CN101423329A - Low boron and fluorine glass formula - Google Patents

Low boron and fluorine glass formula Download PDF

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Publication number
CN101423329A
CN101423329A CNA2008101214731A CN200810121473A CN101423329A CN 101423329 A CN101423329 A CN 101423329A CN A2008101214731 A CNA2008101214731 A CN A2008101214731A CN 200810121473 A CN200810121473 A CN 200810121473A CN 101423329 A CN101423329 A CN 101423329A
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glass
percent
fluorine
low
boron
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CN101423329B (en
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张毓强
杨国明
曹国荣
张兵
章林
高雪林
邢文忠
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Jushi Group Co Ltd
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Jushi Group Co Ltd
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Abstract

The invention relates to a glass formulation, in particular to a low-boron low-fluorine glass formulation. In the prior E glass formulation, more boron and fluorine are contained, and the boron and the fluorine are easily volatile in the glass melting process, thereby causing the emission of waste gas to obvious increase, not only increasing production cost and but also easily causing the secondary pollution of solid waste. The invention provides the low-boron low-fluorine glass formulation, which is characterized in that the formulation comprises the following components in weight percentage: 54 to 60 percent of SiO2, 20 to 28 percent of CaO, 12 to 18 percent of Al2O3, 0 to 5 percent of B2O3, 2 to 6 percent of MgO, 0 to 0.4 percent of F, 0 to 0.8 percent of K2O and Na2O, 0.1 to 1 percent of TiO2, 0.1 to 0.5 percent of Fe2O3, 0 to 0.6 percent of SO3, and less than 1 percent of impurities. The glass fiber produced by the glass formulation has low boron and low fluorine and good performances.

Description

A kind of low boron and fluorine glass formula
Technical field
The present invention relates to a kind of glass formula, relate in particular to a kind of low boron and fluorine glass formula.
Background technology
E glass is to be used to produce the most frequently used glass ingredient of continuous glass fibre, and E glass also claims non-alkali glass.The major advantage of E glass is that poor (the Δ T value) of its log3 mold temperature and liquidus temperature is bigger, so be difficult for taking place the devitrification phenomenon in the glass fibre moulding process, E glass can melt under relatively low temperature and clarify simultaneously.
But contain more boron and fluorine in traditional E glass formula, boron and fluorine are volatile compositions in the glass smelting process, and this will cause the waste gas output obviously to increase.Because boron and fluorine are pollution substances; therefore its discharging is subjected to the strictness control of environment control, and this just needs to build expensive exhaust-gas treatment facilities, guarantees that institute's exhaust gas discharged reaches the environmental protection standard of national regulation; this not only increases production cost, also causes the secondary pollution of solid waste easily.
Therefore, in order to reduce the pollution of environment and the production cost that reduces frit, abroad at low boron of development or low fluorine glass formula, but all there are many defectives in known low boron or low fluorine glass.Exist Δ T value little as disclosed a kind of glass among the English Patent GB520427, easily produce the problem of devitrification phenomenon; And for example disclosed a kind of glass in the U.S. Pat 4542106 though do not have boron and fluorine, is to use a large amount of titanium dioxide to have shortcoming, easily causes glass to produce inappropriate color.And domesticly also there is not low boron and fluorine glass formula at present.
Summary of the invention
The objective of the invention is to overcome above shortcomings in the prior art, and a kind of easy moulding is provided, is difficult for generation devitrification phenomenon and does not have improper painted low boron and fluorine glass formula.
The present invention addresses the above problem the technical scheme that is adopted: a kind of low boron and fluorine glass formula is characterized in that: each composition comprises by weight percentage: SiO 254%～62%, CaO 20%～28%, Al 2O 312%～18%, B 2O 30～5%, MgO 2%～6%, and F 0～0.4%, K 2O and Na 2O amounts to 0～0.8%, TiO 20.1%～1%, Fe 2O 30.1%～0.5%, SO 30～0.6%, and 1% following impurity.
The present invention by weight percentage the content of MgO between 2%～3.5%, B 2O 3Content below 2.5%.
B in the prescription of the present invention 2O 3Content be 0.
B in the prescription of the present invention 2O 3Content be 0, the content of F is below 0.2% by weight percentage.
B in the prescription of the present invention 2O 3Be 0 with the content of F.
The raw material of prescription of the present invention comprises quartz sand, Wingdale, agalmatolite, rhombspar and borocalcite.
The raw material of prescription of the present invention comprises quartz sand, unslaked lime, agalmatolite, rhombspar and borocalcite.
The raw material of prescription of the present invention comprises quartz sand, Wingdale, unslaked lime, agalmatolite, rhombspar and borocalcite.
The raw material of prescription of the present invention comprises quartz sand, Wingdale, kaolin, rhombspar and borocalcite.
The raw material of prescription of the present invention comprises quartz sand, Wingdale, agalmatolite, kaolin, rhombspar and borocalcite.
The present invention compared with prior art has the following advantages and effect: the present invention is by reducing B 2O 3, F and Al 2O 3Content, increase SiO 2, CaO and MgO content, control basic metal, Fe 2O 3And TiO 2Content, obtained to have the advantage, low boron and fluorine, no improper painted and can be easy to the glass component of wire-drawing shape of E glass.With the glass fibre that the present invention produces, its log3 mold temperature is 1180 ℃～1280 ℃, and therefore liquidus temperature the devitrification phenomenon can not take place at least than low 70 ℃ of mold temperature in normal glass spinning process.
In constituent of the present invention, SiO 2Be the main oxides that forms the glass skeleton, and work to stablize each component.The SiO that the present invention limited 2Weight percent content is 54%～62%, if its content is too low, can influences the Stability Analysis of Structures of glass fibre, thereby cause the use properties of glass fibre to degenerate; If its content is too high, the viscosity of glass metal is raise, thereby cause the clarification and homogenization difficulty of glass metal.
In constituent of the present invention, Al 2O 3Also be the oxide compound that forms the glass skeleton, and playing an important role aspect prevention glass phase-splitting and the water resisting property.The Al that the present invention limited 2O 3Weight percent content is 12%～18%, preferably 12%～15%, if its content is too low, can make the water resisting property variation of glass fibre increases the danger of glass devitrification simultaneously; If its content is too high, the viscosity of glass metal is raise, thereby cause the clarification and homogenization difficulty.
In constituent of the present invention, the CaO weight percent content that is limited is 20%～28%, can add weight percent content and be 2%～6% MgO, CaO and MgO is mixed use.The adding proper addition of MgO can effectively reduce the danger of glass devitrification, makes glass have better processing performance.
In constituent of the present invention, B 2O 3Being the network organizer of glass, playing fluxing action preferably, also is a kind of constituent that can reduce glass ware forming temperature and liquidus temperature.F is the constituent that another kind has good fluxing action.But boron and fluorine are volatile pollution substances, need it is removed in exhaust gas discharged, and this not only increases production cost, and causes the secondary pollution of waste easily.Glass component has low boron and fluorine content among the present invention, the B that limits 2O 3Weight percent content be 0～5%, the weight percent content of F is 0～0.4%.
In constituent of the present invention, also can add 0.1%～1% TiO 2, the glass metal viscosity when it not only can reduce high temperature also has certain fluxing action.
The alkali metal content of China regulation E glass must be less than 0.8%, thus in the constituent of the present invention alkali-metal overall control in 0.8%.
Embodiment
By the following examples technical scheme of the present invention is specifically described, but content of the present invention is not subjected to any restriction of following examples.Wherein the composition total content slightly less than or greater than 100%, can be understood as residual volume is the minor constituent that impurity maybe can not analyze.
The main production raw material of E glass adopts quartz sand, Wingdale, agalmatolite, rhombspar, borocalcite etc. usually, and the Wingdale among the present invention can be substituted or both mix use by unslaked lime, and agalmatolite can be substituted or both mix use by kaolin.The detailed process of the embodiment of the invention is as follows: each constituent can obtain from suitable raw material (as the SiO in the quartz sand 2, the CaO in the unslaked lime), various raw materials are mixed with existing method by suitable proportion, make each composition reach final expection weight percent, then mixed admixtion is melted in tank furnace and clarify.
If adopt the present invention to produce glass fibre, the glass metal that only needs to form flow to the fiberizing bushing that is positioned at the path bottom by path, thereby glass metal is drawn out by leting slip a remark on the bushing and forms glass fibre, glass fibre is pulled around form former spinning cake or yarn group to the drawing wire machine rotating head, and these glass fibre can carry out deep processing to meet the expected requirements with ordinary method.
The technical scheme of specific embodiment and processing parameter see Table 1 and 2.Evidence, compare with external typical E glass formula, glass of the present invention has relatively low glass fibre mold temperature, and the difference of mold temperature and liquidus temperature is more than 70 ℃, both help the glass spinning moulding, produced crystallization devitrification phenomenon when helping preventing wire drawing again.The design of low boron and fluorine of the present invention more helps environment protection, has tangible economic benefit and social benefit.
Table 1
Component Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4 Embodiment 5 Embodiment 6 E glass *
SiO 2 54.5 56.87 57.05 57.5 58.52 61.16 55.2
Al 2O 3 14.13 13.82 13.83 13.81 13.26 12.1 14.8
CaO 22.2 22.43 22.38 22.31 22.16 22.05 18.7
B 2O 3 4.98 2.65 2.42 2.03 1.25 0 7.3
MgO 2.35 2.45 2.5 2.52 3 3 3.3
Na 2O 0.51 0.49 0.49 0.5 0.5 0.48 0.3
K 2O 0.23 0.23 0.25 0.26 0.25 0.21 0.2
Fe 2O 3 0.41 0.42 0.41 0.41 0.41 0.38 0.3
TiO 2 0.36 0.34 0.37 0.36 0.35 0.32 /
F 0.33 0.3 0.3 0.3 0.3 0.3 0.3
Mold temperature/℃ 1205 1228 1235 1240 1250 1265 1270
Liquidus temperature/℃ 1100 1132 1142 1150 1165 1190 1140
Δ T value/℃ 105 96 93 90 85 75 130
E glass in the table 1 *Be external typical E glass formula, select from " continuous glass fibre technology basis " that Zhang Bidong etc. is done.
Table 2
Component Embodiment 7 Embodiment 8 Embodiment 9 Embodiment 10
SiO 2 57.56 60.1 60.15 60.2
Al 2O 3 13.95 12.66 12.69 12.7
CaO 22.35 22.16 22.18 22.24
B 2O 3 1.95 0 0 0
MgO 2.65 3.15 3.23 3.35
Na 2O 0.5 0.52 0.51 0.5
K 2O 0.26 0.27 0.26 0.26
Fe 2O 3 0.4 0.39 0.41 0.4
TiO 2 0.38 0.35 0.37 0.35
F 0 0.4 0.2 0
Mold temperature/℃ 1249 1255 1263 1268
Liquidus temperature/℃ 1165 1175 1187 1195
△ T value/℃ 84 80 76 73

Claims (10)

1, a kind of low boron and fluorine glass formula is characterized in that: each composition comprises by weight percentage: SiO 254%～62%, CaO 20%～28%, Al 2O 312%～18%, B 2O 30～5%, MgO 2%～6%, F0～0.4%, K 2O and Na 2O amounts to 0～0.8%, TiO 20.1%～1%, Fe 2O 30.1%～0.5%, SO 30～0.6%, and 1% following impurity.
2, low boron and fluorine glass formula according to claim 1 is characterized in that: by weight percentage the content of MgO between 2%～3.5%, B 2O 3Content below 2.5%.
3, low boron and fluorine glass formula according to claim 1 and 2 is characterized in that: B in the described prescription 2O 3Content be 0.
4, low boron and fluorine glass formula according to claim 1 and 2 is characterized in that: B in the described prescription 2O 3Content be 0, the content of F is below 0.2% by weight percentage.
5, low boron and fluorine glass formula according to claim 1 and 2 is characterized in that: B in the described prescription 2O 3Be 0 with the content of F.
6, low boron and fluorine glass formula according to claim 1 is characterized in that: the raw material of described prescription comprises quartz sand, Wingdale, agalmatolite, rhombspar and borocalcite.
7, low boron and fluorine glass formula according to claim 1 is characterized in that: the raw material of described prescription comprises quartz sand, unslaked lime, agalmatolite, rhombspar and borocalcite.
8, low boron and fluorine glass formula according to claim 1 is characterized in that: the raw material of described prescription comprises quartz sand, Wingdale, unslaked lime, agalmatolite, rhombspar and borocalcite.
9, low boron and fluorine glass formula according to claim 1 is characterized in that: the raw material of described prescription comprises quartz sand, Wingdale, kaolin, rhombspar and borocalcite.
10, low boron and fluorine glass formula according to claim 1 is characterized in that: the raw material of described prescription comprises quartz sand, Wingdale, agalmatolite, kaolin, rhombspar and borocalcite.
CN2008101214731A 2008-10-06 2008-10-06 Low boron and fluorine glass formula Active CN101423329B (en)

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102050583A (en) * 2010-10-27 2011-05-11 泰山玻璃纤维有限公司 Chemical corrosion resistant fiberglass
CN102603197A (en) * 2011-12-20 2012-07-25 内江华原电子材料有限公司 Method for producing alkali-free glass fiber by taking industrial slag as raw material
CN103420608A (en) * 2010-03-18 2013-12-04 杨德宁 Manufacturing technology of glass and glass product
CN104445966A (en) * 2014-11-28 2015-03-25 山东玻纤集团股份有限公司 Novel glass fiber
CN106946464A (en) * 2017-03-16 2017-07-14 江苏九鼎新材料股份有限公司 One kind, which has, carries high performance alkali-free glass fibre and preparation method thereof
CN108773259A (en) * 2018-06-01 2018-11-09 温利军 A kind of automobile windshield substrate and preparation method thereof
TWI715339B (en) * 2019-09-25 2021-01-01 巨石集團有限公司 Electronic grade glass fiber composition and its glass fiber and electronic cloth
US11760687B2 (en) 2020-01-02 2023-09-19 Taishan Fiberglass Zoucheng Co., Ltd. Alkali-free ultrafine glass fiber formula

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103420608A (en) * 2010-03-18 2013-12-04 杨德宁 Manufacturing technology of glass and glass product
CN103420608B (en) * 2010-03-18 2016-12-28 杨德宁 The preparation technology of glass and the application of glass
CN102050583A (en) * 2010-10-27 2011-05-11 泰山玻璃纤维有限公司 Chemical corrosion resistant fiberglass
CN102603197A (en) * 2011-12-20 2012-07-25 内江华原电子材料有限公司 Method for producing alkali-free glass fiber by taking industrial slag as raw material
CN104445966A (en) * 2014-11-28 2015-03-25 山东玻纤集团股份有限公司 Novel glass fiber
CN104445966B (en) * 2014-11-28 2017-06-13 山东玻纤集团股份有限公司 A kind of glass fibre
CN106946464A (en) * 2017-03-16 2017-07-14 江苏九鼎新材料股份有限公司 One kind, which has, carries high performance alkali-free glass fibre and preparation method thereof
CN108773259A (en) * 2018-06-01 2018-11-09 温利军 A kind of automobile windshield substrate and preparation method thereof
TWI715339B (en) * 2019-09-25 2021-01-01 巨石集團有限公司 Electronic grade glass fiber composition and its glass fiber and electronic cloth
US11760687B2 (en) 2020-01-02 2023-09-19 Taishan Fiberglass Zoucheng Co., Ltd. Alkali-free ultrafine glass fiber formula

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