CN1974456B - Microcrystalline glass plate production process - Google Patents

Microcrystalline glass plate production process Download PDF

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Publication number
CN1974456B
CN1974456B CN2006101241443A CN200610124144A CN1974456B CN 1974456 B CN1974456 B CN 1974456B CN 2006101241443 A CN2006101241443 A CN 2006101241443A CN 200610124144 A CN200610124144 A CN 200610124144A CN 1974456 B CN1974456 B CN 1974456B
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China
Prior art keywords
glass
calendering formation
microcrystalline glass
glass plate
plate
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Expired - Fee Related
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CN2006101241443A
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Chinese (zh)
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CN1974456A (en
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巫汉生
孙树江
史杰
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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
    • C03C14/00—Glass compositions containing a non-glass component, e.g. compositions containing fibres, filaments, whiskers, platelets, or the like, dispersed in a glass matrix
    • C03C14/006—Glass compositions containing a non-glass component, e.g. compositions containing fibres, filaments, whiskers, platelets, or the like, dispersed in a glass matrix the non-glass component being in the form of microcrystallites, e.g. of optically or electrically active material
    • 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
    • C03C15/00—Surface treatment of glass, not in the form of fibres or filaments, by etching
    • 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
    • C03C3/087—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 containing calcium oxide, e.g. common sheet or container glass
    • 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
    • C03C3/11—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen
    • C03C3/112—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen containing fluorine
    • 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
    • C03C3/11—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen
    • C03C3/112—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen containing fluorine
    • C03C3/115—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen containing fluorine containing boron
    • C03C3/118—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen containing fluorine containing boron containing aluminium

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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)
  • Crystallography & Structural Chemistry (AREA)
  • Ceramic Engineering (AREA)
  • Dispersion Chemistry (AREA)
  • Glass Compositions (AREA)

Abstract

The present invention discloses one kind of etched microcrystalline glass plate and its production process. The etched microcrystalline glass plate is produced mainly with the mineral materials quartz, feldspar, kaolin, calcite, dolomite, fluorite, etc. Chemically, it consists of SiO2 55-65 wt%, Al2O3 4-15 wt%, certain amount of 15-30 wt%, MgO 1-5 wt%, Na2O+K2O+Li2O 2-8 wt%, B2O3, BaO and/or ZnO 0.5-3 wt%, clarifier Sb2O3 0-1 wt%, coloring agent 0-15 wt%, and crystal nucleus F 0-5 wt%. The production process includes the following steps: preparing the materials, smelting, rolling to form, annealing, cutting and packing. The etched microcrystalline glass plate may be further produced into microcrystalline glass plate or microcrystalline glass-ceramic composite plate.

Description

A kind of production method of etched microcrystalline glass plate
Technical field
The present invention relates to a kind of material of construction work in-process technical field, be specifically related to a kind of devitrified glass entire body plate and glass-ceramic clad plate produced with the production method of the glass hair plates of crystallization not as yet.
Background technology
At present, devitrified glass entire body plate and glass-ceramic clad plate mostly adopt the particle sintering process, and promptly dried being sprinkling upon on diaphragm capsule or the ceramic substrate of glass ceramics frit through shrend forms through calcining, sintering, coring, crystallization.Its technology deficiency is: 1. exist hole to be difficult to get rid of between particle, glass is surperficial 1.5-2mm densification, and there are a large amount of bubbles in inside, occurs needle pore defect after the grinding and polishing.2. the crystallite frit is easy to be polluted through shrend, oven dry, fragmentation, storage and transport process, and spot, impurity defect appear in finished product.3. fire through processes such as exhaust, sintering, coring, crystallization because of it, require the glasswork performance to adapt with it, need to add ZnO, BaO, B 2O 3Come the adjusting process performance etc. valuable industrial chemicals, cost height and BaCO 3Poisonous.4. the glass surface texture becomes particulate state, and pattern is single.The present technology of another kind method calendering devitrified glass is still immature, and domestic have only several families producing, and specification is little, produces unstable.Its process limitation is 1. subsequent annealing kiln requirement very long (about 200 meters), and crystallization temperature can not be above 1000 ℃.2. each zone temperatures of subsequent annealing kiln requires control strict, otherwise defectives such as disconnected plate, roll banding occur.
Summary of the invention
The objective of the invention is to, a kind of weak point and limitation of rolling process and design production at the particle sintering process is provided, adopt the production method of calendering technology glass hair plates, this glass hair plates is fired through secondary again, crystallization is produced the devitrified glass entire body plate and the glass-ceramic clad plate of solid color or different figure colours.
The present invention realizes above-mentioned purpose by following technical solution:
Etched microcrystalline glass plate of the present invention, it mainly is made up of as quartz, feldspar, kaolin, calcite (coarse whiting), rhombspar, fluorite etc. raw mineral materials, it is characterized in that its chemical ingredients scope (WT%) is SiO 255%-65%, Al 2O 34%-15%, CaO15%-30%, MgO1%-5%, R 2O (Na 2O+K 2O+Li 2O) 2%-8%, B 2O 3, at least a its total amount is 0.5%-3%, finings Sb among BaO, the ZnO 2O 30-1%, tinting material 0-15%, nucleus agent F0-5%.
The present invention also provides the production method of this etched microcrystalline glass plate, and it comprises following concrete steps,
1. prepare uniform admixtion; With quartz, feldspar, kaolin, calcite (coarse whiting), rhombspar, soda ash, nitric acid, finings Sb 2O 3, the tinting material nickel oxide, manganese oxide, cobalt oxides etc., the various raw materials of nucleus agent fluorite are weighed by weight percentage by the chemical ingredients scope of above-mentioned glass hair plates, mix;
2. found:, under 1480 ℃-1520 ℃ temperature, in melting furnaces, be fused into uniform glass melt above-mentioned uniform admixtion;
3. calendering formation;
4. glass annealing: the sheet glass behind the above-mentioned calendering formation is annealed under 680 ℃ of-550 ℃ of temperature;
5. cutting, packing: cut into work in-process according to devitrified glass desired size (than the big 1-2mm of final dimension) and composition board ceramic substrate size, the packing back is for devitrified glass factory and ceramics factory produces devitrified glass and composition board is used.
In the above-mentioned calendering formation step, can become as yet the not sheet glass of crystallization for directly rolling; Perhaps, add glass-ceramic colorant or colored frit powder, calendering formation then continuously or intermittently at dog-hole; Perhaps calendering formation after rolling press front glass bath surface evenly adds homochromy or heterochromatic crystallite or non-crystallite frit particle.
Adopt the glass hair plates of foregoing invention prescription and production method to send devitrified glass factory or ceramics factory to fire through secondary, devitrified glass of producing after the crystallization or composition board cost are low, simple and the control easily of technology, free of pinholes, impurity defect, excellent rate height, the surface texture near lithotome, the texture rich color.Its major technique feature is: 1. the glass hair plates is non-crystallized, only need anneal, and annealing furnace is short.Need secondary to fire crystallization, crystallization temperature can height can low (above 1000 ℃), do not have phenomenons such as fried plate and roll banding.2. can produce the pure color devitrified glass and the glass-ceramic clad plate of no decorative pattern, also can produce the devitrified glass and the glass-ceramic clad plate of marble lines and particulate state pattern.3. it is low to produce cost, and the devitrified glass and the glass-ceramic clad plate of free of pinholes, immaculate impurity defect.
Embodiment
Embodiment 1
The present invention produces devitrified glass entire body plate and microcrystal glass-ceramic compounded plate is used as yet the not glass hair plates of crystallization, and its production method comprises following production stage: at first evenly prepare burden, according to chemical composition SiO 263.80%, Al 2O 38.65%, CaO18.62%, MgO2.10%, (Na 2O+K 2O) 5.81%, BaO1.02%, add finings Sb 2O 30.5%, nucleus agent F1.8%.Get corresponding 0.6mm following quartz, feldspar, calcite (coarse whiting), calcined kaolin, fluorite, yellow soda ash, SODIUMNITRATE, barium carbonate, antimonous oxide and weigh uniform mixing in proportion; Put into melting furnaces then in 1500 ℃ ± 10 ℃ fusings, clarification is made the glass hair plates of thick 18mm after calendering formation is annealed; Cut, cut into work in-process according to devitrified glass desired size (than the big 1-2mm of final dimension) and composition board ceramic substrate size, packing is used for devitrified glass factory production entire body rolled glass plate.
Embodiment 2
The present invention is the glass hair plates of crystallization not as yet, and its production method comprises as follows, A: SiO according to chemical composition 262.60%, Al 2O 38.5%, CaO0.2%, MgO2.3%, (Na 2O+K 2O) 5.6%, B 2O 31.0%, adds finings Sb 2O 30.5%.Get corresponding 0.6mm following quartz, feldspar, calcined kaolin, calcite (coarse whiting), rhombspar, sour sodium sodium, boric acid, antimonous oxide, weigh in proportion, uniform mixing, put into melting furnaces in 1500 ℃ ± 10 ℃ fusings, clarification is after calendering formation, anneal, make the glass hair plates of thick 5mm ± 0.3mm.Cutting, packing is produced the pure white microcrystal glass-ceramic compounded plate for ceramics factory.
B: identical with each step of above-mentioned A, just in glass ingredient, add 0.5% manganese oxide, promptly make dark brown transparent glass hair plates, produce light yellow microcrystal glass-ceramic compounded plate for ceramics factory.
C: identical with each step of above-mentioned A, just in glass ingredient, add 0.5% cobalt oxide and 0.3% ferric oxide, promptly make the transparent glass hair plates of mazarine, produce light grey microcrystal glass-ceramic compounded plate for ceramics factory.
Embodiment 3
The chemical ingredients of etched microcrystalline glass plate of the present invention is SiO 258.50%, Al 2O 310.6%, CaO22.2%, MgO1.5%, (Na 2O+K 2O) 5.8%, ZnO1.0%.Get the following quartz of corresponding 0.6mm, feldspar, calcined kaolin, calcite (coarse whiting), rhombspar, zinc oxide, boric acid, weigh by above-mentioned chemical ingredients proportioning, uniform mixing, put into melting furnaces in 1500 ℃ ± 10 ℃ fusings, tubule and an agitator of three different diameters are set to the dog-hole of settling pond at glass metal, black (tubule) is housed respectively in three pipes, dark-grey (middle pipe), three kinds of ceramic glaze colorants of light gray (extra heavy pipe), and constantly in glass metal, add, the non-stirring at the uniform velocity of agitator, after the transparent glass hair plates that to have natural texture is rolled in clarification, produce microcrystal glass-ceramic compounded plate for ceramics factory, this composition board has the grey black lineae ablicantes reason of nature, exactly likes natural marble.
Embodiment 4
Selecting materials to weigh by the chemical ingredients of glass among the embodiment 3 mixes, and puts into melting furnaces and melts in same temperature, clarification.Pair roller top at rolling press is provided with the dry granular distributor, equably to the white micro-crystals glass particle of glass surface charity particle diameter less than 3mm, through calendering annealing moulding.Make 5mm ± 0.3mm heavy sheet glass hair plates, produce microcrystal glass-ceramic compounded plate for ceramics factory, this composition board has sintering process particle shape texture, exactly likes natural granite.
Embodiment 5
Press the chemical ingredients of glass among the embodiment 3, add colorant at dog-hole, add crystallite and non-crystallite transparent grain according to embodiment 4 glass metal surface between the rolling press pair roller again, make the glass hair plates, produce whole-body crystallized glass plate and composition board for devitrified glass factory and ceramics factory, can obtain exactly liking lithotome, the sheet for architectural decoration of pattern texture-rich.
More than shown only be preferred embodiment of the present invention, can not limit the present invention's interest field with this, therefore the equivalent variations of being done according to the present patent application claim still belongs to the scope that the present invention is contained.

Claims (1)

1. the production method of an etched microcrystalline glass plate is characterized in that, it comprises following concrete steps,
1. prepare uniform admixtion; With quartz, feldspar, kaolin, calcite, rhombspar, soda ash, nitric acid, finings Sb 2O 3, the tinting material nickel oxide, manganese oxide, cobalt oxide, the various raw materials of nucleus agent fluorite are weighed by the chemical component weight percentage range of following glass fiber plate and are mixed;
SiO 255%-65%, Al 2O 34%-15%, CaO15%-30%, MgO1%-5%, Na 2O+K 2O+Li 2O 2%-8%, B 2O 3, at least a its total amount is 0.5%-3%, finings Sb among BaO, the ZnO 2O 30-1%, tinting material 0-15%, nucleus agent F 0-5%;
2. found:, under 1480 ℃-1520 ℃ temperature, in melting furnaces, be fused into uniform glass melt above-mentioned uniform admixtion;
3. calendering formation: at dog-hole, add glass-ceramic colorant or colored frit powder continuously or intermittently, then calendering formation, perhaps calendering formation after rolling press front glass bath surface evenly adds homochromy or heterochromatic crystallite or non-crystallite frit particle; Calendering formation is directly to roll by rolling press to become as yet the not sheet glass of crystallization;
4. glass annealing: the sheet glass behind the above-mentioned calendering formation is annealed under 680 ℃ of-550 ℃ of temperature;
5. cutting, packing: according to selected size and composition board ceramic substrate size cutting work in-process than the big 1-2mm of devitrified glass finished product, use for producing devitrified glass and composition board the packing back.
CN2006101241443A 2006-12-11 2006-12-11 Microcrystalline glass plate production process Expired - Fee Related CN1974456B (en)

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CN1974456B true CN1974456B (en) 2010-11-03

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Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101787786B (en) * 2010-02-10 2012-07-18 姚桂龙 Preparation method of non-porous nano crystalline glass ground decoration tile
CN101898867B (en) * 2010-07-19 2012-02-01 浙江大学 Pyroceram-ceramic composite plate and preparation method thereof
CN102795770A (en) * 2012-09-06 2012-11-28 北京大有盛和科技有限公司 Method for producing color pattern type glass ceramics through rolling process or casting process
CN108623166A (en) * 2018-06-13 2018-10-09 浙江西溪玻璃有限公司 A kind of intelligent light-controlled glass high rigidity substrate and preparation method thereof
CN110067492A (en) * 2019-04-16 2019-07-30 邢一帆 A kind of ventilation air filtration glass, ventilation air filtration door and window and preparation method
CN111470754B (en) * 2020-04-09 2022-04-15 惠州市彩玉微晶新材有限公司 Method for calendering and coloring microcrystalline glass and product processing technology thereof
CN112408800A (en) * 2020-11-25 2021-02-26 江西璞晶新材料股份有限公司 Method for preparing marble-like colored microcrystalline glass by using ceramic pigment

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1098706A (en) * 1993-08-10 1995-02-15 肖绍展 Stone-imitative devitrified glass and production method thereof
CN1160687A (en) * 1996-03-30 1997-10-01 大连理工大学 Fast-microcrystallized devitrified agrellite glass and its production process

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1098706A (en) * 1993-08-10 1995-02-15 肖绍展 Stone-imitative devitrified glass and production method thereof
CN1160687A (en) * 1996-03-30 1997-10-01 大连理工大学 Fast-microcrystallized devitrified agrellite glass and its production process

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
北京轻工业学院主编.玻璃工艺学 1.中国财政经济出版社,1961,84-86.
北京轻工业学院主编.玻璃工艺学 1.中国财政经济出版社,1961,84-86. *

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