CN104556709A - High-intensity glass fiber containing cerium oxide and preparation method for glass fiber - Google Patents

High-intensity glass fiber containing cerium oxide and preparation method for glass fiber Download PDF

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Publication number
CN104556709A
CN104556709A CN201410857196.6A CN201410857196A CN104556709A CN 104556709 A CN104556709 A CN 104556709A CN 201410857196 A CN201410857196 A CN 201410857196A CN 104556709 A CN104556709 A CN 104556709A
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China
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glass fiber
glass
high strength
containing cerium
oxidation
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CN201410857196.6A
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Chinese (zh)
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陈培
王宏志
江菀
汪庆卫
李浩业
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Donghua University
National Dong Hwa University
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Donghua University
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Abstract

The invention relates to a high-intensity glass fiber containing cerium oxide and a preparation method for the glass fiber. The high-intensity glass fiber comprises the following components in percentage by weight: 58-66% of SiO2, 16-23% of Al2O3, 9-18% of CaO, 6-12% of MgO, 1-2.5% of ZnO and 0.5-2.5% of CeO2. The preparation method comprises the following steps: (1) calculating the formula; weighting and mixing the components uniformly; (2) conducting founding; (3) casting into glass blocks or glass strips; annealing; (4) conducting melting and wire drawing. According to the invention, under the premise that boric anhydride and fluoride are not contained, the tombarthite oxide CeO2 is added; the performance of the high-intensity glass fiber is improved; meanwhile, under the condition that the founding conditions of the glass are not changed, the prepared high-intensity glass fiber has the characteristics of being medium in founding temperature and glass viscosity, low in liquid phase line, good in vitrification and is not easy to crystallize, and has favorable application prospect.

Description

High strength glass fiber of a kind of oxidation-containing cerium and preparation method thereof
Technical field
The invention belongs to high strength glass fiber field, particularly a kind of high strength glass fiber and preparation method thereof of oxidation-containing cerium.
Background technology
High strength glass fiber is the nonmetal functional materials of a kind of novel inorganic and structured material, have high temperature resistant, corrosion-resistant, tensile strength is high, Young's modulus is large, a series of feature such as antifatigue and impact property.Along with the development in epoch and the continuous progress of science and technology, the range of application of high-strength glass fibre is in continuous expansion, and people are also improving constantly the performance requriements of glass fibre.As strongthener, the lifting of mechanical property is one of main direction of glass fibre development always.Especially in recent years energy dilemma is on the rise, and people are to environment protection pay attention to day by day, more and more higher to the concern of the aspect such as lightweight, big leaf's slice wind power generation of automobile.Now, high strength glass fiber matrix material becomes the focus and emphasis of industry research and exploitation with advantages such as the mechanical properties of its excellence.But meanwhile, the production difficulty of high-strength glass fibre is also larger, and production cost is also higher, and this creates certain impact to the scale operation of high-strength glass fibre and application.
U.S. S-2 high strength glass fiber, its composition is only the oxide compound of silicon, aluminium and magnesium, and content is 65wt%SiO 2, 25wt%Al 2o 3, 10wt%MgO, the advantage of S-2 glass is that tensile strength is high, but glass ware forming temperature is high, its liquidus temperature is up to 1470 DEG C, bushing temperature reaches 1570 DEG C, found inner lining of kiln material require and use special refractory and the precious metal material such as platinum, rhodium, drawing process condition is harsh, and production cost is higher.
The S glass of T glass and the U.S. that Nitto Boseki Co. Ltd of Japan produces belongs to composition of the same race, and the slightly difference because selecting raw material difference, its main component is 65wt%SiO 2, 23wt%Al 2o 3, 11wt%MgO and 0.1 ~ 1wt% transition metal oxide.T glass, from expanding to printed circuit board, apparatus casing material etc. for athletic sports appliance at first, is make the important base material that high-performance fiber strengthens composite plastic.But the founding of T glass, wire-drawing temperature are equally very high, energy consumption is large, and kiln pot life is relatively short, and production cost is higher.
Summary of the invention
Technical problem to be solved by this invention is to provide high strength glass fiber of a kind of oxidation-containing cerium and preparation method thereof, this glass fibre has glass melting temperature, glass viscosity is moderate, liquidus line is low, and the excellent and feature that is not easily crystallization of vitrifying, has a good application prospect.
The high strength glass fiber of a kind of oxidation-containing cerium of the present invention, by weight percentage, composed of the following components: SiO 258 ~ 66%, Al 2o 316 ~ 23%, CaO 9 ~ 18%, MgO 6 ~ 12%, ZnO 1 ~ 2.5% and CeO 20.5 ~ 2.5%.
The present invention adopt the high-strength glass fibre system of technical scheme to be:
SiO 2-Al 2o 3-CaO-MgO-ZnO-CeO 2, oxygen-freeization boron and fluorochemical.
Excellent and be conducive to glass fiber wire-drawing and have the glass fibre of high strength in order to prepare vitrifying, glass ingredient described above also must meet following characteristics:
SiO in described glass ingredient 2preferable range: 60 ~ 65%; Al 2o 3preferable range: 17 ~ 20%; SiO 2+ Al 2o 3preferable range 77 ~ 83%.SiO 2be topmost Network former in silicate glass, in glass system, play main skeleton, improve SiO 2content, although enhance glass skeleton structure, the viscosity of glass metal under identical glass melting temperature rises, and founds clarifying temp and raises.Al 2o 3glass can not be formed separately, but can important impact be produced, appropriate Al to the network structure of glass 2o 3the chemical stability of glass can be improved, improve vitrifying degree and the increased devitrification resistance of glass, improve the chemical stability of glass fibre.
The preferable range of CaO in described glass ingredient: 9 ~ 15%.
In described glass ingredient, the ratio of the preferable range of the preferable range of MgO: 7 ~ 11%, CaO+MgO: 18 ~ 22%, CaO/MgO is greater than 1.2.CaO and MgO is cheap composition conventional in glass.CaO belongs to network-modifying ion, and CaO can reduce the high temperature viscosity of glass metal, but the content increasing CaO can increase the fragility of glass.There are two kinds of coordinations in MgO, mediate state in glass, but when alkali metal content is not enough in glass magnesium ion can not enter network, can only as network outer body.The increase of content of MgO can promote the phase-splitting of glass, makes the liquidus line of glass increase, and make devitrification of glass be inclined to increases simultaneously.The present invention is preferred CaO and MgO simultaneously, and CaO is greater than MgO, now utilizes two kinds of cationic actings in conjunction and drag effect, improve the melting conditions of glass, reach the effect of clarification and homogenization, improve the chemical stability of glass network compact structure degree and glass.
The preferable range of ZnO in described glass ingredient: 1.5 ~ 2.5%; ZnO is a kind of intermediate oxide.In non-alkali glass, ZnO then exists with zinc oxygen octahedra, enter in the space between silicon-oxy tetrahedron and serve as Network modifier, in ZnO and glass, some component forms eutectic mixture, liquid phase can be formed at a lower temperature, facilitate the melting of bulk glass, play the effect reducing glass high temperature viscosity.The present invention selects the main purpose of ZnO to be improve the melting conditions of glass, plays fluxing action when glass smelting, and meanwhile, ZnO can also reduce the coefficient of expansion of glass, improves the corrosion resistance nature of glass, but the too high tendency towards devitrification that can increase glass of ZnO.
CeO in described glass ingredient 2preferable range: 0.8 ~ 1.8%.CeO 2the representative species of the rare earth resources of China's abundant, nontoxic, rich in minerals, CeO 2the high temperature viscosity of glass can not only be reduced, and reaction of at high temperature appraising at the current rate, release O 2, good clarification can be played.CeO 2not only there is the clarifying effect reducing glass viscosity and improve glass metal, eliminate the effect of bubble, and add CeO in glass ingredient 2can promote the connection of glass network skeleton, increase the bridging oxygen in glass network structure, make the connection between silicon-oxy tetrahedron more tight, obtained glass structure is compact, and material mechanical performance and alkali resistance all increase.CeO 2the forming ability of glass fibre can also be improved, reduce the producting process difficulty of high strength glass fiber.
Oxygen-freeization boron and fluorochemical in described glass ingredient.Boron oxide is good glass-former, glass melting temperature and the high temperature viscosity of glass can be reduced, normally use as solubility promoter, but in high-strength glass fibre is founded, boron oxide self volatilization at high temperature brings adverse influence also to the clarification homogenizing of glass, the use of fluorochemical increases the erosion of refractory materials on the one hand, increase of volatilizing on the other hand, therefore does not use boron oxide and fluorochemical in described glass ingredient.
The preparation method of the high strength glass fiber of a kind of oxidation-containing cerium of the present invention, comprising:
(1) aluminum oxide is introduced by aluminium hydroxide, and CaO, MgO are introduced by respective carbonate, and all the other components are introduced by respective oxide compound, then calculates formula, weighing mixes;
(2) select quartz crucible, found in silicon molybdenum rod furnace, glass melting temperature is 1520 ~ 1580 DEG C, is incubated 4 ~ 7 hours;
(3) glass metal melted is cast into glass block or glass bar, puts into annealing furnace and anneal, furnace cooling after insulation;
(4) by the above-mentioned glass melted melt drawing on glass fiber single filament machine, to obtain final product.
Annealing temperature in described step (3) is 660 ~ 740 DEG C.
Wire-drawing temperature in described step (4) is 1310 ~ 1350 DEG C, and drawing wire machine rotating speed is 1200 ~ 1500r/min.
beneficial effect
The present invention is under the prerequisite of oxygen-freeization boron and fluorine, improve the performance of high strength glass fiber, simultaneously when not changing glass smelting condition, the high strength glass fiber prepared has glass melting temperature, glass viscosity is moderate, liquidus line is low, excellent and the feature that is not easily crystallization of vitrifying, has a good application prospect.
Embodiment
Below in conjunction with specific embodiment, set forth the present invention further.Should be understood that these embodiments are only not used in for illustration of the present invention to limit the scope of the invention.In addition should be understood that those skilled in the art can make various changes or modifications the present invention, and these equivalent form of values fall within the application's appended claims limited range equally after the content of having read the present invention's instruction.
Embodiment 1
(1) by weight percentage, SiO 259%, Al 2o 320%, CaO 10%, MgO 8%, ZnO 1.8%, CeO 21.2% weighing mixes;
(2) quartz crucible is selected, and cover lid, found in silicon molybdenum rod furnace, glass melting temperature is 1540 DEG C, is incubated 4 hours;
(3) glass metal melted is cast into glass block or glass bar, puts into annealing furnace and anneal, annealing temperature is 660 DEG C, is incubated furnace cooling after 2 hours;
(4) by the above-mentioned glass melted melt drawing on glass fiber single filament machine, wire-drawing temperature 1320 DEG C, drawing wire machine rotating speed 1200r/min, obtains high strength glass fiber.
Embodiment 2
(1) by weight percentage, SiO 260%, Al 2o 319%, CaO 11%, MgO 8%, ZnO 1%, CeO 21% weighing mixes;
(2) quartz crucible is selected, and cover lid, found in silicon molybdenum rod furnace, glass melting temperature is 1530 DEG C, is incubated 5 hours;
(3) glass metal melted is cast into glass block or glass bar, puts into annealing furnace and anneal, annealing temperature is 670 DEG C, is incubated furnace cooling after 2 hours;
(4) by the above-mentioned glass melted melt drawing on glass fiber single filament machine, wire-drawing temperature 1320 DEG C, drawing wire machine rotating speed 1300r/min, obtains high strength glass fiber.
Embodiment 3
(1) by weight percentage, SiO 262%, Al 2o 320%, CaO 10%, MgO 6%, ZnO 1.5%, CeO 20.5% weighing mixes;
(2) quartz crucible is selected, and cover lid, found in silicon molybdenum rod furnace, glass melting temperature is 1540 DEG C, is incubated 5 hours;
(3) glass metal melted is cast into glass block or glass bar, puts into annealing furnace and anneal, annealing temperature is 680 DEG C, is incubated furnace cooling after 2 hours;
(4) by the above-mentioned glass melted melt drawing on glass fiber single filament machine, wire-drawing temperature 1330 DEG C, drawing wire machine rotating speed 1300r/min, obtains high strength glass fiber.
Embodiment 4
(1) by weight percentage, SiO 262%, Al 2o 318%, CaO 9%, MgO 8%, ZnO 1.5%, CeO 21.5% weighing mixes;
(2) quartz crucible is selected, and cover lid, found in silicon molybdenum rod furnace, glass melting temperature is 1560 DEG C, is incubated 6 hours;
(3) glass metal melted is cast into glass block or glass bar, puts into annealing furnace and anneal, annealing temperature is 700 DEG C, is incubated furnace cooling after 2 hours;
(4) by the above-mentioned glass melted melt drawing on glass fiber single filament machine, wire-drawing temperature 1330 DEG C, drawing wire machine rotating speed 1400r/min, obtains high strength glass fiber.
Embodiment 5
(1) by weight percentage, SiO 263%, Al 2o 318%, CaO 9%, MgO 8%, ZnO 1.5%, CeO 20.5% weighing mixes;
(2) quartz crucible is selected, and cover lid, found in silicon molybdenum rod furnace, glass melting temperature is 1580 DEG C, is incubated 7 hours;
(3) glass metal melted is cast into glass block or glass bar, puts into annealing furnace and anneal, annealing temperature is 740 DEG C, is incubated furnace cooling after 2 hours;
(4) by the above-mentioned glass melted melt drawing on glass fiber single filament machine, wire-drawing temperature 1350 DEG C, drawing wire machine rotating speed 1500r/min, obtains high strength glass fiber.
Chemical durability of glass test sample is the glass block of 50mm × 10mm × 10mm, test condition: the mass loss rate after being incubated 10h respectively in 90 DEG C of deionized waters, 1mol/L sulphuric acid soln and NaOH solution characterizes.
Thermal expansion coefficient of glass α sample glass wafer, density samples is the glass block of 50mm × 10mm × 10mm;
Tensile strength (cN/dtex) is tested, and experiment load measurement scope is 0-3000cN, and clamp distance is 250mm, and draw speed is 100mm/min.
Test the sample after processing, glass composition (weight percent) of embodiment 1-5 and the performance test results see the following form:
Table: fiberglass component and performance

Claims (10)

1. a high strength glass fiber for oxidation-containing cerium, is characterized in that: by weight percentage, composed of the following components: SiO 258 ~ 66%, Al 2o 316 ~ 23%, CaO 9 ~ 18%, MgO 6 ~ 12%, ZnO 1 ~ 2.5% and CeO 20.5 ~ 2.5%.
2. the high strength glass fiber of a kind of oxidation-containing cerium according to claim 1, is characterized in that: described SiO 2weight percent is 60 ~ 65%; Al 2o 3weight percent is 17 ~ 20%.
3. the high strength glass fiber of a kind of oxidation-containing cerium according to claim 1, is characterized in that: described SiO 2, Al 2o 3weight percent sum is 77 ~ 83%.
4. the high strength glass fiber of a kind of oxidation-containing cerium according to claim 1, is characterized in that: described CaO weight percent is 9 ~ 15%; MgO weight percent is 7 ~ 11%.
5. the high strength glass fiber of a kind of oxidation-containing cerium according to claim 1, is characterized in that: described CaO, MgO weight percent sum is 18 ~ 22%; The weight ratio of CaO and MgO is greater than 1.2.
6. the high strength glass fiber of a kind of oxidation-containing cerium according to claim 1, is characterized in that: described ZnO weight percent is 1.5 ~ 2.5%.
7. the high strength glass fiber of a kind of oxidation-containing cerium according to claim 1, is characterized in that: described CeO 2weight percent is 0.8 ~ 1.8%.
8. a preparation method for the high strength glass fiber of oxidation-containing cerium as claimed in claim 1, comprising:
(1) aluminum oxide is introduced by aluminium hydroxide, and CaO, MgO are introduced by respective carbonate, and all the other components are introduced by respective oxide compound, then calculates formula, weighing mixes;
(2) select quartz crucible, found in silicon molybdenum rod furnace, glass melting temperature is 1520 ~ 1580 DEG C, is incubated 4 ~ 7 hours;
(3) glass metal melted is cast into glass block or glass bar, puts into annealing furnace and anneal, furnace cooling after insulation;
(4) by the above-mentioned glass melted melt drawing on glass fiber single filament machine, to obtain final product.
9. the preparation method of the high strength glass fiber of a kind of oxidation-containing cerium according to claim 8, is characterized in that: the annealing temperature in described step (3) is 660 ~ 740 DEG C.
10. the preparation method of the high strength glass fiber of a kind of oxidation-containing cerium according to claim 8, is characterized in that: the wire-drawing temperature in described step (4) is 1310 ~ 1350 DEG C, and drawing wire machine rotating speed is 1200 ~ 1500r/min.
CN201410857196.6A 2014-12-30 2014-12-30 High-intensity glass fiber containing cerium oxide and preparation method for glass fiber Pending CN104556709A (en)

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108290769A (en) * 2015-05-13 2018-07-17 电子玻璃纤维美国有限责任公司 MgO, ZnO and rare earth oxide for manufacturing the improved low dielectric fibers with improved low thermal coefficient of expansion are used for the purposes of high boroaluminosilicate composition
CN112129325A (en) * 2020-08-13 2020-12-25 苏州中科寰宇智能科技有限公司 High-strength and high-thermal-stability glass code disc for rotary encoder
CN112745031A (en) * 2021-01-06 2021-05-04 泰山玻璃纤维有限公司 Low-thermal expansion coefficient high-strength glass fiber
CN113800772A (en) * 2021-07-31 2021-12-17 广东金发科技有限公司 Long-acting antibacterial glass fiber, nylon molding composition, and preparation methods and applications thereof
US11306021B2 (en) 2018-11-26 2022-04-19 Owens Coming Intellectual Capital, LLC High performance fiberglass composition with improved elastic modulus
US11524918B2 (en) 2018-11-26 2022-12-13 Owens Corning Intellectual Capital, Llc High performance fiberglass composition with improved specific modulus

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* Cited by examiner, † Cited by third party
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CN102276153A (en) * 2011-07-27 2011-12-14 中材科技股份有限公司 Composition for high-property heat-resisting corrosion-resisting glass fiber
CN102786223A (en) * 2012-08-28 2012-11-21 泰山玻璃纤维有限公司 High-strength glass fiber composition

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102276153A (en) * 2011-07-27 2011-12-14 中材科技股份有限公司 Composition for high-property heat-resisting corrosion-resisting glass fiber
CN102786223A (en) * 2012-08-28 2012-11-21 泰山玻璃纤维有限公司 High-strength glass fiber composition

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108290769A (en) * 2015-05-13 2018-07-17 电子玻璃纤维美国有限责任公司 MgO, ZnO and rare earth oxide for manufacturing the improved low dielectric fibers with improved low thermal coefficient of expansion are used for the purposes of high boroaluminosilicate composition
US11787732B2 (en) 2015-05-13 2023-10-17 Electric Glass Fiber America, LLC Use of MGO, ZNO, and rare earth oxides for making improved low dielectric fibers with improved low thermal expansion coefficient for high boron aluminosilicate compositions
US11306021B2 (en) 2018-11-26 2022-04-19 Owens Coming Intellectual Capital, LLC High performance fiberglass composition with improved elastic modulus
US11524918B2 (en) 2018-11-26 2022-12-13 Owens Corning Intellectual Capital, Llc High performance fiberglass composition with improved specific modulus
CN112129325A (en) * 2020-08-13 2020-12-25 苏州中科寰宇智能科技有限公司 High-strength and high-thermal-stability glass code disc for rotary encoder
CN112745031A (en) * 2021-01-06 2021-05-04 泰山玻璃纤维有限公司 Low-thermal expansion coefficient high-strength glass fiber
CN112745031B (en) * 2021-01-06 2022-03-18 泰山玻璃纤维有限公司 Low-thermal expansion coefficient high-strength glass fiber
CN113800772A (en) * 2021-07-31 2021-12-17 广东金发科技有限公司 Long-acting antibacterial glass fiber, nylon molding composition, and preparation methods and applications thereof

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