CN103058524A - Arsenic-free low-expansion black and transparent microcrystalline glass - Google Patents

Arsenic-free low-expansion black and transparent microcrystalline glass Download PDF

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CN103058524A
CN103058524A CN2013100050716A CN201310005071A CN103058524A CN 103058524 A CN103058524 A CN 103058524A CN 2013100050716 A CN2013100050716 A CN 2013100050716A CN 201310005071 A CN201310005071 A CN 201310005071A CN 103058524 A CN103058524 A CN 103058524A
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basic components
devitrified glass
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microcrystalline glass
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CN103058524B (en
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毛利球
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ZHEJIANG CHANGXING NOVATECH GLASS CO., LTD.
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ZHEJIANG CHANGXING NOVATECH GLASS CO Ltd
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Abstract

The invention discloses an arsenic-free low-expansion black and transparent microcrystalline glass. The base components of the microcrystalline glass comprise SiO2, Al2O3, Li2O, CaO, MgO, BaO, ZnO and Na2O+K2O, and the microcrystalline glass also comprises SnO2, CeO2, and MnO or NH4Cl as a clarificant, TiO2 and ZrO2 as a nucleation agent and V2O5 as a colorant. The use of SnO2+CeO2+MnO (or NH4Cl) to substitute As2O3 in the invention ensures good fusing and clarification effects without changing the fusing principle or under a condition that the fusing temperature is not increased, so the microcrystalline glass produced in the invention has the advantages of non-toxicity, environmental protection and high quality, and all the indexes of the physical and chemical performances of the microcrystalline glass accord with international product standard requirements.

Description

A kind of without arsenic low bulk black transparent microcrystal glass
Technical field
The present invention relates to devitrified glass.
Background technology
At present, the domestic production devitrified glass all uses As 2O 3As finings, but because the finings As that uses 2O 3For world forbidding highly toxic substance, the working environment of workers is brought great harm.
Only have abroad the product of German Xiao Te, Japanese NEG not contain As 2O 3, it all uses SnO 2Substitute As 2O 3But find aborning, use SnO 2Keep original fusing system namely not improve temperature of fusion, clarifying effect is relatively poor, and the product bubble is more.Therefore, their described patented product may not only need to produce by its prescription, but also on the fusing system unaccounted place may be arranged.
Summary of the invention
Technical problem to be solved by this invention just provide a kind of with existing melting method produce without the arsenic devitrified glass, nontoxic, environmental protection and physical and chemical performance indices meet the international product standard-required.
For solving the problems of the technologies described above, the present invention adopts following technical scheme: a kind of without arsenic low bulk black transparent microcrystal glass, it is characterized in that: its basic components comprises SiO2, A1203, Li2O, CaO, Mg0, Ba0, Zn0 and Na20+K20, also is added with in addition SnO2, CeO2, MnO or NH 4Cl is as finings, and TiO2 and Zr02 be as Nucleating Agent, V 2O 5As tinting material.
Preferably, the weight percent of each component is SiO in the described basic components 2: 60.0-68.0%, A1 2O 3: 18.0-24.0%, Li 2O:3.0-4.0%, CaO:0.1-0.5%, MgO:0.3-1.5%, BaO:0-1.5%, ZnO:0.5-1.5%, Na 2O:0.4-1% K 2O:0-0.2.%.
Preferably, in the described basic components
∑Na 2O+K 2O＜0.70%；
Σ CaO+MgO+BaO+ZnO 〉=3.0% and＜4.5%.
Preferably, the per-cent that each component accounts for the basic components gross weight in the described Nucleating Agent is: ZrO 2: 1.2-2.5%, TiO 2: 2-3%.
Preferably, also be added with P2O5 in the described Nucleating Agent, the per-cent that described P2O5 accounts for the basic components gross weight is 0.5-1.5%.
Preferably, described Nucleating Agent ZrO 2+ TiO 2+ P 2O 5Addition account for the 3.5-5.5% of basic components gross weight, the part by weight between each component of described Nucleating Agent is: ZrO 2: TiO 2: P 2O 5:=0.5-1:1.5-2:0.7-1%.
Preferably, the per-cent that each component accounts for the basic components gross weight in the described finings is: SnO 2: 0.1-0.5%, CeO 2: 0.2-0.6%, MnO or NH 4Cl:0.1-0.40%.
Preferably, to account for the per-cent of basic components gross weight be 0.4-0.8% to the addition of described finings; Part by weight in the described finings between each component is: SnO 2: CeO 2: MnO or: NH 4Cl=0.5-1:1.2-1.5:0.5-0.8.
Preferably, described tinting material V 2O 5The weight percent that accounts for basic components is 0.05-0.15%.
Preferably, this devitrified glass is take β-quartzy Solid solution as principal crystalline phase, and seeing through look is reddish-brown, and reflected colour is black, and its thermal expansivity is-1.5～3X10 between 25 ℃～700 ℃ -7/ ℃.
The present invention uses SnO2+CeO2+MnO(or NH 4Cl) replace As2O3, remain unchanged in the fusing system and namely do not improve temperature of fusion can to guarantee to melt clarifying effect good, produce the devitrified glass of nontoxic, environmental protection, high-quality, the physical and chemical performance indices meets the international product standard-required.
In addition, be added with P in the Nucleating Agent 2O 5, P 2O 5Be the oxide compound that forms glass network, silicate glass is had good nucleation ability, P 2O 5The reason that makes glass produce nucleation is that it can impel phase-splitting, reduces interfacial energy and nucleation activation energy, adds a small amount of P 2O 5With TiO 2, ZrO 2Mix and use, can promote ZrO 2In glass melt, dissolve, improve the glass nucleogenesis, improve nucleation rate, thereby obtain the thinner devitrified glass of crystal grain.
Embodiment
Of the present invention is the black transparent shape without the arsenic devitrified glass, and this devitrified glass is take β-quartzy Solid solution as principal crystalline phase, and seeing through look is reddish-brown, and reflected colour is black, and its thermal expansivity is-1.5～3X 10 between 25 ℃～700 ℃ -7/ ℃.
This devitrified glass basic components comprises SiO2, A1203, Li2O, CaO, Mg0, Ba0, Zn0 and Na20+K20, also is added with in addition SnO2, CeO2, MnO as finings, and TiO2 and Zr02 be as Nucleating Agent, V 2O 5As tinting material, wherein, MnO also can replace with NH 4Cl.
The weight percent of each component is SiO in the described basic components 2: 60.0-68.0%, A1 2O 3: 18.0-24.0%, Li 2O:3.0-4.0%, CaO:0.1-0.5%, MgO:0.3-1.5%, BaO:0-1.5%, ZnO:0.5-1.5%, Na 2O:0.4-1%K 2O:0-0.2.%, and,
∑Na 2O+K 2O＜0.70%；
Σ CaO+MgO+BaO+ZnO 〉=3.0% and＜4.5%.
Each component accounts for the per-cent of basic components gross weight and is in the described Nucleating Agent: ZrO 2: 1.2-2.5%, TiO 2: 2-3%.Also be added with P2O5 in the described Nucleating Agent, the per-cent that described P2O5 accounts for the basic components gross weight is 0.5-1.5%.Described Nucleating Agent ZrO 2+ TiO 2+ P 2O 5Addition account for the 3.5-5.5% of basic components gross weight, the part by weight between each component of described Nucleating Agent is: ZrO 2: TiO 2: P 2O 5:=0.5-1:1.5-2:0.7-1%.
Each component accounts for the per-cent of basic components gross weight and is in the described finings: SnO 2: 0.1-0.5%, CeO 2: 0.2-0.6%, MnO or NH 4Cl:0.1-0.40%.The per-cent that the addition of described finings accounts for the basic components gross weight is 0.4-0.8%; Part by weight in the described finings between each component is: SnO 2: CeO 2: MnO or: NH 4Cl=0.5-1:1.2-1.5:0.5-0.8.
Described tinting material V 2O 5The weight percent that accounts for basic components is 0.05-0.15%.
The specific embodiment of the invention comprises three specific embodiments, and each embodiment chemical ingredients is as shown in the table:
The embodiment numbering No1 No2 No3
SiO 2 65.68 64.10 63.78
Al 2O 3 21.00 21.45 21.72
Li 2O 3.51 3.95 3.38
CaO 0.28 0.31 0.39
MgO 0.14 0.70 0.61
ZnO 1.20 1.30 1.42
BaO 1.60 1.20 1.31
K 2O 0.08 0.08 0.08
Na 2O 0.40 0.60 0.71
ZrO 2 1.28 1.50 1.50
TiO 2 2.82 3.00 3.20
P 2O 5 1.15 1.18 1.02
SnO 2 0.15 0.18 0.33
CeO 2 0.41 0.18 0.28
MnO 2 0.12 0.18
NH4Cl 0.12
V 2O 5 0.18 0.09 0.15
The technique of carrying out devitrified glass production according to upper table is: 1, by the chemical ingredients in the table, various raw materials are carried out weighing, mixing by prescription, add the moisture of the 3%-5% of each raw material gross weight, wet mixing is even;
2, the admixtion that mixes enters in the cross flame kiln, melts under 1600-1650 ℃:;
3, the glass metal that fusing is good is cooled to 1400-1450 ℃ through clarification and sends into the moulding of rolling press continuous calendering;
4, the devitrified glass after the moulding is sent into annealing furnace and is carried out subregion annealing;
5, former of the devitrified glass after the anneal is sent into the crystallization furnace crystallization,
About 720～750 ℃ and be incubated 1-2 hour and make it and form nucleus;
About 860～880 ℃ and be incubated 1-2 hour and make its nucleus growth and separate out crystalline phase.
6, naturally cool to room temperature.
The concrete chemical composition of embodiment of the invention 1.2.3 is produced according to above-mentioned technique, and the product of its acquisition is tested according to relevant criterion, and concrete data are:
Figure BDA00002707889900051

Claims (10)

1. one kind without arsenic low bulk black transparent microcrystal glass, and it is characterized in that: its basic components comprises SiO2, A1203, Li2O, CaO, Mg0, Ba0, Zn0 and Na20+K20, also is added with in addition SnO2, CeO2, MnO or NH 4Cl is as finings, TiO 2And Zr0 2As Nucleating Agent, V 2O 5As tinting material.
2. devitrified glass according to claim 1, it is characterized in that: the weight percent of each component is SiO in the described basic components 2: 60.0-68.0%, A1 2O 3: 18.0-24.0%, Li 2O:3.0-4.0%, CaO:0.1-0.5%, MgO:0.3-1.5%, BaO:0-1.5%, ZnO:0.5-1.5%, Na 2O:0.4-1%K 2O:0-0.2.%.
3. devitrified glass according to claim 2 is characterized in that: in the described basic components
∑Na 2O+K 2O＜0.70%；
Σ CaO+MgO+BaO+ZnO 〉=3.0% and＜4.5%.
4. devitrified glass according to claim 1 is characterized in that: each component accounts for the per-cent of basic components gross weight and is in the described Nucleating Agent: ZrO 2: 1.2-2.5%, TiO 2: 2-3%.
5. devitrified glass according to claim 4, it is characterized in that: also be added with P2O5 in the described Nucleating Agent, the per-cent that described P2O5 accounts for the basic components gross weight is 0.5-1.5%.
6. devitrified glass according to claim 5 is characterized in that: described Nucleating Agent ZrO 2+ TiO 2+ P 2O 5Addition account for the 3.5-5.5% of basic components gross weight, the part by weight between each component of described Nucleating Agent is: ZrO 2: TiO 2: P 2O 5:=0.5-1:1.5-2:0.7-1%.
7. devitrified glass according to claim 1 is characterized in that: each component accounts for the per-cent of basic components gross weight and is in the described finings: SnO 2: 0.1-0.5%, CeO 2: 0.2-0.6%, MnO or NH 4Cl:0.1-0.40%.
8. devitrified glass according to claim 7, it is characterized in that: the per-cent that the addition of described finings accounts for the basic components gross weight is 0.4-0.8%; Part by weight in the described finings between each component is: SnO 2: CeO 2: MnO or: NH 4Cl=0.5-1:1.2-1.5:0.5-0.8.
9. devitrified glass according to claim 1 is characterized in that: described tinting material V 2O 5The weight percent that accounts for basic components is 0.05-0.15%.
10. devitrified glass according to claim 1 is characterized in that: this devitrified glass is take β-quartzy Solid solution as principal crystalline phase, and seeing through look is reddish-brown, and reflected colour is black, and its thermal expansivity is-1.5～3X10 between 25 ℃～700 ℃ -7/ ℃.
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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103951202A (en) * 2014-05-08 2014-07-30 宁波大学 Rare-earth-ion-doped BaYCl5 microcrystalline glass and preparation method thereof
CN103951250A (en) * 2014-05-08 2014-07-30 宁波大学 Rare-earth-ion-doped LiBaCl3 microcrystalline glass and preparation method thereof
CN104609733A (en) * 2015-01-27 2015-05-13 浙江长兴诺万特克玻璃有限公司 Vanadium-free arsenic-free low-expansion black transparent glass ceramic and preparation method thereof
CN105742056A (en) * 2016-01-29 2016-07-06 桂林电子科技大学 High-energy borophosphate microcrystalline glass dielectric material and preparation method thereof
CN106045324A (en) * 2015-06-10 2016-10-26 成都光明光电有限责任公司 Glass ceramic and multilayer inorganic membrane filter
CN108083641A (en) * 2017-11-28 2018-05-29 湖南航天磁电有限责任公司 A kind of preparation method of the devitrified glass of strong mechanical performance
CN110590165A (en) * 2019-10-21 2019-12-20 成都光明光电有限责任公司 Low-expansion glass ceramics and manufacturing method thereof
CN111072276A (en) * 2019-12-25 2020-04-28 温州市康尔微晶器皿有限公司 Lithium-aluminum-silicon microcrystalline glass containing composite clarifying agent and preparation method thereof
CN113336435A (en) * 2021-06-30 2021-09-03 浙江本尊新材料科技有限公司 Non-volatile harmless environment-friendly glass clarifying agent for amorphous arsenic and preparation and application thereof
JP2022001546A (en) * 2020-06-22 2022-01-06 湖州大享玻璃制品有限公司 Li2O-Al2O3-SiO2-based crystallized glass and Li2O-Al2O3-SiO2-based crystalline glass

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Publication number Priority date Publication date Assignee Title
CN1495138A (en) * 2002-09-11 2004-05-12 欧罗克拉公司 Vitrifiable inorganic glass, preparation of glass-ceramic product and its described product
CN1785872A (en) * 2004-12-07 2006-06-14 刘明志 Low expansion transparent black micro crystalline glass and its preparation method
CN101356128A (en) * 2005-12-07 2009-01-28 欧罗克拉公司 Glass, glass-ceramic, articles and fabrication process

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1495138A (en) * 2002-09-11 2004-05-12 欧罗克拉公司 Vitrifiable inorganic glass, preparation of glass-ceramic product and its described product
CN1785872A (en) * 2004-12-07 2006-06-14 刘明志 Low expansion transparent black micro crystalline glass and its preparation method
CN101356128A (en) * 2005-12-07 2009-01-28 欧罗克拉公司 Glass, glass-ceramic, articles and fabrication process

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103951202A (en) * 2014-05-08 2014-07-30 宁波大学 Rare-earth-ion-doped BaYCl5 microcrystalline glass and preparation method thereof
CN103951250A (en) * 2014-05-08 2014-07-30 宁波大学 Rare-earth-ion-doped LiBaCl3 microcrystalline glass and preparation method thereof
CN103951250B (en) * 2014-05-08 2016-04-06 宁波大学 Rare earth ion doped LiBaCl 3devitrified glass and preparation method thereof
CN104609733A (en) * 2015-01-27 2015-05-13 浙江长兴诺万特克玻璃有限公司 Vanadium-free arsenic-free low-expansion black transparent glass ceramic and preparation method thereof
CN111548020A (en) * 2015-06-10 2020-08-18 成都光明光电有限责任公司 Glass ceramics and multilayer inorganic film filter
CN106045324A (en) * 2015-06-10 2016-10-26 成都光明光电有限责任公司 Glass ceramic and multilayer inorganic membrane filter
CN105742056A (en) * 2016-01-29 2016-07-06 桂林电子科技大学 High-energy borophosphate microcrystalline glass dielectric material and preparation method thereof
CN108083641A (en) * 2017-11-28 2018-05-29 湖南航天磁电有限责任公司 A kind of preparation method of the devitrified glass of strong mechanical performance
CN110590165A (en) * 2019-10-21 2019-12-20 成都光明光电有限责任公司 Low-expansion glass ceramics and manufacturing method thereof
CN111072276A (en) * 2019-12-25 2020-04-28 温州市康尔微晶器皿有限公司 Lithium-aluminum-silicon microcrystalline glass containing composite clarifying agent and preparation method thereof
CN111072276B (en) * 2019-12-25 2022-05-03 温州市康尔微晶器皿有限公司 Lithium-aluminum-silicon microcrystalline glass containing composite clarifying agent and preparation method thereof
JP2022001546A (en) * 2020-06-22 2022-01-06 湖州大享玻璃制品有限公司 Li2O-Al2O3-SiO2-based crystallized glass and Li2O-Al2O3-SiO2-based crystalline glass
JP7031094B2 (en) 2020-06-22 2022-03-08 湖州大享玻璃制品有限公司 Li2O-Al2O3-SiO2-based crystallized glass and Li2O-Al2O3-SiO2-based crystalline glass
CN113336435A (en) * 2021-06-30 2021-09-03 浙江本尊新材料科技有限公司 Non-volatile harmless environment-friendly glass clarifying agent for amorphous arsenic and preparation and application thereof
CN113336435B (en) * 2021-06-30 2022-02-25 浙江本尊新材料科技有限公司 Non-volatile harmless environment-friendly glass clarifying agent for amorphous arsenic and preparation and application thereof

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