CN115490429B - Composition for preparing microcrystalline glass, microcrystalline glass and preparation method and application thereof - Google Patents
Composition for preparing microcrystalline glass, microcrystalline glass and preparation method and application thereof Download PDFInfo
- Publication number
- CN115490429B CN115490429B CN202211001255.0A CN202211001255A CN115490429B CN 115490429 B CN115490429 B CN 115490429B CN 202211001255 A CN202211001255 A CN 202211001255A CN 115490429 B CN115490429 B CN 115490429B
- Authority
- CN
- China
- Prior art keywords
- glass
- temperature
- composition
- treatment
- time
- 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
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000011521 glass Substances 0.000 title claims description 127
- 239000002241 glass-ceramic Substances 0.000 claims abstract description 53
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000010931 gold Substances 0.000 claims abstract description 28
- 229910052737 gold Inorganic materials 0.000 claims abstract description 28
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 24
- 229910021532 Calcite Inorganic materials 0.000 claims abstract description 13
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 claims abstract description 12
- 239000010433 feldspar Substances 0.000 claims abstract description 12
- 239000010436 fluorite Substances 0.000 claims abstract description 12
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 12
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 11
- 238000002844 melting Methods 0.000 claims description 45
- 230000008018 melting Effects 0.000 claims description 45
- 238000002425 crystallisation Methods 0.000 claims description 26
- 230000008025 crystallization Effects 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 25
- 238000010438 heat treatment Methods 0.000 claims description 20
- 239000000843 powder Substances 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 238000000498 ball milling Methods 0.000 claims description 19
- 239000007788 liquid Substances 0.000 claims description 18
- 230000006911 nucleation Effects 0.000 claims description 17
- 238000010899 nucleation Methods 0.000 claims description 17
- 238000005245 sintering Methods 0.000 claims description 17
- 238000010791 quenching Methods 0.000 claims description 14
- 230000000171 quenching effect Effects 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 7
- 239000012770 industrial material Substances 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 3
- 229910018068 Li 2 O Inorganic materials 0.000 claims description 3
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 3
- 238000010276 construction Methods 0.000 claims description 3
- 239000004035 construction material Substances 0.000 claims description 3
- 230000000630 rising effect Effects 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 239000000126 substance Substances 0.000 abstract description 8
- 230000009286 beneficial effect Effects 0.000 abstract description 6
- 238000010923 batch production Methods 0.000 abstract description 2
- 239000002893 slag Substances 0.000 description 14
- 238000001035 drying Methods 0.000 description 12
- 238000005520 cutting process Methods 0.000 description 10
- 239000013078 crystal Substances 0.000 description 9
- 238000001816 cooling Methods 0.000 description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 238000000227 grinding Methods 0.000 description 5
- 238000005498 polishing Methods 0.000 description 5
- 238000001514 detection method Methods 0.000 description 4
- 238000005265 energy consumption Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000010128 melt processing Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 238000000137 annealing Methods 0.000 description 3
- 239000000292 calcium oxide Substances 0.000 description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910000174 eucryptite Inorganic materials 0.000 description 3
- 238000010309 melting process Methods 0.000 description 3
- 238000003490 calendering Methods 0.000 description 2
- 238000003426 chemical strengthening reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 239000002440 industrial waste Substances 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 229910052629 lepidolite Inorganic materials 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 239000006060 molten glass Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 2
- 229910010271 silicon carbide Inorganic materials 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 238000007088 Archimedes method Methods 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- 239000002310 Isopropyl citrate Substances 0.000 description 1
- 238000006124 Pilkington process Methods 0.000 description 1
- 239000006004 Quartz sand Substances 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 238000007507 annealing of glass Methods 0.000 description 1
- 239000006121 base glass Substances 0.000 description 1
- 239000011449 brick Substances 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000005329 float glass Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000010434 nepheline Substances 0.000 description 1
- 229910052664 nepheline Inorganic materials 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 description 1
- 229910001950 potassium oxide Inorganic materials 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000010312 secondary melting process Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- 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
- C03C10/16—Halogen containing crystalline phase
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Ceramic Engineering (AREA)
- Organic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Glass Compositions (AREA)
Abstract
The invention relates to the technical field of glass ceramics, and discloses a composition for preparing glass ceramics, a preparation method and application thereof. Based on the total mass of the composition, the composition contains 60-80wt% of gold mine tailings, 2-8wt% of calcite, 2-10wt% of lithium feldspar, 1-9wt% of fluorite and 10-20wt% of sodium carbonate. The glass ceramics prepared by the composition and the preparation method provided by the invention have the advantages of low thermal expansion coefficient, excellent temperature resistance, good mechanical property, low porosity, good chemical stability and high use temperature, can meet the market requirements, and has wide application range. In addition, the preparation method provided by the invention is simple to operate, low in cost, energy-saving and environment-friendly, and is beneficial to large-scale batch production.
Description
Technical Field
The invention relates to the technical field of glass ceramics, in particular to a composition for preparing glass ceramics, a preparation method and application thereof.
Background
The glass ceramics as one of glass materials can be prepared by composition design and controlled crystallization, has higher mechanical properties than amorphous glass, and adopts reasonable chemical strengthening to enhance the anti-drop impact property, has small thermal expansion coefficient and wide application prospect.
Along with the development of economy, the demands for coal and rare earth are increasing, the yield is increasing, and the industrial waste gas is increasing. These wastes not only occupy a lot of land, but also cause serious pollution to the surrounding water resources and soil. The gold mine tailing contains components required by microcrystalline glass such as silicon oxide, aluminum oxide, calcium oxide, potassium oxide, sodium oxide and the like, so that the gold mine tailing is suitable for being used as a raw material for preparing microcrystalline glass, and has high use value. The glass ceramics prepared by using gold mine tailing as a main raw material is one of slag glass ceramics, a large amount of tailings are used as raw materials, the production is relatively resource-saving, the difficult problem of how to treat industrial wastes is solved, and the glass ceramics is the best choice for replacing natural stone and partial porcelain bricks. The renewable resources are fully utilized to develop the energy-saving material, which is not only the strategic requirement of economic development, but also the urgent requirement of establishing a resource and energy-saving society.
At present, the continuous forming process of microcrystalline glass mainly comprises a float method, a calendaring method and a sintering method. The sintering method is that the molten glass is water quenched into broken glass, and then put into a mould for crystallization and annealing treatment, the yield of the product obtained by the method is low, and two high temperature processes (glass melting and microcrystallizing treatment) are needed, so that the energy consumption and the cost are high. The basic technological process for preparing the microcrystalline glass by the sintering method comprises the following steps: batching, melting, water quenching, ball milling, sintering (nucleation crystallization forming) and processing. Float glass has two surfaces in contact with air and with molten tin, which differ in chemical composition, which is not apparent in appearance, but has a small effect on the communication mobile terminal glass substrate that requires chemical strengthening. This effect manifests itself in a maldistribution of the stress layers on both sides after ion exchange, which ultimately results in a considerable compromise in the strengthening effect. While the conventional calendaring method has advantages in producing thicker glass sheets, it has composition and process problems in preparing ultra-thin glass.
The existing technology for preparing microcrystalline glass by using gold mine tailings as raw materials adopts a sintering method and a melting method, and the two technologies for preparing microcrystalline glass are completed through two steps of melting and crystallizing treatment of base glass. The glass is melted by high temperature melting (1500-1600 ℃) of the batch materials to prepare water quenched glass particles or fusion cakes. The crystallization treatment needs to heat the obtained glass sample for the second time (900-1100 ℃), the energy consumption is higher, and the production cost of the product is increased. And the main crystal phase precipitated in the microcrystalline glass prepared by the method is mainly beta-wollastonite and feldspar crystals, the crystallization temperature of the crystal forms is higher, the energy consumption is increased, and the cost of the product is further increased. And the glass ceramic sample obtained by the method has poor mechanical strength and corrosion resistance.
CN101696087a discloses a black glass ceramic plate made of gold tailings and a manufacturing method thereof. Crushing and screening gold tailings, quartz sand, calcite and nepheline; then removing cyanide in the gold tailings by an ion exchange method; weighing the raw materials in proportion and preparing a mixture; and then the batch is sequentially subjected to melting, water quenching and crystallization treatment, the crystallization temperature is higher and is 1020-1070 ℃, the breaking strength of the prepared microcrystalline glass plate is only 60-66MPa, and the microcrystalline glass has higher crystallization temperature, higher energy consumption and poorer mechanical property.
Disclosure of Invention
The invention aims to solve the problems of poor mechanical property and high thermal expansion coefficient of microcrystalline glass in the prior art.
In order to achieve the above object, the first aspect of the present invention provides a composition for preparing glass-ceramic, which comprises 60 to 80wt% of gold mine tailings, 2 to 8wt% of calcite, 2 to 10wt% of lithium feldspar, 1 to 9wt% of fluorite and 10 to 20wt% of sodium carbonate, based on the total mass of the composition.
The second aspect of the invention provides a preparation method of microcrystalline glass, which comprises the following steps:
(1) Contacting and mixing the components in the composition of the first aspect to obtain a batch, and then melting the batch to obtain glass liquid;
(2) Carrying out water quenching and ball milling on the glass liquid in sequence to obtain glass powder;
(3) Sintering the glass powder at high temperature; the high-temperature sintering temperature is not higher than 900 ℃.
The third aspect of the invention provides glass ceramics prepared by the preparation method of the second aspect.
In a fourth aspect, the invention provides the use of the composition according to the first aspect or the glass-ceramic according to the third aspect in construction and industrial materials.
Through the technical scheme, the invention has the following advantages:
1. the composition provided by the invention utilizes the gold mine tailings as a main raw material to produce the glass ceramics, thereby changing waste into valuables, solving the problem that the gold mine tailings cannot be recycled and protecting the environment; meanwhile, the high silicon and high aluminum components in the gold mine tailings are fully utilized, and the lithium feldspar and other components are combined, so that the eucryptite phase with low thermal expansion coefficient, excellent temperature resistance and good chemical stability can be separated out, the thermal expansion coefficient of the microcrystalline glass is further reduced, and the mechanical property, high temperature resistance and chemical stability of the microcrystalline glass are improved;
2. the microcrystalline glass prepared by the composition and the preparation method provided by the invention has the advantages of low thermal expansion coefficient, high refractoriness, good mechanical property, low porosity, good chemical stability and high use temperature, can meet the market requirements, has a wide application range, can be used as a high-grade building and industrial material, and has a wide application prospect;
3. the preparation method provided by the invention is simple to operate, low in cost, energy-saving and environment-friendly, and is beneficial to large-scale batch production.
Drawings
FIG. 1 is an XRD diffraction pattern of glass ceramics prepared in example 1 of the present invention;
FIG. 2 is a schematic diagram showing the change of material temperature with time in the preparation method of glass ceramics according to an embodiment of the present invention.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
In the present invention, the room temperature represents 25.+ -. 2 ℃ unless otherwise stated.
In the present invention, unless explicitly stated, neither "primary nor" secondary "is intended to limit each material or operation, but only to distinguish each material or operation, for example," primary melt processing "and" secondary melt processing "are intended to distinguish only to mean that they are not the same operation.
The first aspect of the invention provides a composition for preparing glass ceramics, which comprises 60-80wt% of gold mine tailings, 2-8wt% of calcite, 2-10wt% of lithium feldspar, 1-9wt% of fluorite and 10-20wt% of sodium carbonate based on the total mass of the composition.
The inventor of the present invention found in the course of the research that by compounding the above-mentioned specific contents of gold ore tailings, calcite, lepidolite, fluorite and sodium carbonate, a eucryptite phase (LiAlSiO) having a low thermal expansion coefficient, excellent temperature resistance and good chemical stability can be precipitated 4 ) Further reduces the thermal expansion coefficient of the glass ceramics and improves the mechanical property, high temperature resistance and chemical stability of the glass ceramics.
According to some embodiments of the invention, the composition preferably comprises 65-75wt% gold tailings, 4-6wt% calcite, 4-8wt% lepidolite, 3-6wt% fluorite and 12-17wt% sodium carbonate, based on the total mass of the composition. The adoption of the preferred embodiment is beneficial to further reducing the thermal expansion coefficient of the microcrystalline glass and further improving the mechanical property of the microcrystalline glass.
According to some embodiments of the inventionPreferably, the gold mine tailings comprise: siO (SiO) 2 55-65wt％；Al 2 O 3 15-25wt％；Na 2 O 2-6wt％；Li 2 O 0-4wt％；MgO 5-8wt％；CaO 0.5-2.5wt％；TiO 2 0.5-2wt% and Fe 2 O 3 6-8wt%. The gold mine tailing adopted by the preferred embodiment is beneficial to further reducing the thermal expansion coefficient of the glass ceramics and further improving the mechanical property of the glass ceramics.
The second aspect of the invention provides a preparation method of microcrystalline glass, which comprises the following steps:
(1) Contacting and mixing the components in the composition of the first aspect to obtain a batch, and then melting the batch to obtain glass liquid;
(2) Carrying out water quenching and ball milling on the glass liquid in sequence to obtain glass powder;
(3) Sintering the glass powder at high temperature; the high-temperature sintering temperature is not higher than 900 ℃.
According to some embodiments of the present invention, preferably, before performing step (1), the preparation method may further include sequentially washing and drying the gold tailings to remove impurities in the gold tailings.
According to some embodiments of the invention, preferably, in step (1), the conditions of contact mixing include: the stirring speed is 10-25rpm, the temperature is 5-35 ℃ and the time is 20-30min.
According to some embodiments of the invention, preferably, the conditions of the melt processing include: the temperature is 1250-1450 ℃ and the time is 1.8-3.5h.
According to some embodiments of the invention, preferably, in step (1), the melting treatment includes a primary melting treatment and a secondary melting treatment performed sequentially, and the temperature of the primary melting treatment is lower than the temperature of the secondary melting treatment.
According to some embodiments of the invention, preferably, the conditions of the primary melting treatment include: the temperature is 1250-1350 ℃ and the time is 20-40min.
According to some embodiments of the invention, preferably, the conditions of the secondary melt processing include: the temperature is 1350-1450 ℃, the time is 1.5-2.5h, and the temperature rising rate is 5-10 ℃/min.
The preferable implementation mode of the melting treatment is beneficial to further reducing the thermal expansion coefficient of the microcrystalline glass and further improving the mechanical property of the microcrystalline glass.
According to some embodiments of the invention, in step (2), the glass liquid is subjected to water quenching and ball milling in sequence to obtain glass powder. The water quenching may be performed in any manner known in the art, for example, the molten glass may be poured into water to obtain glass slag; further, the water quenching is followed by a step of drying the glass frit to remove residual water.
According to some embodiments of the invention, preferably, in step (2), the ball milling is performed for a time period of 5 to 10 hours.
According to some embodiments of the invention, it is preferred that the glass frit has an average particle size of no more than 40 microns. Glass powders having an average particle diameter satisfying the above range can be obtained by passing the ball-milled product through a standard sieve of 250 to 350 mesh.
According to some embodiments of the invention, preferably, in step (3), the conditions of high temperature sintering include: the temperature is 740-900 ℃, the time is 2-4h, and the heating rate is 2-6 ℃/min.
According to some embodiments of the invention, preferably, the high-temperature sintering includes a nucleation treatment and a crystallization treatment performed sequentially, and the temperature of the nucleation treatment is lower than the temperature of the crystallization treatment.
According to some embodiments of the invention, preferably, the conditions of the nucleating process include: the temperature is 740-780 ℃, the time is 1.5-2.5h, and the heating rate is 2-5 ℃/min.
According to some embodiments of the invention, preferably, the crystallization treatment conditions include: the temperature is 850-900 ℃, the time is 0.5-1.5h, and the temperature rising rate is 3-6 ℃/min.
According to some embodiments of the invention, the high temperature sintering is preferably performed by placing the glass frit into a mold. The mold may be, for example, a heat resistant silicon carbide mold, and the inner wall of the mold is sprayed with 400 mesh alumina slurry to facilitate demolding of the high temperature sintered product. The high-temperature sintering may be performed in any conventional apparatus, and is not particularly limited thereto, and for example, the high-temperature sintering may be performed in a muffle furnace.
The adoption of the preferred implementation mode of high-temperature sintering is beneficial to further reducing the thermal expansion coefficient of the microcrystalline glass and further improving the mechanical property of the microcrystalline glass.
According to some embodiments of the invention, preferably, step (3) may further comprise annealing and cooling the high temperature sintered product.
According to some embodiments of the present invention, preferably, the preparation method may further include a step of processing the glass-ceramic prepared in the step (3) to prepare a glass-ceramic sample. For example, the glass ceramics can be cut, ground and polished sequentially according to actual requirements.
Fig. 2 is a schematic diagram showing a change of a material temperature with time in a preparation method of glass ceramic according to an embodiment of the present invention, where a time period 1 corresponds to a first-stage melting process, a time period 2 corresponds to a second-stage melting process, a time period 3 corresponds to a water quenching process, a time period 4 corresponds to a ball milling process, a time period 5 corresponds to a nucleation process, a time period 6 corresponds to a crystallization process, and a time period 7 corresponds to a cooling process. As can be seen from the figure, in the primary melting process, the batch reaches the glass transition temperature Tr, and then is melted from the glass transition temperature Tr to the glass melting temperature Tm to obtain glass liquid in the secondary melting process, and then is quenched to the glass annealing temperature Ta by water to obtain glass slag; after ball milling glass slag to obtain glass powder, firstly heating the glass powder to a glass nucleation temperature Tn, preserving heat for a certain time (the time can be selected according to the above), then heating a nucleated product to a glass crystallization temperature Tc, preserving heat for a certain time (the time can be selected according to the above), and finally annealing and cooling to room temperature to obtain the microcrystalline glass.
The third aspect of the invention provides glass ceramics prepared by the preparation method of the second aspect.
According to some embodiments of the invention, preferably, the glass ceramic has a thermal expansion coefficient of 50×10 -7 ℃ -1 To 58 x 10 -7 ℃ -1 Preferably 50 x 10 -7 ℃ -1 To 55 x 10 -7 ℃ -1 。
According to some embodiments of the present invention, preferably, the glass-ceramic has a Vickers hardness of 420 to 500kgf/mm 2 Preferably 450-500kgf/mm 2 。
According to some embodiments of the invention, the glass-ceramic preferably has a flexural strength of 112-150MPa, preferably 135-150MPa.
According to some embodiments of the invention, the glass-ceramic preferably has a density of 112-150MPa, preferably 135-150MPa.
According to some embodiments of the invention, preferably, the glass ceramics has no more than 5 bubbles/m 2 Preferably not more than 2/m 2 。
According to some embodiments of the invention, preferably, the main crystal phase of the glass-ceramic is a eucryptite phase (LiAlSiO 4 )。
In a fourth aspect, the invention provides the use of the composition according to the first aspect or the glass-ceramic according to the third aspect in construction and industrial materials.
The present invention will be described in detail by examples.
In the following examples, all of the various raw materials used were commercially available unless otherwise specified.
Wherein, the kinds and the contents of each component in the gold mine tailing are as follows: siO (SiO) 2 58wt％；Al 2 O 3 20wt％；Na 2 O 6wt％；Li 2 O 2wt％；MgO 5.5wt％；CaO 1wt％；TiO 2 0.5wt% and Fe 2 O 3 7wt％。
Referring to ASTM E-228-1985 test method for measuring linear thermal expansion of solid Material with transparent Quartz dilatometer, glass ceramics was measured by using a horizontal dilatometer (model number orton SP 900D)Coefficient of thermal expansion of 10 -7 /℃；
The vickers hardness of the glass-ceramic was measured with reference to ASTM E-384 using an HXD-3000 vickers hardness tester, wherein the loading force was 200g and the loading time was 15s;
testing the breaking strength of the glass ceramics by adopting a WEW-/1000E universal testing machine;
testing the density of the microcrystalline glass by adopting an Archimedes method;
the crystalline phase of the glass ceramics was measured by XRD diffractometer (Shimadzu XRD-6000).
The mold used is a heat-resistant silicon carbide mold, and the inner wall of the mold is sprayed with 400-mesh alumina slurry.
Example 1
1) The components in the composition for preparing the microcrystalline glass are contacted and mixed to obtain a batch; wherein, based on the total mass of the composition, the types and the amounts of each component in the composition are specifically as follows: 65wt% of gold ore tailings, 6wt% of calcite, 7wt% of lithium feldspar, 5wt% of fluorite and 17wt% of sodium carbonate;
the conditions of contact mixing are: stirring speed is 20rpm, temperature is 25 ℃, and time is 20min;
2) Placing the batch into an alumina crucible to sequentially perform primary melting treatment and secondary melting treatment to obtain glass liquid; wherein, the conditions of the primary melting treatment are as follows: the temperature is 1300 ℃ and the time is 30min; the conditions of the secondary melting treatment are as follows: the temperature is 1400 ℃, the time is 2 hours, and the heating rate is 8 ℃/min;
3) Sequentially carrying out water quenching and drying on glass liquid to obtain glass slag, and then putting the obtained glass slag into a ball mill for ball milling, and then passing through a 300-target standard sieve to obtain glass powder;
wherein, the conditions of drying are: the temperature is 100 ℃ and the time is 1h; ball milling time is 6 hours;
4) Placing the glass powder into a mould, placing the mould into a muffle furnace, sequentially carrying out nucleation treatment and crystallization treatment, and cooling to room temperature along with the furnace to obtain microcrystalline glass;
wherein, the conditions of the nucleation treatment are as follows: the temperature is 750 ℃, the time is 120min, and the heating rate is 3 ℃/min; the crystallization treatment conditions are as follows: the temperature is 850 ℃, the time is 60min, and the heating rate is 4 ℃/min.
5) Cutting by a cutting machine to obtain microcrystalline glass with the thickness of 8mm, and grinding and polishing to obtain a microcrystalline glass sample.
FIG. 1 shows XRD diffraction patterns of the glass-ceramic, in which the main crystal phase is LiAlSiO 4 。
Example 2
1) The components in the composition for preparing the microcrystalline glass are contacted and mixed to obtain a batch; wherein, based on the total mass of the composition, the types and the amounts of each component in the composition are specifically as follows: 68wt% of gold ore tailings, 4wt% of calcite, 5wt% of lithium feldspar, 6wt% of fluorite and 17wt% of sodium carbonate;
the conditions of contact mixing are: stirring speed is 18rpm, temperature is 28 ℃ and time is 30min;
2) Placing the batch into an alumina crucible to sequentially perform primary melting treatment and secondary melting treatment to obtain glass liquid; wherein, the conditions of the primary melting treatment are as follows: the temperature is 1300 ℃ and the time is 30min; the conditions of the secondary melting treatment are as follows: the temperature is 1400 ℃, the time is 2 hours, and the heating rate is 5 ℃/min;
3) Sequentially carrying out water quenching and drying on glass liquid to obtain glass slag, and then putting the obtained glass slag into a ball mill for ball milling, and then passing through a 300-target standard sieve to obtain glass powder;
wherein, the conditions of drying are: the temperature is 110 ℃ and the time is 1h; the ball milling time is 7 hours;
4) Placing the glass powder into a mould, placing the mould into a muffle furnace, sequentially carrying out nucleation treatment and crystallization treatment, and cooling to room temperature along with the furnace to obtain microcrystalline glass;
wherein, the conditions of the nucleation treatment are as follows: the temperature is 740 ℃, the time is 120min, and the heating rate is 3 ℃/min; the crystallization treatment conditions are as follows: the temperature is 880 ℃, the time is 60min, and the heating rate is 4 ℃/min.
5) Cutting by a cutting machine to obtain microcrystalline glass with the thickness of 8mm, and grinding and polishing to obtain a microcrystalline glass sample.
XRD detection shows thatThe main crystal phase of the microcrystalline glass is LiAlSiO 4 。
Example 3
1) The components in the composition for preparing the microcrystalline glass are contacted and mixed to obtain a batch; wherein, based on the total mass of the composition, the types and the amounts of each component in the composition are specifically as follows: 70wt% of gold ore tailings, 4wt% of calcite, 5wt% of lithium feldspar, 6wt% of fluorite and 15wt% of sodium carbonate;
the conditions of contact mixing are: stirring speed is 15rpm, temperature is 25 ℃, and time is 25min;
2) Placing the batch into an alumina crucible to sequentially perform primary melting treatment and secondary melting treatment to obtain glass liquid; wherein, the conditions of the primary melting treatment are as follows: the temperature is 1300 ℃ and the time is 30min; the conditions of the secondary melting treatment are as follows: the temperature is 1400 ℃, the time is 2 hours, and the heating rate is 6 ℃/min;
3) Sequentially carrying out water quenching and drying on glass liquid to obtain glass slag, and then putting the obtained glass slag into a ball mill for ball milling, and then passing through a 300-target standard sieve to obtain glass powder;
wherein, the conditions of drying are: the temperature is 120 ℃ and the time is 1.2 hours; ball milling time is 10 hours;
4) Placing the glass powder into a mould, placing the mould into a muffle furnace, sequentially carrying out nucleation treatment and crystallization treatment, and cooling to room temperature along with the furnace to obtain microcrystalline glass;
wherein, the conditions of the nucleation treatment are as follows: the temperature is 760 ℃, the time is 120min, and the heating rate is 4 ℃/min; the crystallization treatment conditions are as follows: the temperature is 880 ℃, the time is 60min, and the heating rate is 4 ℃/min.
5) Cutting by a cutting machine to obtain microcrystalline glass with the thickness of 8mm, and grinding and polishing to obtain a microcrystalline glass sample.
XRD detection shows that the main crystal phase of the microcrystalline glass is LiAlSiO 4 。
Example 4
1) The components in the composition for preparing the microcrystalline glass are contacted and mixed to obtain a batch; wherein, based on the total mass of the composition, the types and the amounts of each component in the composition are specifically as follows: 72wt% of gold ore tailings, 5wt% of calcite, 8wt% of lithium feldspar, 3wt% of fluorite and 12wt% of sodium carbonate;
the conditions of contact mixing are: stirring speed is 15rpm, temperature is 20 ℃ and time is 25min;
2) Placing the batch into an alumina crucible to sequentially perform primary melting treatment and secondary melting treatment to obtain glass liquid; wherein, the conditions of the primary melting treatment are as follows: the temperature is 1300 ℃ and the time is 30min; the conditions of the secondary melting treatment are as follows: the temperature is 1400 ℃, the time is 2 hours, and the heating rate is 6 ℃/min;
3) Sequentially carrying out water quenching and drying on glass liquid to obtain glass slag, and then putting the obtained glass slag into a ball mill for ball milling, and then passing through a 300-target standard sieve to obtain glass powder;
wherein, the conditions of drying are: the temperature is 110 ℃ and the time is 1.5h; ball milling time is 8 hours;
4) Placing the glass powder into a mould, placing the mould into a muffle furnace, sequentially carrying out nucleation treatment and crystallization treatment, and cooling to room temperature along with the furnace to obtain microcrystalline glass;
wherein, the conditions of the nucleation treatment are as follows: the temperature is 760 ℃, the time is 120min, and the heating rate is 3 ℃/min; the crystallization treatment conditions are as follows: the temperature is 870 ℃, the time is 60min, and the heating rate is 4 ℃/min.
5) Cutting by a cutting machine to obtain microcrystalline glass with the thickness of 8mm, and grinding and polishing to obtain a microcrystalline glass sample.
XRD detection shows that the main crystal phase of the microcrystalline glass is LiAlSiO 4 。
Example 5
1) The components in the composition for preparing the microcrystalline glass are contacted and mixed to obtain a batch; wherein, based on the total mass of the composition, the types and the amounts of each component in the composition are specifically as follows: 75wt% of gold ore tailings, 4wt% of calcite, 5wt% of lithium feldspar, 4wt% of fluorite and 12wt% of sodium carbonate;
the conditions of contact mixing are: stirring speed is 12rpm, temperature is 30 ℃ and time is 20min;
2) Placing the batch into an alumina crucible to sequentially perform primary melting treatment and secondary melting treatment to obtain glass liquid; wherein, the conditions of the primary melting treatment are as follows: the temperature is 1300 ℃ and the time is 30min; the conditions of the secondary melting treatment are as follows: the temperature is 1400 ℃, the time is 2 hours, and the heating rate is 8 ℃/min;
3) Sequentially carrying out water quenching and drying on glass liquid to obtain glass slag, and then putting the obtained glass slag into a ball mill for ball milling, and then passing through a 300-target standard sieve to obtain glass powder;
wherein, the conditions of drying are: the temperature is 120 ℃ and the time is 1h; ball milling time is 8 hours;
4) Placing the glass powder into a mould, placing the mould into a muffle furnace, sequentially carrying out nucleation treatment and crystallization treatment, and cooling to room temperature along with the furnace to obtain microcrystalline glass;
wherein, the conditions of the nucleation treatment are as follows: the temperature is 780 ℃, the time is 120min, and the heating rate is 3 ℃/min; the crystallization treatment conditions are as follows: the temperature is 850 ℃, the time is 60min, and the heating rate is 4 ℃/min.
5) Cutting by a cutting machine to obtain microcrystalline glass with the thickness of 8mm, and grinding and polishing to obtain a microcrystalline glass sample.
XRD detection shows that the main crystal phase of the microcrystalline glass is LiAlSiO 4 。
Comparative example 1
The procedure of example 1 was followed except that the amounts of the components in the composition were as follows: 55wt% of gold ore tailings, 10wt% of calcite, 12wt% of lithium feldspar, 10wt% of fluorite, 13wt% of sodium carbonate and the balance of the same as in example 1, so as to obtain microcrystalline glass and microcrystalline glass samples.
Test case
The glass ceramics prepared in examples and comparative examples were subjected to performance tests, including thermal expansion coefficient, vickers hardness, flexural strength, density, and bubble condition, respectively, and the results are shown in table 1.
TABLE 1
| Performance parameters | Coefficient of thermal expansion | Vickers hardness of | Flexural Strength | Density of | Air bubble |
| Unit (B) | *10 -7 ℃ -1 | kgf/mm 2 | MPa | g/cm 3 | Individual/m 2 |
| Example 1 | 50 | 460 | 136 | 2.91 | 1 |
| Example 2 | 52 | 472 | 139 | 2.91 | 2 |
| Example 3 | 53 | 480 | 137 | 2.90 | 2 |
| Example 4 | 52 | 475 | 145 | 2.92 | 2 |
| Example 5 | 51 | 473 | 150 | 2.93 | 2 |
| Comparative example 1 | 58 | 420 | 112 | 2.91 | 5 |
As can be seen from the results in Table 1, the microcrystalline glass prepared by the composition and the preparation method provided by the invention has the advantages of low thermal expansion coefficient, high refractoriness, good mechanical property, low porosity, good chemical stability, high use temperature, capability of meeting the market requirements and wide application range.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (12)
1. A composition for preparing glass ceramics, which is characterized in that the composition contains 65-75wt% of gold mine tailings, 4-6wt% of calcite, 4-8wt% of lithium feldspar, 3-6wt% of fluorite and 12-17wt% of sodium carbonate based on the total mass of the composition;
wherein, the gold mine tailings comprise: siO (SiO) 2 55-65wt%；Al 2 O 3 15-25wt%；Na 2 O 2-6wt%；Li 2 O 0-4wt%；MgO 5-8wt%；CaO 0.5-2.5wt%；TiO 2 0.5-2wt% and Fe 2 O 3 6-8wt%。
2. The preparation method of the glass ceramics is characterized by comprising the following steps:
(1) Contacting and mixing the components in the composition of claim 1 to obtain a batch, and then melting the batch to obtain glass liquid;
the melting treatment comprises a primary melting treatment and a secondary melting treatment which are sequentially carried out, and the temperature of the primary melting treatment is lower than that of the secondary melting treatment;
the conditions of the primary melting treatment include: the temperature is 1250-1350 ℃ and the time is 20-40min;
the conditions of the secondary melting treatment include: the temperature is 1350-1450 ℃ and the time is 1.5-2.5h;
(2) Carrying out water quenching and ball milling on the glass liquid in sequence to obtain glass powder;
(3) Sintering the glass powder at high temperature;
the high-temperature sintering comprises a nucleation treatment and a crystallization treatment which are sequentially carried out, wherein the temperature of the nucleation treatment is lower than that of the crystallization treatment;
the conditions of the nucleating process include: the temperature is 740-780 ℃, the time is 1.5-2.5h, and the heating rate is 2-5 ℃/min;
the crystallization treatment conditions include: the temperature is 850-900 ℃, the time is 0.5-1.5h, and the temperature rising rate is 3-6 ℃/min.
3. The method according to claim 2, wherein in the step (1), the conditions of contact mixing include: the stirring speed is 10-25rpm, the temperature is 5-35 ℃ and the time is 20-30min.
4. The method according to claim 2, wherein in the step (1), the temperature rise rate of the secondary melting treatment is 5 to 10 ℃/min.
5. The method according to any one of claims 2 to 4, wherein in the step (2), the time of ball milling is 5 to 10 hours; and/or the glass frit has an average particle size of not more than 40 microns.
6. Glass ceramics prepared by the preparation method according to any one of claims 2 to 5;
the microcrystalline glass has a Vickers hardness of 420-500kgf/mm 2 ；
And/or the breaking strength of the glass ceramics is 112-150 MPa;
and/or the density of the microcrystalline glass is 2.9-2.95 g/cm 3 ；
And/or the bubbles of the microcrystalline glass are not higher than 5/m 2 。
7. The glass-ceramic according to claim 6, wherein the glass-ceramic has a thermal expansion coefficient of 50X 10 -7 ℃ -1 Up to 58×10 -7 ℃ -1 。
8. The glass-ceramic according to claim 7, wherein the glass-ceramic has a thermal expansion coefficient of 50X 10 -7 ℃ -1 To 55X 10 -7 ℃ -1 。
9. According to claim 6The microcrystalline glass is characterized in that the microcrystalline glass has the Vickers hardness of 450-500kgf/mm 2 。
10. The glass-ceramic according to claim 6, wherein the glass-ceramic has a flexural strength of 135 to 150MPa.
11. The glass-ceramic according to claim 6, wherein the number of bubbles in the glass-ceramic is not more than 2/m 2 。
12. Use of the composition of claim 1 or the glass-ceramic of any of claims 6-11 in construction and industrial materials.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211001255.0A CN115490429B (en) | 2022-08-19 | 2022-08-19 | Composition for preparing microcrystalline glass, microcrystalline glass and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211001255.0A CN115490429B (en) | 2022-08-19 | 2022-08-19 | Composition for preparing microcrystalline glass, microcrystalline glass and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115490429A CN115490429A (en) | 2022-12-20 |
| CN115490429B true CN115490429B (en) | 2023-11-03 |
Family
ID=84466298
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211001255.0A Active CN115490429B (en) | 2022-08-19 | 2022-08-19 | Composition for preparing microcrystalline glass, microcrystalline glass and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115490429B (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101851064A (en) * | 2010-06-23 | 2010-10-06 | 浮山县晋盛新型建筑材料有限责任公司 | Blue glass ceramics and preparation method thereof |
| CN101857367A (en) * | 2010-06-23 | 2010-10-13 | 浮山县晋盛新型建筑材料有限责任公司 | Black glass ceramic and production method thereof |
| CN102923958A (en) * | 2012-10-31 | 2013-02-13 | 广东博德精工建材有限公司 | Novel microcrystal glass ceramic composite board and preparation method thereof |
| CN103288351A (en) * | 2013-05-22 | 2013-09-11 | 陕西科技大学 | Diopside phase glass ceramic and preparation method thereof |
| CN109704583A (en) * | 2019-02-25 | 2019-05-03 | 秦皇岛玻璃工业研究设计院有限公司 | A kind of devitrified glass and its production method |
| WO2021022588A1 (en) * | 2019-08-07 | 2021-02-11 | 东北大学 | Microcrystalline foam glass and preparation method therefor |
-
2022
- 2022-08-19 CN CN202211001255.0A patent/CN115490429B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101851064A (en) * | 2010-06-23 | 2010-10-06 | 浮山县晋盛新型建筑材料有限责任公司 | Blue glass ceramics and preparation method thereof |
| CN101857367A (en) * | 2010-06-23 | 2010-10-13 | 浮山县晋盛新型建筑材料有限责任公司 | Black glass ceramic and production method thereof |
| CN102923958A (en) * | 2012-10-31 | 2013-02-13 | 广东博德精工建材有限公司 | Novel microcrystal glass ceramic composite board and preparation method thereof |
| CN103288351A (en) * | 2013-05-22 | 2013-09-11 | 陕西科技大学 | Diopside phase glass ceramic and preparation method thereof |
| CN109704583A (en) * | 2019-02-25 | 2019-05-03 | 秦皇岛玻璃工业研究设计院有限公司 | A kind of devitrified glass and its production method |
| WO2021022588A1 (en) * | 2019-08-07 | 2021-02-11 | 东北大学 | Microcrystalline foam glass and preparation method therefor |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115490429A (en) | 2022-12-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| WO2019114202A1 (en) | Process for preparing glass-ceramic of iron-rich lead slag by sintering method | |
| CN1868946A (en) | Waste residue microcrystal glass and its preparation method | |
| CN102795772B (en) | Method for preparing microcrystalline glass from kaolin-type coal gangue or fly ash and carbide slag | |
| CN105417950B (en) | A kind of fluxing nucleator of micro crystal material and preparation method thereof | |
| CN105884200B (en) | A method of manufacturing devitrified glass ceramics composite material using industrial fly ash and vitrifying slag | |
| CN102753496B (en) | A kind of composition for the preparation of igneous rock crystal glass material, igneous rock crystal glass material and manufacture method thereof | |
| CN101759368B (en) | Green glass-ceramic plate made from lead-zinc smelting slag and manufacturing method thereof | |
| CN103951193B (en) | A kind of nickel-molybdenum ore selects smelting tailing microcrystal glass and preparation method thereof | |
| CN108503224B (en) | Microcrystalline glass using coal gangue and rice hull ash as main raw materials and preparation method thereof | |
| CN105731808A (en) | Method for preparing glass ceramics | |
| CN104193171A (en) | Silicon manganese alloy slag glass ceramic and preparation method thereof | |
| CN108358455B (en) | Method for preparing microcrystalline glass by using lead-zinc tailings and quartz tailings | |
| EP2623614B1 (en) | Method for manufacturing planar inorganic non-metallic material using molten slag | |
| CN110818266A (en) | Preparation method of basalt microcrystalline glass | |
| CN105152536B (en) | A kind of method that microcrystal glass material is synthesized using ferrochrome slag | |
| CN101698567A (en) | Electrolytic manganese slag microcrystalline glass and preparation method thereof | |
| WO2023273199A1 (en) | Method for preparing lead slag glass-ceramic by oxidizing and conditioning silicon-rich silicon slag | |
| CN1329328C (en) | Method for preparing micro crystal glass plate for building using waste glass | |
| CN104108882A (en) | Float microcrystalline glass and preparation method thereof | |
| CN116715506B (en) | Ceramic blank, ceramic brick and preparation method thereof based on lithium slag | |
| CN115490429B (en) | Composition for preparing microcrystalline glass, microcrystalline glass and preparation method and application thereof | |
| CN107879631A (en) | It is adapted to the quenched material of composition and its hardening and tempering method of blast furnace cinder devitrified glass | |
| CN102344251B (en) | Preparation method for lepidolite glass ceramic | |
| CN114368914B (en) | High-alumina microcrystalline glass with large amount of gangue and preparation method thereof | |
| CN113548842B (en) | Method for preparing baking-free brick by using ash |
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 |