CN106673425A - Frit suitable for producing alkali-free glass microfibers with centrifugation process - Google Patents

Frit suitable for producing alkali-free glass microfibers with centrifugation process Download PDF

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Publication number
CN106673425A
CN106673425A CN201710018522.8A CN201710018522A CN106673425A CN 106673425 A CN106673425 A CN 106673425A CN 201710018522 A CN201710018522 A CN 201710018522A CN 106673425 A CN106673425 A CN 106673425A
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China
Prior art keywords
glass
frit
alkali
free glass
centrifuging
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CN201710018522.8A
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Chinese (zh)
Inventor
孙立松
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Shanghai Zhi Zhen Mstar Technology Ltd
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Shanghai Zhi Zhen Mstar Technology Ltd
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Priority to CN201710018522.8A priority Critical patent/CN106673425A/en
Publication of CN106673425A publication Critical patent/CN106673425A/en
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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
    • C03C3/11—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen
    • C03C3/112—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen containing fluorine
    • C03C3/115—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen containing fluorine containing boron
    • C03C3/118—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen containing fluorine containing boron containing aluminium
    • 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
    • C03C13/00—Fibre or filament compositions

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Glass Compositions (AREA)

Abstract

The invention discloses frit suitable for producing alkali-free glass microfibers with a centrifugation process. The frit is characterized by being prepared from substances in percentage by mass as follows: 35%-54% of SiO2, 0.5%-7% of Al2O3, 0-1% of alkali metal oxide, 2%-25% of CaO, 0-12% of BaO, 10%-25% of B2O3, 0-8% of ZnO, 0-6% of MgO, 1%-3% of CaF2, 0-4% of MnO2 and 0-2% of CeO2 and Sb2O3. With adoption of the technical scheme, the frit has the advantage of being suitable for producing the alkali-free glass microfibers with the centrifugation process.

Description

Frit suitable for manufacturing centrifuging alkali-free glass microfibre
Technical field
The invention belongs to glass-fibre technology field, more particularly to it is a kind of suitable for manufacturing centrifuging alkali-free glass fibre Frit
Background technology
Alkali-free glass composition refers to aluminium borosilicate glass composition of the alkali metal oxide content less than 1%, leads in the world Often it is called E glass.It is initially to develop for electrical applications, but the range of application of E glass today is far beyond electric use On the way, a kind of general formulation is become.The mass percent general formulation of E glass is：
The making of E glass fibre has tank furnace method, crucible wire drawing method.The glass melting temperature of E glass more than 1580 DEG C, on crystallize 1135 DEG C of temperature of limit.Glass viscosity 103The temperature of Pa.s is more than 1300 DEG C.
And centrifuging glass microfiber has following performance requirement to glass used：
Have relatively low forming temperature, due to the restriction of centrifuging production centrifuge material used, it is desirable to 1000 DEG C with Lower work.In production technology when glass flows out from the wall aperture of centrifuge side exactly crucial moment of glass fibre molding, It is thus determined that glass viscosity 10-10 used by centrifuging glass fibre3The temperature of Pa.s scopes will be below 1300 DEG C.
In centrifuging production process, glass precursor solution is big with centrifuge contact area, and the time is long, therefore increased crystallize Probability, and the side wall hole diameter of centrifuge is less than 1mm, once producing crystallize in glass, is just easy to block aperture, therefore Devitrification of glass ceiling temperature will be below 1000 DEG C, and crystallize speed is slow.
Can obtain more than comprehensive：Centrifuging glass microfiber composition can not be produced with general E glass formulas, but Centrifuging glass microfiber fibre diameter is little, low production cost, has many applications to utilize, and centrifuging is directed to for this Technique needs to research and develop a kind of frit suitable for manufacturing centrifuging alkali-free glass microfibre.
The content of the invention
The technical problem to be solved is to provide a kind of glass suitable for manufacturing centrifuging alkali-free glass microfibre Glass material, to overcome the shortcomings of that prior art is present.
To solve above-mentioned technical problem, the present invention is adopted the following technical scheme that：
A kind of frit suitable for manufacturing centrifuging alkali-free glass microfibre, it is characterised in that including following quality hundred Divide the material of ratio：
In mass percent shared by each material, if SiO2Amount reduces, and the crystallize ceiling temperature of glass will be improved, and affects fine Dimension molding；If SiO2Amount increase, melt temperature and glass viscosity substantially rise, so as to the reduction of founding for affecting glass produces energy Power, this frit to reach centrifuging production be necessarily less than 54% into fine temperature requirement, be maintained between 40-50% and more manage Think.
Al2O3If increase, liquid glass temperature can be caused to rise, viscosity increases, in addition, Al2O3Addition can make material Intensity is improved, for make frit to reach centrifuging production into fine temperature requirement therefore Al2O3Scope be 0.5-7.0%, The scope of 1.0-6.0% is preferably, even more ideal.
Alkali metal oxide R in the present invention2O needs to introduce a large amount of B between 0-1%2O3Reduce the fusion temperature of glass With the forming temperature of glass；B is introduced in addition2O3The intensity and pliability of material will be improved, but if B in formula2O3Content Higher than 25%, the cost of raw material is substantially higher, is unfavorable for the popularization and application of material, therefore remains in the scope of 10-25% more Properly, the scope for being maintained at 10-20% is even more ideal.
The introducing of CaO is conducive to the thawing of glass, reduces the viscosity of glass precursor solution, also improves the intensity of fiber, but is more than The recrystallization temperature of glass is significantly improved after 25%, is unfavorable for the molding of fiber.So the content of CaO be maintained at 2-25% it Between, it is maintained at even more ideal between 10-20%.
MgO goes replacement CaO to improve the intensity of material, but can cause glass structure loose during more than 6%, lowers fiber strong Degree.The scope therefore remained between 0-6% is advisable, and is maintained at then even more ideal in the range of 1.5-4%.
The presence of BaO can reduce the viscosity of glass, increase material property, be conducive to the molding of fiber, improve the intensity of fiber with Uniformity.Can cause glass structure loose more than 12%, reduce fibre strength, the scope therefore remained between 0-12% is Preferably, it is maintained at then even more ideal in the range of 2-10%.
ZnO Zn in alkali-free formula2+In octahedral structure, there is presence just to improve the intensity of fiber, while also can carry The resistance to water of high microsteping, but the tendency towards devitrification of glass can be increased during more than 8%.The scope therefore remained between 0-8% is advisable, It is maintained at then even more ideal in the range of 2-7%.
Alkali metal oxide R20 includes Na2O、K2O and Li2O, therefore Na2O、K2O and Li2Total content (the i.e. Na of O2O+K2O+ Li2O) must be limited within 1%, this is the component requirements of alkali-free glass, due to Li2O molecules are less, preferably reduce The viscosity of glass, can also make glass structure fine and close, so to limit Na2O and K2Total content (the i.e. Na of O2O+K2O) it is less than 0.5%, equivalent to increase Li2The content of O, is conducive to increasing the intensity of fiber.Na2O+K2The content of O is limited and can improve raw material Cost, so Na2O+K2The content of O just can be with Na less than 0.5%2O+K2O+Li2The total content of O is less than 1%.
CaF2Effect mainly reduce the viscosity of glass, because alkali content is less than 1% in alkali-free glass, glass raw material It is difficult to found, content controls to be conducive to founding for glass in the scope of 1-3%, can also reduce the forming temperature of glass.Control exists 1.5-2.5% scopes are more satisfactory.
MnO2Presence have founding beneficial to glass, be also beneficial to improve fibre strength during fiberizing, cause more than 4% Fiberizing is difficult, reduces fibre strength, and the scope therefore remained between 0-4% is advisable, is maintained in the range of 1-3% then It is even more ideal.
CeO2And Sb2O3Effect mainly reduce the surface tension of glass, CeO2And Sb2O3Total content (i.e. CeO2+ Sb2O3) too little more than the viscosity and surface tension of glass after 2% make fiber formation process difficult.Low-fiber intensity drops. The scope therefore remained between 0-2% is advisable, and is maintained at then even more ideal in the range of 0-1.5%.
Other compositions, such as Fe2O3,TiO2Amount to less than 1% etc. mass percent, shadow is nearly free to glass Ringing, therefore produce raw material can adopt the natural material containing impurity.
The frit of the present invention adopts borosilicate glass, borosilicate glass nature to stablize, and makes fibre strength Height, and it is with low cost, wherein：Alkali metal is less than 1%, viscosity 103Temperature is below 1100 DEG C during Pa.s, devitrification of glass upper limit temperature Degree can be applied to manufacture centrifuging alkali-free glass microfibre below 1000 DEG C.
Specific embodiment
Embodiment 1
The frit suitable for manufacturing centrifuging alkali-free glass microfibre of the present embodiment, including following mass percent Material：
SiO245.9%；
Al2O32.5%；
Na2O+K2O 0.25%, Li2O 0.65%；
CaO 14%；
BaO 10%；
B2O311.5%；
ZnO 6%；
MgO 4%；
CaF22%；
MnO22%；
CeO2+Sb2O30.2%；
Other Fe2O3、TiO2Deng impurity, 1.0%.
The frit of above-mentioned composition measures following property during glass microfiber is prepared：
Fusion temperature：1433 DEG C,
Temperature during viscosity 100Pa.s：1070 DEG C,
Crystallize ceiling temperature：959 DEG C,
Density：2.84KG/M3,
1200 DEG C of surface tension：0.3073N/M,
It is used to make glass microfiber, obtained glass microfiber, with three mesh biology microscopes with the frit of the present embodiment Mirror is measured：4.6 μm of average diameter；Mean intensity is measured by following test method：850ml:
(1) 2-6 μm obtained in the centrifuging to be detected of glass microfiber sample 2g is weighed；
(2) load weighted glass microfiber sample is put in juice extractor, and adds 20 DEG C of distilled water of 600ml, then Start beating by motor switch；Model JYL-C020 of juice extractor, its major parameter is：Power：250W, capacity：1200ml, Maximum (top) speed is：16000rpm.The range of graduated cylinder is 1000ml；
(3) shutdown switch is pressed after being beaten 5 seconds；
(4) the conditioning cup of juice extractor is removed, glass microfiber slurry in cup is poured into indicating value graduated cylinder, and using a small amount of washiness Secondary (each 50-100ml, point 4-8 time) rinses conditioning cup, and the liquid after flushing is poured in indicating value graduated cylinder up to cylinder scale At 1000ml；
(5) 5 minutes are stood, observes layered portion corresponding scale of the fiber in graduated cylinder, the scale value is exactly that fiber is strong Degree.
Embodiment 2
The frit suitable for manufacturing centrifuging alkali-free glass microfibre of the present embodiment, including following mass percent Material：
SiO240.9%；
Al2O33.5%；
Na2O+K2O 0.45%, Li2O 0.45%；
CaO 16%；
BaO 10%；
B2O311.5%；
ZnO 7%；
MgO 4%；
CaF22.5%；
MnO22.5%；
CeO2+Sb2O30.2%；
Other Fe2O3、TiO2Deng impurity 1%；
The frit of above-mentioned composition measures following property during glass microfiber is prepared：
Fusion temperature：1400 DEG C,
Temperature during viscosity 100Pa.s：1040 DEG C,
Crystallize ceiling temperature：940 DEG C,
Density：2.85KG/M3,
1200 DEG C of surface tension：0.3078N/M,
It is used to make glass microfiber, obtained glass microfiber, with three mesh biology microscopes with the frit of the present embodiment Mirror is measured：4.2 μm of average diameter；Mean intensity is measured using test method same as Example 1：860ml.
Embodiment 3
The frit suitable for manufacturing centrifuging alkali-free glass microfibre of the present embodiment, including following mass percent Material：
SiO248.5%；
Al2O33.5%；
Na2O+K2O 0.5%, Li2O 0.2%；
CaO 16.1%；
BaO 5.3%；
B2O316.5%；
MgO 4.2%；
CaF22.5%；
MnO21.5%；
CeO2+Sb2O30.2%；
Other Fe2O3、TiO2Deng impurity 1%.
The frit that above-mentioned composition is mixed measures following property during glass microfiber is prepared：
Fusion temperature：1371 DEG C,
Temperature during viscosity 100Pa.s：1078 DEG C,
Crystallize ceiling temperature：928 DEG C,
Density：2.60KG/M3,
Surface tension when 1200 DEG C：0.3149N/M,
It is used to make glass microfiber, obtained glass microfiber, with three mesh biology microscopes with the frit of the present embodiment Mirror is measured：3.8 μm of average diameter；Mean intensity is measured using test method same as Example 1：940ml.
Embodiment 4
The frit suitable for manufacturing centrifuging alkali-free glass microfibre of the present embodiment, including following mass percent Material：
SiO246.2%；
Al2O36.0%；
Na2O+K2O 0.5%, Li2O 0.3%；
CaO 18.0%；
BaO 4.0%；
B2O314.8%；
MgO 4.5%；
CaF22.5%；
MnO22.0%；
CeO2+Sb2O30.2%；
Other Fe2O3、TiO2Deng impurity 1%；
The frit of above-mentioned composition measures following property during glass microfiber is prepared：
Fusion temperature：1270 DEG C,
Temperature during viscosity 100Pa.s：1076 DEG C,
Crystallize ceiling temperature：952 DEG C,
Density：2.60KG/M3,
Surface tension when 1200 DEG C：0.3298N/M,
It is used to make glass microfiber, obtained glass microfiber, with three mesh biology microscopes with the frit of the present embodiment Mirror is measured：4.8 μm of average diameter；Mean intensity is measured using test method same as Example 1：850ml.

Claims (4)

1. it is a kind of suitable for manufacture centrifuging alkali-free glass microfibre frit, it is characterised in that including following quality percentage The material of ratio：
2. it is according to claim 1 suitable for manufacture centrifuging alkali-free glass microfibre frit, it is characterised in that：Root According to the frit suitable for manufacturing centrifuging alkali-free glass microfibre described in claim 1, it is characterised in that：
3. the frit suitable for manufacturing centrifuging alkali-free glass microfibre according to claim 1 and 2, its feature exists In：The alkali metal oxide is Na2O and K2O is mixed.
4. the frit suitable for manufacturing centrifuging alkali-free glass microfibre according to claim 1 and 2, its feature exists In：The alkali metal oxide is Na2O、K2O and Li2O is mixed, Na2O+K2O is less than 0.5%.
CN201710018522.8A 2017-01-11 2017-01-11 Frit suitable for producing alkali-free glass microfibers with centrifugation process Pending CN106673425A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113307499A (en) * 2021-06-11 2021-08-27 王喜才 Superfine glass microfiber and preparation method thereof

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6086055A (en) * 1983-10-14 1985-05-15 Nippon Muki Zairyo Kk Glass fiber having heat resistance and alkali resistance
CN101166697A (en) * 2005-05-02 2008-04-23 旭硝子株式会社 Alkali-free glass and method for production thereof
WO2009013512A1 (en) * 2007-07-26 2009-01-29 Nova Thera Limited Composite
CN102596837A (en) * 2009-10-30 2012-07-18 株式会社小原 Optical glass and core material for optical fiber
CN104973791A (en) * 2015-04-28 2015-10-14 安徽丹凤集团桐城玻璃纤维有限公司 Alkali-free glass fiber yarn production process

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6086055A (en) * 1983-10-14 1985-05-15 Nippon Muki Zairyo Kk Glass fiber having heat resistance and alkali resistance
CN101166697A (en) * 2005-05-02 2008-04-23 旭硝子株式会社 Alkali-free glass and method for production thereof
WO2009013512A1 (en) * 2007-07-26 2009-01-29 Nova Thera Limited Composite
CN102596837A (en) * 2009-10-30 2012-07-18 株式会社小原 Optical glass and core material for optical fiber
CN104973791A (en) * 2015-04-28 2015-10-14 安徽丹凤集团桐城玻璃纤维有限公司 Alkali-free glass fiber yarn production process

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113307499A (en) * 2021-06-11 2021-08-27 王喜才 Superfine glass microfiber and preparation method thereof
CN113307499B (en) * 2021-06-11 2022-11-25 王喜才 Superfine glass microfiber and preparation method thereof

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Application publication date: 20170517