CN100366560C - Sodium calcium silicon series fire-proofing glass - Google Patents
Sodium calcium silicon series fire-proofing glass Download PDFInfo
- Publication number
- CN100366560C CN100366560C CNB2005101072099A CN200510107209A CN100366560C CN 100366560 C CN100366560 C CN 100366560C CN B2005101072099 A CNB2005101072099 A CN B2005101072099A CN 200510107209 A CN200510107209 A CN 200510107209A CN 100366560 C CN100366560 C CN 100366560C
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- glass
- fire
- calcium silicon
- silicon series
- mgo
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Classifications
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
- C03C3/085—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal
- C03C3/087—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal containing calcium oxide, e.g. common sheet or container glass
Abstract
The present invention discloses calcium silicon series fire-proofing glass. The present invention comprises the following components proportioned by weight: 67% to 75% of SiO2, 1.5% to 4% of Al2O3, 5% to 10% of CaO, 0.5% to 3% of MgO, 3% to 13% of R2O3, 0.2% to 2.5% of ZrO2, 2% to 6% of BaO and 1% to 6% of SrO. On the basis of common float glass, some components are modified: part of MgO is replaced by CaO to increase the density and the hardness of the glass; added plasma Sr< 2+ >, Ba< 3+ > and Zr< 4+ > exists in lattice space and has accumulation action on peripheral silicon-oxy tetrahedron, the structural compactness is increased, the expansion coefficient is lowered, the softening point is enhanced, the fire resistance of the glass is ensured in certain time, and thereby, the fire-proof purpose is achieved. After the modification of the component portion of the common float glass, the components of the present invention is the same as those of a common float glass system, and the forming production which uses the float process is not affected. The glass product which is smelted by using the components has the advantages of low thermal expansion coefficient, high softening point, and good fire-proof performance and chemical stability.
Description
Technical field
The invention belongs to glass production manufacturing technology field, relate generally to a kind of sodium calcium silicon series fire-proofing glass that common float glass process is produced that is useful for.
Background technology
Known composite fireproof glass is to make substrate with borosilicate glass or through the common soda lime glass that tempering is handled, and is composited with the organic or inorganic material.The expansion softening temperature of common soda lime glass generally is lower than 650 ℃, is higher than in the scene of a fire under 650 ℃ the raging fire baking, often shortens fire prevention time of composite fireproof glass because of softening transform with raging fire contact surface glass.Silicate glass or the common soda lime glass handled through tempering because of the expansion softening temperature is lower than 650 ℃ can not be with monolithic form as flame resistant glass, can only be as the substrate of composite fireproof glass, not only weight per unit area is big, inconvenience transportation and scale operation, and not ultraviolet resistance irradiation, aging resistance is poor.Low-expansion boron silicate monolithic flame resistant glass is one-time formed single-sheet fire-resistant glass, and is in light weight, softening temperature height, but temperature of fusion height, and because boracic needs special glass melter structure and special refractory materials, production cost height and complex process.Domestic physical-chemical tempering single-sheet fire-resistant glass, normally adopt common sodium calcium silicon float glass, in specific annealing furnace, spray chemical tempering reagent, by the physical-chemical tempering, reach the fp purpose with the intensity that improves glass itself, the thermal expansivity of glass itself and softening temperature all do not have change, can't be by the fire prevention time of international flame resistant glass standard-required.
Summary of the invention
Purpose of the present invention promptly is to propose a kind of float glass process sodium calcium silicon series fire-proofing glass, makes it have good fire resistance properties and better chemical stability, can use floating process to carry out large-scale industrial production.
Float glass process sodium calcium silicon series fire-proofing glass proposed by the invention, by weight percentage, it comprises following ingredients:
SiO
2 67～75％ Al
2O
3 1.5～4％ CaO 5～10％
MgO 0.5～3％ R
2O 3～13％ ZrO
2 0.2～2.5％
BaO 2～6％ SrO 1～6％。
The glass that glass ingredient of the present invention is founded is 63.98 * 10 at 100 ℃～400 ℃ thermal expansivity
-7/ ℃～71.23 * 10
-7/ ℃, (viscosity is 10 to Qi Lite
7.6DPas) softening temperature is more than 800 ℃.Viscosity is 10
2Temperature during dPas is below 1550 ℃.
Float glass process of the present invention is produced the composition of flame resistant glass, is sodium, calcium-silicate glass, is to do some composition adjustment on the basis of common float glass composition: replace a part of MgO to increase the density and hardness of glass with CaO; The Sr that adds
2+, Ba
3+, Zr
4+Plasma is in cyberspace, and silicon-oxy tetrahedron is on every side worked the effect of gathering, and increases the compactness of structure, impels the coefficient of expansion to descend, and softening temperature increases, and guarantees that with this glass has resistivity against fire in the regular hour, thereby reaches the fp purpose.Through to consistent after the adjustment of common float glass component portion, do not influence with floating process and carry out moulding production with common float glass system composition.The glasswork thermal expansivity of being founded by this one-tenth branch is low, and the softening temperature height has good fire resistance properties and better chemical stability.The organic combination of decoration, environment purification and safety performance can be protected user's life, property safety effectively
The selected raw material of the present invention removes ZrO
2, SrO, BaO select industrial chemicals for use, all the other all adopt the ore powder.For the ease of fusing, improve the glass metal refining quality, the sandstone powder particles and the Feldspar Powder material granularity upper limit are respectively 0.63mm, 0.51mm, and the granularity lower limit does not have particular requirement; All the other raw materials are similar to common float glass requirement, and the chemical constitution of various raw materials, granularity, moisture should satisfy the needs that float glass process is produced; Used industrial chemicals does not have particular requirement.
When preferred glass is formed, consider various compositions are in the preferred range, for ease of fusing, clarification, preferred First Principles makes the clarifying temp of this glass below 1550 ℃; The viscosity of this glass composition should satisfy the needs that the float glass process moulding is produced, and produces needs for satisfying, and it is 10 that preferred second principle is adjusted to glass viscosity with each composition
4Temperature during dPas is below 1150 ℃; Another principle of considering moulding prevents the crystallization in the moulding process for adjusting the recrystallization temperature and the performance of component; Preferred the 3rd principle is 69.13 * 10-7/ ℃ for thermal expansivity in the time of 0～400 ℃.Thus, the content of each moiety of float glass process production flame resistant glass of the present invention is adjusted in the following manner.
[SiO
2]
SiO
2Be the necessary composition of soda-lime-silica glass, in the glass skeleton, account for the composition of leading role.SiO
2Content generally is no more than 75%; Surpass this value, the fusing of component and the clarification of glass just require higher temperature.Be lower than at 66% o'clock, the softening temperature of glass is low excessively, and its content is chosen between 68～75%.
[Al
2O
3]
Al
2O
3Be the effective constituent that improves glass transition temperature and improve chemical stability, in certain content range can and SiO
2Simultaneously as glass-former.According to the aluminium anomalous effect, adjust Al
2O
3Content can change the thermal property and the chemical property of glass.Controlling its content can increase the anti-chemical capacity and the softening point temperature of glass.Add a spot of Al
2O
3Can improve its increased devitrification resistance and water tolerance effectively.Al
2O
3Therefore if during less than 1.5%, then its effect is too small, is being necessary more than 15% at least, when its consumption 5% when above, the fusing of glass and clarification be difficulty, unfavorable to float glass process production, its content is chosen in 2～4%.
[CaO]
CaO can not only improve the pre-arcing characterisitics of single-sheet fire-resistant glass component effectively, and can improve the softening temperature of glass effectively, can effectively reduce fusing, clarifying temp simultaneously.CaO content is lower than at 6% o'clock, DeGrain, so content is selected in more than 6%.Content is higher than at 11% o'clock, can increase glass metal viscosity under the high temperature, is unfavorable for the fusing of flame resistant glass component, and the crystallization property of glass ingredient is increased, so content is not higher than 11%, its content is chosen in 6%～10%.
[MgO]
MgO can not only improve the pre-arcing characterisitics of single-sheet fire-resistant glass admixtion effectively, and can improve the softening temperature of glass effectively, improves the coefficient of expansion of glass body.MgO content is lower than at 0.8% o'clock, DeGrain, and tendency towards devitrification increases by 4.5% the time when MgO content surpasses.Therefore content is preferably 0.8%～2.5%.
[CaO]+[MgO]
CaO and MgO have its best amount ranges, but it is also had best service requirements with measuring, and are to improve to melt and chemical stability, so must be the crystallization of feed glass more than 6.8% with amount, and it must be controlled at below the 13 weight % with measuring.
[R
2O](R＝Na，K)
Na
2O, K
2O is a solubility promoter, has the effect that reduces fusion, clarifying temp, simultaneously Na
2O and K
2The interaction of O can improve the processability of glass effectively, reduces the tendency towards devitrification of glass body significantly.When it does not have effect during with quantity not sufficient 1.5, therefore preferably more than 1.5%.Yet, even R
2O adds slightly also can make the softening temperature of glass reduce greatly, the aggressiveness of refractory brick is increased, so the two should be controlled at 7%～13% with amount.
[ZrO
2]
ZrO
2Can improve the softening temperature of glass effectively, and can improve the water tolerance of glass, increase thereupon but increase temperature of fusion with content.ZrO
2With Al
2O
3Equally influential to physical and chemical performances such as the chemical stability of glass, thermostability, physical strengths.Content is 02%～2.0%.
[BaO]
BaO can improve the melting properties of glass effectively, reduces the thermal expansivity of glass body, but its consumption surpasses 5%, causes raw materials cost to increase, and simultaneously refractory corrosion is increased the weight of.The present invention selects its content 3%～5%.
[SrO]
SrO can improve the melting properties of glass effectively, is the effective constituent that improves glass softening point simultaneously.Its consumption is too high, can cause raw materials cost to increase, and increase the tendency towards devitrification of glass, and the present invention selects its content 2%～4%.
[BaO]+[SrO]
Except control BaO, SrO content separately, BaO+SrO also must strictly control in composition of the present invention, otherwise influential to fusing and glass properties.It is 5%～9% that the present invention selects BaO+SrO content.
Embodiment
The present invention is described further (composition is all by weight percentage) in conjunction with following example:
Embodiment 1:
Following component concentration is all represented with the weight percent form.
Silica sand 62.9% feldspar 8.91% Wingdale 11.74% rhombspar 9.05%
Soda ash 3.8% saltcake 1.04% fluorite 1.2% zircon sand 1.52%
K
2CO
3 7.48％ BaCO
3 6.5％ SrCO
3 2.88％ C 0.05％
Surplus is the impurity brought into of raw mineral materials or the finings of adding.
According to the composition of this glass, adopt the glass fining agent of sandstone, rhombspar, Wingdale, soda ash, barium salt, strontium salt, aluminum oxide, lithium salts, boric acid, zircon sand, sylvite and suitable proportion to make glass batch.Use saltcake+C powder or NaCl+KNO as finings.Drop into crucible with being in harmonious proportion good a collection of admixtion, selected charge temperature is 1400 ℃, and this temperature is insulation half an hour down, is warming up to 1520 ℃ of insulations 2 hours then, comes out of the stove and waters the rectangularity fritter, goes into 600 ℃ of annealing of retort furnace immediately, allows its slow cooling.
Embodiment 2
Following component concentration is all represented with the weight percent form.
Silica sand 60.5% feldspar 10.3% Wingdale 10.6% rhombspar 10.5%
Soda ash 33% saltcake 1.04% fluorite 1.2% zircon sand 1.4%
K
2CO
3 6.9％ BaCO
3 5.4％ SrCO
3 3.6％ C 0.05％
Surplus is the impurity brought into of raw mineral materials or the finings of adding.
According to the composition of this glass, adopt the glass fining agent of sandstone, rhombspar, Wingdale, soda ash, barium salt, strontium salt, aluminum oxide, lithium salts, boric acid, zircon sand, sylvite and suitable proportion to make glass batch.Use saltcake+C powder or NaCl+KNO as finings.Drop into crucible with being in harmonious proportion good a collection of admixtion, selected charge temperature is 1400 ℃, and this temperature is insulation half an hour down, is warming up to 1520 ℃ of insulations 2 hours then, comes out of the stove and waters the rectangularity fritter, goes into 600 ℃ of annealing of retort furnace immediately, allows its slow cooling.
The glass sample that embodiment 1 and embodiment 2 obtained carries out the mensuration of transition point, softening temperature, thermal expansivity, and data are as follows:
| The coefficient of expansion (10 -7/℃) | ||
| Temperature (℃) | Embodiment 1 | Embodiment 2 |
| α 400 | 71.23×10 -7/℃ | 71.20×10 -7/℃ |
| α 300 | 69.30×10 -7/℃ | 68.96×10 -7/℃ |
| α 200 | 67.13×10 -7/℃ | 68.23×10 -7/℃ |
| α 100 | 63.98×10 -7/℃ | 64.68×10 -7/℃ |
| Transition temperature (Tg) | 613℃ | 614℃ |
| Softening point temperature (10 7.6dPa.s) | 8413℃ | 8393℃ |
| Viscosity is 10 2The temperature of dPa.s | 1540℃ | 1538℃ |
Claims (5)
1. sodium calcium silicon series fire-proofing glass, it is characterized in that: by weight percentage, it comprises following composition:
SiO
2 67～75％ Al
2O
3 1.5～4％ CaO 5～10％
MgO 0.5～3％ R
2O 3～13％ ZrO
2 0.2～2.5％
BaO 2～6％ SrO 1～6％， CaO+MgO 6.8～13％，
BaO+SrO 5%～9%, wherein, and R=Na, K.
2. sodium calcium silicon series fire-proofing glass according to claim 1 is characterized in that: its thermal expansivity at 100 ℃～400 ℃ is 63.98 * 10
-7/ ℃～71.23 * 10
-7/ ℃.
3. sodium calcium silicon series fire-proofing glass according to claim 1 is characterized in that: viscosity is 10
7.6Softening temperature during dPa.s is greater than 800 ℃.
4. sodium calcium silicon series fire-proofing glass according to claim 1 is characterized in that: in the employed raw material, the sandstone powder particles and the Feldspar Powder material granularity upper limit are respectively 0.63mm, 0.51mm.
5. sodium calcium silicon series fire-proofing glass according to claim 1 is characterized in that: its viscosity is 10
2Temperature during dPa.s is below 1550 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005101072099A CN100366560C (en) | 2005-11-25 | 2005-11-25 | Sodium calcium silicon series fire-proofing glass |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005101072099A CN100366560C (en) | 2005-11-25 | 2005-11-25 | Sodium calcium silicon series fire-proofing glass |
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| Publication Number | Publication Date |
|---|---|
| CN1792919A CN1792919A (en) | 2006-06-28 |
| CN100366560C true CN100366560C (en) | 2008-02-06 |
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ID=36804587
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005101072099A Active CN100366560C (en) | 2005-11-25 | 2005-11-25 | Sodium calcium silicon series fire-proofing glass |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10683231B2 (en) | 2015-03-26 | 2020-06-16 | Pilkington Group Limited | Glasses |
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| CN109052940A (en) * | 2018-10-30 | 2018-12-21 | 湛江市百德玻璃制品有限公司 | A kind of heat-insulated compound glass material and preparation method thereof |
| CN109824267A (en) * | 2019-03-05 | 2019-05-31 | 安徽千辉节能玻璃科技有限公司 | A kind of flame resistant glass and preparation method thereof |
| CN110922051A (en) * | 2019-12-25 | 2020-03-27 | 中建材蚌埠玻璃工业设计研究院有限公司 | High-softening-point glass for thin-film solar cell |
| CN114195381B (en) * | 2021-12-16 | 2023-11-24 | 清远南玻节能新材料有限公司 | Soda-lime silicate glass, reinforced glass, and preparation methods and applications thereof |
| CN116903265B (en) * | 2023-09-12 | 2023-11-28 | 山东蓝玻玻璃科技有限公司 | Preparation method of high-boron silicon fireproof glass |
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|---|---|---|---|---|
| CN1188746A (en) * | 1994-10-13 | 1998-07-29 | 圣戈班玻璃制造公司 | Composite of silicon-sodium-calcium glass and its use |
| US5858897A (en) * | 1996-03-14 | 1999-01-12 | Asahi Glass Company Ltd. | Glass composition for a substrate |
| CN1214029A (en) * | 1996-11-21 | 1999-04-14 | 日本板硝子株式会社 | Fireproof flat glass |
| CN1226878A (en) * | 1997-03-13 | 1999-08-25 | 圣戈班玻璃制造公司 | Soda-lime-silica glass compositions and applications |
| JP2002293567A (en) * | 2001-04-02 | 2002-10-09 | Nippon Electric Glass Co Ltd | Glass substrate for flat panel display |
| WO2004099096A2 (en) * | 2003-05-07 | 2004-11-18 | Saint-Gobain Glass France | Silico-sodo-calcic glass composition for the production of substrates. |
-
2005
- 2005-11-25 CN CNB2005101072099A patent/CN100366560C/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1188746A (en) * | 1994-10-13 | 1998-07-29 | 圣戈班玻璃制造公司 | Composite of silicon-sodium-calcium glass and its use |
| US5858897A (en) * | 1996-03-14 | 1999-01-12 | Asahi Glass Company Ltd. | Glass composition for a substrate |
| CN1214029A (en) * | 1996-11-21 | 1999-04-14 | 日本板硝子株式会社 | Fireproof flat glass |
| CN1226878A (en) * | 1997-03-13 | 1999-08-25 | 圣戈班玻璃制造公司 | Soda-lime-silica glass compositions and applications |
| JP2002293567A (en) * | 2001-04-02 | 2002-10-09 | Nippon Electric Glass Co Ltd | Glass substrate for flat panel display |
| WO2004099096A2 (en) * | 2003-05-07 | 2004-11-18 | Saint-Gobain Glass France | Silico-sodo-calcic glass composition for the production of substrates. |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10683231B2 (en) | 2015-03-26 | 2020-06-16 | Pilkington Group Limited | Glasses |
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| Publication number | Publication date |
|---|---|
| CN1792919A (en) | 2006-06-28 |
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| 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 | ||
| EE01 | Entry into force of recordation of patent licensing contract |
Assignee: Luoyang Luobo Glass Fiber Co., Ltd. Assignor: Luoyang Float Process Glass Group. Co., Ltd. Contract fulfillment period: 2008.5.20 to 2014.5.20 contract change Contract record no.: 2009410000144 Denomination of invention: Sodium calcium silicon series fire-proofing glass Granted publication date: 20080206 License type: Exclusive license Record date: 2009.5.19 |
|
| LIC | Patent licence contract for exploitation submitted for record |
Free format text: EXCLUSIVE LICENSE; TIME LIMIT OF IMPLEMENTING CONTACT: 2008.5.20 TO 2014.5.20; CHANGE OF CONTRACT Name of requester: LUOYANG LUOBO FIBERGLASS CO., LTD. Effective date: 20090519 |