CN108950296A - A kind of preparation method of ultra-white float glass tin liquor additive - Google Patents
A kind of preparation method of ultra-white float glass tin liquor additive Download PDFInfo
- Publication number
- CN108950296A CN108950296A CN201810966192.XA CN201810966192A CN108950296A CN 108950296 A CN108950296 A CN 108950296A CN 201810966192 A CN201810966192 A CN 201810966192A CN 108950296 A CN108950296 A CN 108950296A
- Authority
- CN
- China
- Prior art keywords
- tin
- float glass
- germanium
- tin liquor
- ultra
- Prior art date
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Classifications
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C13/00—Alloys based on tin
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B18/00—Shaping glass in contact with the surface of a liquid
- C03B18/02—Forming sheets
- C03B18/18—Controlling or regulating the temperature of the float bath; Composition or purification of the float bath
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
Abstract
The invention belongs to glass technology fields, propose a kind of preparation method of ultra-white float glass tin liquor additive.A kind of ultra-white float glass proposed is mixed with the tin that the preparation method of tin liquor additive is the germanium and 85-92% that are 8%-15% by mass percent; 1000-1100 DEG C of progress melting is heated in the high temperature furnace for having nitrogen protection; smelting time is 20-30min; continue to be passed through nitrogen protection after the completion of the melting of tin germanium alloy, until high temperature furnace temperature drop is to 200 DEG C or less；Tin germanium alloy is taken out, tin germanium alloy top and bottom are inverted, the above-mentioned melting process of repetition is primary, to obtain the tin germanium alloy of uniform ingredients, and is granulated to alloy；The mass fraction for obtaining germanium is the tin liquor additive of 8-15%；High temperature furnace will carry out nitrogen purging 20-30min before heating.The present invention does not cause to significantly affect while improving float glass quality to the transmitance of float glass.
Description
Technical field
The invention belongs to glass technology fields, and in particular to a kind of preparation side of ultra-white float glass tin liquor additive
Method.
Background technique
Operations for forming is completed in the production of float glass in molten tin bath, due to floating support medium tin liquor and protection in forming process
Gas nitrogen, hydrogen are contaminated and glass are made to produce defect related with tin, we are commonly called as tin defects.Mainly there is light distortion
Several major class such as point, cassiterite, iris and tin sticky.The reason of molten tin bath pollutes essentially consists in the design defect of molten tin bath itself, molten tin bath operates,
Bad wait of the leakproofness of molten tin bath can introduce oxygen, and tin liquor is caused to aoxidize.The source of sulphur pollution is mainly glass metal itself.Float glass process glass
Glass molten tin bath environment and design feature determine that the generation of tin defects is inevitable, and only can be effectively controlled in actual production,
And it cannot eliminate.
Since float technology is born, domestic and international many glass circle personages and float glass factory have been devoted to seep tin
The research of work, PPG company of the U.S. in tin liquor by adding iron to realize the production substantially without the float glass product for seeping tin layers.
In the research of molten tin bath tin liquor reduction technique and reducing agent, mostly use the iron plate of high-purity as reducing agent greatly, using 3Fe+
Sn2+ + Sn4+ 3Fe2+ + 2Sn chemically reacts to restore the tin being oxidized.Iron can reduce the infiltration of tin really,
But the infiltration of Float Glass Surface iron is also resulted in, the ultra-clear glasses of demand not only have tin class defect stringent currently on the market
It is required that while also have very high requirement to glass transmitance, but the presence of iron can seriously affect the transmitance of glass, therefore ultrawhite
Glass adds iron to be not optimal selection when producing with floating process in tin liquor.
Summary of the invention
To reduce in float glass inevitable tin class defect in process of production, especially ultra-white float glass production
Tin class defect problem, the purpose of the present invention is to propose to a kind of ultra-white float glass preparation methods of tin liquor additive.
The present invention adopts the following technical solutions to accomplish the above objectives:
A kind of preparation method of ultra-white float glass tin liquor additive, it is 8%- that the preparation method, which is by mass percent,
The tin mixing of 15% germanium and 85-92%, is heated to 1000-1100 DEG C of progress melting, melting in the high temperature furnace for having nitrogen protection
Time is 20-30min, continues to be passed through nitrogen protection after the completion of the tin germanium alloy melting, until high temperature furnace temperature drop is to 200 DEG C
Below；Tin germanium alloy is taken out, tin germanium alloy top and bottom are inverted, the above-mentioned melting process of repetition is primary, to obtain uniform ingredients
Tin germanium alloy, and alloy is granulated, the mass fraction for obtaining germanium is the tin liquor additive of 8-15%；The high temperature furnace is adding
Nitrogen purging 20-30min is carried out before heat.
The mass percent content of the germanium is 10-13%；The mass percent of the tin is 87-90%.
High temperature furnace furnace inner environment during melted tin germanium alloy keeps micro-positive pressure 90-130Pa.
High temperature furnace furnace inner environment during melted tin germanium alloy keeps micro-positive pressure 100-120Pa.
The smelting time is 25-30min.
The tin liquor additive when in use, is added at 650-750 DEG C of molten tin bath contraction section.
The tin liquor additive when in use, is added at 700-730 DEG C of molten tin bath contraction section.
The injected volume control of the tin liquor additive total mass fraction of the germanium in entire tin liquor 0.001-0.02% it
Between.
The injected volume of the tin liquor additive controls the total mass fraction in germanium in entire tin liquor in 0.003-0.015%
Between.
The partial size of the tin germanium alloy is 1-5mm.
The partial size of the tin germanium alloy is 2-3mm.
The preparation method of a kind of ultra-white float glass tin liquor additive proposed by the present invention, using prepared by the present invention
The tin liquor additive, the mass fraction control of germanium in entire tin liquor is added in tin liquor additive at 650-750 DEG C of molten tin bath contraction section
System is in 0.001-0.02%；By the addition of the tin liquor additive, there is a small amount of enrichment, germanium preferential oxidation, germanium oxygen in tin liquor face in germanium
Mainly with Ge after change4+In the presence of, when glass metal forms in molten tin bath, because the ionic radius of germanium is smaller than the ionic radius of tin, germanium
Ion is easier to enter in glass body, to hinder Sn2+Into glass body, reduces seep tin amount to a certain extent；
When the generation of float glass trising from tempering float glass is primarily due to float glass forming, tin face penetrate into SnO, and the quilt in toughening process
It is oxidized to SnO2, volume expansion, then there is fine fold in glass surface, and light is made to generate interference colours.But the infiltration master of germanium
It will be with Ge4+Based on, there is no the problem of volume expansion, therefore can alleviate the rainbow problem due to caused by tempering after oxidation.With
The prior art is compared, which does not cause obvious shadow while improving float glass quality, to the transmitance of float glass
It rings, the more applicable production with ultra-white float glass.
Specific embodiment
To further understand the present invention, the preferred embodiment of the invention is described below with reference to embodiment, but this hair
It is bright to be not limited to embodiment described below.
The embodiment of the invention discloses a kind of float glass tin liquor additive, the tin liquor additive is germanic quality point
Number is the tin germanium alloy of 8-15%, and the amount that alloy is added in production is that total mass fraction control of the germanium in entire tin liquor exists
Between 0.001-0.02%, the high-temperature oxidation resistance of liquid tin in molten tin bath can be improved by the addition of the additive, effectively drop
The tin class defect such as low Tin Concentration In Float Glass, iris, while the transmitance of ultra-white float glass is not caused significantly to influence, no
It is only suitable for the production of common float glass, is more suitably applied to the production of ultra-white float glass.
In the present invention, glass is carried out to melted, preferably following ultra-white float glass first: with the quality hundred of oxide benchmark
Fraction representation: contain SiO2: 65-78%, Al2O3: 1.1-3.2%, CaO:6-10%, MgO:0.1-5%, Na2O:11-16%, K2O:0.5-
2%、Fe2O3: 0.006-0.02%.
Heretofore described tin liquor additive is tin germanium alloy, and wherein the mass fraction of germanium is 8-15%.
Tin liquor additive of the present invention when in use, is added, preferably 700- at 650-750 DEG C of molten tin bath contraction section
730℃；Institute's injected volume controls the total mass fraction in germanium in entire tin liquor between 0.001-0.02%, can be using automatic
Charger is added or is manually added, and considers from actual production and cost, is suitable for being controlled using the addition manner of high frequency low amounts
Concentration of the germanium processed in entire tin liquor.
The preparation method of the tin liquor additive preferably includes following steps:
The tin of germanium and 85-92% that mass percent is 8%-15% is mixed, 1000 DEG C are heated in the high temperature furnace for having nitrogen protection
Melting is carried out, obtains the uniform alloy of ingredient, and be granulated to alloy, the tin liquor that the mass fraction for obtaining germanium is 8-15% adds
Add agent.
The present invention is mixed using tin and germanium as raw material first, in accordance with mass ratio, and the mass percentage of the germanium is 8-
15%, preferably 10-13%.The mass percentage of the tin is 85-92%, preferably 87-90%.
After tin and germanium are mixed, it is melted in the high temperature furnace for having atmosphere protection, obtains the uniform alloy of ingredient；The high temperature
Furnace in-furnace temperature is higher than 938.25 DEG C of melting temperature, preferably 1000 DEG C of germanium；The high temperature furnace will be into before alloy is melted
Row nitrogen purges 20-30min, preferably 25-30min；The high temperature furnace needs the protection of nitrogen during alloy is melted,
Furnace inner environment keeps micro-positive pressure 90-130Pa, preferably 100-120Pa；Alloy melting time in high temperature furnace is 25-
30min；Continue to be passed through nitrogen protection after the completion of the alloy melting, until high temperature furnace temperature drop is to 200 DEG C or less；Preferably,
After taking out alloy, alloy top and bottom are inverted, the above-mentioned melting process of repetition is primary, to obtain the tin germanium alloy of uniform ingredients.
After obtaining alloy, alloy is granulated, partial size 1-5mm, preferably 2-3mm.
The control of institute's injected volume is total mass fraction of the germanium in entire tin liquor between 0.001-0.02%, preferably
0.003-0.015% is launched by the way of repeatedly launching on a small quantity, can be improved in molten tin bath by the addition of the additive
The tin class defect such as Tin Concentration In Float Glass, iris is effectively reduced in the high-temperature oxidation resistance of liquid tin, while to ultrawhite float glass process glass
The transmitance of glass does not cause significantly to influence, and is not only suitable for the production for common float glass, and it is floating to be more suitably applied to ultrawhite
The production of method glass.
For a further understanding of the present invention, below with reference to embodiment to tin liquor additive provided by the invention and its preparation side
Method and use are illustrated, and protection scope of the present invention is not limited by embodiment once.
Embodiment 1:
10g germanium and 90g tin are mixed, nitrogen is carried out before high temperature stove heating and purges 20min, keeps positive pressure 100Pa, high temperature in furnace
Stove heating is to 1000 DEG C and the constant 25min of temperature is kept to carry out being melted for tin germanium alloy, closes high temperature furnace after the completion of melting, continues
It is passed through nitrogen protection, until temperature drop inverts alloy top and bottom, in repetition to 200 DEG C hereinafter, after taking out alloy in high temperature furnace
It is primary to state melting process.
Tin germanium be melted is granulated, the tin liquor additive that partial size is 3mm is obtained.
At 720 DEG C of molten tin bath, tin liquor additive be melted is added in tin liquor with automatic charging equipment, to have in molten tin bath
For 150t liquid tin, 75kg tin liquor additive is launched for the first time, launches and finishes in 24 hours, reach the Ge content in tin liquor
0.005% or so.After stabilization to be produced, the germanium in molten tin bath can be supplemented weekly, to guarantee that there are suitable concentrations in molten tin bath
Germanium.
Glass raw material is carried out melted, melten glass liquid is obtained in the above-mentioned tin liquor surface forming after annealing for having additive
Float glass carry out power spectrum and transmitance analysis.
Embodiment 2:
12g germanium and 88g tin are mixed, nitrogen is carried out before high temperature stove heating and purges 20min, keeps positive pressure 100Pa, high temperature in furnace
Stove heating is to 1000 DEG C and the constant 25min of temperature is kept to carry out being melted for tin germanium alloy, closes high temperature furnace after the completion of melting, continues
It is passed through nitrogen protection, until temperature drop inverts alloy top and bottom, in repetition to 200 DEG C hereinafter, after taking out alloy in high temperature furnace
It is primary to state melting process.
Tin germanium be melted is granulated, the tin liquor additive that partial size is 3mm is obtained.
At 720 DEG C of molten tin bath, tin liquor additive be melted is added in tin liquor with automatic charging equipment, to have in molten tin bath
For 150t liquid tin, 125kg tin liquor additive is launched for the first time, launches and finishes in 24 hours, reach the Ge content in molten tin bath
To 0.01% or so.After stabilization to be produced, the germanium in molten tin bath can be supplemented weekly, to guarantee that there are suitable concentrations in molten tin bath
Germanium.
Glass raw material is carried out melted, melten glass liquid is obtained in the above-mentioned tin liquor surface forming after annealing for having additive
Float glass carry out power spectrum and transmitance analysis.
| Sample number into spectrum | Sn | Sn-0.005%Ge | Sn-0.01%Ge |
| Germanium amount wt% is added | 0 | 0.005 | 0.01 |
| Penetrate into Theil indices wt% | 9.14 | 5.40 | 5.93 |
| Penetrate into Ge content wt% | 0 | 2.06 | 2.18 |
| Uv transmittance | 85.48 | 85.36 | 85.30 |
Float Glass Surface can be effectively reduced in tin liquor additive of the invention it can be seen from the experimental result of embodiment
Infiltration tin amount, be beneficial to reduce iris grade, while the transmitance of ultra-clear glasses do not caused to significantly affect.
Abstract: the present invention provides a kind of tin liquor additive of suitable ultra-white float glass production, the tin liquor additive
The tin germanium alloy for being 8-15% for germanic mass fraction, the amount that alloy is added in production is gross mass of the germanium in entire tin liquor
The high-temperature oxidation resistant of liquid tin in molten tin bath can be improved by the addition of the additive between 0.001-0.02% for Fractional domination
The tin class defect such as Tin Concentration In Float Glass, iris is effectively reduced in performance, while not causing to the transmitance of ultra-white float glass bright
Aobvious influence is not only suitable for the production for common float glass, is more suitably applied to the production of ultra-white float glass.
Claims (10)
1. a kind of ultra-white float glass preparation method of tin liquor additive, it is characterised in that: the preparation method is by matter
The tin mixing for measuring germanium and 85-92% that percentage is 8%-15%, is heated to 1000-1100 DEG C in the high temperature furnace for having nitrogen protection
Melting is carried out, smelting time 20-30min continues to be passed through nitrogen protection after the completion of the tin germanium alloy melting, until high temperature furnace
Furnace temperature is down to 200 DEG C or less；Tin germanium alloy is taken out, tin germanium alloy top and bottom are inverted, the above-mentioned melting process of repetition is primary, with
To the tin germanium alloy of uniform ingredients, and alloy is granulated；The partial size of the tin germanium alloy is 1-5mm；Obtain the quality of germanium
Score is the tin liquor additive of 8-15%；The high temperature furnace will carry out nitrogen purging 20-30min before heating.
2. a kind of preparation method of ultra-white float glass tin liquor additive as described in claim 1, it is characterised in that: described
The mass percent content of germanium is 10-13%；The mass percent of the tin is 87-90%.
3. a kind of preparation method of ultra-white float glass tin liquor additive as described in claim 1, it is characterised in that: described
High temperature furnace furnace inner environment during melted tin germanium alloy keeps micro-positive pressure 90-130Pa.
4. a kind of preparation method of ultra-white float glass tin liquor additive as claimed in claim 3, it is characterised in that: described
High temperature furnace furnace inner environment during melted tin germanium alloy keeps micro-positive pressure 100-120Pa.
5. a kind of preparation method of ultra-white float glass tin liquor additive as described in claim 1, it is characterised in that: described
Smelting time be 25-30min.
6. a kind of preparation method of ultra-white float glass tin liquor additive as described in claim 1, it is characterised in that: described
Tin liquor additive when in use, at 650-750 DEG C of molten tin bath contraction section be added.
7. a kind of preparation method of ultra-white float glass tin liquor additive as claimed in claim 6, it is characterised in that: described
Tin liquor additive when in use, at 700-730 DEG C of molten tin bath contraction section be added.
8. a kind of preparation method of ultra-white float glass tin liquor additive as described in claim 1, it is characterised in that: described
The injected volume of tin liquor additive controls the total mass fraction in germanium in entire tin liquor between 0.001-0.02%.
9. a kind of preparation method of ultra-white float glass tin liquor additive as claimed in claim 8, it is characterised in that: described
The injected volume of tin liquor additive controls the total mass fraction in germanium in entire tin liquor between 0.003-0.015%.
10. a kind of preparation method of ultra-white float glass tin liquor additive as described in claim 1, the tin germanium alloy
Partial size is 2-3mm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810966192.XA CN108950296A (en) | 2018-08-23 | 2018-08-23 | A kind of preparation method of ultra-white float glass tin liquor additive |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810966192.XA CN108950296A (en) | 2018-08-23 | 2018-08-23 | A kind of preparation method of ultra-white float glass tin liquor additive |
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| Publication Number | Publication Date |
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| CN108950296A true CN108950296A (en) | 2018-12-07 |
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| CN201810966192.XA Withdrawn CN108950296A (en) | 2018-08-23 | 2018-08-23 | A kind of preparation method of ultra-white float glass tin liquor additive |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113912268A (en) * | 2021-11-09 | 2022-01-11 | 中国洛阳浮法玻璃集团有限责任公司 | Method for reducing lower surface tin penetration in float glass manufacturing process |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6065309A (en) * | 1997-09-20 | 2000-05-23 | Wisconsin Alumni Research Foundation | Float processing of high-temperature complex silicate glasses and float baths used for same |
| CN102603182A (en) * | 2011-12-29 | 2012-07-25 | 信义光伏产业(安徽)控股有限公司 | Ultra-white float glass and production method thereof |
| CN104108859A (en) * | 2014-04-11 | 2014-10-22 | 海南大学 | Production method of float glass |
| CN105837038A (en) * | 2016-05-19 | 2016-08-10 | 台玻安徽玻璃有限公司 | Super white float glass production method |
-
2018
- 2018-08-23 CN CN201810966192.XA patent/CN108950296A/en not_active Withdrawn
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6065309A (en) * | 1997-09-20 | 2000-05-23 | Wisconsin Alumni Research Foundation | Float processing of high-temperature complex silicate glasses and float baths used for same |
| CN102603182A (en) * | 2011-12-29 | 2012-07-25 | 信义光伏产业(安徽)控股有限公司 | Ultra-white float glass and production method thereof |
| CN104108859A (en) * | 2014-04-11 | 2014-10-22 | 海南大学 | Production method of float glass |
| CN105837038A (en) * | 2016-05-19 | 2016-08-10 | 台玻安徽玻璃有限公司 | Super white float glass production method |
Non-Patent Citations (3)
| Title |
|---|
| 司敏杰等: "浮法玻璃锡缺陷治理的研究及进展", 《玻璃》 * |
| 唐健正: "《真空玻璃》", 31 July 2018 * |
| 王艳霞等: "浮法工艺锡槽环境下锡的高温抗氧化研究", 《玻璃》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113912268A (en) * | 2021-11-09 | 2022-01-11 | 中国洛阳浮法玻璃集团有限责任公司 | Method for reducing lower surface tin penetration in float glass manufacturing process |
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Application publication date: 20181207 |