CN102171151B - Apparatus and process for glassmaking - Google Patents
Apparatus and process for glassmaking Download PDFInfo
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- CN102171151B CN102171151B CN200880131462.XA CN200880131462A CN102171151B CN 102171151 B CN102171151 B CN 102171151B CN 200880131462 A CN200880131462 A CN 200880131462A CN 102171151 B CN102171151 B CN 102171151B
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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
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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
- C03B5/167—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
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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
As the constituent material of glass manufacturing apparatus (melting channel, clarifying tank, steel basin and their connection stream), use the alloy (in this manual platinum and platinum alloy being referred to as to platinum material below) of other precious metal elements such as platinum or platinum and such as rhodium (Rh), gold (Au), iridium (Ir) or ruthenium (Ru).Use platinum material to be as the reason of above-mentioned constituent material, the fusing point of platinum material is high, does not form oxide skin in atmosphere, therefore can be not deteriorated, the possibility that deforms, damages in the time of device running is low, and chemical stability, and the possibility of the glass of pollution molten state is low.
Unit temp in glass manufacture operation is according to its contents processing and difference, under more than approximately 900 DEG C hot environments.Due to above-mentioned characteristic, the melten glass that platinum material can polluting device inside under such hot environment yet, can the enough weather resistance of long term maintenance.
But, use the glass manufacturing apparatus of platinum material to have this problem of bubble being caused by the moisture in melten glass at the generation of interfaces of platinum material while manufacturing glass.This is because contained moisture contacts and dissociation with platinum material in melten glass, generates hydrogen and oxygen.Think that hydrogen can see through platinum material and be released into outside, and oxygen cannot see through platinum material, exceedes solubility limit if residue in the concentration of the oxygen of melten glass, at the generation of interfaces bubble (with reference to patent documentation 1～4) of platinum material.If consequent bubble residues in the glasswork of manufacturing, can make the quality of glasswork reduce.
Particularly for the alkali-free glass substrate of the metal oxide of alkali-free in fact using in liquid-crystal display (LCD), display of organic electroluminescence (OLED), inorganic EL display etc., because the fusing point of non-alkali glass is high, higher with alkali-containing glass phase specific viscosity, so the bubble in melten glass is difficult for floating, is difficult to suppress bubble.
For addressing this problem, propose to arrange at the outer surface of platinum material the technical scheme (with reference to patent documentation 1～4) of the tunicle of fine and close hydrogen impermeability.As the material of the tunicle of fine and close hydrogen impermeability, can exemplify glass, pottery, metal etc.
Patent documentation 1: the special table of Japanese Patent 2004-523449 communique
Patent documentation 2: International Publication WO2006/030738 text
Patent documentation 3: International Publication WO2005/063634 text
Patent documentation 4: the special table of Japanese Patent 2006-522001 communique
The fine and close tunicle of the hydrogen impermeability that prior art proposes is conceived to molecular diameter or the ionic diameter of hydrogen, by fine and close tunicle being set by 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 bubble cannot fully reduce glass manufacture 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 desired fine and close film, the tunicle causing because of the use under hot environment deteriorated, because 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 the bubble can effectively and stably prevent glass manufacture time generation, 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 contacting with melten glass of this member is formed with the layer that comprises 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 melten glass temperature range, there is Fe redox ratio, i.e. Fe
2+/ Fe
2++ Fe
3+the change point rising.
Be better in glass manufacturing apparatus of the present invention, the member of described platinum system or platinum alloy system is the container of storage melten glass.
Be better in glass manufacturing apparatus of the present invention, described melten glass temperature range is 1250～1650 DEG C.
Be better in glass manufacturing apparatus of the present invention, described alumina type ceramic particle contains mullites more than 10 quality %.
In addition, the present invention also provides the glass-making processes that uses glass manufacturing apparatus of the present invention.
In glass-making processes of the present invention, the glass that is better manufacturing is non-alkali glass, and its mass percent with oxide compound benchmark represents to contain:
SiO
250～70％、
Al
2O
35～25％、
B
2O
31～20％、
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, in the time of glass manufacture, can effectively 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 being inhibited of bubble.
The non-alkali glass of particularly 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.
The announcement of invention
The simple declaration of accompanying drawing
Fig. 1 is the schematic diagram that represents a structure example of glass manufacturing apparatus.
Fig. 2 (a) is the figure that represents the crucible of the platinum alloy system using in embodiment, Fig. 2 (b) is the figure that represents the pedestal of the zirconia brick system using in embodiment, and Fig. 2 (c) is the figure that represents the crucible of Fig. 2 (a) to be arranged at the state of the recess of the pedestal of Fig. 2 (b).
Fig. 3 is the alumina type ceramic particle for example 1, example 3 and example 5, the figure that the relation mapping of Fe redox ratio and temperature is obtained.
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 carrying out an invention
Below glass manufacturing apparatus of the present invention is described.
Fig. 1 is the schematic diagram that represents a structure example of glass manufacturing apparatus.Glass manufacturing apparatus 1 shown in Fig. 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 connected for the conduit (connection stream) 6,7,8 that makes melten glass circulation.
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 communicated with by the conduit 6 taking this spout as upstream extremity.
Clarifying tank 3 is mainly the position of carrying out the clarification of glass, in melten glass contained fine bubble at the effect float downward of the clarification gas being discharged 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 communicated with by the conduit 7 taking this spout as upstream extremity.
Steel basin 4 is mainly, by agitator etc., melten glass is stirred to 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 communicated with by the conduit 8 taking spout as upstream extremity.
Building mortion 5 is to be mainly the position of required shape by forming of glass, can suitably select according to the shape of the glasswork of manufacturing.For example, glasswork is in the situation of the glass substrate used of flat-panel monitor, can use float forming device, under draw method building mortion etc.
In glass manufacturing apparatus 1 shown in Fig. 1, the part contacting with melten glass of melting channel 2～conduit 8 require to have can withstand high temperatures environment thermotolerance and the erosion resistance to melten glass, therefore preferably use platinum material (being platinum or platinum alloy).
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 contacting with melten glass of this member is formed with the layer that comprises 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 melten glass temperature range, there is Fe redox ratio (Fe
2+/ Fe
2++ Fe
3+) rise change point.
Here as the concrete example of the member of the platinum system contacting with melten glass or platinum alloy system, can exemplify the storage platinum system of melten glass or the container of platinum alloy system.But be not limited to this, the platinum system that described member contacts with melten glass while being extensively included in use glass manufacturing apparatus or the member of platinum alloy system.Below, in this manual, as the concrete example of the member of the platinum system contacting with melten glass or platinum alloy system, exemplifying the storage platinum system of melten glass or the container of platinum alloy system describes, and for the platinum system beyond the container of storage melten glass or the member of platinum alloy system, be the member of platinum system or platinum alloy system by the partial interpretation of the container that is recited as storage melten glass.
The container of storage melten glass extensively comprises the container that temporarily keeps or receive melten glass in glass manufacture operation, in a structure example of the glass manufacturing apparatus 1 shown in Fig. 1, melting channel 2, clarifying tank 3, steel basin 4 and conduit 6,7,8 are equivalent to receive the container of melten glass.
Therefore, in glass manufacturing apparatus of the present invention, at least one in the container of above-mentioned storage melten glass is platinum material system, in the reverse side of the face contacting with melten glass of the container of this platinum material system, the outside of the container wall of the platinum material system in a structure example of the glass manufacturing apparatus shown in Fig. 1 is formed with above-mentioned alumina type ceramic particle layer.
In the past, people were conceived to molecular diameter or the ionic diameter of hydrogen, thought as long as form fine and close tunicle by modes such as hydrogen impermeability material apply.But the inventor is through conscientiously finding after research, the fine and close tunicle not forming with hydrogen impermeability material but in alumina type ceramic particle the valence mumber of contained Fe change (Fe
3+→ Fe
2+) contribute to suppress the residual of bubble.
It is that the temperature that is accompanied by the platinum material being caused by the rising of melten glass temperature raises and (temperature and the melten glass temperature of outside of containers of supposing platinum material system is roughly the same) that produce that the valence mumber of Fe changes, Fe occurs after valence mumber variation, can think in the temperature of platinum material subsequently keeps constant process, suppressing the residual effect of bubble can remain constant substantially.
In the present invention, in order to allow the performance of alumina type ceramic particle layer suppress the residual effect of bubble, alumina type ceramic particle need comprise enough Fe.Particularly, alumina type ceramic particle need contain total amount with respect to alumina type ceramic particle with Fe
2o
3being scaled the Fe of 0.2～5 quality %, is better the Fe containing more than 0.5 quality %.But, if the amount of Fe is many, can not be integrated in the crystalline structure of alumina type pottery, but still maintain Fe
2o
3form, remaining with the form of rhombohedral iron ore, the change point that therefore Fe redox ratio described later rises reduces.So Fe content is with Fe
2o
3convert preferably below 5 quality %.
In the time using glass manufacturing apparatus, Fe contained in alumina type ceramic particle also need be in easy generation from Fe
3+to Fe
2+valence mumber change state.Therefore, in alumina type ceramic particle, contained Fe must have Fe redox ratio (Fe in melten glass temperature range
2+/ Fe
2++ Fe
3+) rise change point.Taking temperature as transverse axis, with Fe redox ratio (Fe
2+/ Fe
2++ Fe
3+) in 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 to Fe redox ratio (Fe
2+/ Fe
2++ Fe
3+) rise change point.More specifically, the point that the first derivative values of the curve of approximation of above-mentioned curve is started to increase with the rising of temperature 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 the speed of 300 DEG C per hour, at the temperature of regulation, keeps, after 1 hour, being cooled to room temperature, measure sample with hydrofluoric acid dissolution, in gained lysate, add Fe
2+indicator, measures Fe by spectral photometry method
2+amount.In addition measure after sample, by the Fe in lysate with hydrofluoric acid dissolution,
3+reduction is processed into Fe
2+, similarly measure Fe with aforesaid method
2+amount, obtains Fe
3++ Fe
2+amount.
Fe redox ratio (Fe
2+/ Fe
2++ Fe
3+if) rise change point in melten glass temperature range, in the time using glass manufacturing apparatus, more specifically that under the state contacting with melten glass at the wall of platinum material system of the container of storage melten glass, Fe contained in alumina type ceramic particle is in easy generation valence mumber variation (Fe
3+→ Fe
2+) state.
The temperature range that in glass manufacture operation till melten glass temperature range refers to before shaping is played in fusing, melten glass lives through.For the glass manufacturing apparatus 1 shown in Fig. 1, refer to the temperature range that in the process till melting channel 2 plays conduit 8, melten glass lives through.Melten glass temperature range is according to the integrant of the kind of glass and glass manufacturing apparatus and difference, in the situation for non-alkali glass, is generally 1250～1650 DEG C.It is better the melten glass temperature range of the whole container of formation glass manufacturing apparatus described later.
For making alumina type ceramic particle used in the present invention there is the change point that Fe redox ratio rises in melten glass temperature range, when melten glass temperature range is 1250～1650 DEG C, in the present invention, alumina type ceramic particle used preferably contains mullites more than 10 quality %.Mullite content is preferably more than 20 quality %, more preferably more than 30 quality %, more more preferably more than 40 quality %.
Alumina type ceramic particle can be only to contain the particle of mullite as crystallization phases, but as long as mullite content meets above-mentioned scope, also can contain other crystallization phases, particularly has baddeleyite, corundum.As other composition, can also contain zirconium, sillimanite etc.
The content of the glassy phase in alumina type ceramic particle is preferably below 50 quality %, more preferably below 30 quality %, more more preferably below 20 quality %, particularly preferably below 10 quality %.If the content of glassy phase is higher than 50 quality %, mullite phase surface is covered by glassy phase, has and cannot 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 glass manufacturing apparatus of the present invention, for in the reverse side of the face contacting with melten glass of the container of platinum material system, wall of a container face (for example, for crucible shape container time be side and bottom surface) outside forms alumina type ceramic particle layer, fills alumina type ceramic particle in wall of a container face outside with required thickness.If consider that performance suppresses the residual effect of bubble, thickness is preferably more than 1mm, more preferably more than 2mm.In addition, if blocked up, need too much ceramic particle, therefore thickness is preferably below 40mm.Particularly, at wall of a container face outside and the interval that container separates regulation, resistivity against fire block is set, in the gap of container and this resistivity against fire block, fills alumina type ceramic particle.Resistivity against fire block is as long as having resistivity against fire and can keeping the material of alumina type ceramic particle, be not particularly limited, can exemplify and for example burn till refractory body, particularly have the brick of aluminium-zirconium oxide matter, zirconium matter, sillimanite matter, grog (chamotte) matter, aluminum oxide, magnesia etc.But, if consider produceability (plasticity, processibility etc.) and cost aspect, the preferential oxidation aluminium matter brick of resistivity against fire block.
In the present invention, why using emboliform alumina type pottery, is the wall of a container face outside for the ease of being filled to platinum material system.Therefore,, as long as being crushed to the particle of the following left and right of particle diameter 2mm, do not refer to the particle that is adjusted to specific size-grade distribution.
In the present invention, particle diameter refers to by the size of the particle of the sieve in the aperture of this size.For example, the particle below particle diameter 2mm refers to by the particle of the sieve in 2mm aperture.Therefore, the shape of ceramic particle is unrestricted, can be spherical, square, irregularly shaped etc.If consider to fill ceramic particle with the state around container with enough point of contact, particle diameter is preferably below 2mm.If consider dispersing while preventing from filling, particle diameter is preferably more than 10 μ m.
In 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 container.The temperature of the melten glass in glass manufacturing apparatus is according to the container of platinum material system, the i.e. integrant of the glass manufacturing apparatus of the platinum material system container of melten glass (storage) and different.For example, for non-alkali glass, in the glass manufacturing apparatus 1 shown in Fig. 1, the temperature of the melten glass in melting channel 2 is 1400～1650 DEG C of left and right, the temperature that dissolves glass in clarifying tank 3 is 1300～1550 DEG C of left and right, the temperature that dissolves glass in steel basin 4 is 1250～1400 DEG C of left and right, the temperature that dissolves glass in conduit 6 is 1400～1600 DEG C of left and right, the temperature that dissolves glass in conduit 7 is 1300～1500 DEG C of left and right, and the temperature that dissolves glass in conduit 8 is 1250～1350 DEG C of left and right.
Therefore, in the present invention, fill alumina type ceramic particle in the wall of a container face outside of the platinum material system that forms glass manufacturing apparatus, this alumina type ceramic particle has Fe redox ratio (Fe in the melten glass temperature range being accommodated in this container
2+/ Fe
2++ Fe
3+) rise change point.
In glass-making processes of the present invention, except using glass manufacturing apparatus this point of the present invention as above, identical with existing method.Therefore, in the melting channel 2 of the glass manufacturing apparatus shown in Fig. 1, drop into according to the raw material of required glass composition allotment, 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 manufacture various glass.As the glass that is applicable to manufacturing with the present invention, an example of non-alkali glass is shown hereinafter.Non-alkali glass shown below is suitably used as the base plate glass of liquid-crystal display (LCD) use.
This non-alkali glass represents to contain with the mass percent of oxide compound benchmark:
SiO
250～70％、
Al
2O
35～25％、
B
2O
31～20％、
MgO 0～10％、
CaO 0～17％、
SrO 0～17％、
BaO 0～20％、
MgO+CaO+SrO+BaO 8～30％。
During above-mentioned mass percent represents, SiO
2, Al
2o
3, B
2o
3, MgO, CaO, SrO and BaO amount to 100%.
SiO
2be essential composition, while exceeding 70%, the melting of glass declines, and easy devitrification.Better below 64%.When less than 50%, can cause that proportion increases, strain point reduces, thermal expansivity increases, chemical resistant properties declines.Better more than 55%.
Al
2o
3being the composition that suppresses the phase-splitting of glass and improve strain point, is essential.While exceeding 25%, easily devitrification, causes that chemical-resistant declines.Better below 22%.When less than 5%, the easy phase-splitting of glass, and strain point reduces.Better more than 10%.
B
2o
3be reduce proportion, improve glass melting, make glass be difficult for the composition of devitrification, be essential.While exceeding 20%, strain point reduces, and loss when chemical resistant properties decline or glass melting becomes obviously, and the inhomogeneity of glass increases.Better below 12%.When less than 1%, proportion increases, and the melting of glass declines, and easy devitrification.Better more than 6%.
MgO is the composition that reduces proportion, improves the melting of glass.While exceeding 10%, the easy phase-splitting of glass, easily devitrification or chemical resistant properties decline.Better below 7%.Better the MgO containing more than 1%.
In order to improve the melting of glass, make glass be difficult for devitrification, can contain 17% CaO at the most.While exceeding 17%, proportion increases, and thermal expansivity increases, and easy devitrification on the contrary.Better below 14%.Better the CaO containing 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.While exceeding 17%, proportion increases, and thermal expansivity increases, and easy devitrification on the contrary.Better below 14%.Better the SrO containing 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.While exceeding 20%, proportion increases, and thermal expansivity increases.BaO is better below 1%, is more preferably in fact not containing BaO.
The total amount of the content of alkaline earth metal oxide (RO), (MgO+CaO+SrO+BaO) if very few, can make the fusing of glass become difficulty, therefore more than 8%.Otherwise if too much, the density of glass increases, therefore below 30%.Better 10～30%.
Therefore, non-alkali glass is more preferably with the mass percent of oxide compound benchmark and represents to contain:
SiO
255～64％、
Al
2O
310～22％、
B
2O
36～12％、
MgO 1～7％、
CaO 2～14％、
SrO 3～14％、
BaO 0～1％、
MgO+CaO+SrO+BaO 10～30％。
During above-mentioned mass percent represents, SiO
2, Al
2o
3, B
2o
3, MgO, CaO, SrO and BaO amount to 100%.
In order further to suppress the bubble in melten glass, also can add with respect to the frit of 100 quality % and count F, Cl, the SO below 5 quality % with total amount
3, SnO
2, Fe
2o
3deng as finings.
Embodiment
Below, adopt embodiment to further illustrate the present invention, but the present invention is not limited thereto.
In the present embodiment, the pedestal (resistivity against fire block) of the zirconia brick system shown in crucible (taking JIS H6201 (1986.11.1) as benchmark) and the Fig. 2 (b) of the platinum alloy system (platinum rhodium, rhodium 10 quality %) shown in use Fig. 2 (a) is evaluated 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 in embodiment is shown in table 1.Particle diameter is 10 μ m～2mm.In table 1, the crystallization phases in alumina type ceramic particle and the ratio of glassy phase (quality % benchmark) are tried to achieve by the ratio of measuring each crystallization phases by powder x-ray diffraction (XRD) method.Particularly, obtain the ratio of crystallization phases according to the XRD strength ratio of the pure substance of each crystallization phases (baddeleyite, zirconium, mullite, corundum etc.) and sample, obtain the ratio of glassy phase according to the difference of the summation of the ratio of sample and each crystallization phases.The ratio of components (quality % benchmark) of alumina type ceramic particle is tried to achieve by x-ray fluorescence analysis.∑ RO in ratio of components
xrepresent except 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, by the relation mapping of Fe redox ratio and temperature and be illustrated in Fig. 3.
The crucible of Fig. 2 (a) is arranged to the recess of the pedestal of Fig. 2 (b), as shown in Fig. 2 (c) to the alumina type ceramic particle shown in ST Stuffing Table 1 in gap (gap of the recess of pedestal and the bottom surface of crucible is 3～5mm), products therefrom is arranged in process furnace, is heated to 1400 DEG C.Then, under the state that is held in 1400 DEG C, in the crucible of Fig. 2, drop into non-alkali glass, 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 non-alkali glass fusing, then in 1400 DEG C of maintenances 1 hour, observe platinum alloy interface, the i.e. generation of the bubble of crucible wall.The results are shown in table 1.In table 1, example 1～example 4 represents embodiment, and example 5～example 7 represents comparative example.In table 1, 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 determination limit.
As shown in Table 1, the alumina type ceramic particle of example 1～example 4 can effectively and stably suppress 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 DEG C, therefore thinks that this particle cannot bring into play by the valence mumber of Fe and change (Fe in the melten glass temperature (1400 DEG C) of embodiment
3+→ Fe
2+) produce the residual effect of inhibition bubble.The redox ratio change point of the alumina type ceramic particle of example 7 is 1350 DEG C, but Fe
2o
3containing quantity not sufficient 0.2 quality %, therefore think that this particle cannot be given full play to by the valence mumber of Fe and change (Fe
3+→ Fe
2+) produce the residual effect of inhibition bubble.
The possibility of utilizing in industry
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 the flat-panel monitors such as liquid-crystal display (LCD), display of organic electroluminescence (OLED), inorganic EL display use.
Claims (4)
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 contacting with melten glass of this member is formed with the particle layer that comprises alumina type ceramic particle, and this layer fine and close tunicle that not use hydrogen impermeability material forms, and this particle 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 melten glass temperature range, there is Fe redox ratio, i.e. Fe
2+/ (Fe
2++ Fe
3+) rise change point;
Described melten glass temperature range is 1250～1650 DEG C;
Described alumina type ceramic particle contains mullites more than 10 quality %;
The content of the glassy phase in described alumina type ceramic particle is below 50 quality %.
2. glass manufacturing apparatus as claimed in claim 1, is characterized in that, the member of described platinum system or platinum alloy system is the container of storage melten glass.
3. glass-making processes, is characterized in that, right to use requires the glass manufacturing apparatus described in 1 or 2.
4. glass-making processes as claimed in claim 3, is characterized in that,
The glass of manufacturing is non-alkali glass, and its mass percent with oxide compound benchmark represents to contain:
MgO+CaO+SrO+BaO8～30％；
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 CN102171151A (en) | 2011-08-31 |
| CN102171151B true CN102171151B (en) | 2014-10-08 |
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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 |
| JPWO2013024649A1 (en) * | 2011-08-16 | 2015-03-05 | 旭硝子株式会社 | Float glass manufacturing apparatus and float glass manufacturing method using the 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 |
Family Cites Families (12)
| 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 |
| JP3988209B2 (en) * | 1996-06-03 | 2007-10-10 | 旭硝子株式会社 | Alkali-free glass and liquid crystal display panel |
| JP2000302457A (en) | 1999-04-23 | 2000-10-31 | Asahi Glass Co Ltd | Piping structure for flowing high-temperature melt |
| US7338714B2 (en) * | 2000-11-30 | 2008-03-04 | Schott Ag | Coated metal element used for producing glass |
| US6993936B2 (en) * | 2003-09-04 | 2006-02-07 | Corning Incorporated | 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 |
| US7475568B2 (en) * | 2005-04-27 | 2009-01-13 | Corning Incorporated | 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 |
-
2008
- 2008-10-06 CN CN200880131462.XA patent/CN102171151B/en not_active Expired - Fee Related
- 2008-10-06 KR KR1020107028073A patent/KR101292854B1/en active IP Right Grant
- 2008-10-06 WO PCT/JP2008/068195 patent/WO2010041305A1/en active Application Filing
Also Published As
| Publication number | Publication date |
|---|---|
| WO2010041305A1 (en) | 2010-04-15 |
| CN102171151A (en) | 2011-08-31 |
| KR20110036535A (en) | 2011-04-07 |
| KR101292854B1 (en) | 2013-08-02 |
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| C14 | Grant of patent or utility model | ||
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Address after: Tokyo, Japan Patentee after: ASAHI GLASS Co.,Ltd. Address before: Tokyo, Japan Patentee before: ASAHI GLASS Co.,Ltd. |
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| 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 |