CN101244889A - Non-fluorin environment protection opacifiedglass material and method for manufacturing same - Google Patents
Non-fluorin environment protection opacifiedglass material and method for manufacturing same Download PDFInfo
- Publication number
- CN101244889A CN101244889A CNA2008100147689A CN200810014768A CN101244889A CN 101244889 A CN101244889 A CN 101244889A CN A2008100147689 A CNA2008100147689 A CN A2008100147689A CN 200810014768 A CN200810014768 A CN 200810014768A CN 101244889 A CN101244889 A CN 101244889A
- Authority
- CN
- China
- Prior art keywords
- glass
- opaque
- batch
- bao
- preparation
- 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.)
- Pending
Links
Images
Abstract
The invention relates to a fluorine-free environmental opaque glass material and a preparation method thereof and belongs to the new material field of glass. Composition of the glass material is SiO2-Al2O3-B2O3P2O5-MgO-CaO-SrO-BaO-Li2O-Na2O-K2O. The preparation method comprises that raw materials are mixed to make an even batch, then the batch is put into a corundum crucible, and then the batch is casted and molded after being melted and insulated under 1500 DEG C to 1520 DEG C for 3 hours, and then the batch is insulated and annealed under 550 DEG C to 560 DEG C for 1 hour. The preparation of the invention replaces the fluoride with a small amount of phosphate to generate opaque effect, and no environmental pollution can be caused in the industrial production of the opaque glass, and the short service life of glass furnaces and safety problems caused by fluorine can be avoided, and a compact net structure reconstruction technology is adopted to adjust the relative contents of SiO2 and P2O5, meanwhile, alkali metals or alkaline earth metal oxides are introduced, and the glass produces significant opaque effect under the spontaneous phase separation in the process of cooling, and a small amount of B2O3 is introduced to enhance the opaque effect of the glass, meanwhile, a certain amount of Al2O3 is introduced to endow the glass with excellent chemical stability.
Description
Technical field
The invention relates to a kind of non-fluorin environment protection opacifiedglass material and manufacture method thereof, belong to the glass field of new.
Background technology
Compare with conventional clear glass, emulsion opal glass has characteristics such as color and luster is soft, noble and unsullied grace.In recent years, the application of emulsion opal glass is increasingly extensive, except being used for aspects such as daily utensil, architectural lighting and cosmetic package, also is used for various bottles, building and ornament materials and dental material etc., industrial scale also progressively enlarging, demonstrates good market development prospect.
The glass opaque mechanism mainly contains four kinds of crystal grain milkiness, phase-splitting milkiness, no cofusing particle milkiness and micro-bubble milkiness, producer nearly all adopts first kind of milkiness method both at home and abroad at present, wherein fluorite and Sodium Silicofluoride are modal opacifying agent, separate out a large amount of CaF when glass metal cools off
2With NaF crystal grain, because the specific refractory power difference of these two kinds of crystal grain and host glass is bigger, make light produce scattering, cause opaque effect.The report that with the fluorochemical is opacifying agent in recent years is more, and Wang Ning etc. (referring to document: Wang Ning, Tao Ying, Chen Min. Dalian Polytechnic College journal, 1999,18 (3): 16-19) introduced Al
2O
3Content is to the influence of fluorochemical emulsion opal glass microscopic appearance, Tian Fang is (referring to document: Tian Fang, Zhang Zhi's rosy clouds, Xie Zhiqiang. glass and enamel, 2003,31 (6): 30-32) and Pan Ling (referring to document: Pan Ling, Li Haiying. glass, 2004,2:47-48) reported the solution of various defectives in the fluorine-containing emulsion opal glass bottle production process respectively.The content of fluorochemical between 1～10wt%, has advantages such as opaque effect is good, milkiness speed is fast usually in this emulsion opal glass, and therefore this class milkiness mode is still mainly adopted in emulsion opal glass production both at home and abroad.But the shortcoming of this fluorochemical emulsion opal glass is also very outstanding, and fluorochemical in the process of founding following reaction: 4RF+SiO can take place on the one hand
2→ 2R
2O+SiF
4↑, this erosion to refractory materials is very serious, shortens the work-ing life of glass furnace; Fluorochemical volatilization easily in the process of founding on the other hand, be unfavorable for the control of glass milkiness degree, more seriously the volatilization of fluorine is bigger to the hazard ratio of surrounding environment, if will thoroughly solve the problem of environmental pollution that exhaust gas emission causes, will certainly increase the cost of product; Once more, fluorochemical makes this fluorine-containing glass be difficult for making various tablewares etc. as a kind of toxic substance, has limited its range of application.Developing floride-free emulsion opal glass has become the problem of various countries scholar and production technology personnel common concern,
W etc. (referring to document:
W, Frank M and Rheinberger V.Thermochimica Acta, 1996,280-281:491-499.) reported interpolation P
2O
5, TiO
2And ZrO
2The silicate system emulsion opal glass, this glass occurs phase-splitting at 1020 ℃ after carrying out certain thermal treatment can cause opaque effect, Shepilov M P etc. are (referring to document: Shepilov M P, Kalmykov A E, Sycheva G A.Journal of Non-Crystalline Solids, 2007,353:2415-2430.) Bao Dao 13.9Na
2O-36.0B
2O
3-50.1SiO
2(mol%) system glass is a melting at 1250 ℃, about 610 ℃, heat-treat and phase-splitting milkiness phenomenon also can occur, Wang Xiaofeng etc. are (referring to document: Wang Xiaofeng, soup Hua Juan, Wang Cheng meets, Tao Ying. glass and enamel, 2007,35 (5): 36-42) set forth the relative merits of floride-free emulsion opal glass production technique theoretically, pointed out that phase-splitting milkiness, crystallite milkiness and phosphoric acid salt emulsion opal glass need thermal treatment could produce the ideal opaque effect usually.But utilize thermal treatment to produce the continuous production that milkiness is unfavorable for glass, also can increase the production cost of glass simultaneously.Up to the present, yet there are no in the world and utilize glass to divide facies principle to come development research low-phosphorous, floride-free and do not need the report of heat treated emulsion opal glass.
Summary of the invention
The objective of the invention is to overcome the above-mentioned deficiency of emulsion opal glass, preparation has the low-phosphorous, floride-free of good mechanics, thermal property and chemical stability and does not need heat treated emulsion opal glass.
A kind of non-fluorin environment protection opacifiedglass, its glass material consists of SiO
2-Al
2O
3-B
2O
3-P
2O
5-MgO-CaO-SrO-BaO-Li
2O-Na
2O-K
2O.The concrete mass percent of forming is: SiO
2(58.5～61), Al
2O
3(4.0-5.2), B
2O
3(3.3-4.5), P
2O
5(6.7-7.5), MgO (0-3.6), CaO (0-2.2) SrO (0-6), BaO (5.6-12.2), Li
2O (0-1.5), Na
2O (10.2-12.5), K
2O (0-4.6).The glass melting temperature is 1500～1520 ℃, is incubated 3 hours, and annealing temperature is 550～560 ℃, is incubated 1 hour.
Manufacture method of the present invention, replace fluorochemical with the carbamate additives for low phosphorus hydrochlorate and produce opaque effect, in the industrial production of emulsion opal glass, phosphoric acid salt is introduced with the form of Rock Phosphate (72Min BPL) neither can cause environmental pollution, can avoid the short and safety problem of glass furnace life-span that is caused by fluorine again.Adopt fine and close network structural remodeling technology, adjust SiO
2And P
2O
5The composition of two kinds of network organizers is introduced basic metal or alkaline earth metal oxide simultaneously, and glass metal forms the rich phosphoric acid salt face drop that is of a size of 0.15～0.30 μ m in process of cooling, give glass significant opaque effect.Do not contain common expensive TiO
2And ZrO
2Deng the nucleus agent, can reduce the cost of product, the milkiness of glass is that spontaneous phase-splitting produces in addition, does not need to heat-treat, can save energy.An amount of B
2O
3Introducing, can reduce the glass melting temperature of glass, also help the opaque effect of reinforcing glass; Introduce a small amount of Al in addition
2O
3Make the glass network structure be tending towards fine and close, help improving the chemical stability of glass.
Density by the non-fluorin environment protection opacifiedglass material of method provided by the invention preparation is 2.51～2.82gcm
-3, the thermal expansivity between 25～300 ℃ is 56.5～68.2 * 10
-7℃
-1Between, bending strength is 79.3～96.2MPa, whiteness is 78～86%, the water tolerance that is recorded by standard DIN method is I～II level, and acid resistance is III～III level, and alkali resistance is II～III level, this glass has glossiness preferably, is the practical glass novel material that a class has wide application prospect.
Salient features by the obtained glass of the present invention is as shown in table 1:
Table 1 glass properties provided by the present invention
| Performance | Unit | Goods of the present invention |
| Density | g·cm -3 | 2.51～2.82 |
| Thermal expansivity | ×10 -7℃ -1 | 56.5～68.2 |
| Bending strength | MPa | 79.3～96.2 |
| Whiteness | ％ | 78～86 |
| Water tolerance | Level | I～II |
| Acid resistance | Level | II～III |
| Alkali resistance | Level | II～III |
Description of drawings
Fig. 1 is the microstructure photograph of emulsion opal glass among the embodiment 1.
Embodiment
Embodiment 1:
Glass is formed (wt%):
SiO
2 Al
2O
3 B
2O
3 P
2O
5 MgO CaO BaO Na
2O
SiO
2 Al
2O
3 B
2O
3 P
2O
5 MgO CaO BaO Na
2O
61 4 4.2 7 2.1 1.2 8 12.5
With silicon-dioxide, aluminium sesquioxide, boric acid, DAP, magnesium oxide, lime carbonate, barium carbonate, yellow soda ash is raw material, by said components weighing, evenly mixed, in 1520 ℃ electric furnace, be incubated 3 hours then, the glass metal that melts is cooled off the block glass of formation fast in mould, send in 560 ℃ the annealing furnace and anneal, be incubated 1 hour, be cooled to then room temperature no silicofluoride emulsion opal glass material.Its thermal expansivity is 56.5 * 10
-7℃
-1, bending strength is 96.2MPa, and whiteness is 84%, and other performance is as shown in table 1.
Embodiment 2:
Glass is formed (wt%):
SiO
2 Al
2O
3 B
2O
3 P
2O
5 SrO BaO Na
2O K
2O
60.5 4.2 3.3 7.2 6 5.6 11.2 2
With silicon-dioxide, aluminium sesquioxide, boric acid, DAP, Strontium carbonate powder, barium carbonate, yellow soda ash, salt of wormwood is raw material, by said components weighing, evenly mixed, in 1520 ℃ electric furnace, be incubated 3 hours then, the glass metal that melts is cooled off the block glass of formation fast in mould, send in 560 ℃ the annealing furnace and anneal, be incubated 1 hour, be cooled to then room temperature no silicofluoride emulsion opal glass material.Its thermal expansivity is 58.7 * 10
-7℃
-1, bending strength is 90.3MPa, and whiteness is 86%, and other performance is as shown in table 1.
Embodiment 3:
Glass is formed (wt%):
SiO
2 Al
2O
3 B
2O
3 P
2O
5 MgO CaO BaO Li
2O Na
2O
60 4.2 4 7.2 2.1 2.2 7.8 1.5 11
With silicon-dioxide, aluminium sesquioxide, boric acid, DAP, magnesium oxide, lime carbonate, barium carbonate, Quilonum Retard, yellow soda ash is raw material, by said components weighing, evenly mixed, in 1510 ℃ electric furnace, be incubated 3 hours then, the glass metal that melts is cooled off the block glass of formation fast in mould, send in 560 ℃ the annealing furnace and anneal, be incubated 1 hour, be cooled to then room temperature no silicofluoride emulsion opal glass material.Its thermal expansivity is 61.3 * 10
-7℃
-1, bending strength is 87.3MPa, and whiteness is 84%, and other performance is as shown in table 1.
Embodiment 4:
Glass is formed (wt%):
SiO
2 Al
2O
3 B
2O
3 P
2O
5 MgO CaO BaO Na
2O K
2O
59.5 4.3 4.5 7 1.7 1.5 8 12.5 1
With silicon-dioxide, aluminium sesquioxide, boric acid, DAP, magnesium oxide, lime carbonate, barium carbonate, yellow soda ash, salt of wormwood is raw material, by said components weighing, evenly mixed, in 1510 ℃ electric furnace, be incubated 3 hours then, the glass metal that melts is cooled off the block glass of formation fast in mould, send in 560 ℃ the annealing furnace and anneal, be incubated 1 hour, be cooled to then room temperature no silicofluoride emulsion opal glass material.Its thermal expansivity is 65.1 * 10
-7℃
-1, bending strength is 84.6MPa, and whiteness is 81%, and other performance is as shown in table 1.
Embodiment 5:
Glass is formed (wt%):
SiO
2 Al
2O
3 B
2O
3 P
2O
5 MgO BaO Na
2O
59 4.5 3.8 6.7 3.6 12.2 10.2
With silicon-dioxide, aluminium sesquioxide, boric acid, DAP, magnesium oxide, barium carbonate, yellow soda ash is raw material, by said components weighing, evenly mixed, in 1500 ℃ electric furnace, be incubated 3 hours then, the glass metal that melts is cooled off the block glass of formation fast in mould, send in 550 ℃ the annealing furnace and anneal, be incubated 1 hour, be cooled to then room temperature no silicofluoride emulsion opal glass material.Its thermal expansivity is 67.2 * 10
-7℃
-1, bending strength is 80.2MPa, and whiteness is 78%, and other performance is as shown in table 1.
Embodiment 6:
Glass is formed (wt%):
SiO
2 Al
2O
3 B
2O
3 P
2O
5 MgO BaO Na
2O K
2O
58.5 5.2 3.6 7.5 1.8 7.5 11.3 4.6
With silicon-dioxide, aluminium sesquioxide, boric acid, DAP, magnesium oxide, barium carbonate, yellow soda ash, salt of wormwood is raw material, by said components weighing, evenly mixed, in 1500 ℃ electric furnace, be incubated 3 hours then, the glass metal that melts is cooled off the block glass of formation fast in mould, send in 550 ℃ the annealing furnace and anneal, be incubated 1 hour, be cooled to then room temperature no silicofluoride emulsion opal glass material.Its thermal expansivity is 68.2 * 10
-7℃
-1, bending strength is 79.3MPa, and whiteness is 80%, and other performance is as shown in table 1.
Claims (2)
1. fluorin environment protection opaque glass material and manufacture method thereof, it is characterized in that: glass material consists of SiO
2-Al
2O
3-B
2O
3-P
2O
5-MgO-CaO-SrO-BaO-Li
2O-Na
2O-K
2O.The concrete mass percent of forming is: SiO
2(58.5～61), Al
2O
3(4.0-5.2), B
2O
3(3.3-4.5), P
2O
5(6.7-7.5), MgO (0-3.6), CaO (0-2.2) SrO (0-6), BaO (5.6-12.2), Li
2O (0-1.5), Na
2O (10.2-12.5), K
2O (0-4.6).
2. fluorin environment protection opaque glass material and manufacture method thereof, it is characterized in that: take by weighing raw materials such as silicon-dioxide, aluminium sesquioxide, boric acid, DAP, magnesium oxide, lime carbonate, Strontium carbonate powder, barium carbonate, Quilonum Retard, yellow soda ash, salt of wormwood by the described proportioning of claim 1, be mixed and made into uniform admixtion, admixtion is put into corundum crucible, after 1500～1520 ℃ of fusions are incubated 3 hours, casting was 550～560 ℃ of insulation annealings 1 hour.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2008100147689A CN101244889A (en) | 2008-03-19 | 2008-03-19 | Non-fluorin environment protection opacifiedglass material and method for manufacturing same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2008100147689A CN101244889A (en) | 2008-03-19 | 2008-03-19 | Non-fluorin environment protection opacifiedglass material and method for manufacturing same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101244889A true CN101244889A (en) | 2008-08-20 |
Family
ID=39945613
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2008100147689A Pending CN101244889A (en) | 2008-03-19 | 2008-03-19 | Non-fluorin environment protection opacifiedglass material and method for manufacturing same |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101244889A (en) |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102295413A (en) * | 2011-06-14 | 2011-12-28 | 武汉理工大学 | Preparation method of Zr-P fluoride-free opaque glass |
| CN102596838A (en) * | 2009-10-26 | 2012-07-18 | 旭硝子欧洲玻璃公司 | Phase-separated soda-lime-silica glass |
| CN102718403A (en) * | 2012-05-21 | 2012-10-10 | 安徽鑫民玻璃制品有限公司 | Energy-saving and environmentally friendly glass and preparation method thereof |
| CN102910818A (en) * | 2012-11-19 | 2013-02-06 | 东华大学 | Zinc-boron-silicon system heat-resisting environmental-friendly emulsion opal glass and preparation method thereof |
| CN103833218A (en) * | 2014-01-21 | 2014-06-04 | 江苏奥蓝工程玻璃有限公司 | Fracture-resistant composite glass material and preparation method thereof |
| CN104507885A (en) * | 2012-07-25 | 2015-04-08 | 旭硝子株式会社 | White glass |
| CN104837783A (en) * | 2012-10-12 | 2015-08-12 | 旭硝子株式会社 | Manufacturing method for phase-separated glass, and phase-separated glass |
| CN104854052A (en) * | 2012-12-07 | 2015-08-19 | 旭硝子株式会社 | White glass |
| CN104854051A (en) * | 2012-12-07 | 2015-08-19 | 旭硝子株式会社 | White glass |
| CN107777881A (en) * | 2016-08-30 | 2018-03-09 | 江苏杰龙晶瓷科技有限公司 | A kind of method that milky white heat resistant glass is produced using lepidolite as raw material |
| US9938181B2 (en) * | 2013-01-29 | 2018-04-10 | Asahi Glass Company, Limited | White glass |
| CN109502967A (en) * | 2018-11-22 | 2019-03-22 | 东华大学 | A kind of acid and alkali-resistance free-floride opal glass and its preparation method and application |
| CN115385672A (en) * | 2022-09-20 | 2022-11-25 | 成都贝施美生物科技有限公司 | Opalescent porcelain powder and preparation method thereof |
-
2008
- 2008-03-19 CN CNA2008100147689A patent/CN101244889A/en active Pending
Cited By (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102596838A (en) * | 2009-10-26 | 2012-07-18 | 旭硝子欧洲玻璃公司 | Phase-separated soda-lime-silica glass |
| CN102295413B (en) * | 2011-06-14 | 2013-08-14 | 武汉理工大学 | Preparation method of Zr-P fluoride-free opaque glass |
| CN102295413A (en) * | 2011-06-14 | 2011-12-28 | 武汉理工大学 | Preparation method of Zr-P fluoride-free opaque glass |
| CN102718403A (en) * | 2012-05-21 | 2012-10-10 | 安徽鑫民玻璃制品有限公司 | Energy-saving and environmentally friendly glass and preparation method thereof |
| CN104507885A (en) * | 2012-07-25 | 2015-04-08 | 旭硝子株式会社 | White glass |
| US9580353B2 (en) | 2012-10-12 | 2017-02-28 | Asahi Glass Company, Limited | Manufacturing method for phase-separated glass, and phase-separated glass |
| US9902647B2 (en) | 2012-10-12 | 2018-02-27 | Asahi Glass Company, Limited | Manufacturing method for phase-separated glass, and phase-separated glass |
| CN104837783A (en) * | 2012-10-12 | 2015-08-12 | 旭硝子株式会社 | Manufacturing method for phase-separated glass, and phase-separated glass |
| CN102910818A (en) * | 2012-11-19 | 2013-02-06 | 东华大学 | Zinc-boron-silicon system heat-resisting environmental-friendly emulsion opal glass and preparation method thereof |
| CN104854051A (en) * | 2012-12-07 | 2015-08-19 | 旭硝子株式会社 | White glass |
| US10005692B2 (en) | 2012-12-07 | 2018-06-26 | Asahi Glass Company, Limited | White glass |
| US9546104B2 (en) | 2012-12-07 | 2017-01-17 | Asahi Glass Company, Limited | White glass |
| CN104854052A (en) * | 2012-12-07 | 2015-08-19 | 旭硝子株式会社 | White glass |
| US9938181B2 (en) * | 2013-01-29 | 2018-04-10 | Asahi Glass Company, Limited | White glass |
| CN103833218A (en) * | 2014-01-21 | 2014-06-04 | 江苏奥蓝工程玻璃有限公司 | Fracture-resistant composite glass material and preparation method thereof |
| CN103833218B (en) * | 2014-01-21 | 2016-05-11 | 江苏奥蓝工程玻璃有限公司 | Compound glass material of a kind of anti-fracture and preparation method thereof |
| CN107777881A (en) * | 2016-08-30 | 2018-03-09 | 江苏杰龙晶瓷科技有限公司 | A kind of method that milky white heat resistant glass is produced using lepidolite as raw material |
| CN109502967A (en) * | 2018-11-22 | 2019-03-22 | 东华大学 | A kind of acid and alkali-resistance free-floride opal glass and its preparation method and application |
| CN109502967B (en) * | 2018-11-22 | 2021-12-07 | 东华大学 | Acid and alkali resistant fluoride-free opal glass and preparation method and application thereof |
| CN115385672A (en) * | 2022-09-20 | 2022-11-25 | 成都贝施美生物科技有限公司 | Opalescent porcelain powder and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101244889A (en) | Non-fluorin environment protection opacifiedglass material and method for manufacturing same | |
| US8629072B2 (en) | Boron-free glass | |
| CN101012105B (en) | Glass fiber with low permittivity | |
| CN101066837B (en) | Environment friendly heat resistant opal crystalline glass and its preparation process | |
| CN101439932B (en) | Low-expansion glass-ceramics with lithia ore tailings as principal raw material and manufacturing method thereof | |
| CN103922599B (en) | A kind of method utilizing red mud-flyash-titanium slag to prepare devitrified glass | |
| AU689278B2 (en) | High-zirconia fused refractories | |
| JP5650751B2 (en) | Phase separated soda lime silica glass | |
| JP5764084B2 (en) | Glass composition, glass composition for chemical strengthening, tempered glass article, cover glass for display and method for producing tempered glass article | |
| CN102092941A (en) | Ultra-white glass | |
| CN102659314A (en) | Barium oxide based crystal lead-free glass and preparation method thereof | |
| CN103819089A (en) | Method for preparing glass ceramics through melting and glass ceramics with high flatness | |
| CN100340522C (en) | New type bone china, and producing method | |
| CN101353225B (en) | Soda-lime silicate plate-like glass and manufacturing method thereof | |
| CN103193387A (en) | Enamel material for 1Cr18Ni9Ti stainless steel surface and preparation method thereof | |
| CN106810079A (en) | The method that mica glass ceramic is prepared using granite waste residues | |
| JP4630190B2 (en) | High zirconia refractories | |
| CN105110648A (en) | Mechanical rotating shaft | |
| CN104108882A (en) | Float microcrystalline glass and preparation method thereof | |
| CN100366560C (en) | Sodium calcium silicon series fire-proofing glass | |
| JP4979047B2 (en) | High zirconia refractories | |
| CN102344251B (en) | Preparation method for lepidolite glass ceramic | |
| KR20030056840A (en) | borosilicate cellular glass and manufacture method of cellular glass using it | |
| JPH04193766A (en) | High zirconia fused and cast refractory | |
| CN103058630A (en) | Construction ceramic body |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Open date: 20080820 |