glass-ceramic containing the composite clarifying agent is obtained.
The XRD pattern is shown in figure 1, and the microstructure is shown in figure 2.
The prepared lithium-aluminum-silicon glass-ceramic product has no bubbles, good uniformity and good luster, the main crystal phase of the product is β -quartz solid solution, the grain size is about 100nm, and the thermal expansion coefficient is 0-0.5 multiplied by 10-6The bending strength is 140-150 MPa at/° C.
Example 1-2, the crystallization temperature in step 5) of example 1-1 was changed from 950 ℃ to 850 ℃, 900 ℃, 1050 ℃, respectively, and the remainder was the same as example 1-1.
The comparison of the XRD patterns is shown in figure 1, and the microstructure is shown in figures 3, 4 and 5:
when the crystallization treatment temperature is 850 ℃, the crystalline phase is β -quartz solid solution, the grain size is 50nm, and the crystallinity is not high;
when the crystallization treatment temperature is 900 ℃, the crystalline phase is β -quartz solid solution, the grain size is 70nm, and the crystallinity is not high;
when the crystallization temperature is 1050 ℃, the crystalline phase is β -spodumene, the grain size is 300nm, and the grains are coarse.
In addition, 500 ℃ shown in FIG. 1 means a mother glass after glass annealing, and has no crystal phase.
Embodiment 2, a lithium aluminum silicon glass-ceramic containing composite clarifier, which comprises the following raw materials by weight: SiO 2270％、Li2O 3.8％、Al2O316％、MgO 1.0％、ZnO 1.3％、TiO22.0％、ZrO21.5％、P2O51.0％、K2O+Na2O 2.0％、BaO 0.7％、SrO 0.2％、SnO20.4 percent and carbon powder 0.1 percent.
The preparation method was identical to example 1-1.
The prepared lithium-aluminum-silicon glass-ceramic product has no bubbles, good uniformity and good luster, the main crystal phase of the product is β -quartz solid solution, the grain size is about 100nm, and the thermal expansion coefficient is 0.6-1.0 multiplied by 10-6The bending strength is 120-130 MPa at/° C.
Embodiment 3, a lithium aluminum silicon glass ceramic containing composite clarifier, which comprises the following components by weight: SiO 2270％、Li2O 3.8％、Al2O316％、MgO 1.0％、ZnO 1.3％、TiO22.0％、ZrO21.5％、P2O51.0％、K2O+Na2O 2.0％、BaO 0.4％、SrO 0.4％、SnO20.6％。
The preparation method was identical to example 1-1.
The prepared lithium aluminum silicon glass-ceramic product has no bubbles, good uniformity and good luster, the main crystal phase of the product is β -quartz solid solution, the grain size is about 100nm, and the thermal expansion coefficient is 1.1-1.2 multiplied by 10-6/° c, the bending strength is 110 MPa.
Embodiment 4, a lithium aluminum silicon glass ceramic containing composite clarifier, which comprises the following components by weight: SiO 2270％、Li2O 3.8％、Al2O316％、MgO 1.0％、ZnO 1.3％、TiO22.0％、ZrO21.5％、P2O51.0％、K2O+Na2O 2.0％、BaO 0.3％、SrO 0.2％、SnO20.6 percent and 0.3 percent of carbon powder.
The preparation method was identical to example 1-1.
The prepared lithium-aluminum-silicon glass-ceramic product has no bubbles, good uniformity and good luster, the main crystal phase of the product is β -quartz solid solution, the grain size is about 100nm, and the thermal expansion coefficient is 0.2-0.6 multiplied by 10-6The bending strength is 130-140 MPa at/° C.
Comparative example 1, "BaO 0.2%, SrO 0.4%, SnO in example 1-120.5% "was changed as described in the following Table 1, respectively, and the remainder was equivalent to examples 1 to 1; a comparison of the results obtained is shown in Table 1 below.
TABLE 1
Finally, it is also noted that the above-mentioned lists merely illustrate a few specific embodiments of the invention. It is obvious that the invention is not limited to the above embodiments, but that many variations are possible. All modifications which can be derived or suggested by a person skilled in the art from the disclosure of the present invention are to be considered within the scope of the invention.
Claims (7)
1. The lithium aluminum silicon glass ceramic containing the composite clarifying agent comprises the following raw materials of a main material and the clarifying agent, and is characterized in that the clarifying agent comprises the following components in parts by weight:
0.2 to 0.7 percent of BaO, 0.2 to 0.4 percent of SrO and 0.4 to 0.7 percent of SnO2And 0 to 0.3 percent of carbon.
2. The lithium aluminosilicate glass ceramic containing the composite clarifying agent according to claim 1, wherein the clarifying agent is composed of the following components by weight:
0.2 to 0.7 percent of BaO, 0.2 to 0.4 percent of SrO and 0.4 to 0.7 percent of SnO2And 0.1 to 0.3 percent of carbon.
3. The lithium aluminosilicate glass ceramic containing the composite clarifying agent according to claim 2, wherein the clarifying agent is composed of the following components by weight: BaO 0.2%, SrO 0.4%, SnO20.5% and carbon 0.3%.
4. The lithium aluminum silicon glass ceramic containing the composite clarifying agent according to any one of claims 1 to 3, wherein the main materials of the lithium aluminum silicon glass ceramic comprise the following components in parts by weight:
SiO270％、Li2O 3.8％、Al2O316％、MgO 1.0％、ZnO 1.3％、TiO22.0％、ZrO21.5％、P2O51.0％、(K2O+Na2O)2.0％。
5. the lithium aluminosilicate glass-ceramic containing composite clarifier according to claim 4, characterized in that: k2O+Na2In O, K2O account for (K)2O+Na2O) 40 to 60% by weight.
6. The preparation method of the lithium aluminum silicon glass ceramic containing the composite clarifying agent as claimed in claim 1-5, which is characterized by comprising the following steps:
1) mixing and grinding the raw materials consisting of the main material and the clarifying agent to obtain a uniform mixture;
2) melting and clarifying the mixture at 1600-1650 ℃ for 10-15 hours to obtain molten glass;
3. carrying out forming treatment on the molten glass to obtain plate-shaped glass;
4) annealing the plate-shaped glass at the annealing temperature of 500-550 ℃ for 1 +/-0.2 hours;
5) nucleating the annealed plate-shaped glass obtained in the step 4) for 1-2 hours at 600-800 ℃, then heating to 800-950 ℃, performing heat preservation crystallization treatment for 2-4 hours, and finally cooling to room temperature; the lithium-aluminum-silicon glass-ceramic containing the composite clarifying agent is obtained.
7. The method for preparing lithium aluminosilicate glass ceramics containing composite clarifier according to claim 6, characterized in that:
the forming treatment in the step 3) is compression forming or calendaring forming.
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| DE102021126968A1 (en) | 2021-10-18 | 2023-04-20 | Schott Ag | Ceramic printing ink, in particular for inkjet printing, for producing a coating on a glass ceramic and coated glass ceramic plate |
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