CN106830669A - One kind is without arsenic combined oxidation fining agent - Google Patents
One kind is without arsenic combined oxidation fining agent Download PDFInfo
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- CN106830669A CN106830669A CN201710013151.4A CN201710013151A CN106830669A CN 106830669 A CN106830669 A CN 106830669A CN 201710013151 A CN201710013151 A CN 201710013151A CN 106830669 A CN106830669 A CN 106830669A
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- Prior art keywords
- fining agent
- combined oxidation
- calcium
- glass
- sodium
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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
- C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
- C03C1/004—Refining agents
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B13/00—Rolling molten glass, i.e. where the molten glass is shaped by rolling
-
- 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
- C03C4/00—Compositions for glass with special properties
- C03C4/005—Compositions for glass with special properties for opaline glass
-
- 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
- C03C4/00—Compositions for glass with special properties
- C03C4/0092—Compositions for glass with special properties for glass with improved high visible transmittance, e.g. extra-clear glass
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Glass Compositions (AREA)
- Printing Plates And Materials Therefor (AREA)
Abstract
The invention discloses one kind without arsenic combined oxidation fining agent, according to percentage by weight, component constitutes as follows：Sb2O39.5wt%~15.0 wt%, Na2SO433.0 wt%~49.0 wt%, NaNO340.0wt%~55 wt%, Fe2O3＜ 0.006 wt%, NaCl≤0.35 wt%.The method have the characteristics that：The fining agent that low ferrisodium calcium-silicate very white rolled glass is used is redesigned and is combined into a kind of brand-new composite components, reduction feeding link is the advantage is that, the batch weighing time is saved, is saved manpower, mitigate labor strength, saved outside cost, the prior material that is the reduction of flies upward pollution on the environment, reduces the hygroscopy of material, improves the chemical stability of fining agent.
Description
Technical field
It is specifically a kind of multiple without arsenic the present invention relates to low ferrisodium calcium-silicate very white rolled glass production technical field
Close oxidation fining agent.
Background technology
Ultrawhite（Low iron）Sodium-calcium-silicate rolled glass is widely used in solar energy industry, wherein, influence ultrawhite（Low iron）
The principal element of sodium-calcium-silicate rolled glass transmitance and whiteness is ferriferous oxide form and content in glass, is contained in glass
Some ferriferous oxides mainly have ferrous oxide（FeO）And iron oxide（Fe2O3）Two kinds of forms, ferrous oxide（FeO）Glass can
Into pale bluish green, iron oxide（Fe2O3）Glass can be made into chartreuse, the change between them is also reversible, i.e. Fe2O3
The O of 2FeO+1/22, under the high temperature conditions and in the presence of having reducing agent, ferrous oxide content is dominant, makes glass
Display pale bluish green；In the presence of having oxidant in batch, then batch is more to form Fe2O3 in fusion process,
Make glass display yellow green, low price iron（Fe2+）Colorability be high price iron（Fe3+）15 times of colorability, its presence is tight
The transmitance of glass is affected again.
When generally producing ultrawhite sodium-calcium-silicate rolled glass in addition to the special low raw material of ferriferous oxide content is selected, in production
During, in order to improve the whiteness and transmitance of glass it is necessary to Fe2+ oxidations are become into Fe3+.In order to produce oxidizing atmosphere and add
Fast glass metal clarification, will be in frit（Batch）Middle addition is a certain amount of can to play oxidation, and clarification can be played again
The oxidation fining agent of effect, the fining agent commonly used at present has oxidation antimony powder（Sb2O3）, sodium pyroantimonate（Na[Sb(OH)6]）, containing arsenic
Compound clarifier etc., but in order that Sb2O3Or Na [Sb (OH)6] maximum effect is played in glass metal clarification, and make glass
Middle Fe2+ is oxidized to Fe3+, also to be used cooperatively with sodium nitrate and saltcake, at present, existing fining agent do not have with sodium nitrate,
Saltcake is engaged, therefore effect is poor, existing upper material process is numerous and diverse in addition, the batch weighing time long, labor intensive, workman
Labour intensity is big, high cost, and the easy deliquescence of material, and the chemical stability of fining agent is poor, and then also results in and produce
Glass whiteness and transmitance difference defect, it is necessary to be improved.
The content of the invention
The invention aims to solve it is of the prior art in clarifying effect it is poor, upper material process is numerous and diverse, work is strong
Spend big, dispensing time long, the easy deliquescence of fining agent, the defect of poor chemical stability, there is provided a kind of to come without arsenic combined oxidation fining agent
Solve the above problems.
The invention discloses one kind without arsenic combined oxidation fining agent, according to percentage by weight, component constitutes as follows：Sb2O3
9.5wt%~15.0 wt%, Na2SO433.0 wt%~49.0 wt%, NaNO340.0wt%~55 wt%, Fe2O3＜ 0.006
wt%、NaCl ≤0.35 wt%。
Preferably, the invention discloses one kind without arsenic combined oxidation fining agent, according to mass percent, by following raw material
It is prepared from：Antimony sesquioxide powder 9.52wt%~15.20 wt%, wt%~52.0 wt% of saltcake 34.2, sodium nitrate
40.2wt%~56 wt%, the wt% of water ＜ 1.0.
Preferably, preparing ultrawhite sodium calcium silicic acid without arsenic combined oxidation fining agent using above-mentioned the invention also discloses one kind
The method of salt rolled glass, comprises the following steps that：
（1）, by saltcake, sodium nitrate, antimony powder be added in mixer stir mixing, then using packaging bag hermetic package, prepare
Obtain standby without arsenic combined oxidation fining agent；
（2）, weigh silica sand, soda ash, dolomite, calcite, aluminium powder, be added in mixer without arsenic combined oxidation fining agent and carry out
Mixing, obtains batch；
（3）, batch is added to using batch charger high temperature melting into glass melts is carried out in melting furnaces；
（4）, calendering formation carried out to glass melts using calender；
（5）, anneal in the annealing kiln after prepare ultrawhite sodium-calcium-silicate rolled glass.
Preferably, described step（2）In, according to mass percent, each raw material accounting is as follows：It is silica sand 59.68%, pure
Alkali 16.7%, dolomite 14.92%, calcite 6.14%, aluminium powder 1.22%, without arsenic combined oxidation fining agent 1.34%.
Preferably, described step（3）In, described fusion temperature is 1350 DEG C~1580 DEG C.
Preferably, described step（4）In, described forming temperature is 1075 DEG C~1085 DEG C, described calendering speed
It is 290~460m/h to spend.
Preferably, described step（5）In, described annealing temperature is 600 DEG C~70 DEG C, and annealing time is 20~40
Minute.
The present invention has advantages below compared to existing technology：
Ultrawhite sodium-calcium-silicate rolled glass obtained by the present invention, by adding without arsenic combined oxidation fining agent, saltcake and nitre
Sour sodium is used cooperatively with antimony sesquioxide powder, solves the problems, such as to fly when sodium nitrate, the deliquescence of saltcake and antimony sesquioxide powder feeding
Raise and problem is polluted to environment, make the chemical stability of antimony oxide, sodium nitrate, saltcake more preferable, and glass can be made
Middle Fe2+ is oxidized to Fe3+, clarifying effect more preferably, therefore obtained ultrawhite sodium-calcium-silicate rolled glass whiteness and transmitance
It is relatively good, and subtract without feeding of arsenic compound clarifier during production prepares ultrawhite sodium-calcium-silicate rolled glass
Program is weighed less, the dispensing time is saved, and is compared saving manpower, is reduced labor strength, and obtains combined oxidation in preparation
When fining agent is standby, using packaging bag hermetic package, effectively avoid the defect that saltcake and sodium nitrate occur deliquescence, saltcake and
Sodium nitrate is not susceptible to deliquescence, also just effectively avoids hard because forming after sodium nitrate, saltcake water suction occur deliquescence or be dried
The defect of block, therefore more convenient, the batch weighing precision that feeds is more accurate, and it is not susceptible to weighing accident, more conducively ultrawhite
The raising of the whiteness and transmitance of sodium-calcium-silicate rolled glass.
Specific embodiment
Embodiments of the invention are elaborated below, the present embodiment is carried out under premised on technical solution of the present invention
Implement, give detailed implementation method and specific operating process, but protection scope of the present invention is not limited to following implementations
Example.
The invention discloses one kind without arsenic combined oxidation fining agent, according to percentage by weight, component constitutes as follows：Sb2O3
9.5wt%~15.0 wt%, Na2SO433.0 wt%~49.0 wt%, NaNO340.0wt%~55 wt%, Fe2O3＜ 0.006
wt%、NaCl ≤0.35 wt%。
Preferably, the invention discloses one kind without arsenic combined oxidation fining agent, according to mass percent, by following raw material
It is prepared from：Antimony sesquioxide powder 9.52wt%~15.20 wt%, wt%~52.0 wt% of saltcake 34.2, sodium nitrate
40.2wt%~56 wt%, the wt% of water ＜ 1.0.
Preferably, preparing ultrawhite sodium calcium silicic acid without arsenic combined oxidation fining agent using above-mentioned the invention also discloses one kind
The method of salt rolled glass, comprises the following steps that：
（1）, by saltcake, sodium nitrate, antimony powder be added in mixer stir mixing, then using packaging bag hermetic package, prepare
Obtain standby without arsenic combined oxidation fining agent；
（2）, weigh silica sand, soda ash, dolomite, calcite, aluminium powder, be added in mixer without arsenic combined oxidation fining agent and carry out
Mixing, obtains batch；
（3）, batch is added to using batch charger high temperature melting into glass melts is carried out in melting furnaces；
（4）, calendering formation carried out to glass melts using calender；
（5）, anneal in the annealing kiln after prepare ultrawhite sodium-calcium-silicate rolled glass.
Preferably, described step（2）In, according to mass percent, each raw material accounting is as follows：It is silica sand 59.68%, pure
Alkali 16.7%, dolomite 14.92%, calcite 6.14%, aluminium powder 1.22%, without arsenic combined oxidation fining agent 1.34%.
Preferably, described step（3）In, described fusion temperature is 1350 DEG C~1580 DEG C.
Preferably, described step（4）In, described forming temperature is 1075 DEG C~1085 DEG C, described calendering speed
It is 290~460m/h to spend.
Preferably, described step（5）In, described annealing temperature is 600 DEG C~70 DEG C, and annealing time is 20~40
Minute.
Embodiment 1
The invention discloses one kind without arsenic combined oxidation fining agent, according to percentage by weight, component constitutes as follows：Sb2O3
10.82 wt%、Na2SO4 33.90 wt%、NaNO3 54.51 wt%、Fe2O3 0.005 wt%、NaCl 0.35 wt%。
The invention discloses one kind without arsenic combined oxidation fining agent, according to mass percent, it is prepared from the following materials：
Antimony sesquioxide powder 10.87wt%, the wt% of saltcake 34.24, sodium nitrate 54.89wt%.
Preferably, preparing ultrawhite sodium calcium silicic acid without arsenic combined oxidation fining agent using above-mentioned the invention also discloses one kind
The method of salt rolled glass, comprises the following steps that：
（1）, by saltcake, sodium nitrate, antimony powder be added in mixer stir mixing, then using packaging bag hermetic package, prepare
Obtain standby without arsenic combined oxidation fining agent；
（2）, weigh silica sand, soda ash, dolomite, calcite, aluminium powder, be added in mixer without arsenic combined oxidation fining agent and carry out
Mixing, obtains batch；
（3）, batch is added to using batch charger high temperature melting into glass melts is carried out in melting furnaces；
（4）, calendering formation carried out to glass melts using calender；
（5）, anneal in the annealing kiln after prepare ultrawhite sodium-calcium-silicate rolled glass.
Described step（2）In, according to mass percent, each raw material accounting is as follows：It is silica sand 59.68%, soda ash 16.7%, white
Marble 14.92%, calcite 6.14%, aluminium powder 1.22%, without arsenic combined oxidation fining agent 1.34%.
Described step（3）In, described fusion temperature is 1350 DEG C~1580 DEG C.
Described step（4）In, described rolling velocity is 290m/h, and described forming temperature is 1075 DEG C.
Described step（5）In, described annealing temperature is 600 DEG C~70 DEG C, and annealing time is 40 minutes.
Embodiment 2
The invention discloses one kind without arsenic combined oxidation fining agent, according to percentage by weight, component constitutes as follows：Sb2O3
11.19wt%、Na2SO4 42.39 wt%、NaNO345.66wt%、Fe2O3 0.004 wt%、NaCl 0.35 wt%。
The invention discloses one kind without arsenic combined oxidation fining agent, according to mass percent, it is prepared from the following materials：
Antimony sesquioxide powder 11.25wt%, saltcake 42.82wt%, sodium nitrate 45.98wt%, the wt% of water 0.5.
The invention also discloses one kind ultrawhite sodium-calcium-silicate calendering glass is prepared using above-mentioned without arsenic combined oxidation fining agent
The method of glass, comprises the following steps that：
（1）, by saltcake, sodium nitrate, antimony powder be added in mixer stir mixing, then using packaging bag hermetic package, prepare
Obtain standby without arsenic combined oxidation fining agent；
（2）, weigh silica sand, soda ash, dolomite, calcite, aluminium powder, be added in mixer without arsenic combined oxidation fining agent and carry out
Mixing, obtains batch；
（3）, batch is added to using batch charger high temperature melting into glass melts is carried out in melting furnaces；
（4）, calendering formation carried out to glass melts using calender；
（5）, anneal in the annealing kiln after prepare ultrawhite sodium-calcium-silicate rolled glass.
Described step（2）In, according to mass percent, each raw material accounting is as follows：It is silica sand 59.68%, soda ash 16.7%, white
Marble 14.92%, calcite 6.14%, aluminium powder 1.22%, without arsenic combined oxidation fining agent 1.34%.
Described step（3）In, described fusion temperature is 1350 DEG C~1580 DEG C.
Described step（4）In, described rolling velocity is 375m/h, and described forming temperature is 1078 DEG C.
Described step（5）In, described annealing temperature is 610 DEG C~70 DEG C, and annealing time is 30 minutes.
Embodiment 3
The invention discloses one kind without arsenic combined oxidation fining agent, according to percentage by weight, component constitutes as follows：Sb2O3
11.44 wt%、Na2SO4 41.55 wt%、NaNO3 46.20 wt%、Fe2O3 0.003 wt%、NaCl 0.35 wt%。
The invention discloses one kind without arsenic combined oxidation fining agent, according to mass percent, it is prepared from the following materials：
Antimony sesquioxide powder 11.50wt%, saltcake 41.97wt%, sodium nitrate 46.53wt%, the wt% of water 0.5.
The invention also discloses one kind ultrawhite sodium-calcium-silicate calendering glass is prepared using above-mentioned without arsenic combined oxidation fining agent
The method of glass, comprises the following steps that：
（1）, by saltcake, sodium nitrate, antimony powder be added in mixer stir mixing, then using packaging bag hermetic package, prepare
Obtain standby without arsenic combined oxidation fining agent；
（2）, weigh silica sand, soda ash, dolomite, calcite, aluminium powder, be added in mixer without arsenic combined oxidation fining agent and carry out
Mixing, obtains batch；
（3）, batch is added to using batch charger high temperature melting into glass melts is carried out in melting furnaces；
（4）, calendering formation carried out to glass melts using calender；
（5）, anneal in the annealing kiln after prepare ultrawhite sodium-calcium-silicate rolled glass.
Described step（2）In, according to mass percent, each raw material accounting is as follows：It is silica sand 59.68%, soda ash 16.7%, white
Marble 14.92%, calcite 6.14%, aluminium powder 1.22%, without arsenic combined oxidation fining agent 1.34%.
Described step（3）In, described fusion temperature is 1350 DEG C~1580 DEG C.
Described step（4）In, described rolling velocity is 460m/h, and described forming temperature is 1080 DEG C.
Described step（5）In, described annealing temperature is 580 DEG C~70 DEG C, and annealing time is 25 minutes.
General principle of the invention, principal character and advantages of the present invention has been shown and described above.The technology of the industry
Personnel it should be appreciated that the present invention is not limited to the above embodiments, the simply present invention described in above-described embodiment and specification
Principle, various changes and modifications of the present invention are possible without departing from the spirit and scope of the present invention, these change and
Improvement is both fallen within the range of claimed invention.The protection domain of application claims by appending claims and its
Equivalent is defined.
Claims (7)
1. one kind is without arsenic combined oxidation fining agent, it is characterised in that：According to percentage by weight, component constitutes as follows：Sb2O3
9.5wt%~15.0 wt%, Na2SO433.0 wt%~49.0 wt%, NaNO340.0wt%~55 wt%, Fe2O3＜ 0.006
wt%、NaCl ≤0.35 wt%。
2. one kind according to claim 1 is without arsenic combined oxidation fining agent, it is characterised in that：According to mass percent, by
Following raw material is prepared from：Antimony sesquioxide powder 9.52wt%~15.20 wt%, wt%~52.0 wt% of saltcake 34.2, nitric acid
Sodium 40.2wt%~56 wt%, the wt% of water ＜ 1.0.
3. a kind of use claim 1-2 is any described prepares ultrawhite sodium-calcium-silicate calendering glass without arsenic combined oxidation fining agent
The method of glass, it is characterised in that：Comprise the following steps that：
（1）, by saltcake, sodium nitrate, antimony powder be added in mixer stir mixing, then using packaging bag hermetic package, prepare
Obtain standby without arsenic combined oxidation fining agent；
（2）, weigh silica sand, soda ash, dolomite, calcite, aluminium powder, be added in mixer without arsenic combined oxidation fining agent and carry out
Mixing, obtains batch；
（3）, batch is added to using batch charger high temperature melting into glass melts is carried out in melting furnaces；
（4）, calendering formation carried out to glass melts using calender；
（5）, anneal in the annealing kiln after prepare ultrawhite sodium-calcium-silicate rolled glass.
4. a kind of method for preparing ultrawhite sodium-calcium-silicate rolled glass according to claim 3, it is characterised in that：It is described
The step of（2）In, according to mass percent, each raw material accounting is as follows：Silica sand 59.68%, soda ash 16.7%, dolomite 14.92%,
Calcite 6.14%, aluminium powder 1.22%, without arsenic combined oxidation fining agent 1.34%.
5. a kind of method for preparing ultrawhite sodium-calcium-silicate rolled glass according to claim 3, it is characterised in that：It is described
The step of（3）In, described fusion temperature is 1350 DEG C~1580 DEG C.
6. a kind of method for preparing ultrawhite sodium-calcium-silicate rolled glass according to claim 3, it is characterised in that：It is described
The step of（4）In, described forming temperature is 1075 DEG C~1085 DEG C, and described rolling velocity is 290~460m/h.
7. a kind of method for preparing ultrawhite sodium-calcium-silicate rolled glass according to claim 3, it is characterised in that：It is described
The step of（5）In, described annealing temperature is 600 DEG C~70 DEG C, and annealing time is 20~40 minutes.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710013151.4A CN106830669A (en) | 2017-01-09 | 2017-01-09 | One kind is without arsenic combined oxidation fining agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710013151.4A CN106830669A (en) | 2017-01-09 | 2017-01-09 | One kind is without arsenic combined oxidation fining agent |
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| Publication Number | Publication Date |
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| CN106830669A true CN106830669A (en) | 2017-06-13 |
Family
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
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| CN201710013151.4A Pending CN106830669A (en) | 2017-01-09 | 2017-01-09 | One kind is without arsenic combined oxidation fining agent |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107162418A (en) * | 2017-06-29 | 2017-09-15 | 合肥利裕泰玻璃制品有限公司 | A kind of glass and its production technology |
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| CN102976587A (en) * | 2012-12-22 | 2013-03-20 | 蚌埠玻璃工业设计研究院 | Clarification method of alumina silicate glass melts |
| CN105960381A (en) * | 2014-02-06 | 2016-09-21 | 旭硝子株式会社 | Method for producing granulated body and method for producing glass article |
| CN106007362A (en) * | 2016-03-05 | 2016-10-12 | 深圳市久通锑业化工有限公司 | Low-iron soda-lime silicate ultra-white calendered photovoltaic glass bubble-removing auxiliary agent and glass preparation method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1522977A (en) * | 2002-12-03 | 2004-08-25 | Ф�ز������쳧 | Preferably pb-free and as-free optical glasses with tg less than or equal to 500 degree centigrade |
| CN101913769A (en) * | 2010-08-03 | 2010-12-15 | 忻州鑫洋玻璃制品有限公司 | Arsenic-free glass bottle |
| CN102976587A (en) * | 2012-12-22 | 2013-03-20 | 蚌埠玻璃工业设计研究院 | Clarification method of alumina silicate glass melts |
| CN105960381A (en) * | 2014-02-06 | 2016-09-21 | 旭硝子株式会社 | Method for producing granulated body and method for producing glass article |
| CN106007362A (en) * | 2016-03-05 | 2016-10-12 | 深圳市久通锑业化工有限公司 | Low-iron soda-lime silicate ultra-white calendered photovoltaic glass bubble-removing auxiliary agent and glass preparation method |
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| CN107162418A (en) * | 2017-06-29 | 2017-09-15 | 合肥利裕泰玻璃制品有限公司 | A kind of glass and its production technology |
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