CN112125528A - High modulus glass fiber with excellent alkali resistance and preparation method thereof - Google Patents
High modulus glass fiber with excellent alkali resistance and preparation method thereof Download PDFInfo
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- CN112125528A CN112125528A CN202011067464.6A CN202011067464A CN112125528A CN 112125528 A CN112125528 A CN 112125528A CN 202011067464 A CN202011067464 A CN 202011067464A CN 112125528 A CN112125528 A CN 112125528A
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- glass fiber
- alkali resistance
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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
- C03C13/00—Fibre or filament compositions
- C03C13/001—Alkali-resistant fibres
- C03C13/002—Alkali-resistant fibres containing zirconium
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B37/00—Manufacture or treatment of flakes, fibres, or filaments from softened glass, minerals, or slags
- C03B37/01—Manufacture of glass fibres or filaments
- C03B37/02—Manufacture of glass fibres or filaments by drawing or extruding, e.g. direct drawing of molten glass from nozzles; Cooling fins therefor
- C03B37/022—Manufacture of glass fibres or filaments by drawing or extruding, e.g. direct drawing of molten glass from nozzles; Cooling fins therefor from molten glass in which the resultant product consists of different sorts of glass or is characterised by shape, e.g. hollow fibres, undulated fibres, fibres presenting a rough surface
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Abstract
The invention provides high-modulus glass fiber with excellent alkali resistance and a preparation method thereof, wherein the raw material of the glass fiber is 55-60% of SiO215-20% of Al2O312-18% of YSZ and 0.5-2% of Y2O3+Nd2O3+CeO25-8% of CaO + MgO and less than or equal to 2% of Li2O+Na2O+K2O、≤1%Fe3O4、≤1%TiO2. By replacing the traditional zirconia with YSZ and combining a small amount of rare earth oxide and other components, the high-modulus glass fiber with excellent alkali resistance can be prepared at a lower spinning temperature.
Description
Technical Field
The invention relates to the field of glass fiber manufacturing, in particular to high-modulus glass fiber with excellent alkali resistance and a manufacturing method thereof.
Background
The high modulus glass fiber is a composite inorganic fiber material with excellent performance, and has wide application in various fields such as aerospace, automobile manufacturing, electronic equipment and the like.
SiO2-Al2O3-ZrO2Glass-based fibers are the most commonly used high modulus glass fibers. In such high modulus glass fibers, SiO2As a main body of the skeleton structure, Al is added2O3Al in (1)3+Of tetrahedral and octahedral coordination structure of (A) to (B), so that SiO2The skeleton structure is communicated, and the high-temperature viscosity and the chemical stability of the glass are improved. ZrO (ZrO)2It is intended to improve the alkali resistance of the glass fiber and to ensure high modulus, hardness, viscosity, etcEssential components.
However, because of ZrO2Too high a melting point of (b), too much ZrO2The addition of (2) will increase the liquidus temperature of the glass, and further the forming temperature of the glass fiber has to be increased, otherwise crystallization is easy to generate in the forming process, a bushing nozzle is blocked, and the breakage (or filament breakage) of the glass fiber is easy to occur. However, the higher the temperature for spinning the glass fiber, the higher the requirements for bushing devices, the more difficult the production and the higher the cost.
The addition of B to glass fibers was proposed by Nanjing glass fiber research and design institute at home and Japan electric glass Kaisha at abroad2O3、TiO2The components are used for reducing the liquidus temperature of the glass, so that the spinning forming of the glass fiber can be realized under the condition of not increasing the spinning forming temperature. However, the introduction of these components tends to cause segregation and inhomogeneity of the components in the glass fiber (i.e., glass), which in turn affects the modulus level of the glass fiber.
The addition of Y to glass fibers has also been proposed by the national Jushi group2O3、Nd2O3The rare earth oxides can improve the elastic modulus of the glass, can also obviously reduce the liquidus temperature, the clarification temperature and the forming temperature of the glass, and are beneficial to improving the efficiency of the spinning forming process of the glass fiber. However, the solution is to reduce or even eliminate the use of ZrO2The alkali resistance of the prepared glass fiber is insufficient.
For this purpose, the invention is based on SiO2-Al2O3-ZrO2Based on glass fiber with excellent alkali resistance, high modulus glass fiber with excellent alkali resistance and a preparation method thereof are provided.
Disclosure of Invention
A high modulus glass fiber composition having excellent alkali resistance, comprising the following components, wherein each component is represented by weight percent:
SiO2 55-60%
Al2O3 15-20%
YSZ 12-18%
Y2O3+Nd2O3+CeO2 0.5-2%
CaO+MgO 5-8%
Li2O+ Na2O+ K2O ≤2%
Fe3O4 ≤1%
TiO2 ≤1%
wherein 0.5-2% of Y2O3+Nd2O3+CeO2Represents Y2O3、Nd2O3、CeO2The total weight percentage of one, any two or three of the three components is 0.5-2%, for Y2O3、Nd2O3、CeO2The individual content of (A) is not limited at all, and may be any value of 0 to 2%; similarly, ≦ 2% Li2O+ Na2O+ K2O represents Li2O、 Na2O、K2The total weight percentage of one, any two or three of the three components of O is less than or equal to 2 percent, for Li2O、 Na2O、K2The individual content of O is not limited at all, and may be any value from 0 to 2%.
Wherein YSZ used in the invention is a shell-core structure of yttria-coated zirconia, Y: the mass ratio of Zr is 1: (10-20).
In the present invention, the zirconia is replaced with YSZ, and the inventors have found that the addition of YSZ to a glass composition for glass fibers also increases the liquidus temperature of the glass fiber composition, but to a lesser extent than the addition of the same amount of ZrO2The liquid phase temperature is increased. This facilitates the use of high levels of YSZ in the glass fiber composition without undue concern for elevated forming temperatures due to excessive liquidus temperatures and high requirements for bushing assemblies. Furthermore, the effect of YSZ on improving the alkali resistance of glass fibers and ZrO2The effect of improving the alkali resistance of the glass fiber is similar. Thus, the present invention uses YSZ instead of zirconiaIt is advantageous for producing a glass fiber composition excellent in alkali resistance.
For the control of the formability and elastic modulus of glass fibers, Y is used in the present invention2O3、Nd2O3、CeO2、Fe3O4、TiO2CaO, MgO and the like.
Wherein, Y2O3、Nd2O3、CeO2All belong to rare earth oxides, and have similar effect on improving the elastic modulus of the glass fiber. Y is3+、Nd3+、Ce4+The ions have a large radius and are difficult to enter the glass network, usually between the pores of the glass network. The rare earth metal ions have high coordination number and high charge, can be matched with free oxygen to form a coordination structure, fill the pores of the glass network among the pores of the glass network, and improve the structural stability of the glass network, thereby improving the modulus of the glass fiber. Y is3+、Nd3+、Ce4+The coordination structure with oxygen is octahedral hexa-coordination structure, and can be well matched with SiO2As the skeleton structure, Al is added3+The gaps of the glass network with the tetrahedral and octahedral coordination structure improve the stability of the structure, and meanwhile, the metal rare earth ions with large ionic radius and the coordination structure thereof generate great obstruction for the movement of other ions among the glass network structures, so that the component segregation and crystallization in the glass fiber composition are effectively inhibited, and the clarification effect of the glass is improved.
Fe3O4Can improve the crystallization performance of the glass fiber composition. For glass fiber compositions containing high levels of Al and Zr, the liquidus temperature is relatively high, Fe3O4The introduction of the glass fiber is beneficial to the temperature uniformity of the glass fiber composition in the processes of temperature rising and temperature lowering, and the local crystallization rate of the glass is improved.
TiO less than or equal to 1 percent2The water resistance and the alkali resistance of the glass fiber can be properly improved, the spinning forming temperature and the liquid phase temperature can be effectively reduced, and the formability of the glass fiber is improved. CaO and MgO can effectively regulate glassMeltability, viscosity, control of glass devitrification.
Detailed Description
The invention is further illustrated below with reference to specific examples.
The high modulus glass fiber composition with excellent alkali resistance contains the following components:
SiO2 55-60%
Al2O3 15-20%
YSZ 12-18%
Y2O3+Nd2O3+CeO2 0.5-2%
CaO+MgO 5-8%
Li2O+ Na2O+ K2O ≤2%
Fe3O4 ≤1%
TiO2 ≤1%。
the spinning temperature of the glass fiber composition is about 1200-1300 ℃, and the spinning temperature does not exceed 1300 ℃; the liquidus temperature of the glass fiber composition is about 1090-1145 ℃; the temperature difference between the spinning temperature and the liquid phase temperature is about 110-.
First, a glass fiber composition raw material in a desired ratio is charged into a glass melting furnace, and subjected to vitrification and melting treatment. The melting temperature is preferably 1400-1600 ℃ in order to obtain a homogenized glass melt. Then, the molten glass was supplied to a bushing device and spun to obtain glass fibers.
Examples 1 to 7
The specific components and corresponding properties of examples 1-7 listed in this invention are given in table 1. Of these, Nos. 1 to 3 and 5 to 6 are preferred examples of the present invention, and Nos. 4 and 7 are comparative examples. In the performance test, the liquidus temperature, elastic modulus, alkali resistance, water resistance of the glass fiber composition and the glass fiber prepared therefrom are mainly tested, and a proper spinning temperature and a corresponding temperature difference between the spinning temperature and the liquidus temperature are set.
TABLE 1
As can be seen from Table 1, the substitution of YSZ for zirconia in the present invention is effective in reducing the liquidus temperature of the glass fiber composition, thereby reducing the desired proper spinning temperature. Meanwhile, the substitution between YSZ and zirconia does not affect the alkali resistance of the glass fiber. Namely, YSZ is also effective in improving the alkali resistance of the glass fiber. For rare earth oxides, e.g. Y2O3、Nd2O3、CeO2The use of (2) can obviously improve the modulus strength of the glass fiber. Small amount of TiO2The water resistance and the alkali resistance of the glass fiber can be properly improved, the spinning forming temperature and the liquid phase temperature can be effectively reduced, and the formability of the glass fiber is improved.
The liquid phase temperature of the glass fiber composition is 1090-1145 ℃, and the required proper spinning temperature can be selected from 1200-1300 ℃ and is not higher than 1300 ℃.
Claims (7)
1. A high modulus glass fiber composition having excellent alkali resistance, comprising the following components, wherein each component is represented by weight percent:
SiO2 55-60%
Al2O3 15-20%
YSZ 12-18%
Y2O3+Nd2O3+CeO2 0.5-2%
CaO+MgO 5-8%
Li2O+ Na2O+ K2O ≤2%
Fe3O4 ≤1%
TiO2 ≤1%
wherein 0.5-2% of Y2O3+Nd2O3+CeO2Represents Y2O3、Nd2O3、CeO2The total weight percentage of one, any two or three of the three components is 0.5-2%, for Y2O3、Nd2O3、CeO2The individual content of (A) is not limited at all, and may be any value of 0 to 2%; similarly, ≦ 2% Li2O+ Na2O+ K2O represents Li2O、 Na2O、K2The total weight percentage of one, any two or three of the three components of O is less than or equal to 2 percent, for Li2O、 Na2O、K2The individual content of O is not limited at all, and may be any value from 0 to 2%.
2. The high modulus glass fiber composition with excellent alkali resistance of claim 1, wherein: the YSZ is a shell-core structure of yttria-coated zirconia, and Y: the mass ratio of Zr is 1: (10-20).
3. The high modulus glass fiber composition with excellent alkali resistance of claim 1, wherein: the liquid phase temperature of the glass fiber composition is between 1090-1145 ℃.
4. The high modulus glass fiber composition with excellent alkali resistance of claim 1, wherein: the spinning temperature of the glass fiber composition is between 1200 ℃ and 1300 ℃, and the spinning temperature and the liquid phase temperature are between 110 ℃ and 200 ℃.
5. A high modulus glass fiber with excellent alkali resistance, characterized in that it is prepared by using the high modulus glass fiber composition with excellent alkali resistance of claim 1 as a raw material.
6. A method for producing a high modulus glass fiber having excellent alkali resistance, characterized in that the high modulus glass fiber composition having excellent alkali resistance according to claim 1 is charged into a glass melting furnace as a raw material, vitrified and melted, and then the molten glass is supplied to a bushing device and spun to form a glass fiber.
7. The method of claim 6, wherein the high modulus glass fiber with excellent alkali resistance is prepared by the following steps: the melting temperature is preferably 1400-1600 ℃.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112811824A (en) * | 2021-03-12 | 2021-05-18 | 山东墨匠新材料科技有限公司 | High alkali-resistant glass fiber composition |
| CN114276001A (en) * | 2021-09-18 | 2022-04-05 | 长兴旗滨玻璃有限公司 | Float glass preparation method with low bubble content and float glass |
| CN114276014A (en) * | 2021-09-30 | 2022-04-05 | 长兴旗滨玻璃有限公司 | Curtain wall glass and preparation process thereof |
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| JPS58167444A (en) * | 1982-03-29 | 1983-10-03 | Nichias Corp | Alkali-resistant glass fiber |
| US4530909A (en) * | 1982-10-14 | 1985-07-23 | National Institute For Researches In Inorganic Materials | Aluminosilicate glass containing Y2 O3 concentrate and ZrO2 |
| CN105731813A (en) * | 2016-02-29 | 2016-07-06 | 巨石集团有限公司 | High-modulus glass fiber composition as well as glass fiber and composite material thereof |
| CN109982982A (en) * | 2016-12-27 | 2019-07-05 | 日本电气硝子株式会社 | The manufacturing method of glass fibre glass composition, glass fibre and glass fibre |
| CN110156327A (en) * | 2019-06-28 | 2019-08-23 | 鲁米星特种玻璃科技股份有限公司 | A kind of high zirconium alkali-proof glass and its application |
| CN110240405A (en) * | 2019-06-26 | 2019-09-17 | 鲁米星特种玻璃科技股份有限公司 | A kind of alkaline-resisting alumina silicate glass and its application |
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2020
- 2020-10-06 CN CN202011067464.6A patent/CN112125528B/en active Active
Patent Citations (6)
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| JPS58167444A (en) * | 1982-03-29 | 1983-10-03 | Nichias Corp | Alkali-resistant glass fiber |
| US4530909A (en) * | 1982-10-14 | 1985-07-23 | National Institute For Researches In Inorganic Materials | Aluminosilicate glass containing Y2 O3 concentrate and ZrO2 |
| CN105731813A (en) * | 2016-02-29 | 2016-07-06 | 巨石集团有限公司 | High-modulus glass fiber composition as well as glass fiber and composite material thereof |
| CN109982982A (en) * | 2016-12-27 | 2019-07-05 | 日本电气硝子株式会社 | The manufacturing method of glass fibre glass composition, glass fibre and glass fibre |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112811824A (en) * | 2021-03-12 | 2021-05-18 | 山东墨匠新材料科技有限公司 | High alkali-resistant glass fiber composition |
| CN114276001A (en) * | 2021-09-18 | 2022-04-05 | 长兴旗滨玻璃有限公司 | Float glass preparation method with low bubble content and float glass |
| CN114276001B (en) * | 2021-09-18 | 2024-03-26 | 长兴旗滨玻璃有限公司 | Float glass preparation method with low bubble content and float glass |
| CN114276014A (en) * | 2021-09-30 | 2022-04-05 | 长兴旗滨玻璃有限公司 | Curtain wall glass and preparation process thereof |
| CN114276014B (en) * | 2021-09-30 | 2024-03-26 | 长兴旗滨玻璃有限公司 | Preparation process of curtain wall glass and curtain wall glass |
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Inventor after: Li Xuewen Inventor after: Sun Qingyun Inventor before: Sun Qingyun |
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Effective date of registration: 20210824 Address after: 251700 north of Lehu Road, Huji Town, Huimin County, Binzhou City, Shandong Province (West office building of Shandong Nongxing Seed Industry Co., Ltd.) Applicant after: Binzhou Xintai Energy Saving Technology Co.,Ltd. Address before: 266000 new energy R & D center, 402, 1st floor, building 4, Qianwan bonded port area, Qingdao area, China (Shandong) pilot Free Trade Zone, Qingdao City, Shandong Province Applicant before: Qingdao lanchuang Kexin New Energy Technology Co.,Ltd. |
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