CN101595068B - Process for producing glass and vacuum degassing apparatus - Google Patents
Process for producing glass and vacuum degassing apparatus Download PDFInfo
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- CN101595068B CN101595068B CN2008800032486A CN200880003248A CN101595068B CN 101595068 B CN101595068 B CN 101595068B CN 2008800032486 A CN2008800032486 A CN 2008800032486A CN 200880003248 A CN200880003248 A CN 200880003248A CN 101595068 B CN101595068 B CN 101595068B
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- vacuum deaerator
- melten glass
- air
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- gas
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B5/00—Melting in furnaces; Furnaces so far as specially adapted for glass manufacture
- C03B5/16—Special features of the melting process; Auxiliary means specially adapted for glass-melting furnaces
- C03B5/225—Refining
- C03B5/2252—Refining under reduced pressure, e.g. with vacuum refiners
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B5/00—Melting in furnaces; Furnaces so far as specially adapted for glass manufacture
- C03B5/16—Special features of the melting process; Auxiliary means specially adapted for glass-melting furnaces
- C03B5/20—Bridges, shoes, throats, or other devices for withholding dirt, foam, or batch
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B5/00—Melting in furnaces; Furnaces so far as specially adapted for glass manufacture
- C03B5/16—Special features of the melting process; Auxiliary means specially adapted for glass-melting furnaces
- C03B5/225—Refining
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B5/00—Melting in furnaces; Furnaces so far as specially adapted for glass manufacture
- C03B5/16—Special features of the melting process; Auxiliary means specially adapted for glass-melting furnaces
- C03B5/235—Heating the glass
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/50—Glass production, e.g. reusing waste heat during processing or shaping
- Y02P40/57—Improving the yield, e-g- reduction of reject rates
Abstract
A process for producing a glass in which an excessive vacuum is prevented from enlarging a bubble layer and thereby reducing the effect of vacuum degassing; and a vacuum degassing apparatus suitable for use in the process for glass production. The process for glass production includes a step in which a molten glass is degassed under vacuum in a vacuum degassing tank. It is characterized by forming at least one gas stream over the molten glass passing through the vacuum degassing tank, the gas stream being selected from the group consisting of a gas stream in the flow direction for the molten glass and a gas stream in the direction opposite to the flow direction for the molten glass.
Description
Technical field
The present invention relates to be included in interior glass-making processes and the vacuum degassing apparatus that melten glass is carried out the operation of vacuum deaerator of vacuum deaerator groove.
Background technology
In the past, the quality of the glasswork that obtains for improve being shaped was carried out clarifying treatment before utilizing shaping appts that the melten glass that the raw material fusing is formed with smelting furnace is formed, and this clarifying treatment is based on the clarification operation that the bubble that produces in the melten glass is removed.
Method as clarifying treatment; The known vacuum deaerator method that is described below: melten glass is imported in the reduced atmosphere; Under this reduced atmosphere, make the bubble in the melten glass of continuous flow grow up and float; Make the broken bubble of bubble and remove bubble at molten glass surface, from reduced atmosphere, discharge then.
In above-mentioned clarification operation, for the growth that promotes the bubble in the molten glass flow or make the broken bubble of bubble, the whole bag of tricks has been proposed.
Proposed in the patent documentation 1 for the performance of improving the clarification operation can vitrified material, be the technical schemes that comprise various clarification promotor in the frit.In addition, in the patent documentation 1, as the key element that the growth of under reduced pressure, implementing in the clarifying process bubble impacts, enumerated the gas of molten mass material top character, be the character of the gas of melten glass top.
In addition, the decompression that has disclosed in the patent documentation 2 through melten glass is received in the clarifying chamber destroys the foamy foam destruction methods that has produced.As the foam destruction methods, disclosed the method that is used to make air bubble expansion, disruptive mechanical rotation body, and made injection stream impact the foamy method.
Patent documentation 1: Japanese Patent Laid table 2001-515453 communique
Patent documentation 2: Japanese Patent Laid is opened the 2003-89529 communique
The announcement of invention
In the patent documentation 1; Method as the character of the gas that changes the melten glass top; Enumerated the dividing potential drop of selecting air method, select method and the method for selecting the dividing potential drop of nitrogen type rare gas element of the atmosphere of nitrogen type rare gas element enrichment, but be the fully announcement of growth this point what kind of character could promote bubble about the gas of melten glass top.In addition; When under reduced pressure, clarifying; Gaseous constituent from the contained bubble of the volatile gases composition of melten glass and melten glass discharges in a large number, therefore exists through the dividing potential drop of the air selected and the problem that descends easily through the dividing potential drop of the nitrogen type rare gas element selected.In addition, the problem that exists the gas composition of the atmosphere of selected nitrogen type rare gas element enrichment to change easily.
In addition, not enough to some extent aspect the foam that the method for record produces in destroying the clarifying chamber in the patent documentation 2.That is,, can make melten glass stream sinuous flow, thereby cause new bubble to produce though the use of mechanical rotation body or injection stream can destroy the foam that has been present on the melten glass.In addition, in the clarifying chamber,, can't destroy the new foam that produces in the downstream side of mechanical rotation body or injection stream though can destroy foam partly.In addition, the use of mechanical rotation body may become the source of pollution of melten glass, and the use of injection stream may make the temperature of melten glass descend, and the quality of glass is descended.
In addition, theoretically, the vacuum tightness of atmosphere high more (absolute pressure of atmosphere is low more), the effect of vacuum deaerator should be good more, and the bubble in the molten glass flow is just few more.But in fact, after the vacuum tightness of atmosphere (absolute pressure of atmosphere) arrived a certain stage, the formation speed of bubble surpassed the bubble collapse speed based on broken bubble, and the alveolar layer of molten glass surface thickens, thereby causes the vacuum deaerator ability drop.This phenomenon is called " thickening of the alveolar layer that is caused by excessive decompression ".As a result, the bubble in the molten glass flow increases on the contrary.Therefore, the scope of vacuum tightness of atmosphere of effect that can give full play to vacuum deaerator is quite narrow, even the problem that external cause such as atmospheric change also can influence the effect of vacuum deaerator occurs.
For solving above-mentioned prior art problems; The good glass-making processes of effect that the purpose of this invention is to provide vacuum deaerator; More specifically, the purpose of this invention is to provide the glass-making processes that the effect that thickens the vacuum deaerator that causes of the alveolar layer that caused by excessive decompression descends and is prevented.
In addition, the purpose of this invention is to provide the vacuum degassing apparatus that is applicable to glass-making processes of the present invention.
The inventor conscientiously studies the back and finds for achieving the above object, the gaseous constituent that produces because of the broken bubble of the bubble of molten glass surface is trapped in the top of the melten glass that circulates in the vacuum deaerator groove, thereby the effect of vacuum deaerator is descended.Below; In this manual; The gaseous constituent that will produce because of the broken bubble of the bubble of molten glass surface is called " from the gaseous constituent of melten glass ", and the phenomenon that will be trapped in the top of the melten glass that circulates in the vacuum deaerator groove from the gaseous constituent of melten glass is called " from the delay of the gaseous constituent of melten glass ".
Can think; If the gaseous constituent from melten glass is detained; Then the dividing potential drop from the gaseous constituent of melten glass raises in the atmosphere of melten glass top (upper space that the vacuum deaerator groove is inner), floats to the bubble of molten glass surface to be difficult to broken bubble, the effect decline of vacuum deaerator.
In addition, the inventor finds that through eliminating the delay from the gaseous constituent of melten glass, the broken bubble speed of molten glass surface improves, the thickening of the alveolar layer that can suppress to be caused by excessive decompression.
In addition, also form and different according to glass from the gaseous constituent of melten glass, for example HCl, H can give an example < > 2 <> SO < > 4 <> , boronic acid compounds, HF etc.
The present invention is based on the invention described above people's discovery and the invention accomplished, and a kind of glass-making processes is provided, and this method is included in the vacuum deaerator groove operation of melten glass being carried out vacuum deaerator, the method is characterized in that,
Form air-flow above the melten glass that in said vacuum deaerator groove, circulates, this air-flow is at least a kind of air-flow of air-flow and the direction opposite with the circulating direction of said melten glass that is selected from the circulating direction of said melten glass.
In addition, the present invention provides a kind of glass-making processes, and this method is included in the vacuum deaerator groove operation of melten glass being carried out vacuum deaerator, the method is characterized in that,
The air-flow of the vertical direction of circulating direction of formation and melten glass above the melten glass that in said vacuum deaerator groove, circulates.
In the glass-making processes of the present invention, be preferably the gas that forms said air-flow and do not contain the gaseous constituent that produces from melten glass in fact.
In the glass-making processes of the present invention, being preferably the gas that forms said air-flow is to be selected from hydrogen (H < > 2 <> ), nitrogen (N < > 2 <> ), oxygen (O < > 2 <> ), air, carbon monoxide (CO), carbonic acid gas (CO < > 2 <> ), argon (Ar), helium (He), neon (Ne), krypton (Kr), xenon (Xe), hydrocarbon gas, fluorocarbon class gas and ammonia (NH < > 3 <> ) at least a kind.
In the glass-making processes of the present invention, be preferably the gas that forms said air-flow and be directed to position near the surface of melten glass.
In addition, the present invention provides a kind of vacuum degassing apparatus of melten glass, and this device comprises decompression housing, vacuum deaerator groove, imports unit and lead-out unit; Said decompression housing is vacuumized; Said vacuum deaerator groove is arranged in the said decompression housing, is used to carry out the vacuum deaerator of melten glass; Said importing unit is arranged to be communicated with said vacuum deaerator groove, is used for the melten glass before the vacuum deaerator is imported said vacuum deaerator groove; Said lead-out unit is arranged to be communicated with said vacuum deaerator groove, is used for the melten glass behind the vacuum deaerator is derived from said vacuum deaerator groove, and this vacuum degassing apparatus is characterised in that,
Comprise that also air-flow forms the unit, this air-flow forms the unit and constitutes by the gas introduction unit that gas is imported to the inner upper space of said vacuum deaerator groove and with the gas lead-out unit of gas from said upper space derivation.
In the vacuum degassing apparatus of melten glass of the present invention, be preferably said air-flow is formed top or the side that the unit is arranged at the vacuum deaerator groove of formation upper space above the inner melten glass of vacuum deaerator groove.
By the present invention,, can eliminate delay from the gaseous constituent of melten glass through forming air-flow above the melten glass that in the vacuum deaerator groove, circulates.Through eliminating delay, can prevent that the effect of vacuum deaerator from descending from the gaseous constituent of melten glass.In addition, through eliminating the delay from the gaseous constituent of melten glass, the thickening to become of the alveolar layer that is caused by excessive decompression is difficult for taking place.Consequently, the vacuum tightness in the vacuum deaerator groove can be further improved, the effect of vacuum deaerator can be improved.
The simple declaration of accompanying drawing
Fig. 1 is the sectional view of a structure example of expression vacuum degassing apparatus of the present invention.
Fig. 2 is the sectional view of a structure example of the preferred configuration of expression vacuum degassing apparatus of the present invention.
Fig. 3 is the figure of the dependency of the interior absolute pressure of bubble density measurement result and the vacuum deaerator groove 12 at downstream slot 24 places among expression comparative example 2 and the embodiment 3.
Nomenclature
10: vacuum degassing apparatus
11: the decompression housing
12: the vacuum deaerator groove
121,122: upper space
123,124: window
13: upcast
14: downtake
15: lagging material
20: melting channel
22: upstream slot
24: downstream slot
30: gas introduction unit
300: hollow tube
31: the gas lead-out unit
40: gas (importing gas)
41: air-flow
42: gas (emitting gas)
G: melten glass
The best mode that carries out an invention
The present invention will be described with reference to the accompanying drawings.
Fig. 1 is the sectional view of a structure example of expression vacuum degassing apparatus of the present invention.In the vacuum degassing apparatus 10 shown in Figure 1, be vacuum deaerator groove 12 cylindraceous and take in and be disposed in the decompression housing 11, and the major axis that makes vacuum deaerator groove 12 is towards horizontal direction.The lower surface of the upstream side of vacuum deaerator groove 12 is equipped with the upcast 13 towards vertical direction, and the lower surface in downstream side is equipped with downtake 14.In addition, the upstream side of vacuum deaerator layer 12 and downstream side are meant in vacuum deaerator groove 12 upstream side and the downstream side on the flow direction of melten glass G of circulation.The part of upcast 13 and downtake 14 is positioned at decompression housing 11.
As shown in Figure 1, upcast 13 is communicated with vacuum deaerator groove 12, is with the importing unit that imports vacuum deaerator groove 12 from the melten glass G of melting channel 20.Therefore, the bottom of upcast 13 embeds the opening end of upstream slot 22, impregnated among the melten glass G in this upstream slot 22.
In decompression housing 11, dispose around vacuum deaerator groove 12, upcast 13 and the downtake 14 they are carried out the heat insulation with lagging materials such as brick 15 of heat insulation lining.
In the vacuum degassing apparatus 10 shown in Figure 1, vacuum deaerator groove 12, upcast 13 and downtake 14 be owing to be the conduit of melten glass G, therefore uses thermotolerance and the good material of the solidity to corrosion of melten glass is processed.As an example, the hollow tube of platinum or the platinum alloy system of can giving an example.As the object lesson of platinum alloy, can give an example platinum-au-alloy, platinum-rhodium alloy.In addition, as another example, the non-metal inorganic material system of the ceramic-like of can giving an example, be the hollow tube of compact substance refractory body system.Object lesson as the compact substance refractory body; The for example electroforming refractory bodies such as alumina type electroforming refractory body, zirconium white class electroforming refractory body, alumina-zirconia-silica class electroforming refractory body of can giving an example, and compact substances such as compact substance alumina type refractory body, compact substance zirconium white-silica-based refractory body and compact substance alumina-zirconia-silica class refractory body burn till refractory body.The decompression housing 11 of taking in the part of vacuum deaerator groove 12 and upcast 13 and downtake 14 is metal system, the housing of stainless steel for example.
In the vacuum degassing apparatus of the present invention 10 shown in Figure 1, be provided with in the upstream side at vacuum deaerator groove 12 tops and downstream side and be used for window 122,123 that vacuum deaerator groove 12 inside are monitored.Window the 122, the 123rd, the hollow tube of platinum system or platinum alloy system or compact substance refractory body system, an end is communicated with the upstream side and the downstream side at the top of vacuum deaerator groove 12, and the other end runs through the wall of the housing 11 that reduces pressure, and is positioned at the outside of decompression housing 11.
In the vacuum degassing apparatus 10 shown in Figure 1, window 122 also is the gas introduction unit 30 that gas is imported to the upper space 121 of vacuum deaerator groove 12 inside.The gas 40 that imports the inner upper space 121 of vacuum deaerator grooves 12 from window 122 forms the air-flow 41 of the direction identical with the circulating direction of melten glass G above the melten glass G of vacuum deaerator groove 12 internal circulations, promptly form from the upstream side of vacuum deaerator groove 12 air-flow 41 of side flow downstream.Then, gas 42 is emitted to the outside from the window in the downstream side that is arranged at vacuum deaerator groove 12 123.That is, in the vacuum degassing apparatus 10 shown in Figure 1, window 123 also is the gas lead-out unit 31 that gas 42 is emitted from the upper space 121 of vacuum deaerator groove 12.
In the vacuum degassing apparatus 10 shown in Figure 1, through above the melten glass G of vacuum deaerator groove 12 internal circulations, forming air-flow 41, thereby eliminate delay from the gaseous constituent of melten glass.That is, be not detained, but taken away, from window 123(gas lead-out unit 31 by air-flow 41 from the gaseous constituent of melten glass) emit to the outside.
Can think; If the gaseous constituent from melten glass is detained; Then in the atmosphere (upper space 121 of vacuum deaerator groove 12) of melten glass G top; Dividing potential drop from the gaseous constituent of melten glass raises; Therefore float to the difficult broken bubble of the bubble on melten glass G surface, the effect of vacuum deaerator descends.
Among the present invention, be eliminated from the delay of the gaseous constituent of melten glass, thereby the decline of the effect of vacuum deaerator can not take place, the effect of vacuum deaerator is good.
In addition; If the gaseous constituent from melten glass is detained; Thickening of the alveolar layer that then takes place to cause by excessive decompression; The effect of vacuum deaerator declines to a great extent, but in the present invention, is not detained from the gaseous constituent of melten glass; Taken away by air-flow 41; Emit to the outside from gas lead-out unit 31, even therefore the vacuum tightness of vacuum deaerator groove 12 is increased to than higher in the past degree, the thickening of the alveolar layer that also can further suppress to cause by excessive decompression.Therefore, can the vacuum tightness of vacuum deaerator groove 12 be increased to, can further improve the effect of vacuum deaerator than higher in the past degree (can the absolute pressure of vacuum deaerator groove 12 be reduced to than lower in the past degree).
In addition, be the inventor's newly discovered through eliminating the effect this point that delay from the gaseous constituent of melten glass can improve vacuum deaerator.Among Fig. 1, the pressure of upper space 121 is to be described below only to have 38～460mmHg(51～the so-called vacuum state of pressure about 613hPa).Do not think in the past and can be detained gaseous constituent in the upper space 121 that reaches above-mentioned so-called vacuum state from melten glass.The inventor conscientiously studies the back and finds, reaches in the upper space 121 of above-mentioned so-called vacuum state to be detained the gaseous constituent from melten glass, finds that also the delay from the gaseous constituent of melten glass can influence the effect of vacuum deaerator.
Can know that by above viewpoint in the present invention, above melten glass G, forming air-flow 41 is in order to eliminate the delay from the gaseous constituent of melten glass.Therefore, the air-flow 41 that is formed at the top of melten glass G does not preferably contain the gaseous constituent from melten glass.In addition, the gas that forms air-flow 41 preferably can not cause dysgenic gas to glasswork and glass manufacturing equipment, the particularly vacuum degassing apparatus of melten glass or manufacturing.
As the gas that satisfies above-mentioned requirements, hydrogen (H can give an example < > 2 <> ), nitrogen (N < > 2 <> ), oxygen (O < > 2 <> ), air, carbon monoxide (CO), carbonic acid gas (CO < > 2 <> ), argon (Ar), helium (He), neon (Ne), krypton (Kr), xenon (Xe), hydrocarbon gas, fluorocarbon class gas and ammonia (NH < > 3 <> ) etc.These gases can use separately or use with the form of two or more mixed gass.
In addition; As long as can eliminate delay from the gaseous constituent of melten glass; The air-flow that is formed at the top of melten glass G be not limited to the air-flow 41 of image pattern 1 such with vacuum deaerator groove 12 in the identical direction of circulating direction of melten glass G, also can be the direction opposite, the i.e. air-flow of side flow upstream from the downstream side of vacuum deaerator groove 12 with the circulating direction of the interior melten glass G of vacuum deaerator groove 12.At this moment, the window 123 that is arranged at the downstream side at vacuum deaerator groove 12 tops becomes gas introduction unit, and the window 122 that is arranged at the upstream side at vacuum deaerator groove 12 tops becomes the gas lead-out unit.
In addition; Among Fig. 1; On the whole long side direction of vacuum deaerator groove 12, be formed with the air-flow 41 with the circulating direction equidirectional of melten glass G, but, also can above melten glass G, form the multiply air-flow as long as can eliminate delay from the gaseous constituent of melten glass.The direction of multiply air-flow can be identical with the circulating direction of melten glass G, also can be opposite.In addition, the circulating direction of multiply air-flow can be mutually the same or opposite.In addition, gas lead-out unit and gas import unitary quantity not only can be one, also can have a plurality of.
For example, through adopting following structure, can above melten glass G, form the multiply air-flow.
[structure example 1]
In the vacuum degassing apparatus 10 shown in Figure 1, the long side direction middle body at vacuum deaerator groove 12 tops also is set to the window of gas lead-out unit, and window 123 is as gas introduction unit.Form the air-flow of the direction identical from the gas that imports as the window of gas introduction unit 122 at the upstream side of fusion deaeration groove 12, emit to the outside from the window of the long side direction middle body that is arranged at vacuum deaerator groove 12 tops then with the circulating direction of melten glass G.In addition; Form the air-flow of the direction opposite in the downstream side of fusion deaeration groove 12 from the gas that imports as the window of gas introduction unit 123, emit to the outside from the window of the long side direction middle body that is arranged at vacuum deaerator groove 12 tops then with the circulating direction of melten glass G.
[structure example 2]
In the vacuum degassing apparatus 10 shown in Figure 1, the long side direction middle body at vacuum deaerator groove 12 tops also is set to the window of gas introduction unit, and window 122 is used as the gas lead-out unit with window 123.The part of the gas that imports from the window of the long side direction middle body that is arranged at vacuum deaerator groove 12 tops forms the air-flow of the direction opposite with the circulating direction of melten glass G at the upstream side of fusion deaeration groove 12, emits to the outside from the window that becomes the gas lead-out unit 122 then.In addition; Another part of the gas that imports from the window of the long side direction middle body that is arranged at vacuum deaerator groove 12 tops forms the air-flow of the direction identical with the circulating direction of melten glass G in the downstream side of fusion deaeration groove 12, emit to the outside from the window that becomes the gas lead-out unit 123 then.
In addition; Among Fig. 1; Import gases 40 from the window 122 of the upstream side that is arranged at vacuum deaerator groove 12 tops; As long as but can above melten glass G, form air-flow (is air-flow 41) of the direction identical with the circulating direction of melten glass G among Fig. 1; Elimination is from the delay of the gaseous constituent of melten glass; Also can form window, import gas from this window at the end face of vacuum deaerator groove 12 upstream sides.At this moment, the window that is formed at the end face (side) of vacuum deaerator groove 12 upstream sides is a gas introduction unit.
In addition; Among Fig. 1; From the window 123 in the downstream side that is arranged at vacuum deaerator groove 12 tops gas 42 is emitted to the outside; As long as but can above melten glass G, form air-flow (is air-flow 41) of the direction identical with the circulating direction of melten glass G among Fig. 1; Elimination is from the delay of the gaseous constituent of melten glass; Also can form window, emit gas from this window at the end face in vacuum deaerator groove 12 downstream sides.At this moment, the window that is formed at the end face (side) of vacuum deaerator groove is the gas lead-out unit.
In addition, vacuum deaerator groove 12 shown in Figure 1 is on the circulating direction of melten glass G long perpendicular microscler shape, but the vacuum deaerator groove also can be the wide cut shape that the length on the circulating direction of melten glass G is lacked.When adopting above-mentioned vacuum deaerator groove, also can form the width of vacuum deaerator groove, promptly with the air-flow of the vertical direction of circulating direction of melten glass.In the time of will on the width of vacuum deaerator groove, forming air-flow, for example window is set, a window as gas introduction unit, is got final product another window as the gas lead-out unit in the two sides of vacuum deaerator groove.
Fig. 2 representes an example of the preferred configuration of glass manufacturing apparatus of the present invention.In the vacuum degassing apparatus 10 shown in Figure 2, be inserted with platinum system or platinum alloy system, or the hollow tube 300 of the pottery system of salic, zirconium white etc. at window 122 places of the upstream side that is arranged at vacuum deaerator groove 12.In vacuum deaerator groove 12, the front end of hollow tube 300 is positioned at the top of melten glass G.
In the vacuum degassing apparatus 10 shown in Figure 2, hollow tube 300 is the gas introduction units 30 that gas imported to the upper space 121 of vacuum deaerator groove 12 inside.The gas 40 that imports the inner upper space 121 of vacuum deaerator grooves 12 from hollow tube 300 forms the air-flow of the direction identical with the circulating direction of melten glass G above the melten glass G of vacuum deaerator groove 12 internal circulations, promptly form from the upstream side of vacuum deaerator groove 12 air-flow 41 of side flow downstream.Then, gas 42 is emitted to the outside from the window in the downstream side that is arranged at vacuum deaerator groove 12 123.
In addition, be not limited in form shown in Figure 2, use, also can in above-mentioned arbitrary form, use as the hollow tube 300 of gas introduction unit.For example, when importing gas, can insert hollow tube at window 123 places in the downstream side that is arranged at vacuum deaerator groove 12 as gas introduction unit from the downstream side of vacuum deaerator groove 12; When the long side direction middle body of vacuum deaerator groove imports gas, can insert hollow tube at the window place of the long side direction middle body that is arranged at the vacuum deaerator groove as gas introduction unit.In addition, when the upstream side end face of vacuum deaerator groove or downstream side end face import gas, can insert hollow tube at the window place that is arranged at upstream side end face or downstream side end face as gas introduction unit.In addition, when importing gas, can insert hollow tube at the lateral window place that is arranged at the vacuum deaerator groove as gas introduction unit from the side of vacuum deaerator groove.
Among Fig. 2, the position of the front end of hollow tube 300 does not have special qualification, can suitably select as required.For example, think when eliminating the gaseous constituent that is trapped in melten glass G top, be preferably and near the surface of melten glass G (liquid level), form air-flow 41, therefore can make the front end of hollow tube 300 be close to position near the surface (liquid level) of melten glass G.
In addition, in order near the surface of melten glass G (liquid level), to form air-flow 41, also can be provided for the baffle plate of directing air flow downwards in the inboard at vacuum deaerator groove 12 tops.
In addition, disclosed the hollow tube 300 of front end towards the straight tube shape of below among Fig. 2, but be not limited thereto, the shape of hollow tube can suitably be selected.For example, for the gas 40 downstream guiding that will import vacuum deaerator groove 12, also can use front end to the crooked hollow tube of the flow direction (being downstream direction among Fig. 2) of melten glass G.
Glass-making processes of the present invention is included in the interior operation of melten glass being carried out vacuum deaerator of vacuum deaerator groove; The method is characterized in that, form the air-flow of the circulating direction of melten glass, air-flow or this two kinds of air-flows of the direction opposite above the melten glass that in the vacuum deaerator groove, circulates with the circulating direction of melten glass.In addition, as stated, above melten glass, can form the multiply air-flow that each other circulating direction can be identical or opposite.
When forming air-flow 14 above the melten glass G that in vacuum deaerator groove 12, circulates, adopt the vacuum degassing apparatus of the present invention that utilizes Fig. 1 to be illustrated to get final product.In addition, in the glass-making processes of the present invention,,, therefore omit owing to be recorded in the part of vacuum degassing apparatus of the present invention about through forming the effect that air-flow obtains above the melten glass that in the vacuum deaerator groove, circulates.
In addition, in the present invention,, therefore in the process of implementing vacuum deaerator, may not above melten glass, form air-flow all the time as long as can eliminate delay from the gaseous constituent of melten glass through above melten glass, forming air-flow.Therefore,, eliminate delay, in the process of implementing vacuum deaerator, also can form air-flow termly, for example can per hour form the air-flow about 1～30 second from the gaseous constituent of melten glass as long as can above melten glass, form air-flow.In addition, when forming air-flow termly, import gas termly from gas introduction unit and get final product, for example open and close the SV (not shown) be used for to window 122 supply gas of vacuum degassing apparatus shown in Figure 1 10 termly and get final product.
In the glass-making processes of the present invention, above the melten glass that in the vacuum deaerator groove, circulates, form the air-flow this point, can likewise implement with glass-making processes in the past.For example, when implementing vacuum deaerator, be preferably 12 heating of vacuum deaerator groove, making its inside reach 1100 ℃～1600 ℃, spy is well 1150 ℃～1450 ℃ TR.In addition, vacuum deaerator groove 12 inside are represented to be preferably with absolute pressure and are decompressed to 38～460mmHg(51～613hPa), are more preferably to be decompressed to 60～350mmHg(80～467hPa).In addition, from productive angle, the flow of the melten glass G of circulation is preferably 1～2000 ton/day in vacuum deaerator groove 12.
Glass-making processes of the present invention is preferably and comprises the vacuum deaerator operation, as early stage operation and subsequent handling comprise raw materials melt operation and forming process.This raw materials melt operation for example can be present known operation, for example be heated to through kind according to glass about more than 1400 ℃ and with the operation of raw materials melt.The starting material that adopt are also so long as be suitable for the starting material of the glass of manufacturing and get final product; There is not special the qualification; For example can use present material known such as silica sand, boric acid, Wingdale is concocted the starting material that form according to the composition of final glasswork, also can contain needed finings.In addition, this forming process for example can be present known operation, can give an example for example float forming operation, rolling formation operation, melt-shaping operation etc.
Utilize glass that the present invention makes so long as the glass through the heating and melting manufactured, it forms just unrestricted.Therefore, both can be non-alkali glass, also can be to be the sodium calcium class glass of representative with the soda-lime glass or as to contain alkali-containing glass such as alkali borosilicate glass.The present invention is particularly suitable for the manufacturing of non-alkali glass used in non-alkali glass, the especially liquid crystal display glass substrate.
Embodiment
Below, based on embodiment the present invention is specified.But the present invention is not limited by it.
Among the embodiment, use vacuum degassing apparatus shown in Figure 1 to implement the vacuum deaerator of melten glass.Melten glass uses non-alkali glass.
Temperature in the vacuum deaerator groove 12 remains on 1400 ℃.Utilize vacuum pump that decompression is carried out exhaust in the housing 11, thereby indirectly to carrying out exhaust in the vacuum deaerator groove 12 that is accommodated in decompression housing 11.That is, decompression housing 11 is sealed and inside and outside partition, but vacuum deaerator groove 12 with melten glass above the upper space part of joining be provided with peristome, communicate with the decompression enclosure interior.Therefore, if to carrying out exhaust in the decompression housing, then also decompression naturally in the vacuum deaerator groove.Implement to use weather gauge that normal atmosphere is monitored all the time in the process of vacuum deaerator.Regulate the vacuum tightness in the vacuum deaerator groove 12 through the gauge pressure of regulating vacuum pump, the absolute pressure in the control vacuum deaerator groove 12.
In addition, the level change of the melten glass G in the vacuum deaerator groove 12 that produces for the adjusting because of the vacuum tightness in the vacuum deaerator groove 12 moves up and down through the position that makes decompression housing 11 and to revise.
The liquid level of melten glass G is monitored through visual inspection from the window 122 of the upstream side that is arranged at vacuum deaerator groove 12 tops.Vacuum deaerator groove 12 inner can be provided with from the position that window 122 is confirmed expression from the bottom surface of vacuum deaerator groove 12 scale (not shown) to the distance of the liquid level of melten glass G.Liquid level through with this scale and melten glass G compares, thereby the variation in thickness that has or not and result from the alveolar layer on melten glass G top layer of the level change of melten glass G is monitored.
(comparative example 1)
Regulate the vacuum tightness in the vacuum deaerator groove 12 according to atmospheric variation, make the absolute pressure in the vacuum deaerator groove 12 remain on 300mmHg(400hPa), and implement vacuum deaerator simultaneously.The level change of melten glass G in the vacuum deaerator groove 12 that produces for the adjusting because of vacuum tightness moves up and down through the position that makes decompression housing 11 and to revise.At this moment, the thickness from window 122 observed alveolar layers is about 30mm.Infer thus, the bubble defective of the glass of making through the vacuum deaerator in this vacuum deaerator groove is a lot.
(embodiment 1)
Likewise implement vacuum deaerator with comparative example 1.But, implement in the process of vacuum deaerator, import nitrogen (Ns with the flow that 100L/ divides to vacuum deaerator groove 12 inner upper spaces 121 from the window 122 of the upstream side that is arranged at vacuum deaerator groove 12 tops < > 2 <> ).Through inserting the thermopair (not shown) of window 122, confirmed importing nitrogen after temperature descend.In addition, be arranged at the thermopair (not shown) of window 123 in the downstream side at vacuum deaerator groove 12 tops through insertion, confirmed importing nitrogen after temperature rise.These temperature variation are represented; The nitrogen that imports the inner upper space 121 of vacuum deaerator groove 12 forms the air-flow 41 of the direction identical with the circulating direction of melten glass G above the melten glass G of vacuum deaerator groove 12 internal circulations, promptly from the upstream side of vacuum deaerator groove 12 air-flow 41 of side flow downstream, emit to the outside from window 123 then.
In addition, among the embodiment 1, compare with comparative example 1, reduced more than the 20mm from the thickness of window 122 observed alveolar layers, confirm that the broken bubble on melten glass G surface carries out actively, promptly the vacuum deaerator effect improves.Infer thus, the bubble defective of the glass of making through the vacuum deaerator in this vacuum deaerator groove reduces.
(embodiment 2)
Likewise implement vacuum deaerator with embodiment 1.But, import nitrogen with the flow that 100L/ divides to vacuum deaerator groove 12 inner upper spaces 121 from the window 123 in the downstream side that is arranged at vacuum deaerator groove 12 tops.Through inserting the thermopair (not shown) of window 123, confirmed importing nitrogen after temperature descend.In addition, be arranged at the thermopair (not shown) of window 122 of the upstream side at vacuum deaerator groove 12 tops through insertion, confirmed importing nitrogen after temperature rise.These temperature variation are represented; The nitrogen that imports the inner upper space 121 of vacuum deaerator grooves 12 from window 123 forms the air-flow of the direction opposite with the circulating direction of melten glass G, the i.e. air-flow of side flow upstream from the downstream side of vacuum deaerator groove 12 above the melten glass G of vacuum deaerator groove 12 internal circulations, emit to the outside from the window of the upstream side that is arranged at vacuum deaerator groove 12 122 then.
In addition, among the embodiment 2, compare with comparative example 1, reduced more than the 20mm from the thickness of window 122 observed alveolar layers, confirm that the broken bubble on melten glass G surface carries out actively, promptly the vacuum deaerator effect improves.Infer thus, the bubble defective of the glass of making through the vacuum deaerator in this vacuum deaerator groove reduces.
Among the embodiment 2, even also carrying out actively at the broken bubble of opposition side (window 122) of the importing side (window 123) of nitrogen, hence one can see that, and through forming air-flow, the effect of the vacuum deaerator of whole vacuum deaerator groove improves.In addition; Result by embodiment 1,2 can confirm; No matter be under the situation of the air-flow that forms the direction identical with the circulating direction of melten glass G, still under the situation of the air-flow that forms the direction opposite with the circulating direction of melten glass G, the effect of vacuum deaerator all improves.
(comparative example 2)
Likewise implement vacuum deaerator with comparative example 1.But, make the absolute pressure variation in the scope of 307～319mmHg(409～425hPa) in the vacuum deaerator groove 12.
(embodiment 3)
Likewise implement vacuum deaerator with embodiment 1.But, make the absolute pressure variation in the scope of 295～315mmHg(393～420hPa) in the vacuum deaerator groove 12.
Among comparative example 2 and the embodiment 3, gather the melten glass G of groove 24 discharges downstream, the annealing back is through the number density of range estimation mensuration bubble.Fig. 3 representes the bubble density mensuration result at downstream slot 24 places among comparative example 2 and the embodiment 3 and the dependency of the absolute pressure in the vacuum deaerator groove 12.Here, bubble density is used the absolute pressure 315mmHg(420hPa with embodiment 3) bubble density be made as 1 relative value and represent.Can know that by Fig. 3 in the comparative example 2, bubble density is about 312mmHg(416hPa in absolute pressure) time be mnm., be higher than a side of this value and the side that absolute pressure is lower than this value in absolute pressure, bubble density all increases.Promptly can find out, with 312mmHg(416hPa) be the boundary, cause bubble to increase because of excessively reducing pressure.On the other hand; Among the embodiment 3; With comparative example 2 likewise; Be higher than about 312mmHg(416hPa in absolute pressure) a side confirm the increase of bubble density; In the lower side of absolute pressure; To about 307mmHg(409hPa) till the bubble density minimizing, even absolute pressure further is reduced to about 295mmHg(393hPa), do not observe the increase of bubble density yet.Can know that by this result embodiment 3 compares with comparative example 2, the increase of the bubble that can prevent to cause by excessive decompression, thereby can obtain the few glass of bubble density.
The possibility of utilizing on the industry
The present invention is applicable to the manufacturing of the high quality glass products that bubble is less, is specially adapted to the manufacturing of non-alkali glass used in liquid crystal display glass substrate etc.
Here quote of the announcement of the full content of Japanese patent application 2007-020417 number specification sheets, claims, accompanying drawing and the summary of filing an application on January 31st, 2007 as specification sheets of the present invention.
Claims (6)
1. glass-making processes is included in the vacuum deaerator groove operation of melten glass being carried out vacuum deaerator, it is characterized in that,
Form air-flow above the melten glass that in said vacuum deaerator groove, circulates, this air-flow is at least a kind of air-flow of air-flow and the direction opposite with the circulating direction of said melten glass that is selected from the circulating direction of said melten glass,
The gas that forms said air-flow is to be selected from hydrogen (H < > 2 <> ), nitrogen (N < > 2 <> ), oxygen (O < > 2 <> ), air, carbon monoxide (CO), carbonic acid gas (CO < > 2 <> ), argon (Ar), krypton (Kr), xenon (Xe), hydrocarbon gas, gaseous carbon fluorine cpd and ammonia (NH < > 3 <> ) at least a kind.
2. glass-making processes is included in the vacuum deaerator groove operation of melten glass being carried out vacuum deaerator, it is characterized in that,
The air-flow of the vertical direction of circulating direction of formation and melten glass above the melten glass that in said vacuum deaerator groove, circulates,
The gas that forms said air-flow is to be selected from hydrogen (H < > 2 <> ), nitrogen (N < > 2 <> ), oxygen (O < > 2 <> ), air, carbon monoxide (CO), carbonic acid gas (CO < > 2 <> ), argon (Ar), krypton (Kr), xenon (Xe), hydrocarbon gas, gaseous carbon fluorine cpd and ammonia (NH < > 3 <> ) at least a kind.
3. according to claim 1 or claim 2 glass-making processes is characterized in that, the gas that forms said air-flow does not contain the gaseous constituent that produces from melten glass in fact.
4. according to claim 1 or claim 2 glass-making processes is characterized in that, the gas that forms said air-flow is imported to the position near the surface of melten glass.
5. the vacuum degassing apparatus of a melten glass, this device comprise decompression housing, vacuum deaerator groove, import unit and lead-out unit; Said decompression housing is vacuumized; Said vacuum deaerator groove is arranged in the said decompression housing, is used to carry out the vacuum deaerator of melten glass; Said importing unit is arranged to be communicated with said vacuum deaerator groove, is used for the melten glass before the vacuum deaerator is imported said vacuum deaerator groove; Said lead-out unit is arranged to be communicated with said vacuum deaerator groove, is used for the melten glass behind the vacuum deaerator is derived from said vacuum deaerator groove, it is characterized in that,
Comprise that also air-flow forms the unit, this air-flow forms the unit and constitutes by the gas introduction unit that gas is imported to the inner upper space of said vacuum deaerator groove and with the gas lead-out unit of gas from said upper space derivation,
The gas that forms said air-flow is to be selected from hydrogen (H < > 2 <> ), nitrogen (N < > 2 <> ), oxygen (O < > 2 <> ), air, carbon monoxide (CO), carbonic acid gas (CO < > 2 <> ), argon (Ar), krypton (Kr), xenon (Xe), hydrocarbon gas, gaseous carbon fluorine cpd and ammonia (NH < > 3 <> ) at least a kind.
6. the vacuum degassing apparatus of melten glass as claimed in claim 5 is characterized in that, said air-flow forms the unit and is arranged at top or the side that above the inner melten glass of vacuum deaerator groove, forms the vacuum deaerator groove of upper space.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2007020417 | 2007-01-31 | ||
| JP020417/2007 | 2007-01-31 | ||
| PCT/JP2008/050913 WO2008093580A1 (en) | 2007-01-31 | 2008-01-23 | Process for producing glass and vacuum degassing apparatus |
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| Publication Number | Publication Date |
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| CN101595068A CN101595068A (en) | 2009-12-02 |
| CN101595068B true CN101595068B (en) | 2012-07-25 |
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| JP (1) | JP5470853B2 (en) |
| KR (2) | KR20120032041A (en) |
| CN (1) | CN101595068B (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| TWI392657B (en) * | 2008-02-29 | 2013-04-11 | Asahi Glass Co Ltd | A vacuum degassing device for molten glass |
| JPWO2010147188A1 (en) * | 2009-06-19 | 2012-12-06 | 旭硝子株式会社 | Vacuum degassing apparatus for molten glass, and method for producing molten glass using the same |
| KR101341741B1 (en) | 2009-07-16 | 2013-12-16 | 아사히 가라스 가부시키가이샤 | Method for producing molten glass, vacuum degassing apparatus, and method for producing glass product |
| KR20120121874A (en) * | 2010-01-08 | 2012-11-06 | 아사히 가라스 가부시키가이샤 | Vacuum degassing apparatus for molten glass, method of producing molten glass using same, and method of producing glass article |
| TWI571448B (en) * | 2012-09-04 | 2017-02-21 | Avanstrate Inc | A method for manufacturing a glass substrate, and a manufacturing apparatus for a glass substrate |
| CN203625224U (en) * | 2013-09-17 | 2014-06-04 | 安瀚视特控股株式会社 | Molten glass treatment device and manufacturing device of glass substrate |
| CN203513469U (en) * | 2013-09-25 | 2014-04-02 | 安瀚视特控股株式会社 | Clarification tank for molten glass and manufacturing device of glass substrate |
| JP5976863B2 (en) * | 2014-03-31 | 2016-08-24 | ＡｖａｎＳｔｒａｔｅ株式会社 | Glass substrate manufacturing method and glass substrate manufacturing apparatus |
| CN106098968B (en) * | 2016-08-12 | 2018-06-22 | 京东方科技集团股份有限公司 | A kind of sintering method |
| KR102522616B1 (en) | 2017-03-16 | 2023-04-17 | 코닝 인코포레이티드 | Method for reducing cell life on the surface of a glass melt |
| CN106865956B (en) * | 2017-03-21 | 2019-10-15 | 东旭科技集团有限公司 | Clarifier and glass furnace for glass melts |
| US10974986B2 (en) | 2017-09-20 | 2021-04-13 | AGC Inc. | Alkali-free glass substrate |
| JP2022507801A (en) | 2018-11-21 | 2022-01-18 | コーニング インコーポレイテッド | How to shorten the bubble life on the surface of glass melt |
| KR102141856B1 (en) | 2019-03-19 | 2020-08-07 | 에이지씨 가부시키가이샤 | Alkali-free glass substrate |
| US11718553B2 (en) | 2019-03-19 | 2023-08-08 | AGC Inc. | Alkali-free glass substrate |
| JP7127587B2 (en) | 2019-03-19 | 2022-08-30 | Ａｇｃ株式会社 | Alkali-free glass substrate |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1270148A (en) * | 1999-04-13 | 2000-10-18 | 旭硝子株式会社 | Vacuum degassing method for molten glass |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPH05208845A (en) * | 1992-01-30 | 1993-08-20 | Asahi Glass Co Ltd | Production of colored glass and its apparatus |
| PT966406E (en) * | 1998-01-09 | 2001-11-30 | Saint Gobain | A PROCESS AND DEVICE FOR THE FUSING AND RELINKING OF VITRIFICABLE MATERIALS |
| JP3785792B2 (en) * | 1998-03-11 | 2006-06-14 | 旭硝子株式会社 | Vacuum degassing equipment for molten glass |
| JP3861460B2 (en) * | 1998-06-26 | 2006-12-20 | 旭硝子株式会社 | Vacuum degassing method for molten glass |
| US6854290B2 (en) * | 2001-07-18 | 2005-02-15 | Corning Incorporated | Method for controlling foam production in reduced pressure fining |
| DE60233832D1 (en) * | 2001-09-28 | 2009-11-05 | Asahi Glass Co Ltd | Vacuum degassing apparatus for molten glass |
| JP2004091307A (en) * | 2002-07-10 | 2004-03-25 | Nippon Electric Glass Co Ltd | Method for producing glass |
| JP4446283B2 (en) * | 2002-11-29 | 2010-04-07 | 日本電気硝子株式会社 | Glass melting furnace |
-
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- 2008-01-23 KR KR1020127005315A patent/KR20120032041A/en not_active Application Discontinuation
- 2008-01-23 WO PCT/JP2008/050913 patent/WO2008093580A1/en active Application Filing
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|---|---|---|---|---|
| CN1270148A (en) * | 1999-04-13 | 2000-10-18 | 旭硝子株式会社 | Vacuum degassing method for molten glass |
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| Title |
|---|
| JP特开2004-91307A 2004.03.25 |
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| JP5470853B2 (en) | 2014-04-16 |
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| KR20120032041A (en) | 2012-04-04 |
| WO2008093580A1 (en) | 2008-08-07 |
| TWI380965B (en) | 2013-01-01 |
| TW200900367A (en) | 2009-01-01 |
| JPWO2008093580A1 (en) | 2010-05-20 |
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| KR101160495B1 (en) | 2012-06-28 |
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