CN102171151A - Apparatus and process for glassmaking - Google Patents
Apparatus and process for glassmaking Download PDFInfo
- Publication number
- CN102171151A CN102171151A CN200880131462XA CN200880131462A CN102171151A CN 102171151 A CN102171151 A CN 102171151A CN 200880131462X A CN200880131462X A CN 200880131462XA CN 200880131462 A CN200880131462 A CN 200880131462A CN 102171151 A CN102171151 A CN 102171151A
- Authority
- CN
- China
- Prior art keywords
- glass
- platinum
- manufacturing apparatus
- ceramic particle
- melten glass
- 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.)
- Granted
Links
Images
Classifications
-
- 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
-
- 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
- C03B5/167—Means for preventing damage to equipment, e.g. by molten glass, hot gases, batches
- C03B5/1672—Use of materials therefor
- C03B5/1675—Platinum group metals
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Glass Compositions (AREA)
Abstract
A glassmaking apparatus and a glassmaking process, which make it possible to inhibit bubble formation in glassmaking and give glass articles free from residual bubbles. A glassmaking apparatus having a platinum- or platinum alloy-made member to come into contact with molten glass, characterized in that a layer containing alumina-base ceramic particles which contain 0.2 to 5 mass% of Fe in terms of Fe2O3 based on the whole of the particles and has a change point at which Fe redox (Fe2+/ Fe2+ + Fe3+) rises within a glass melting temperature range is formed on the back of the member which is reverse to the face to come into contact with molten glass.
Description
Technical field
The present invention relates to glass manufacturing apparatus and use the glass-making processes of this manufacturing installation.
Background technology
Constituent material as glass manufacturing apparatus (melting channel, clarifying tank, steel basin and their connection stream), use platinum or platinum and for example rhodium (Rh), golden (Au), iridium (Ir) or ruthenium (Ru) to wait the alloy (below, in this manual platinum and platinum alloy are referred to as platinum material) of other precious metal element.Use platinum material to be that as the reason of above-mentioned constituent material the fusing point height of platinum material does not form oxide skin in atmosphere, therefore can deterioration, the possibility that deforms, damages when the device running is low, and chemical stability, and the possibility of the glass of pollution molten state is low.
Unit temp in the glass manufacturing process is according to its contents processing and difference is under about hot environment more than 900 ℃.Because above-mentioned characteristic, the melten glass that platinum material can polluting device inside under such hot environment yet, but the enough weather resistance of long term maintenance.
But, use the glass manufacturing apparatus of platinum material to have this problem of bubble that causes by the moisture in the melten glass in the generation of the interface of platinum material when making glass.This is because contained moisture contacts with platinum material and dissociates in the melten glass, generation hydrogen and oxygen.Think that hydrogen can see through platinum material and be released into the outside, and oxygen can't see through platinum material, surpasses solubility limit if residue in the concentration of the oxygen of melten glass, then produces bubble (with reference to patent documentation 1～4) at the interface of platinum material.If consequent bubble residues in the glasswork of manufacturing, the quality of glasswork is reduced.
Particularly for the alkali-free glass substrate of the metal oxide of alkali-free in fact that uses in liquid-crystal display (LCD), display of organic electroluminescence (OLED), the inorganic EL display etc., because the fusing point height of non-alkali glass, specific viscosity is higher mutually with alkali-containing glass, so the bubble in the melten glass is difficult for come-up, is difficult to suppress bubble.
For addressing this problem, proposed to be provided with the technical scheme (with reference to patent documentation 1～4) of the tunicle of fine and close hydrogen impermeability at the outer surface of platinum material.Material as the tunicle of the hydrogen impermeability of densification can exemplify glass, pottery, metal etc.
Patent documentation 1: the special table of Japanese Patent 2004-523449 communique
Patent documentation 2: international open WO2006/030738 text
Patent documentation 3: international open WO2005/063634 text
Patent documentation 4: the special table of Japanese Patent 2006-522001 communique
The announcement of invention
The tunicle of the densification of the hydrogen impermeability that prior art proposed is conceived to the molecular diameter or the ionic diameter of hydrogen, by fine and close tunicle is set with modes such as hydrogen impermeability material apply, prevent that by this hydrogen from seeing through tunicle and being released into outside phenomenon, but the generation of the bubble can't fully reduce glass and make the time.Think that hydrogen sees through tunicle and is released into outside reason and has: the tunicle that is arranged at the outer surface of platinum material may not be the film of desired densification, the deterioration of the tunicle that causes because of the use under the hot environment is because of the tunicle that the difference of the thermal expansivity of platinum material and tunicle causes is peeled off etc.
For addressing the above problem, the object of the present invention is to provide can be effectively and the generation of the bubble when preventing stably that glass from making, can prevent residual glass manufacturing apparatus and the glass-making processes of bubble in the glasswork of manufacturing.
For achieving the above object, the invention provides a kind of glass manufacturing apparatus, it is characterized in that,
Comprise the platinum system that contacts with melten glass or the member of platinum alloy system;
The reverse side of the face that contacts with melten glass of this member is formed with the layer that comprises the alumina type ceramic particle, and this layer contains with Fe with respect to the total amount of alumina type ceramic particle
2O
3Be scaled the Fe of 0.2～5 quality %, in the melten glass temperature range, have the Fe redox ratio, be Fe
2+/ Fe
2++ Fe
3+The change point that rises.
Better be in the glass manufacturing apparatus of the present invention, the member of described platinum system or platinum alloy system is a container of taking in melten glass.
Better be in the glass manufacturing apparatus of the present invention, described melten glass temperature range is 1250～1650 ℃.
Better be in the glass manufacturing apparatus of the present invention, described alumina type ceramic particle contains the above mullite of 10 quality %.
In addition, the present invention also provides the glass-making processes that uses glass manufacturing apparatus of the present invention.
In the glass-making processes of the present invention, the glass that better is manufacturing is non-alkali glass, and its mass percent with the oxide compound benchmark is represented to contain:
SiO
2?50～70％、
Al
2O
3?5～25％、
B
2O
3?1～20％、
MgO?0～10％、
CaO?0～17％、
SrO?0～17％、
BaO?0～20％、
MgO+CaO+SrO+BaO?8～30％；
SiO
2, Al
2O
3, B
2O
3, MgO, CaO, SrO and BaO amount to 100%.
Utilize glass manufacturing apparatus of the present invention and glass-making processes, can be effectively when glass is made and stably prevent the generation of the bubble at the platinum interface that contacts with melten glass or platinum alloy interface.Consequently, can be made into the good glass of the residual quality that is inhibited of bubble.
Particularly the non-alkali glass of making by glass manufacturing apparatus of the present invention and glass-making processes is suitable for the purposes of the base plate glass that flat-panel monitor uses, and is particularly suitable for the purposes of the base plate glass that flat-panel monitors such as liquid-crystal display (LCD), display of organic electroluminescence (OLED), inorganic EL display use.
The simple declaration of accompanying drawing
Fig. 1 is the synoptic diagram of a structure example of expression glass manufacturing apparatus.
Fig. 2 (a) is the figure of the crucible of the platinum alloy system used among the embodiment of expression, and Fig. 2 (b) is the figure of the pedestal of the zirconia brick system used among the expression embodiment, and to be expression be arranged at the figure of state of recess of the pedestal of Fig. 2 (b) with the crucible of Fig. 2 (a) to Fig. 2 (c).
Fig. 3 is the alumina type ceramic particle for example 1, example 3 and example 5, with the mapping of the relation of Fe redox ratio and temperature and figure.
The explanation of symbol
1: glass manufacturing apparatus
2: melting channel
3: clarifying tank
4: steel basin
5: building mortion
6,7,8: conduit
The best mode that carries out an invention
Below glass manufacturing apparatus of the present invention is described.
Fig. 1 is the synoptic diagram of a structure example of expression glass manufacturing apparatus.Glass manufacturing apparatus 1 shown in Figure 1 comprises melting channel 2, be arranged at the clarifying tank 3 in the downstream side of this melting channel 2, be arranged at the downstream side of clarifying tank 3 steel basin 4, be arranged at the building mortion 5 in the downstream side of steel basin 4, melting channel 2, clarifying tank 3, steel basin 4 and building mortion 5 are respectively by being used to that the conduit (being connected stream) 6,7,8 of melten glass circulation is connected.
Melting channel 2 is provided with burner, electrode etc., fusible frit.The downstream side of melting channel 2 is formed with the spout of melten glass, and melting channel 2 and clarifying tank 3 are by with this spout being conduit 6 connections of upstream extremity.
Clarifying tank 3 mainly is the clarifying position of carrying out glass, in the melten glass contained fine bubble at the effect float downward of the clarification gas that discharges by finings, thereby from melten glass, remove.The downstream side of clarifying tank 3 is formed with the spout of melten glass, and clarifying tank 3 and steel basin 4 are by with this spout being conduit 7 connections of upstream extremity.
Steel basin 4 mainly is by agitator etc. melten glass to be stirred the position that it is homogenized.The downstream side of steel basin 4 is formed with spout, and steel basin 4 and building mortion 5 are by with the spout being conduit 8 connections of upstream extremity.
Building mortion 5 mainly is to be the position of required shape with forming of glass, can suitably select according to the shape of the glasswork of manufacturing.For example, glasswork is under the situation of glass basal plates of flat panel display, can use the float forming device, draw method building mortion etc. down.
In the glass manufacturing apparatus 1 shown in Figure 1, but the part that contacts with melten glass of melting channel 2～conduit 8 requires to have the thermotolerance of withstand high temperatures environment and to the erosion resistance of melten glass, the therefore preferred platinum material (being platinum or platinum alloy) that uses.
Glass manufacturing apparatus of the present invention is characterised in that, comprise the platinum system that contacts with melten glass or the member of platinum alloy system, the reverse side of the face that contacts with melten glass of this member is formed with the layer that comprises the alumina type ceramic particle, and this layer contains with Fe with respect to the total amount of alumina type ceramic particle
2O
3Be scaled the Fe of 0.2～5 quality %, in the melten glass temperature range, have Fe redox ratio (Fe
2+/ Fe
2++ Fe
3+) change point that rises.
Here, as the concrete example of the member of platinum system that contacts with melten glass or platinum alloy system, can exemplify the platinum system of taking in melten glass or the container of platinum alloy system.But be not limited thereto the platinum system that described member contacts with melten glass when extensively being included in the use glass manufacturing apparatus or the member of platinum alloy system.Below, in this manual, concrete example as the member of platinum system that contacts with melten glass or platinum alloy system, exemplifying the platinum system of taking in melten glass or the container of platinum alloy system describes, and for the platinum system beyond the container of taking in melten glass or the member of platinum alloy system, be the member of platinum system or platinum alloy system with the partial interpretation that is recited as the container of taking in melten glass.
The container of taking in melten glass extensively comprises the container that temporarily keeps or take in melten glass in the glass manufacturing process, in a structure example of glass manufacturing apparatus shown in Figure 11, melting channel 2, clarifying tank 3, steel basin 4 and conduit 6,7,8 are equivalent to take in the container of melten glass.
Therefore, in the glass manufacturing apparatus of the present invention, in the above-mentioned container of taking in melten glass at least one is platinum material system, in the reverse side of the face that contacts with melten glass of the container of this platinum material system, be that the outside of the container wall of the platinum material system in the structure example of glass manufacturing apparatus shown in Figure 1 is formed with above-mentioned alumina type ceramic particle layer.
In the past, people were conceived to the molecular diameter or the ionic diameter of hydrogen, thought as long as form fine and close tunicle with modes such as hydrogen impermeability material apply.But the inventor finds through conscientious research back, be not the densification that forms with hydrogen impermeability material tunicle but in the alumina type ceramic particle valence mumber of contained Fe change (Fe
3+→ Fe
2+) help to suppress the residual of bubble.
The valence mumber of Fe changes that the temperature that is to be accompanied by the platinum material that the rising by the melten glass temperature causes raises and (temperature and the melten glass temperature of outside of containers of supposing platinum material system is roughly the same) that produce, after the valence mumber variation takes place in Fe, can think that the temperature at subsequently platinum material keeps in the constant process, suppresses the residual effect of bubble and can keep constant substantially.
Among the present invention, in order to allow the performance of alumina type ceramic particle layer suppress the residual effect of bubble, the alumina type ceramic particle need comprise the Fe of capacity.Particularly, the alumina type ceramic particle need contain total amount with respect to the alumina type ceramic particle with Fe
2O
3Being scaled the Fe of 0.2～5 quality %, better is to contain the above Fe of 0.5 quality %.But, if the amount of Fe is many, then can not be integrated in the crystalline structure of alumina type pottery, but still keep Fe
2O
3Form, remaining with the form of rhombohedral iron ore, the change point that Fe redox ratio therefore described later rises reduces.So Fe content is with Fe
2O
3Conversion is preferably below the 5 quality %.
When using glass manufacturing apparatus, contained Fe also need be in easy generation from Fe in the alumina type ceramic particle
3+To Fe
2+The state that changes of valence mumber.Therefore, contained Fe must have Fe redox ratio (Fe in the alumina type ceramic particle in the melten glass temperature range
2+/ Fe
2++ Fe
3+) change point that rises.Be transverse axis with the temperature, with Fe redox ratio (Fe
2+/ Fe
2++ Fe
3+) under the situation for longitudinal axis mapping, at a certain temperature Fe of place redox ratio (Fe
2+/ Fe
2++ Fe
3+) sharply rise.In this specification sheets, this temperature is called Fe redox ratio (Fe
2+/ Fe
2++ Fe
3+) change point that rises.More specifically, the point that the first derivative values of the curve of approximation of above-mentioned curve is begun the rising with temperature and increase is called change point.
Fe redox ratio (the Fe of alumina type ceramic particle
2+/ Fe
2++ Fe
3+) can try to achieve by redox titration.Particularly, the sample of alumina type ceramic particle is warming up to the temperature of regulation with 300 ℃ speed per hour, after keeping 1 hour under the temperature of regulation, is cooled to room temperature, measure sample, in the gained lysate, add Fe with hydrofluoric acid dissolution
2+Indicator is measured Fe by the spectral photometry method
2+Amount.In addition, behind hydrofluoric acid dissolution mensuration sample, with the Fe in the lysate
3+Reduction is processed into Fe
2+, similarly measure Fe with aforesaid method
2+Amount is obtained Fe
3++ Fe
2+Amount.
Fe redox ratio (Fe
2+/ Fe
2++ Fe
3+If) change point that rises is in the melten glass temperature range, then when using glass manufacturing apparatus, more specifically be under the wall and melten glass state of contact of the platinum material system of the container of taking in melten glass, contained Fe is in easy generation valence mumber and changes (Fe in the alumina type ceramic particle
3+→ Fe
2+) state.
The temperature range that melten glass lived through in the glass manufacturing process till the melten glass temperature range is meant before shaping is played in fusing.For glass manufacturing apparatus shown in Figure 11, be meant the temperature range that melten glass lived through in the process till melting channel 2 plays conduit 8.The melten glass temperature range under the situation for non-alkali glass, is generally 1250～1650 ℃ according to the integrant of the kind of glass and glass manufacturing apparatus and different.It better is the melten glass temperature range of the entire container of formation glass manufacturing apparatus described later.
For making alumina type ceramic particle used among the present invention in the melten glass temperature range, have the change point that the Fe redox ratio rises, when the melten glass temperature range was 1250～1650 ℃, used alumina type ceramic particle preferably contained the above mullite of 10 quality % among the present invention.Mullite content is preferably more than the 20 quality %, more preferably more than the 30 quality %, more more preferably more than the 40 quality %.
The alumina type ceramic particle can be only to contain the particle of mullite as crystallization phases, but as long as mullite content satisfies above-mentioned scope, then also can contain other crystallization phases, and baddeleyite, corundum are particularly arranged.As other composition, can also contain zirconium, sillimanite etc.
The content of the glassy phase in the alumina type ceramic particle is preferably below the 50 quality %, and more preferably below the 30 quality %, more preferably below the 20 quality %, good especially is below the 10 quality % again.If the content of glassy phase is higher than 50 quality %, then the mullite phase surface is covered by glassy phase, has to give full play to the trend that is changed the residual effect of the inhibition bubble that produces by the valence mumber of Fe.
In the glass manufacturing apparatus of the present invention, for in the reverse side of the face that contacts with melten glass of the container of platinum material system, be that wall of a container face (for example for crucible shape container time is side and the bottom surface) outside forms the alumina type ceramic particle layer, fill the alumina type ceramic particle in the wall of a container face outside with required thickness.Suppress the residual effect of bubble if consider performance, then thickness is preferably more than the 1mm, more preferably more than the 2mm.In addition, if blocked up, then need too much ceramic particle, so thickness is preferably below the 40mm.Particularly, the resistivity against fire block is set, in the gap of container and this resistivity against fire block, fills the alumina type ceramic particle at the wall of a container face outside and the interval that container separates regulation.The resistivity against fire block is so long as have resistivity against fire and can keep the material of alumina type ceramic particle to get final product, be not particularly limited, can exemplify and for example burn till refractory body, the brick of aluminium-zirconium oxide matter, zirconium matter, sillimanite matter, grog (chamotte) matter, aluminum oxide, magnesia etc. is particularly arranged.But, if consider the produceability (plasticity, processibility etc.) and the cost aspect of resistivity against fire block, then preferred aluminum oxide brick.
Why using emboliform alumina type pottery among the present invention, is for the ease of being filled to the wall of a container face outside of platinum material system.Therefore, so long as the particle about being crushed to below the particle diameter 2mm gets final product, be not meant the particle that is adjusted to specific size-grade distribution.
Among the present invention, particle diameter is meant the size by the particle of the sieve in the aperture of this size.For example, the following particle of particle diameter 2mm is meant the particle by the sieve in 2mm aperture.Therefore, the shape of ceramic particle is unrestricted, can be spherical, square, irregularly shaped etc.If consider that then particle diameter is preferably below the 2mm to fill ceramic particle with the state that has enough point of contact around the container.If consider dispersing when preventing to fill, then particle diameter is preferably more than the 10 μ m.
Among the present invention, the alumina type ceramic particle that is filled in the wall of a container face outside of platinum material system can suitably be selected according to the temperature that is accommodated in the melten glass in the container.The temperature of the melten glass in the glass manufacturing apparatus according to the container of platinum material system, be the integrant (taking in the container of melten glass) of the glass manufacturing apparatus of platinum material system and difference.For example, for non-alkali glass, in glass manufacturing apparatus shown in Figure 11, the temperature of the melten glass in the melting channel 2 is about 1400～1650 ℃, the temperature that dissolves glass in the clarifying tank 3 is about 1300～1550 ℃, the temperature that dissolves glass in the steel basin 4 is about 1250～1400 ℃, the temperature that dissolves glass in the conduit 6 is about 1400～1600 ℃, the temperature that dissolves glass in the conduit 7 is about 1300～1500 ℃, and the temperature that dissolves glass in the conduit 8 is about 1250～1350 ℃.
Therefore, among the present invention, fill the alumina type ceramic particle, have Fe redox ratio (Fe in the melten glass temperature range of this alumina type ceramic particle in being accommodated in this container in the wall of a container face outside of the platinum material system that constitutes glass manufacturing apparatus
2+/ Fe
2++ Fe
3+) change point that rises.
In the glass-making processes of the present invention, except using aforesaid glass manufacturing apparatus this point of the present invention, identical with existing method.Therefore, in the melting channel 2 of glass manufacturing apparatus shown in Figure 1, drop into the raw material of forming allotment according to required glass, heating for dissolving and obtain melten glass, make this melten glass successively by conduit 6, clarifying tank 3, conduit 7, steel basin 4, conduit 8 and building mortion 5, thereby obtain the glasswork of required shape.
Utilize the present invention can make various glass.As the glass that is fit to make, an example of non-alkali glass is shown hereinafter with the present invention.Non-alkali glass shown below is suitably used as the base plate glass of liquid-crystal display (LCD) usefulness.
This non-alkali glass is represented to contain with the mass percent of oxide compound benchmark:
SiO
2?50～70％、
Al
2O
3?5～25％、
B
2O
3?1～20％、
MgO?0～10％、
CaO?0～17％、
SrO?0～17％、
BaO?0～20％、
MgO+CaO+SrO+BaO?8～30％。
During above-mentioned mass percent is represented, SiO
2, Al
2O
3, B
2O
3, MgO, CaO, SrO and BaO amount to 100%.
SiO
2Be essential composition, surpass at 70% o'clock, the melting of glass descends, and easy devitrification.Better be below 64%.During less than 50%, can cause that proportion increases, strain point reduces, thermal expansivity increases, chemical resistant properties descends.Better be more than 55%.
Al
2O
3Being the composition that suppresses the phase-splitting of glass and improve strain point, is essential.Surpass at 25% o'clock, devitrification causes that chemical-resistant descends easily.Better be below 22%.During less than 5%, the easy phase-splitting of glass, and strain point reduces.Better be more than 10%.
B
2O
3Be reduce proportion, improve glass melting, make glass be difficult for the composition of devitrification, be essential.Surpass at 20% o'clock, strain point reduces, and the loss when chemical resistant properties decline or glass melting becomes obviously, and the inhomogeneity of glass increases.Better be below 12%.During less than 1%, proportion increases, and the melting of glass descends, and easy devitrification.Better be more than 6%.
MgO is the composition that reduces proportion, improves the melting of glass.Surpass at 10% o'clock, the easy phase-splitting of glass, devitrification or chemical resistant properties descend easily.Better be below 7%.Better be the MgO that contains more than 1%.
In order to improve the melting of glass, make glass be difficult for devitrification, can contain 17% CaO at the most.Surpass at 17% o'clock, proportion increases, and thermal expansivity increases, and easy on the contrary devitrification.Better be below 14%.Better be the CaO that contains more than 2%.
In order to suppress the phase-splitting of glass, make glass be difficult for devitrification, can contain 17% SrO at the most.Surpass at 17% o'clock, proportion increases, and thermal expansivity increases, and easy on the contrary devitrification.Better be below 14%.Better be the SrO that contains more than 3%.
In order to suppress the phase-splitting of glass, make glass be difficult for devitrification, can contain 20% BaO at the most.Surpass at 20% o'clock, proportion increases, and thermal expansivity increases.BaO better is below 1%, is more preferably not contain BaO in fact.
The total amount of the content of alkaline earth metal oxide (RO), promptly (MgO+CaO+SrO+BaO) then can make the fusing of the glass difficulty that becomes, therefore more than 8% if very few.Otherwise if too much, then the density of glass increases, therefore below 30%.Better be 10～30%.
Therefore, non-alkali glass is more preferably with the mass percent of oxide compound benchmark and represents to contain:
SiO
2?55～64％、
Al
2O
3?10～22％、
B
2O
3?6～12％、
MgO?1～7％、
CaO?2～14％、
SrO?3～14％、
BaO?0～1％、
MgO+CaO+SrO+BaO?10～30％。
During above-mentioned mass percent is represented, SiO
2, Al
2O
3, B
2O
3, MgO, CaO, SrO and BaO amount to 100%.
In order further to suppress the bubble in the melten glass, also can add with respect to the frit of 100 quality % and count F, Cl, SO below the 5 quality % with total amount
3, SnO
2, Fe
2O
3Deng as finings.
Embodiment
Below, adopt embodiment to further specify the present invention, but the present invention is not limited thereto.
In the present embodiment, the crucible (is benchmark with JIS H6201 (1986.11.1)) of the platinum alloy system (platinum rhodium, rhodium 10 quality %) shown in use Fig. 2 (a) and the pedestal (resistivity against fire block) of the zirconia brick system shown in Fig. 2 (b) are estimated the production of the bubble at platinum alloy interface.The size of the pedestal shown in the crucible shown in Fig. 2 (a) and Fig. 2 (b) is as described below respectively.
Crucible
Highly: 27mm
Upper diameter: 25mm
Base diameter: 15mm
Capacity: 10cc
Quality: 8.0g
Pedestal
Outside dimension: 48mm * 48mm * 48mm
Recess depths: 26mm
Recess diameter: 35mm
Alumina type ceramic particle used among the embodiment is shown in table 1.Particle diameter is 10 μ m～2mm.In the table 1, the crystallization phases in the alumina type ceramic particle and the ratio of glassy phase (quality % benchmark) are tried to achieve by the ratio of measuring each crystallization phases with powder x-ray diffraction (XRD) method.Particularly, obtain the ratio of crystallization phases, obtain the ratio of glassy phase according to the difference of the summation of the ratio of sample and each crystallization phases according to the XRD strength ratio of the pure substance (baddeleyite, zirconium, mullite, corundum etc.) of each crystallization phases and sample.The ratio of components of alumina type ceramic particle (quality % benchmark) is tried to achieve by x-ray fluorescence analysis.∑ RO in the ratio of components
xExpression removes Al
2O
3, SiO
2, ZrO
2, Fe
2O
3The summation of oxidation impurities in addition, R represents metallic element, and O represents oxygen, and x represents stoichiometric ratio.
[table 1]
For the alumina type ceramic particle of example 1, example 3 and example 5, with the mapping of the relation of Fe redox ratio and temperature and be illustrated in Fig. 3.
The crucible of Fig. 2 (a) is arranged at the recess of the pedestal of Fig. 2 (b), (gap of the recess of pedestal and the bottom surface of crucible is the alumina type ceramic particle shown in the ST Stuffing Table 1 in 3～5mm) to the gap shown in Fig. 2 (c), products therefrom is arranged in the process furnace, is heated to 1400 ℃.Then, in the crucible of Fig. 2, drop into non-alkali glass remaining under 1400 ℃ the state, make its fusing.The composition of non-alkali glass is expressed as SiO with the mass percent of oxide compound benchmark
259.4%, Al
2O
317.6%, B
2O
37.9%, MgO 3.3%, CaO 3.8%, SrO 8.0%, MgO+CaO+SrO 15.1%.
After the non-alkali glass fusing, in 1400 ℃ of maintenances 1 hour, observe the platinum alloy interface, be the generation of the bubble of crucible wall again.The results are shown in table 1.In the table 1, example 1～example 4 expression embodiment, example 5～example 7 expression comparative examples.In the table 1, the bubble occupation rate is the ratio of the shared area of bubble in the crucible bottom surface of Fig. 2 (a), and 0% is illustrated in below the determination limit.
As shown in Table 1, the alumina type ceramic particle of example 1～example 4 can be effectively and is stably suppressed the residual of bubble.On the other hand, the redox ratio change point of the alumina type ceramic particle of example 5, example 6 is 950 ℃, thinks that therefore the valence mumber that this particle can't be brought into play by Fe in the melten glass temperature (1400 ℃) of embodiment changes (Fe
3+→ Fe
2+) the residual effect of inhibition bubble that produces.The redox ratio change point of the alumina type ceramic particle of example 7 is 1350 ℃, but Fe
2O
3Contain quantity not sufficient 0.2 quality %, think that therefore the valence mumber that this particle can't be given full play to by Fe changes (Fe
3+→ Fe
2+) the residual effect of inhibition bubble that produces.
The possibility of utilizing on the industry
The alkali-free glass of making by glass manufacturing apparatus of the present invention and glass-making processes is suitable for the purposes of the base plate glass that flat-panel monitor uses, and is particularly suitable for the purposes of the base plate glass that the flat-panel monitors such as liquid crystal display (LCD), display of organic electroluminescence (OLED), inorganic EL display use.
Claims (6)
1. glass manufacturing apparatus is characterized in that,
Comprise the platinum system that contacts with melten glass or the member of platinum alloy system;
The reverse side of the face that contacts with melten glass of this member is formed with the layer that comprises the alumina type ceramic particle, and this layer contains with Fe with respect to the total amount of alumina type ceramic particle
2O
3Be scaled the Fe of 0.2～5 quality %, in the melten glass temperature range, have the Fe redox ratio, be Fe
2+/ Fe
2++ Fe
3+The change point that rises.
2. glass manufacturing apparatus as claimed in claim 1 is characterized in that, the member of described platinum system or platinum alloy system is a container of taking in melten glass.
3. glass manufacturing apparatus as claimed in claim 1 or 2 is characterized in that, described melten glass temperature range is 1250～1650 ℃.
4. as each the described glass manufacturing apparatus in the claim 1～3, it is characterized in that described alumina type ceramic particle contains the above mullite of 10 quality %.
5. glass-making processes is characterized in that, uses each the described glass manufacturing apparatus in the claim 1～4.
6. glass-making processes as claimed in claim 5 is characterized in that,
The glass of manufacturing is non-alkali glass, and its mass percent with the oxide compound benchmark is represented to contain:
SiO
2?50～70％、
Al
2O
3?5～25％、
B
2O
3?1～20％、
MgO?0～10％、
CaO?0～17％、
SrO?0～17％、
BaO?0～20％、
MgO+CaO+SrO+BaO?8～30％；
SiO
2, Al
2O
3, B
2O
3, MgO, CaO, SrO and BaO amount to 100%.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/JP2008/068195 WO2010041305A1 (en) | 2008-10-06 | 2008-10-06 | Apparatus and process for glassmaking |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102171151A true CN102171151A (en) | 2011-08-31 |
| CN102171151B CN102171151B (en) | 2014-10-08 |
Family
ID=42100270
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200880131462.XA Expired - Fee Related CN102171151B (en) | 2008-10-06 | 2008-10-06 | Apparatus and process for glassmaking |
Country Status (3)
| Country | Link |
|---|---|
| KR (1) | KR101292854B1 (en) |
| CN (1) | CN102171151B (en) |
| WO (1) | WO2010041305A1 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5796731B2 (en) * | 2011-03-02 | 2015-10-21 | 日本電気硝子株式会社 | Glass article manufacturing apparatus and glass article manufacturing method |
| WO2013024649A1 (en) * | 2011-08-16 | 2013-02-21 | 旭硝子株式会社 | Float glass production device, and float glass production method employing same |
| CN108529853B (en) * | 2018-04-10 | 2019-12-27 | 湖北新华光信息材料有限公司 | Glass continuous melting furnace and melting method |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2438552A (en) * | 1940-10-14 | 1948-03-30 | Corhart Refractories Co | Cast refractory product |
| JPS5122712A (en) * | 1974-08-19 | 1976-02-23 | Hoya Glass Works Ltd | RINSANKEIGARASUNOSEIZOHO |
| JPS62212228A (en) * | 1986-03-13 | 1987-09-18 | Tanaka Kikinzoku Kogyo Kk | Platinum container for high temperature |
| JPH01201033A (en) * | 1988-02-04 | 1989-08-14 | Canon Inc | Melting device and melting vessel using same |
| JP2000302457A (en) * | 1999-04-23 | 2000-10-31 | Asahi Glass Co Ltd | Piping structure for flowing high-temperature melt |
| US6169047B1 (en) * | 1994-11-30 | 2001-01-02 | Asahi Glass Company Ltd. | Alkali-free glass and flat panel display |
| CN1526035A (en) * | 2000-11-30 | 2004-09-01 | Ф�ز������쳧 | Coated metal element used for producing glass |
| JP2006077318A (en) * | 2004-09-13 | 2006-03-23 | Tanaka Kikinzoku Kogyo Kk | Method for modifying surface of apparatus for producing glass |
| CN1845880A (en) * | 2003-09-04 | 2006-10-11 | 康宁股份有限公司 | System and method for suppressing the formation of oxygen inclusions and surface blisters in glass sheets and the resulting glass sheets |
| JP2007077004A (en) * | 2005-08-19 | 2007-03-29 | Nippon Electric Glass Co Ltd | Heat resistant material for glass melting, glass article producing apparatus and process for producing glass article |
| CN101189191A (en) * | 2005-04-27 | 2008-05-28 | 康宁股份有限公司 | Method of fining glass |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3988209B2 (en) * | 1996-06-03 | 2007-10-10 | 旭硝子株式会社 | Alkali-free glass and liquid crystal display panel |
-
2008
- 2008-10-06 KR KR1020107028073A patent/KR101292854B1/en active IP Right Grant
- 2008-10-06 CN CN200880131462.XA patent/CN102171151B/en not_active Expired - Fee Related
- 2008-10-06 WO PCT/JP2008/068195 patent/WO2010041305A1/en active Application Filing
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2438552A (en) * | 1940-10-14 | 1948-03-30 | Corhart Refractories Co | Cast refractory product |
| JPS5122712A (en) * | 1974-08-19 | 1976-02-23 | Hoya Glass Works Ltd | RINSANKEIGARASUNOSEIZOHO |
| JPS62212228A (en) * | 1986-03-13 | 1987-09-18 | Tanaka Kikinzoku Kogyo Kk | Platinum container for high temperature |
| JPH01201033A (en) * | 1988-02-04 | 1989-08-14 | Canon Inc | Melting device and melting vessel using same |
| US6169047B1 (en) * | 1994-11-30 | 2001-01-02 | Asahi Glass Company Ltd. | Alkali-free glass and flat panel display |
| JP2000302457A (en) * | 1999-04-23 | 2000-10-31 | Asahi Glass Co Ltd | Piping structure for flowing high-temperature melt |
| CN1526035A (en) * | 2000-11-30 | 2004-09-01 | Ф�ز������쳧 | Coated metal element used for producing glass |
| CN1845880A (en) * | 2003-09-04 | 2006-10-11 | 康宁股份有限公司 | System and method for suppressing the formation of oxygen inclusions and surface blisters in glass sheets and the resulting glass sheets |
| JP2006077318A (en) * | 2004-09-13 | 2006-03-23 | Tanaka Kikinzoku Kogyo Kk | Method for modifying surface of apparatus for producing glass |
| CN101189191A (en) * | 2005-04-27 | 2008-05-28 | 康宁股份有限公司 | Method of fining glass |
| JP2007077004A (en) * | 2005-08-19 | 2007-03-29 | Nippon Electric Glass Co Ltd | Heat resistant material for glass melting, glass article producing apparatus and process for producing glass article |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20110036535A (en) | 2011-04-07 |
| CN102171151B (en) | 2014-10-08 |
| KR101292854B1 (en) | 2013-08-02 |
| WO2010041305A1 (en) | 2010-04-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR102169675B1 (en) | High volume production of display quality glass sheets having low zirconia levels | |
| TWI389862B (en) | Glass manufacturing apparatus and manufacturing method thereof | |
| CN104136383A (en) | Production method for non-alkali glass | |
| JP4658870B2 (en) | High electrical resistance high zirconia cast refractory | |
| CN102325729B (en) | There is the refractory product of high zirconia content | |
| EP1613559A1 (en) | Methods of manufacturing glass sheets with reduced blisters | |
| TW201213246A (en) | Alumina isopipes for use with tin-containing glasses | |
| JP6983377B2 (en) | Glass | |
| TW201136865A (en) | Refractory product having a high zirconia content | |
| JP5763538B2 (en) | Method and apparatus for manufacturing glass plates | |
| US20190322563A1 (en) | Apparatus and methods for producing glass comprising crystal zirconia | |
| KR20180102543A (en) | Glass | |
| TWI400216B (en) | High zirconia cast refractory | |
| WO2013150912A1 (en) | Method for producing glass substrate and device for producing glass substrate | |
| CN109923082A (en) | Glass | |
| CN102066288A (en) | High zirconia refractory material | |
| CN102171151B (en) | Apparatus and process for glassmaking | |
| KR101798288B1 (en) | Method and apparatus for making glass substrate | |
| JP2008201617A (en) | Method for production of glass | |
| JP2008019110A (en) | Material for glass flow passage, apparatus for manufacturing glass and method for manufacturing glass articles | |
| JP5347424B2 (en) | Glass manufacturing apparatus and manufacturing method | |
| CN102515476B (en) | For producing the pressure pipes such as the aluminium oxide of stanniferous glass | |
| KR20200129165A (en) | Exhaust conduit for glass melt system |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CP03 | Change of name, title or address | ||
| CP03 | Change of name, title or address |
Address after: Tokyo, Japan Patentee after: ASAHI GLASS Co.,Ltd. Address before: Tokyo, Japan Patentee before: ASAHI GLASS Co.,Ltd. |
|
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20141008 |