CN1994948A - Black high-strength microcrystalline glass and its preparation method - Google Patents

Black high-strength microcrystalline glass and its preparation method Download PDF

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Publication number
CN1994948A
CN1994948A CNA2006101553248A CN200610155324A CN1994948A CN 1994948 A CN1994948 A CN 1994948A CN A2006101553248 A CNA2006101553248 A CN A2006101553248A CN 200610155324 A CN200610155324 A CN 200610155324A CN 1994948 A CN1994948 A CN 1994948A
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oxide
glass
black
strength
black high
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CN100558665C (en
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郭兴忠
陈明形
杨辉
李海淼
项延杭
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Zhejiang University ZJU
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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
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
    • C03C3/085—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
    • C03C3/091—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
    • C03C3/091—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium
    • C03C3/093—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium containing zinc or zirconium
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/097—Glass compositions containing silica with 40% to 90% silica, by weight containing phosphorus, niobium or tantalum
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C4/00—Compositions for glass with special properties
    • C03C4/02—Compositions for glass with special properties for coloured glass

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Ceramic Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Glass Compositions (AREA)

Abstract

The invention discloses a black high-strength microcrystal glass, which comprises the following parts: 70% SiO2, 3. 5% Lithia, 17% alumina, 0.1%-0.5% ferric trioxide, 0.5%- 1% cobalt trioxide, 0.5%-1% nickel trioxide, 3. 1% -3. 5% at least one of titania, zirconia and phosphorus pentoxide, 1%-1. 5% at least one of magnesia, zinc oxide, barium oxide and boric oxide, 2. 0%-2. 1% potassium oxide and or sodium oxide and 1% arsenic oxide and or antimony oxide. The making method of microcrystal glass comprises the following steps: grinding evenly; adding reducer to allocate composite material; fusing under 1580 -1650 deg. c; shaping; annealing; coring under 600-800 deg. c for 1-4h; heating to 700-1000 deg. c to crystallize for 1-12h.

Description

A kind of black high-strength microcrystalline glass and preparation method thereof
Technical field
The present invention relates to a kind of black high-strength microcrystalline glass and preparation method thereof.
Background technology
The parent glass that devitrified glass is made up of special component is crystallization control and the polycrystalline composite materials that makes at a certain temperature; Lithium aluminium silicon series (Li wherein 2O-Al 2O 3-SiO 2Abbreviation LAS) devitrified glass is as an important kind in the devitrified glass, because of it has super-low expansion, high strength, high temperature resistant, heat shock resistance, and be widely used in making astronomical telescope, cooker, tableware, high temperature electric light source glass, electromagnetic oven panel, microelectronics with substrate, laboratory with heating appliances, high-temperature heat exchanger, for silica glass, window pyrometer, radome etc.Black glass ceramic is to be matrix with the devitrified glass, and the black colorant that mixed in the process of founding makes; It not only has the high-performance of general devitrified glass, but also have that color is serious, color and luster is magnificent, with advantages such as other household electrical appliance and house ornamentation environment matching are good, therefore can replace rare expensive black granite, be used as the senior city flooring of the indoor and outdoor weather resistance of all kinds of buildingss, also can be used for making the high-end product of devitrified glass kitchen range.
About described black glass ceramic, in publication number CN 85100521,1056857,1263059, once reported the method for utilizing flyash, slag, mine tailing or industrial residue to make black glass ceramic for black colorant and raw material; Its advantage is to utilize cheap waste residue as raw material, both can reduce the production cost of devitrified glass, is of value to the protection environment again.But owing to adopt waste residue as raw material, also exist waste residue composition instability, can introduce problem such as tramp material, also can produce certain influence the performance of devitrified glass.
CN 1785872 has reported with CeO 2, V 2O 5, Fe 2O 3, CaO, NiO, CoO is a tinting material, and having made with β-quartz solid solution is the black transparent microcrystal glass of principal crystalline phase, and it sees through look is black for the reddish-brown reflected colour.But CN 1785872A also exists following weak point: 1) coloring agent component complexity, and composition is difficult for coupling and causes colour cast; 2) CeO in the coloring components 2Toxicity bigger; 3) nucleus agent composition ZrO 2At no P 2O 5Solubleness is lower under the condition, influences the crystallization effect; 4) do not relate to the mechanical property of devitrified glass.
CN1699233 has also reported with NiO, V 2O 5And Fe 2O 3For a kind of black transparent microcrystal glass of tinting material with and the production method of goods, be used to prepare crystallized glass articles such as electromagnetic oven plate, dish, microwave plate, but CN1699233 has the following disadvantages: 1) do not relate to control of glass atmosphere and coloring ion and appraise at the current rate; 2) V 2O 5V after composition appraises at the current rate 3+It is green that ion becomes, and is difficult for and Ni, Fe ion coupling.
Summary of the invention
The technical problem to be solved in the present invention provides a kind of black high-strength microcrystalline glass and preparation method thereof, the black high-strength microcrystalline glass that adopts present method to prepare has grain-size and can reach nano level, black is stable, pure, and the advantage that thermal expansivity is low, physical strength is high, heat-resisting corrosion-resistant property is good.
In order to solve the problems of the technologies described above, the invention provides a kind of black high-strength microcrystalline glass, the weight percent of this devitrified glass consists of: silicon-dioxide 70%, Lithium Oxide 98min 3.5%, aluminum oxide 17%, ferric oxide 0.1%-0.5%, cobalt sesquioxide 0.5%-1%, nickel sesquioxide 0.5%-1%, at least a 3.1%-3.5% in titanium oxide, zirconium white and the Vanadium Pentoxide in FLAKES, at least a 1%-1.5% in magnesium oxide, zinc oxide, barium oxide and the boron oxide, potassium oxide and/or sodium oxide 2.0%-2.1%, arsenic oxide arsenoxide and/or weisspiessglanz 1%.
Specifically: select at least a in titanium oxide, zirconium white and the Vanadium Pentoxide in FLAKES for use, mean any a kind or any 2 kinds mixture that can select for use in titanium oxide, zirconium white and the Vanadium Pentoxide in FLAKES (these 2 kinds arbitrarily part by weight mix mutually, but all can not weight be 0) or above-mentioned 3 kinds mixture (these 3 kinds arbitrarily part by weight mix mutually, but all can not weight be 0).In like manner, select at least a in magnesium oxide, zinc oxide, barium oxide and the boron oxide for use, mean any a kind or any 2 kinds mixture or any 3 kinds mixture or the above-mentioned 4 kinds mixture that to select for use in magnesium oxide, zinc oxide, barium oxide and the boron oxide.
The present invention also provides the preparation method of above-mentioned black high-strength microcrystalline glass: add reductive agent after grinding above-mentioned devitrified glass moiety evenly and be configured to compound, the weight of described reductive agent is 3%～10% of devitrified glass moiety gross weight; Found moulding, annealing through 1580～1650 ℃; Through 600～800 ℃ of coring 1～4 hour, be warming up to 700～1000 ℃ of crystallization then and handled 1～12 hour again.
Improvement as preparation method of the present invention: reductive agent can be selected carbon dust for use.
In preparation method of the present invention, the purpose that adds reductive agent is to found atmosphere for feed glass, impels coloring ion to appraise at the current rate.
Black high-strength microcrystalline glass of the present invention and preparation method thereof obtains through scrutinizing, test the back the contriver.The present invention is with Fe 2O 3, Co 2O 3, Ni 2O 3Be the composite coloration agent, utilize the difference of different ions, make it to produce stack, thereby (400～700nm) produce large-area absorption, make devitrified glass be black in visible-range photoabsorption to the visible absorption wavelength.Tie Tong is often with Fe 3+And Fe 2+Ionic condition is present in the glass, and the absorption band of light wave is respectively 300～400nm and 650～1000nm; Cobalt ion can have [CoO in glass 6] and [CoO 4] two kinds of co-ordination states, the former light wave absorption band is 500～600nm, the latter's absorption band is 520～700nm; The light wave absorption band of nickel ion is 400～570nm.Black high-strength microcrystalline glass of the present invention is owing to adopt Fe 2O 3, Co 2O 3, Ni 2O 3Form the composite coloration agent, therefore can be implemented in and produce large-area absorption in the visible-range; Have advantages such as the black that is obtained is stable, pure, even, and avoided defectives such as variegated, color spot, background color be gloomy.
The present invention selects for use by TiO 2, ZrO 2, P 2O 5The compound nucleus agent of forming utilizes " synergistic effect " of nucleus agent, impels a large amount of forming cores of glass; And be equipped with accurate control coring, crystallization and thermal treatment process system, control the generation of nucleus and growing up of crystal grain; Realize that grain-size reaches nano level, glass surface is moist, and low thermal expansivity, high physical strength and good heat-resisting corrosion-resistant property are arranged, and has realized the advantage of high-strength temperature-resistant.
The reductive agent that the present invention is selected, carbon dust for example, it is volatilized to become gas in preparation process, therefore is not present in the product (black high-strength microcrystalline glass) of final formation.
The principal crystalline phase of black high-strength microcrystalline glass of the present invention is β-triphane (Li 2OAl 2O 3NSiO 2, n 〉=4), crystal shape is spherical, and black is stable, pure, even, and grain-size is between 30～40nm, and thermal expansivity is 5～10 * 10 in 30～700 ℃ of scopes -7/ ℃, folding strength is 110～150MPa, anti-erosion rank reaches GB6582-1.
Compare with the present invention, among the publication CN 85100521,1056857,1263059,1785872,1699233, the coefficient of expansion that removes CN1699233 reaches-5～5 * 10 -7/ ℃ being higher than patent of the present invention, the coefficient of expansion of other patents all is lower than patent of the present invention, and the folding strength of the devitrified glass of listed whole patents all is lower than patent of the present invention.
Description of drawings
Below in conjunction with accompanying drawing the specific embodiment of the present invention is described in further detail.
Fig. 1 is that the crystalline substance of black high-strength microcrystalline glass of the embodiment of the invention 1 gained is as synoptic diagram;
Fig. 2 is that the crystalline substance of black high-strength microcrystalline glass of the embodiment of the invention 2 gained is as synoptic diagram.
Embodiment
Embodiment 1: a kind of black high-strength microcrystalline glass, and its weight percent consists of:
SiO 2?70％、LiO 2?3.5％、Al 2O 3?17％、Fe 2O 3?0.3％、Co 2O 3?0.9％、Ni 2O 30.6％、TiO 2?2％、ZrO 2?1％、P 2O 5?0.4％、MgO?0.5％、ZnO?0.5％、BaO?0.2％、B 2O 3?0.1％、K 2O?1.0％、Na 2O?1.0％、As 2O 3?0.5％、Sb 2O 3?0.5％。
Add reductive agent after grinding above-mentioned devitrified glass moiety evenly and be configured to compound, the weight of reductive agent is 5% of devitrified glass moiety gross weight; This reductive agent is the commercially available prod, for example is carbon dust.Compound is founded moulding, annealing through 1600 ℃; Through 600～800 ℃ of coring 2 hours, be warming up to 800 ℃ of crystallization then and handled 12 hours again.Obtain folding strength 110～150MPa, thermal expansivity is 5～21 * 10 -7/ ℃, black stabilized uniform devitrified glass, the spheric grain size is between 30～40nm, as shown in Figure 1.
Embodiment 2: a kind of black high-strength microcrystalline glass, and its weight percent consists of:
SiO 2?70％、LiO 2?3.5％、Al 2O 3?17％、Fe 2O 3?0.3％、Co 2O 3?0.7％、Ni 2O 30.8％、TiO 2?2％、ZrO 2?1％、P 2O 5?0.4％、MgO?0.5％、ZnO?0.5％、BaO?0.2％、B 2O 3?0.1％、K 2O?1％、Na 2O?1％、As 2O 3?0.4％、Sb 2O 3?0.6％。
Add reductive agent after grinding above-mentioned devitrified glass moiety evenly and be configured to compound, the weight of reductive agent is 10% of devitrified glass moiety gross weight; This reductive agent is the commercially available prod, for example is carbon dust.Compound is founded moulding, annealing through 1580 ℃; Through 700 ℃ of coring 4 hours, be warming up to 1000 ℃ of crystallization then and handled 2 hours again.Obtain folding strength 110～150MPa, thermal expansivity is 5～10 * 10 -7/ ℃, black stabilized uniform devitrified glass, the spheric grain size is between 30～40nm, as shown in Figure 2.
Embodiment 3: a kind of black high-strength microcrystalline glass, and its weight percent consists of:
SiO 2?70％、LiO 2?3.5％、Al 2O 3?17％、Fe 2O 3?0.5％、Co 2O 3?0.5％、Ni 2O 31％、TiO 2?3.2％、MgO?0.7％、ZnO?0.5％、K 2O?2.1％、Sb 2O 3?1％。
Add reductive agent after grinding above-mentioned devitrified glass moiety evenly and be configured to compound, the weight of reductive agent is 8% of devitrified glass moiety gross weight; This reductive agent is the commercially available prod, for example is carbon dust.Compound is founded moulding, annealing through 1630 ℃; Through 600～800 ℃ of coring 1 hour, be warming up to 700 ℃ of crystallization then and handled 6 hours again.Obtain folding strength 110～150MPa, thermal expansivity is 5～10 * 10 -7/ ℃, black stabilized uniform devitrified glass, the spheric grain size is between 30～40nm.
Embodiment 4: a kind of black high-strength microcrystalline glass, and its weight percent consists of:
SiO 2?70％、LiO 2?3.5％、Al 2O 3?17％、Fe 2O 3?0.1％、Co 2O 3?1％、Ni 2O 30.5％、TiO 2?2.5％、P 2O 5?0.8％、BaO?1.5％、Na 2O2.1％、As 2O 3?1％。
Add reductive agent after grinding above-mentioned devitrified glass moiety evenly and be configured to compound, the weight of reductive agent is 3% of devitrified glass moiety gross weight; This reductive agent is the commercially available prod, for example is carbon dust.Compound is founded moulding, annealing through 1620 ℃; Through 600～800 ℃ of coring 2 hours, be warming up to 900 ℃ of crystallization then and handled 5 hours again.Obtain folding strength 110～150MPa, thermal expansivity is 5～10 * 10 -7/ ℃, black stabilized uniform devitrified glass, the spheric grain size is between 30～40nm.
At last, it is also to be noted that what more than enumerate only is several specific embodiments of the present invention.Obviously, the invention is not restricted to above embodiment, many distortion can also be arranged.All distortion that those of ordinary skill in the art can directly derive or associate from content disclosed by the invention all should be thought protection scope of the present invention.

Claims (3)

1, a kind of black high-strength microcrystalline glass, the weight percent that it is characterized in that this devitrified glass consists of: silicon-dioxide 70%, Lithium Oxide 98min 3.5%, aluminum oxide 17%, ferric oxide 0.1%-0.5%, cobalt sesquioxide 0.5%-1%, nickel sesquioxide 0.5%-1%, at least a 3.1%-3.5% in titanium oxide, zirconium white and the Vanadium Pentoxide in FLAKES, at least a 1%-1.5% in magnesium oxide, zinc oxide, barium oxide and the boron oxide, potassium oxide and/or sodium oxide 2.0%-2.1%, arsenic oxide arsenoxide and/or weisspiessglanz 1%.
2, the preparation method of black high-strength microcrystalline glass as claimed in claim 1, it is characterized in that: add reductive agent after grinding described devitrified glass moiety evenly and be configured to compound, the weight of described reductive agent is 3%～10% of devitrified glass moiety gross weight; Found moulding, annealing through 1580～1650 ℃; Through 600～800 ℃ of coring 1～4 hour, be warming up to 700～1000 ℃ of crystallization then and handled 1～12 hour again.
3, the preparation method of black high-strength microcrystalline glass according to claim 2 is characterized in that: described reductive agent is a carbon dust.
CNB2006101553248A 2006-12-20 2006-12-20 A kind of black high-strength microcrystalline glass and preparation method thereof Expired - Fee Related CN100558665C (en)

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101973709A (en) * 2010-10-28 2011-02-16 南昌航空大学 Method for preparing calcium aluminosilicate nanometer microcrystal glass by utilizing natrium silica calcium glass waste slag
CN102173590A (en) * 2011-01-22 2011-09-07 广东三圆微晶玻璃科技有限公司 Pure-black glass ceramic
CN103896488A (en) * 2014-03-12 2014-07-02 河北省沙河玻璃技术研究院 Black fluoride-free microcrystalline glass for gravestones and preparation method thereof
CN103896494A (en) * 2014-03-10 2014-07-02 苏州捷德瑞精密机械有限公司 Glass optical fiber and preparation method thereof
CN107235633A (en) * 2017-06-06 2017-10-10 梧州水森林纳米材料科技有限公司 Transparent nano crystal glass and preparation method thereof
CN111646696A (en) * 2020-02-21 2020-09-11 山东三汇玻璃有限公司 Black glass and preparation method thereof
CN111727176A (en) * 2018-10-26 2020-09-29 成都光明光电股份有限公司 Glass ceramics, glass ceramics product and manufacturing method thereof
CN114772935A (en) * 2022-04-13 2022-07-22 万津实业(赤壁)有限公司 Black microcrystalline glass and preparation method and application thereof
CN115784617A (en) * 2022-11-22 2023-03-14 湖南旗滨微晶新材料有限公司 Black microcrystalline glass, preparation method thereof and covering piece

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101973709A (en) * 2010-10-28 2011-02-16 南昌航空大学 Method for preparing calcium aluminosilicate nanometer microcrystal glass by utilizing natrium silica calcium glass waste slag
CN102173590A (en) * 2011-01-22 2011-09-07 广东三圆微晶玻璃科技有限公司 Pure-black glass ceramic
CN103896494A (en) * 2014-03-10 2014-07-02 苏州捷德瑞精密机械有限公司 Glass optical fiber and preparation method thereof
CN103896488A (en) * 2014-03-12 2014-07-02 河北省沙河玻璃技术研究院 Black fluoride-free microcrystalline glass for gravestones and preparation method thereof
CN103896488B (en) * 2014-03-12 2016-09-14 河北省沙河玻璃技术研究院 A kind of tombstone black free-floride devitrified glass and preparation method thereof
CN107235633A (en) * 2017-06-06 2017-10-10 梧州水森林纳米材料科技有限公司 Transparent nano crystal glass and preparation method thereof
CN111727176A (en) * 2018-10-26 2020-09-29 成都光明光电股份有限公司 Glass ceramics, glass ceramics product and manufacturing method thereof
CN111646696A (en) * 2020-02-21 2020-09-11 山东三汇玻璃有限公司 Black glass and preparation method thereof
CN114772935A (en) * 2022-04-13 2022-07-22 万津实业(赤壁)有限公司 Black microcrystalline glass and preparation method and application thereof
CN114772935B (en) * 2022-04-13 2024-04-05 万津实业(赤壁)有限公司 Black microcrystalline glass and preparation method and application thereof
CN115784617A (en) * 2022-11-22 2023-03-14 湖南旗滨微晶新材料有限公司 Black microcrystalline glass, preparation method thereof and covering piece

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