Glass fiber composition and glass fiber and composite material thereof

Abstract

The present invention provides a glass fiber composition, a glass fiber and a composite material therefrom. The glass fiber composition comprises the following components expressed as percentage by weight: 58-64% SiO2, 14-19% Al203, ≧8.8% and <11.8% CaO, 7.5-11% MgO, 0.2-2.7% SrO, 0.1-2% Na2O+K2O, 0.05-0.9% Li2O, 0.05-1% Fe2O3, 0.05-1.1% TiO2 and <0.5% F2, wherein the range of the weight percentage ratio C1=(MgO+SrO)/CaO is 0.75-1.1, and the range of the weight percentage ratio C2=CaO/MgO is less than 1.4. Said composition can effectively inhibit the crystallization tendency of glass, significantly decrease the liquidus temperature and crystallization degree of glass and also has an outstanding glass refractive index and outstanding modulus.

Claims

1. A glass fiber composition, comprising the following components expressed as percentage by weight: TABLE-US-00017 SiO.sub.2 58-64% Al.sub.2O.sub.3 14-19% CaO ≧8.8% and <11.8% MgO 7.5-11%  SrO 0.2-2.7% Na.sub.2O + K.sub.2O 0.1-2%   Li.sub.2O 0.05-0.9%  Fe.sub.2O.sub.3 0.05-1%   TiO.sub.2 0.05-1.1%  F.sub.2 <0.5% wherein, the range of the weight percentage ratio C1=(MgO+SrO)/CaO is 0.75-1.1 and the range of the weight percentage ratio C2=CaO/MgO is less than 1.4.

2. The glass fiber composition according to claim 1, wherein the range of the weight percentage ratio C2=CaO/MgO is greater than 1 and less than 1.3.

3. The glass fiber composition according to claim 1, wherein the range of the weight percentage ratio C1=(MgO+SrO)/CaO is 0.8-1.

4. The glass fiber composition according to claim 1, wherein the content of CaO expressed as percentage by weight is greater than 10.5% and less than 11.8%.

5. The glass fiber composition according to claim 1, comprising the following components expressed as percentage by weight: TABLE-US-00018 SiO.sub.2   59-62% Al.sub.2O.sub.3 14.5-18% CaO >10.5% and <11.8% MgO   8-10.5% SrO 0.5-2% Na.sub.2O + K.sub.2O 0.1-2% Li.sub.2O  0.05-0.9% Fe.sub.2O.sub.3 0.05-1%  TiO.sub.2  0.05-1.1% F.sub.2 <0.5% wherein, the weight percentage ratio C1=(MgO+SrO)/CaO is 0.75-1.1, and the range of the weight percentage ratio C2=CaO/MgO is less than 1.4.

6. The glass fiber composition according to claim 1, comprising the following components expressed as percentage by weight: TABLE-US-00019 SiO.sub.2   59-62% Al.sub.2O.sub.3 14.5-18% CaO >10.5% and <11.8% MgO   8-10.5% SrO 0.5-2% Na.sub.2O + K.sub.2O 0.1-2% Li.sub.2O  0.05-0.9% Fe.sub.2O.sub.3 0.05-1%  TiO.sub.2  0.05-1.1% F.sub.2 <0.5% wherein, the range of the weight percentage ratio C1=(MgO+SrO)/CaO is 0.8-1, and the range of the weight percentage ratio C2=CaO/MgO is greater than 1 and less than 1.3.

7. The glass fiber composition according to claim 1, comprising the following components expressed as percentage by weight: TABLE-US-00020 SiO.sub.2   59-61.5% Al.sub.2O.sub.3  14.5-16.5% CaO  10.6-11.7% MgO  8-10% SrO 0.5-2%  Na.sub.2O + K.sub.2O 0.1-1%  Li.sub.2O 0.05-0.7% Fe.sub.2O.sub.3 0.05-0.7% TiO.sub.2 0.05-0.8% F.sub.2 <0.5% wherein, the range of the weight percentage ratio C1=(MgO+SrO)/CaO is 0.8-1, and the range of the weight percentage ratio C2=CaO/MgO is greater than 1 and less than 1.3.

8. A glass fiber being produced from the glass fiber compositions described in claim 1.

9. The glass fiber of claim 8, wherein the range of the weight percentage ratio C2=CaO/MgO is greater than 1 and less than 1.3, and the range of the weight percentage ratio C1=(MgO+SrO)/CaO is 0.8-1.

10. The glass fiber of claim 8, wherein the content of CaO expressed as percentage by weight is greater than 10.5% and less than 11.8%.

11. The glass fiber of claim 8, comprising the following components expressed as percentage by weight: TABLE-US-00021 SiO.sub.2  59-62% Al.sub.2O.sub.3 14.5-18%  CaO >10.5% and <11.8% MgO    8-10.5% SrO 0.5-2%  Na.sub.2O + K.sub.2O 0.1-2%  Li.sub.2O 0.05-0.9% Fe.sub.2O.sub.3 0.05-1%   TiO.sub.2 0.05-1.1% F.sub.2 <0.5% wherein, the weight percentage ratio C1=(MgO+SrO)/CaO is 0.75-1.1, and the range of the weight percentage ratio C2=CaO/MgO is less than 1.4.

12. The glass fiber of claim 8, comprising the following components expressed as percentage by weight: TABLE-US-00022 SiO.sub.2  59-62% Al.sub.2O.sub.3 14.5-18%  CaO >10.5% and <11.8% MgO    8-10.5% SrO 0.5-2%  Na.sub.2O + K.sub.2O 0.1-2%  Li.sub.2O 0.05-0.9% Fe.sub.2O.sub.3 0.05-1%   TiO.sub.2 0.05-1.1% F.sub.2 <0.5% wherein, the range of the weight percentage ratio C1=(MgO+SrO)/CaO is 0.8-1, and the range of the weight percentage ratio C2=CaO/MgO is greater than 1 and less than 1.3.

13. The glass fiber of claim 8, comprising the following components expressed as percentage by weight: TABLE-US-00023 SiO.sub.2   59-61.5% Al.sub.2O.sub.3  14.5-16.5% CaO  10.6-11.7% MgO  8-10% SrO 0.5-2%  Na.sub.2O + K.sub.2O 0.1-1%  Li.sub.2O 0.05-0.7% Fe.sub.2O.sub.3 0.05-0.7% TiO.sub.2 0.05-0.8% F.sub.2 <0.5% wherein, the range of the weight percentage ratio C1=(MgO+SrO)/CaO is 0.8-1, and the range of the weight percentage ratio C2=CaO/MgO is greater than 1 and less than 1.3.

14. A composite material incorporating the glass fiber described in claim 8.

15. The composite material of claim 14, wherein the range of the weight percentage ratio C2=CaO/MgO is greater than 1 and less than 1.3, and the range of the weight percentage ratio C1=(MgO+SrO)/CaO is 0.8-1.

16. The composite material according to claim 14, wherein the content of CaO expressed as percentage by weight is greater than 10.5% and less than 11.8%.

17. The composite material according to claim 14, comprising the following components expressed as percentage by weight: TABLE-US-00024 SiO.sub.2 >59-62% Al.sub.2O.sub.3 14.5-18% CaO >10.5% and <11.8% MgO    8-10.5% SrO 0.5-2%  Na.sub.2O + K.sub.2O 0.1-2%  Li.sub.2O 0.05-0.9% Fe.sub.2O.sub.3 0.05-1%   TiO.sub.2 0.05-1.1% F.sub.2 <0.5% wherein, the weight percentage ratio C1=(MgO+SrO)/CaO is 0.75-1.1, and the range of the weight percentage ratio C2=CaO/MgO is less than 1.4.

18. The composite material according to claim 14, comprising the following components expressed as percentage by weight: TABLE-US-00025 SiO.sub.2  59-62% Al.sub.2O.sub.3 14.5-18%  CaO >10.5% and <11.8% MgO    8-10.5% SrO 0.5-2%  Na.sub.2O + K.sub.2O 0.1-2%  Li.sub.2O 0.05-0.9% Fe.sub.2O.sub.3 0.05-1%   TiO.sub.2 0.05-1.1% F.sub.2 <0.5% wherein, the range of the weight percentage ratio C1=(MgO+SrO)/CaO is 0.8-1, and the range of the weight percentage ratio C2=CaO/MgO is greater than 1 and less than 1.3.

19. The composite material according to claim 14, comprising the following components expressed as percentage by weight: TABLE-US-00026 SiO.sub.2   59-61.5% Al.sub.2O.sub.3  14.5-16.5% CaO  10.6-11.7% MgO  8-10% SrO 0.5-2%  Na.sub.2O + K.sub.2O 0.1-1%  Li.sub.2O 0.05-0.7% Fe.sub.2O.sub.3 0.05-0.7% TiO.sub.2 0.05-0.8% F.sub.2 <0.5% wherein, the range of the weight percentage ratio C1=(MgO+SrO)/CaO is 0.8-1, and the range of the weight percentage ratio C2=CaO/MgO is greater than 1 and less than 1.3.

Description

DETAILED DESCRIPTION AND EMBODIMENTS OF THE INVENTION

(1) In order to better clarify the purposes, technical solutions and advantages of the examples of the present invention, the technical solutions in the examples of the present invention are clearly and completely described below. Obviously, the examples described herein are just part of the examples of the present invention and are not all the examples. All other exemplary embodiments obtained by one skilled in the art on the basis of the examples in the present invention without performing creative work shall all fall into the scope of protection of the present invention. What needs to be made clear is that, as long as there is no conflict, the examples and the features of examples in the present application can be arbitrarily combined with each other.

(2) The basic concept of the present invention is that the components of the glass fiber composition expressed as percentage by weight are: 58-64% SiO.sub.2, 14-19% Al.sub.2O.sub.3, ≧8.8% and <11.8% CaO, 7.5-11% MgO, 0.2-2.7% SrO, 0.1-2% Na.sub.2O+K.sub.2O, 0.05-0.9% Li.sub.2O, 0.05-1% Fe.sub.2O.sub.3, 0.05-1.1% TiO.sub.2 and <0.5% F.sub.2, wherein the range of the weight percentage ratio C1=(MgO+SrO)/CaO is 0.75-1.1 and the range of the weight percentage ratio C2=CaO/MgO is less than, 1.4. Preferably, the range of the weight percentage ratio C2=CaO/MgO can be further defined to be greater than 1 and less than 1.3. The glass fiber composition according to the present invention can overcome the issue of too high liquidus temperature and too high rate of crystallization in traditional high-performance glasses which lead to high tendency to crystallization and difficulty to achieve large-scale high-efficiency production, significantly decreases the liquidus temperature of high performance glass, increases the glass crystallization peak temperature, decreases the degree of glass crystallization under the same conditions and, meanwhile, has an outstanding glass refractive index which greatly improves transparency of glass fiber-reinforced articles.

(3) The specific content values of SiO.sub.2, Al.sub.2O.sub.3, CaO, MgO, SrO, Na.sub.2O, K.sub.2O, Fe.sub.2O.sub.3, Li.sub.2O and TiO.sub.2 in the glass fiber composition of the present invention are selected to be used in the examples and comparisons with boron-free E glass, traditional R glass and improved R glass are made in terms of the following six property parameters,

(4) (1) Forming temperature, the temperature at which the glass melt has a viscosity of 10.sup.3 poise.

(5) (2) Liquidus temperature, the temperature at which the crystal nucleuses begin to form when the glass melt cools off—i.e., the upper limit temperature for glass crystallization.

(6) (3) ΔT value, which is the difference between the forming temperature and the liquidus temperature and indicates the temperature range at which fiber drawing can be performed.

(7) (4) Peak crystallization temperature, the temperature which corresponds to the strongest peak of glass crystallization during the DTA testing. Generally, the higher this temperature is, the more energy is needed by crystal nucleuses to grow and the lower the glass crystallization tendency is.

(8) (5) Refractive index, the ratio of the speed of light in air and the speed of light in glass.

(9) (6) Young's modulus, the linear elastic modulus which define the ability of glass to resist elastic deformation.

(10) The aforementioned six parameters and the methods of measuring them are well-known to one skilled in the art. Therefore, the aforementioned parameters can be effectively used to explain the properties of the glass fiber composition of the present invention. In addition, the inventors also employ an X-ray diffractometer and a scanning electron microscope to observe the type, appearance and crystallization status of crystal phases.

(11) The specific procedures for the experiments are as follows: Each component can be acquired from the appropriate raw materials. Mix the raw materials in the appropriate proportions so that each component reaches the final expected weight percentage. The mixed batch melts and the molten glass refines. Then the molten glass is drawn out through the tips of the bushings, thereby forming the glass fiber. The glass fiber is attenuated onto the rotary collet of a winder to form cakes or packages. Of course, conventional methods can be used to deep process these glass fibers to meet the expected requirements.

(12) The exemplary embodiments of the glass fiber composition according to the present invention are given below.

EXAMPLE 1

(13) TABLE-US-00009 SiO.sub.2 60.5% Al.sub.2O.sub.3 15.5% CaO 11.4% MgO  9.1% SrO  1.3% Li.sub.2O  0.5% Na.sub.2O 0.21% K.sub.2O 0.62% Fe.sub.2O.sub.3 0.42% TiO.sub.2 0.35%

(14) Wherein, the weight percentage ratio C1=(MgO+SrO)/CaO is 0.91, and the weight percentage ratio C2=CaO/MgO is 1.25.

(15) In Example 1, the measured values of the six parameters are respectively:

(16) TABLE-US-00010 Forming temperature 1274° C. Liquidus temperature 1192° C. ΔT 82° C. Peak crystallization temperature 1034° C. Refractive index 1.569 Young's modulus 89.3 GPa

EXAMPLE 2

(17) TABLE-US-00011 SiO.sub.2 61.0% Al.sub.2O.sub.3 16.0% CaO 11.4% MgO 8.95% SrO  0.5% Li.sub.2O 0.55% Na.sub.2O 0.24% K.sub.2O 0.54% Fe.sub.2O.sub.3 0.42% TiO.sub.2  0.3%

(18) Wherein, the weight percentage ratio C1=(MgO+SrO)/CaO is 0.82, and the weight percentage ratio C2=CaO/MgO is 1.27.

(19) In Example 2, the measured values of the six parameters are respectively:

(20) TABLE-US-00012 Forming temperature 1276° C. Liquidus temperature 1194° C. ΔT 82° C. Peak crystallization temperature 1026° C. Refractive index 1.568 Young's modulus 90 GPa

EXAMPLE 3

(21) TABLE-US-00013 SiO.sub.2 60.2% Al.sub.2O.sub.3 15.55%  CaO 11.0% MgO  9.0% SrO  2.0% Li.sub.2O 0.55% Na.sub.2O 0.24% K.sub.2O 0.54% Fe.sub.2O.sub.3 0.42% TiO.sub.2  0.4%

(22) Wherein, the weight percentage ratio C1=(MgO+SrO)/CaO is 1.0, and the weight percentage ratio C2=CaO/MgO is 1.22.

(23) In example 3, the measured values of the six parameters are respectively:

(24) TABLE-US-00014 Forming temperature 1279° C. Liquidus temperature 1190° C. ΔT 89° C. Peak crystallization temperature 1039° C. Refractive index 1.570 Young's modulus 89.5 GPa

(25) Comparisons of the property parameters of the aforementioned examples and other examples of the glass fiber composition of the present invention with those of the boron-free E glass, traditional R glass and improved R glass are further made below by way of tables, wherein the component contents of the glass fiber composition are expressed as weight percentage. What needs to be made clear is that the total amount of the components in the examples is slightly less than 100%, and it should be understood that the remaining amount is trace impurities or a small amount of components which cannot be analyzed.

(26) TABLE-US-00015 TABLE 1 A1 A2 A3 A4 A5 A6 A7 Component SiO.sub.2 60.5 61.0 60.2 59.5 61.5 60.5 59.8 Al.sub.2O.sub.3 15.5 16.0 15.55 15.8 15.3 15.7 15.5 CaO 11.4 11.4 11.0 11.5 11.7 11.6 10.6 MgO 9.1 8.95 9.0 8.4 9.2 9.0 9.1 SrO 1.3 0.5 2.0 2.7 0.2 1.0 2.6 Na.sub.2O 0.21 0.24 0.24 0.22 0.23 0.2 0.4 K.sub.2O 0.62 0.54 0.54 0.56 0.55 0.6 0.4 Li.sub.2O 0.5 0.55 0.55 0.5 0.5 0.48 0.48 Fe.sub.2O.sub.3 0.42 0.42 0.42 0.42 0.42 0.42 0.42 TiO.sub.2 0.35 0.3 0.4 0.3 0.3 0.4 0.6 Ratio C1 0.91 0.82 1.0 0.96 0.80 0.86 1.1 C2 1.25 1.27 1.22 1.36 1.27 1.28 1.16 Parameter Forming 1274 1276 1279 1280 1278 1277 1278 temperature/ ° C. Liquidus 1192 1194 1190 1196 1193 1194 1193 temperature/ ° C. ΔT/° C. 82 82 89 84 85 83 85 Peak 1034 1026 1039 1023 1028 1025 1035 crystallization temperature/ ° C. Refractive 1.569 1.568 1.570 1.570 1.566 1.568 1.570 index Young's 89.3 90 89.5 88.7 88.9 89.1 89 modulus/GPa Crystallization Type of Crystal Diopside and Diopside and Diopside and Diopside and Diopside and Diopside and Diopside and status phase and anorthite anorthite anorthite anorthite anorthite anorthite anorthite diffraction 1:0.45 1:0.5 1:0.45 1:0.55 1:0.5 1:0.5 1:0.4 intensity ratio Main crystal Crystal grains Crystal grains Crystal grains Crystal grains Crystal grains Crystal grains Crystal grains phase show poor show poor show low show poor show poor show poor show poor appearance crystallinity, crystallinity, crystallinity, crystallinity, crystallinity, crystallinity, crystallinity, needle-like needle-like needle-like needle-like needle-like needle-like needle-like shapes, shapes, shapes, shapes, shapes, shapes, shapes, small sizes and small sizes and small sizes and small sizes and small sizes and small sizes and small sizes and disorderly disorderly disorderly disorderly disorderly disorderly disorderly arrangement. arrangement. arrangement. arrangement. arrangement. arrangement. arrangement.

(27) TABLE-US-00016 TABLE 2 Boron-free Traditional Improved A8 A9 A10 A11 E glass R glass R glass Component SiO.sub.2 61.3 60.6 59.4 60.4 60 60 60.75 Al.sub.2O.sub.3 15.4 15.4 17.0 15.6 13.57 25 15.80 CaO 11.3 11.0 11.2 11.5 22.46 9 13.90 MgO 8.7 9.5 9.05 8.95 2.81 6 7.90 SrO 1.0 1.3 1.05 1.25 0 0 0 Na.sub.2O 0.21 0.25 0.4 0.24 0.27 trace amount 0.73 K.sub.2O 0.36 0.47 0.43 0.53 0.32 trace amount Li.sub.2O 0.81 0.46 0.55 0.51 0 0 0.48 Fe.sub.2O.sub.3 0.42 0.42 0.42 0.42 0.29 trace amount 0.18 TiO.sub.2 0.4 0.5 0.4 0.5 0.2 trace amount 0.12 Ratio C1 0.85 1.0 0.9 0.88 0.12 0.66 0.57 C2 1.29 1.15 1.23 1.28 7.99 1.5 1.75 Parameter Forming 1268 1279 1280 1278 1270 1430 1278 temperature/ ° C. Liquidus 1188 1191 1194 1191 1190 1350 1210 temperature/ ° C. ΔT/° C. 80 88 86 87 80 80 68 Peak 1043 1033 1030 1036 / 1010 1016 crystallization temperature/ ° C. Refractive 1.569 1.568 1.567 1.569 1.564 1.561 1.563 index Young's 89.4 88.7 89.3 89.1 81 91 87.5 modulus/GPa Crystallization Type of Crystal Diopside and Diopside and Diopside and Diopside and Wollastonite and Diopside and Diopside and status phase and anorthite anorthite anorthite anorthite anorthite anorthite anorthite diffraction 1:0.5 1:0.4 1:0.45 1:0.5 — 1:0.8 1:0.6 intensity ratio Main crystal Crystal Crystal Crystal Crystal grains / Crystal grains Crystal grains phase grains grains grains show poor show complete show complete appearance show poor show low show poor crystallinity, crystallinity, crystallinity, crystallinity, crystallinity, crystallinity, needle-like shapes, rod-like shapes, rod-like shapes, needle-like needle-like needle-like small sizes and bigger sizes bigger sizes shapes, shapes, shapes, disorderly and orderly and orderly small sizes small sizes small sizes arrangement. arrangement. arrangement. and and and disorderly disorderly disorderly arrangement. arrangement. arrangement.

(28) It can be seen from the values in the above tables that, compared with the traditional R glass and the improved R glass, the glass fiber composition of the present invention has the following advantages: (1) much lower liquidus temperature, which helps to reduce crystallization risk and increase the fiber drawing efficiency; (2) relatively high peak crystallization temperature, which indicates that more energy is needed for the formation and growth of crystal nucleuses during the crystallization process of glass, i.e. the crystallization risk of the glass of the present invention is smaller under the same conditions; (3) The crystal phases show less complete crystallinity, relatively small crystal grain size and disorderly arrangement, which indicate that the crystallization degree of the glass of the present invention is lower, thereby further reducing crystallization risk; in addition, the examples which meet the preferred ranges of both the ratios C1 and C2 have more significantly improved effects, and (4) significantly improved glass refractive index. At the same time, compared with the improved R glass, the glass fiber composition of the present invention has higher modulus, which indicates that the compact stacking structure achieved by the designed ternary alkali earth effect of the present invention has a greater effect on improving the mechanical properties of the glass. In addition, compared with the mainstream boron-free E glass, the crystallization performance and forming performance of the glass fiber composition of the present invention are similar and meet the requirements of large-scale high-efficiency production with refractory-lined furnaces.

(29) It can be seen from the above that the glass fiber composition of the present invention has breakthrough progress in improving the crystallization performance and in the refractive index of the R glass-grade glasses, has greatly reduced crystallization risk and significantly increased refractive index under the same conditions. In addition, the crystallization performance and fiberizing performance of the overall technical solution are similar to those of the mainstream boron-free E glass and enables easy achievement of large-scale high-efficiency production with a direct-melt process in a refractory-lined furnace.

(30) The glass fiber composition according to the present invention can be used for making glass fibers having the aforementioned excellent properties.

(31) The glass fiber composition according to the present invention in combination with one or more organic and/or inorganic materials can be used for preparing composite materials having excellent performances, such as glass fiber reinforced base materials.

(32) Finally, what is should be made clear is that, in this text, the terms “contain”, “comprise” or any other variants are intended to mean “nonexclusively include” so that any process, method, article or equipment that contains a series of factors shall include not only such factors, but also include other factors that are not explicitly listed, or also include intrinsic factors of such process, method, object or equipment. Without more limitations, factors defined by the phrase “contain a . . . ” do not rule out that there are other same factors in the process, method, article or equipment which include said factors.

(33) The above examples are provided only for the purpose of illustrating instead of limiting the technical solutions of the present invention. Although the present invention is described in details by way of aforementioned examples, one skilled in the art shall understand that modifications can also be made to the technical solutions embodied by all the aforementioned examples or equivalent replacement can be made to some of the technical features. However, such modifications or replacements will not cause the resulting technical solutions to substantially deviate from the spirits and ranges of the technical solutions respectively embodied by all the examples of the present invention.

INDUSTRIAL APPLICABILITY OF THE INVENTION

(34) The glass fiber composition of the present invention not only ensures that the glass fiber has high mechanical properties and low forming temperature, but also overcomes the issue of too high liquidus temperature and too high rate of crystallization in traditional high-performance glasses which lead to high tendency to crystallization and difficulty to achieve large-scale high-efficiency production, significantly decreases the liquidus temperature of high performance glass, increases the glass crystallization peak temperature, decreases the degree of glass crystallization under the same conditions and, meanwhile, has an outstanding glass refractive index which greatly improves transparency of glass fiber-reinforced articles.