CN101456670B - Floating preparation process of Na2O-CaO-SiO2 system flat-plate opacified glass - Google Patents
Floating preparation process of Na2O-CaO-SiO2 system flat-plate opacified glass Download PDFInfo
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- CN101456670B CN101456670B CN2009100604388A CN200910060438A CN101456670B CN 101456670 B CN101456670 B CN 101456670B CN 2009100604388 A CN2009100604388 A CN 2009100604388A CN 200910060438 A CN200910060438 A CN 200910060438A CN 101456670 B CN101456670 B CN 101456670B
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- cao
- opacified
- emulsion opal
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Abstract
The invention relates to flat opacified glass of a Na2O-CaO-SiO2 system and a float preparation process thereof. The process comprises the following steps: evenly mixing clarifier and raw materials such as SiO2, Al2O3, B2O3, CaO, MgO, Na2O and P2O5, heating the mixture to melt into molten glass; clarifying and cooling the molten glass, and carrying out formation by a float process to obtain an opacified glass tape; and cooling the obtained opacified glass tape, drawing the opacified glass tape to become thin by adopting a side drawing machine, or stacking the opacified glass tape by adopting a graphite retaining wall method, then cooling and evenly annealing the obtained glass tape, and cutting the annealed glass tape to obtain an opacified glass board. The flat opacified glass has the following advantages: the thermal expansion coefficient of the flat opacified glass is between 6.0*10<-6> and 6.8*10<-6>/K, and the three-point bending strength is between 60 and 76 MPa; and the flat opacified glass has the advantages of environmental protection, low product cost, adjustable thickness, soft color, high whiteness, good integral opacifying effect, wide board surface, high surface quality, no need of mechanical polishing, and the like.
Description
Technical field
The present invention relates to a kind of emulsion opal glass, relate to a kind of Na more specifically
2O-CaO-SiO
2System flat-plate emulsion opal glass and floating preparation process thereof.
Background technology
The emulsion opal glass color and luster is soft, and color is pure, and the whiteness height is high-grade building decorative plates.Compare with the sintering process devitrified glass, emulsion opal glass inside does not contain pore, and water-intake rate is very low, is difficult for being detained dirt.In addition, emulsion opal glass can cut and treatment process such as hot bending easily, and decapacitation also can be made into the furniture of different shape as outside the finishing material.At present, emulsion opal glass adopts fluorochemical as opacifying agent usually, as fluorite, Sodium Silicofluoride etc.In the process of founding, fluorochemical is serious erosion of refractory not only, shortens furnace service life, and can a large amount of volatilizations, and the environment around workers'health and the factory is produced significant damage.In order to prevent to produce fluoride pollution, key is to develop floride-free emulsion opal glass.Number of patent application is 200810014768.9, denomination of invention discloses a kind of non-fluorin environment protection opacifiedglass material for " a kind of non-fluorin environment protection opacifiedglass material and manufacture method thereof ", the raw material of this patent of invention emulsion opal glass need be introduced Strontium carbonate powder, barium carbonate, Quilonum Retard, salt of wormwood, its price is more expensive, and adopt teeming practice to form, can't realize the preparation of dull and stereotyped emulsion opal glass.
Summary of the invention
Problem to be solved by this invention is to propose a kind of environmentally safe at above-mentioned prior art, and raw material is easy to get the Na that cost is low
2O-CaO-SiO
2System flat-plate emulsion opal glass and floating preparation process thereof.
The present invention is adopted solution to be by the problem of the above-mentioned proposition of solution: a kind of Na
2O-CaO-SiO
2The system flat-plate emulsion opal glass is characterized in that including SiO
2, Al
2O
3, B
2O
3, CaO, MgO, Na
2O, P
2O
5Form through being mixed with finings, the content of each raw material is by mass percentage:
MgO 1～4 Na
2O 6～14 P
2O
52～6 finingss 0.5～2.
Press such scheme, preferably the content of each raw material is by mass percentage:
SiO
2 63-72 Al
2O
3?1-3 B
2O
3 3-7 CaO 7-13
MgO 1-4 Na
2O 9-11 P
2O
53-6 finings 0.5-2.
Na of the present invention
2O-CaO-SiO
2The floating preparation process of system flat-plate emulsion opal glass is characterized in that including following steps:
1) each raw material is mixed in proportion, in glass melter, be heated to 1500 ℃～1550 ℃, be fused into glass metal; The content of described each raw material is by mass percentage:
MgO 1～4 Na
2O 6～14 P
2O
52～6 finingss 0.5～2.
2) with step 1) gained glass metal through clarification, cool to 1250 ℃～1180 ℃, by runner glass metal is introduced in the molten tin bath, adopt floating process to form, when temperature was 1160 ℃～1080 ℃, promptly the corresponding viscosity value was 10
2.7～10
3.2The Shi Jinhang polishing obtains the emulsion opal glass band;
3) with step 2) the emulsion opal glass band of gained cools off, and when the emulsion opal glass band was cooled to 990 ℃～950 ℃, promptly corresponding viscosity was 10
4.25～10
5.75, it is thin to adopt edge machine to draw, and the feed glass tape thickness is 4～8mm; Or when the emulsion opal glass band was cooled to 980 ℃～830 ℃, promptly corresponding viscosity was 10
4.25～10
5.75, it is thick to adopt graphite barricade method to pile, and the feed glass tape thickness is 12～14mm;
4) treat step 3) gained glass ribbon cools to 600 ℃～580 ℃ after, glass ribbon is left molten tin bath enters annealing furnace and carry out homo genizing annelaing, the glass ribbon after the annealing obtains emulsion opal glass sheet material after cutting.
Beneficial effect of the present invention is:
1) in order to adapt to floating process, Na of the present invention
2O-CaO-SiO
2The content of aluminum oxide suitably reduced during the system flat-plate emulsion opal glass was formed, and adopting Vanadium Pentoxide in FLAKES and boron oxide to form compound opacifier promotion opaque effect, make emulsion opal glass have suitable crystalline phase and microtexture (as depicted in figs. 1 and 2) simultaneously, play the effect of improving glass heat stability, whiteness and physical strength.Use emulsion opal glass whiteness that this prescription makes between 83～89, thermal expansivity is between 6.0～6.8 * 10
-6/ K, three-point bending resistance intensity is between 60～76MPa;
2) calcium oxide is regulated frit for strengthening whiteness, regulates the recrystallization temperature upper limit and all plays an important role, and makes emulsion opal glass in molten tin bath shaping district crystallization take place again easily but introduce too many calcium oxide.The emulsion opal glass of float glass process production simultaneously requires the synthermal Changing Pattern of viscosity to be complementary with floating process, and the introducing amount of therefore necessary controlled oxidation calcium is adjusted expecting property, the control crystallization.Na of the present invention
2O-CaO-SiO
2The amount that the system flat-plate emulsion opal glass is introduced calcium oxide is very suitable, can satisfy above-mentioned a series of requirement;
3) the present invention can adapt to the requirement of float glass process production technique, and the Changing Pattern of its viscosity with temperature can adapt to the requirement of floating process, can realize the production of large-scale dull and stereotyped emulsion opal glass;
4) the present invention is with Na
2O-CaO-SiO
2System glass is that the basis is formed, and selects B for use
2O
3And P
2O
5As compound opacifier, adopt raw materials such as phosphatic rock, borax, quartz sand, feldspar, prepare high-quality dull and stereotyped emulsion opal glass by floating process, whole process of production production efficiency height, low to refractory corrosion, environmentally safe, product cost is low, thickness is adjustable, adopts this composition and technology and the dull and stereotyped emulsion opal glass for preparing, and color and luster is soft, the whiteness height, whole opaque effect is good, has the plate face width simultaneously, the surface quality height, need not advantages such as mechanical polishing, can be used as high-grade glass dalle and all kinds of furniture.
Description of drawings
Fig. 1 is the XRD figure spectrum of the floride-free emulsion opal glass of the present invention
Fig. 2 is the SEM photo of floride-free emulsion opal glass
Embodiment
The invention will be further described below in conjunction with embodiment, but this embodiment is just to of the present invention further describing and can not be as limitation of the invention.
Embodiment 1:
Select for use following component as raw material (quality %)
SiO
2 63.9 Al
2O
3 1.5 B
2O
3 5.0 CaO 11.7
MgO 2.4 Na
2O 10.4 P
2O
54.6 finings 0.5
(1) above-mentioned raw materials is mixed, in glass melter, be heated to 1500 ℃, be fused into glass metal;
(2) glass metal cools to 1200 ℃ through clarification, by runner glass metal is introduced in the molten tin bath, adopts floating process to form, and polishes in 1120 ℃;
(3) when glass cools to 950 ℃, promptly corresponding viscosity is between 10
4.25～10
5.75Between, it is thin to adopt edge machine to draw, and the feed glass tape thickness is 4～6mm;
(4) enter annealing furnace after the glass ribbon cools to 580 ℃ and carry out homo genizing annelaing, the glass ribbon after the annealing obtains emulsion opal glass sheet material through cutting, cutting out.
Embodiment 2:
Select for use following component as raw material (quality %)
SiO
2 67.9 Al
2O
3 1.5 B
2O
3 5.0 CaO 9.7
MgO 1.4 Na
2O 9.4 P
2O
54.6 finings 0.5
(1) above-mentioned raw materials is mixed, in glass melter, be heated to 1525 ℃, be fused into glass metal.
(2) glass metal cools to 1250 ℃ through clarification, by runner glass metal is introduced in the molten tin bath, adopts floating process to form, and polishes in 1160 ℃;
(3) when glass cools to 970 ℃, promptly corresponding viscosity is between 10
4.25～10
5.75Between, it is thin to adopt edge machine to draw, and the feed glass tape thickness is 6～8mm;
(4) glass ribbon enters annealing furnace at 600 ℃, carries out homo genizing annelaing, and the glass ribbon after the annealing obtains emulsion opal glass sheet material through cutting, cutting out.
Embodiment 3:
Select for use following component as raw material (quality %)
SiO
2 71.0 Al
2O
3 1.0 B
2O
3 4.0 CaO 7.0
MgO 2.1 Na
2O 9.4 P
2O
55.0 finings 0.5
(1) above-mentioned raw materials is mixed, in glass melter, be heated to 1550 ℃, be fused into glass metal.
(2) glass metal cools to 1180 ℃ through clarification, by runner glass metal is introduced in the molten tin bath, adopts floating process to form, and polishes in 1080 ℃;
(3) when glass cools to 980 ℃～880 ℃, promptly corresponding viscosity is 10
4.25～10
5.75, it is thick to adopt graphite barricade method to pile, and the feed glass tape thickness is 12～14mm;
(4) glass ribbon enters annealing furnace at 600 ℃, carries out homo genizing annelaing, and the glass ribbon after the annealing obtains emulsion opal glass sheet material through cutting, cutting out.
The viscosity number and the temperature range of table 1, floride-free emulsion opal glass float forming technical process correspondence
| Technical process | Viscosity number (PaS) | Temperature value (℃) |
| |
10? | 1500～1550? |
| Be shaped | 10 2 | 1180～1250? |
| Polishing | 10 2.7-10 3.2 | 1080～1160? |
| Draw thin/heap thick | 10 4.25-10 5.75 | 830～990? |
| |
10 10 | 580～600? |
| |
10 12-13.6 | 500～550? |
Claims (1)
1.Na
2O-CaO-SiO
2The floating preparation process of system flat-plate emulsion opal glass is characterized in that including following steps:
1) each raw material is mixed in proportion, in glass melter, be heated to 1500 ℃～1550 ℃, be fused into glass metal; The content of described each raw material is by mass percentage:
SiO
2 60～75?Al
2O
3?0～4 B
2O
3 3～7 CaO 4～17
MgO 1～4 Na
2O 6～14 P
2O
52～6 finingss 0.5～2
2) with step 1) gained glass metal through clarification, cool to 1250 ℃～1180 ℃, by runner glass metal is introduced in the molten tin bath, adopt floating process to form, when temperature was 1160 ℃～1080 ℃, promptly the corresponding viscosity value was 10
2.7～10
3.2The Shi Jinhang polishing obtains the emulsion opal glass band;
3) with step 2) the emulsion opal glass band of gained cools off, and when the emulsion opal glass band was cooled to 990 ℃～950 ℃, promptly corresponding viscosity was 10
4.25～10
5.75, it is thin to adopt edge machine to draw, and the feed glass tape thickness is 4～8mm; Or when the emulsion opal glass band was cooled to 980 ℃～830 ℃, promptly corresponding viscosity was 10
4.25～10
5.75, it is thick to adopt graphite barricade method to pile, and the feed glass tape thickness is 12～14mm;
4) treat step 3) gained glass ribbon cools to 600 ℃～580 ℃ after, glass ribbon is left molten tin bath enters annealing furnace and carry out homo genizing annelaing, the glass ribbon after the annealing obtains emulsion opal glass sheet material after cutting.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100604388A CN101456670B (en) | 2009-01-06 | 2009-01-06 | Floating preparation process of Na2O-CaO-SiO2 system flat-plate opacified glass |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100604388A CN101456670B (en) | 2009-01-06 | 2009-01-06 | Floating preparation process of Na2O-CaO-SiO2 system flat-plate opacified glass |
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| Publication Number | Publication Date |
|---|---|
| CN101456670A CN101456670A (en) | 2009-06-17 |
| CN101456670B true CN101456670B (en) | 2011-05-11 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2314551A1 (en) * | 2009-10-26 | 2011-04-27 | AGC Glass Europe | Phase separated soda-lime glass |
| CN102295413B (en) * | 2011-06-14 | 2013-08-14 | 武汉理工大学 | Preparation method of Zr-P fluoride-free opaque glass |
| CN102910818B (en) * | 2012-11-19 | 2015-07-08 | 东华大学 | Zinc-boron-silicon system heat-resisting environmental-friendly emulsion opal glass and preparation method thereof |
| CN105967515A (en) * | 2016-05-11 | 2016-09-28 | 周琦钧 | Ultrathin opaque glass and preparation method thereof |
| JP2022504551A (en) * | 2018-10-09 | 2022-01-13 | コーニング インコーポレイテッド | Compositions and Methods to Prevent Sagging Strain Defects |
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