GLASS FIBER COMPOSITION, GLASS FIBER AND COMPOSITE MATERIAL THEREFROM

Abstract

The present invention provides a glass fiber composition, glass fiber and composite material therefrom. The glass fiber composition comprises the following components expressed as percentage by weight: 58-63% SiO.sub.2, 13-17% Al.sub.2O.sub.3, 6-11.8% CaO, 7-11% MgO, 3.05-8% SrO, 0.1-2% Na.sub.2O+K.sub.2O+Li.sub.2O, 0.1-1% Fe.sub.2O.sub.3, 0-1% CeO.sub.2 and 0-2% TiO.sub.2, wherein a weight percentage ratio C1=(MgO+SrO)/CaO is greater than 1. Said composition greatly improves the refractive index of glass, significantly shields against harmful rays for humans and further reduces glass crystallization risk and production costs, thereby making it more suitable for large-scale production with refractory-lined furnaces.

Claims

1. A glass fiber composition, comprising the following components expressed as percentage by weight: TABLE-US-00017 SiO.sub.2 58-63% Al.sub.2O.sub.3 13-17% CaO 6-11.8% MgO 7-11% SrO 3.05-8% Na.sub.2O + K.sub.2O + Li.sub.2O 0.1-2% Fe.sub.2O.sub.3 0.1-1% CeO.sub.2 .sup.0-1% TiO.sub.2 .sup.0-2% wherein, a weight percentage ratio C1=(MgO+SrO)/CaO is greater than 1.

2. The glass fiber composition according to claim 1, wherein a weight percentage ratio C2=MgO/SrO is greater than 2.

3. The glass fiber composition according to claim 1, wherein a weight percentage ratio C3=K.sub.2O/(Na.sub.2O+Li.sub.2O) is 0.8-1.5, and a weight percentage ratio C4=Li.sub.2O/Na.sub.2O is 1-4.

4. The glass fiber composition according to claim 1, wherein the weight percentage ratio C1=(MgO+SrO)/CaO is 1.05-1.85.

5. The glass fiber composition according to claim 1, wherein the content range of CeO.sub.2, by weight, is 0.02-0.4%.

6. 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 14-16.5% CaO 8-11% MgO 8-10% SrO 3.05-5% Na.sub.2O + K.sub.2O + Li.sub.2O 0.1-2% Fe.sub.2O3 0.1-1% CeO.sub.2 .sup.0-1% TiO.sub.2 .sup.0-2% wherein, the weight percentage ratio C1=(MgO+SrO)/CaO is 1.05-1.85, and a weight percentage ratio C2=MgO/SrO is greater than 2.

7. 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 14-16.5% CaO 8-11% MgO 8-10% SrO 3.1-4.5% Na.sub.2O + K.sub.2O + Li.sub.2O .sup.0.1-2% Fe.sub.2O.sub.3 .sup.0.1-1% CeO.sub.2 0.02-0.4% TiO.sub.2 0.1-1.5% wherein, the weight percentage ratio C1=(MgO+SrO)/CaO is greater than 1; a weight percentage ratio C2=MgO/SrO is greater than 2; a weight percentage ratio C3=K.sub.2O/(Na.sub.2O+Li.sub.2O) is 0.8-1.5; and a weight percentage ratio C4=Li.sub.2O/Na.sub.2O is 1-4.

8. The glass fiber composition according to claim 1, comprising the following components expressed as percentage by weight: TABLE-US-00020 SiO.sub.2 59-62% Al.sub.2O.sub.3 14-16.5% CaO 8-11% MgO 8-10% SrO 3.1-4.5%.sup. Na.sub.2O + K.sub.2O + Li.sub.2O 0.1-2% Fe.sub.2O.sub.3 0.1-1% TiO.sub.2 0.1-1.5%.sup. wherein, the weight percentage ratio C1=(MgO+SrO)/CaO is 1.05-1.85; a weight percentage ratio C2=MgO/SrO is 2.05-3.0; a weight percentage ratio C3=K.sub.2O/(Na.sub.2O+Li.sub.2O) is 0.85-1.25; and a weight percentage ratio C4=Li.sub.2O/Na.sub.2O is 1.5-3.0.

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

10. A composite material incorporating the glass fiber described in claim 9.

11. The glass fiber composition according to claim 1, wherein the content range of CaO, by weight, is 8-11%.

12. The glass fiber composition according to claim 2, wherein the content range of CaO, by weight, is 8-11%.

13. The glass fiber according to claim 9, wherein a weight percentage ratio C2=MgO/SrO is greater than 2, and a weight percentage ratio C3=K.sub.2O/(Na.sub.2O+Li.sub.2O) is 0.8-1.5, and a weight percentage ratio C4=Li.sub.2O/Na.sub.2O is 1-4.

14. The glass fiber according to claim 9, wherein a weight percentage ratio C2=MgO/SrO is greater than 2, and the weight percentage ratio C1=(MgO+SrO)/CaO is 1.05-1.85.

15. The glass fiber according to claim 9, comprising the following components expressed as percentage by weight: TABLE-US-00021 SiO.sub.2 59-62% Al.sub.2O.sub.3 14-16.5% CaO 8-11% MgO 8-10% SrO 3.05-5% Na.sub.2O + K.sub.2O + Li.sub.2O 0.1-2% Fe.sub.2O.sub.3 0.1-1% CeO.sub.2 .sup.0-1% TiO.sub.2 .sup.0-2% wherein, the weight percentage ratio C1=(MgO+SrO)/CaO is 1.05-1.85, and a weight percentage ratio C2=MgO/SrO is greater than 2.

16. The glass fiber according to claim 9, comprising the following components expressed as percentage by weight: TABLE-US-00022 SiO.sub.2 59-62% Al.sub.2O.sub.3 14-16.5% CaO 8-11% MgO 8-10% SrO 3.1-4.5% Na.sub.2O + K.sub.2O + Li.sub.2O .sup.0.1-2% Fe.sub.2O.sub.3 .sup.0.1-1% CeO.sub.2 0.02-0.4% TiO.sub.2 0.1-1.5% wherein, the weight percentage ratio C1=(MgO+SrO)/CaO is greater than 1; a weight percentage ratio C2=MgO/SrO is greater than 2; a weight percentage ratio C3=K.sub.2O/(Na.sub.2O+Li.sub.2O) is 0.8-1.5; and a weight percentage ratio C4=Li.sub.2O/Na.sub.2O is 1-4.

17. The composite material according to claim 10, wherein the content range of CaO, by weight, is 8-11%.

18. The composite material according to claim 10, wherein a weight percentage ratio C2=MgO/SrO is greater than 2, and the content range of CaO, by weight, is 8-11%.

19. The composite material according to claim 10, comprising the following components expressed as percentage by weight: TABLE-US-00023 SiO.sub.2 59-62% Al.sub.2O.sub.3 14-16.5% CaO 8-11% MgO 8-10% SrO 3.05-5% Na.sub.2O + K.sub.2O + Li.sub.2O 0.1-2% Fe.sub.2O.sub.3 0.1-1% CeO.sub.2 .sup.0-1% TiO.sub.2 .sup.0-2% wherein, the weight percentage ratio C1=(MgO+SrO)/CaO is 1.05-1.85, and a weight percentage ratio C2=MgO/SrO is greater than 2.

20. The composite material according to claim 10, comprising the following components expressed as percentage by weight: TABLE-US-00024 SiO.sub.2 59-62% Al.sub.2O.sub.3 14-16.5% CaO 8-11% MgO 8-10% SrO 3.1-4.5%.sup. Na.sub.2O + K.sub.2O + Li.sub.2O 0.1-2% Fe.sub.2O.sub.3 0.1-1% TiO.sub.2 0.1-1.5%.sup. wherein, the weight percentage ratio C1=(MgO+SrO)/CaO is 1.05-1.85; a weight percentage ratio C2=MgO/SrO is 2.05-3.0; a weight percentage ratio C3=K.sub.2O/(Na.sub.2O+Li.sub.2O) is 0.85-1.25; and a weight percentage ratio C4=Li.sub.2O/Na.sub.2O is 1.5-3.0.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0066] 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 by way of the drawings in the examples. 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.

[0067] The basic concept of the present invention is, by making full use of the synergistic effect of CaO, MgO and SrO, selecting an appropriate content range for each of them and the ratios therebetween, and adjusting the proportions for trace amounts of other components introduced, a glass fiber is formed with an improved refractive index and an excellent effect in shielding against harmful rays for humans.

[0068] In accordance with the specific embodiments mentioned above, 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, CeO.sub.2 and TiO.sub.2 in the glass fiber composition of the present invention are selected to be used in the examples, which are compared with the properties of traditional E and R glasses in terms of the following five property parameters,

[0069] (1) Forming temperature, the temperature at which the glass melt has a viscosity of 10.sup.3 poise.

[0070] (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.

[0071] (3) ?T 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.

[0072] (4) Filament strength, the tensile strength that a filament of glass fiber strand can withstand.

[0073] 5) Refractive index, the ratio of the speed of light in air and the speed of light in glass.

[0074] The aforementioned five 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.

[0075] The specific procedures for the experiments are as follows: Each component can be acquired from the appropriate raw materials; the raw materials are mixed in the appropriate proportions so that each component reaches the final expected weight percentage; the mixed batch is melted and clarified; 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 deeply process these glass fibers to meet the expected requirements.

[0076] The exemplary embodiments of the glass fiber composition according to the present invention are given below.

Example 1

[0077] A glass fiber composition comprises the following components expressed as percentage by weight,

TABLE-US-00009 SiO.sub.2 59.5% Al.sub.2O.sub.3 15.2% CaO 11.2% MgO 8.0% SrO 3.85% Na.sub.2O 0.2% K.sub.2O 0.6% Li.sub.2O 0.4% Fe.sub.2O.sub.3 0.4% CeO.sub.2 0% TiO.sub.2 0.65%

[0078] wherein, the weight percentage ratio C1=(MgO+SrO)/CaO is 1.06, and the weight percentage ratio C2=MgO/SrO is 2.08, and the weight percentage ratio C3=K.sub.2O/(Na.sub.2O+Li.sub.2O) is 1.0.

[0079] In Example 1, the measured values of the five parameters are respectively:

TABLE-US-00010 Forming temperature 1280? C. Liquidus temperature 1196? C. ?T 84? C. Filament strength 4153 MPa Refractive index 1.571

Example 2

[0080] A glass fiber composition comprises the following components expressed as percentage by weight,

TABLE-US-00011 SiO.sub.2 59.7% Al.sub.2O.sub.3 15.4% CaO 8.3% MgO 10% SrO 4.5% Na.sub.2O 0.2% K.sub.2O 0.5% Li.sub.2O 0.4% Fe.sub.2O.sub.3 0.3% CeO.sub.2 .sup.0% TiO.sub.2 0.7%

[0081] wherein, the weight percentage ratio C1=(MgO+SrO)/CaO is 1.65, and the weight percentage ratio C2=MgO/SrO is 2.50, and the weight percentage ratio C3=K.sub.2O/(Na.sub.2O+Li.sub.2O) is 0.84.

[0082] In Example 2, the measured values of the five parameters are respectively:

TABLE-US-00012 Forming temperature 1282? C. Liquidus temperature 1195? C. ?T 87? C. Filament strength 4164 MPa Refractive index 1.570

Example 3

[0083] A glass fiber composition comprises the following components expressed as percentage by weight,

TABLE-US-00013 SiO.sub.2 59.0% Al.sub.2O.sub.3 15.3% CaO 10.5% MgO 9.3% SrO 3.1% Na.sub.2O 0.2% K.sub.2O 0.55% Li.sub.2O 0.45% Fe.sub.2O.sub.3 0.4% CeO.sub.2 0% TiO.sub.2 0.5%

[0084] wherein, the weight percentage ratio C1=(MgO+SrO)/CaO is 1.18, and the weight percentage ratio C2=MgO/SrO is 3.0, and the weight percentage ratio C3=K.sub.2O/(Na.sub.2O+Li.sub.2O) is 0.85.

[0085] In Example 3, the measured values of the five parameters are respectively:

TABLE-US-00014 Forming temperature 1280? C. Liquidus temperature 1196? C. ?T 84? C. Filament strength 4140 MPa Refractive index 1.569

[0086] 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 traditional 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.

TABLE-US-00015 TABLE 1 A1 A2 A3 A4 A5 A6 A7 Component SiO.sub.2 60.0 59.5 59.7 59.4 59.0 59.3 60.3 Al.sub.2O.sub.3 15.5 15.2 15.4 15.4 15.3 16.0 14.5 CaO 10.8 11.2 8.3 8.25 10.5 10.2 11.0 MgO 8.3 8.0 10 10.25 9.3 8.4 8.6 SrO 3.05 3.85 4.5 5.0 3.1 3.3 3.5 Na.sub.2O 0.2 0.2 0.2 0.15 0.2 0.2 0.2 K.sub.2O 0.65 0.6 0.5 0.55 0.55 0.5 0.6 Li.sub.2O 0.5 0.4 0.4 0.5 0.45 0.2 0.5 Fe.sub.2O.sub.3 0.4 0.4 0.3 0.3 0.4 0.4 0.3 TiO.sub.2 0.6 0.65 0.7 0.2 0.5 1.5 0.5 CeO.sub.2 0 0 0 0 0 0 0 Ratio C1 1.05 1.06 1.65 1.85 1.18 1.15 1.10 C2 2.72 2.08 2.50 2.05 3.0 2.55 2.46 C3 0.93 1.0 0.84 0.85 0.85 1.25 0.86 C4 Parameter Forming 1279 1280 1282 1284 1280 1278 1282 tempera- ture/? C. Liquidus 1198 1196 1195 1193 1196 1193 1195 tempera- ture/? C. ?T/? C. 81 84 87 91 84 85 87 Filament 4136 4153 4164 4172 4140 4100 4152 strength/ MPa Refractive 1.568 1.571 1.570 1.572 1.569 1.569 1.570 index

TABLE-US-00016 TABLE 2 Traditional Traditional Improved A8 A9 A10 A11 E glass R glass R glass Component SiO.sub.2 59.2 59.3 58.7 59.5 54.16 60 58 Al.sub.2O.sub.3 15.2 15.0 15.0 15.5 14.32 25 17.9 CaO 9.0 8.7 9.0 11.1 22.12 9 14.4 MgO 8.6 8.0 7.0 8.7 0.41 6 8.5 SrO 6.0 7.0 8.0 3.1 0 0 0 B.sub.2O.sub.3 0 0 0 0 7.6 0 0 Na.sub.2O 0.2 0.2 0.2 0.2 0.45 trace 0.1 amount K.sub.2O 0.6 0.6 0.6 0.65 0.25 trace 0.6 amount Li.sub.2O 0.5 0.5 0.5 0.45 0 0 0 Fe.sub.2O.sub.3 0.38 0.3 0.4 0.4 0.35 trace trace amount amount TiO.sub.2 0.3 0.3 0.6 0.4 0.34 trace 0.2 amount CeO.sub.2 0.02 0 0 0 0 0 0 Ratio C1 1.62 1.72 1.66 1.06 0.02 0.67 0.59 C2 1.43 1.14 0.88 2.81 C3 0.86 0.86 0.86 1.0 0.55 6.0 C4 Parameter Forming 1285 1287 1288 1282 1175 1430 1289 tempera- ture/? C. Liquidus 1205 1206 1208 1196 1075 1350 1280 tempera- ture/? C. ?T/? C. 80 81 80 86 100 80 9 Filament 4110 4105 4102 4146 3265 4220 4089 strength/ MPa Refractive 1.571 1.572 1.573 1.569 1.566 1.561 1.562 index

[0087] It can be seen from the values in the above tables that, compared with the traditional R glass, the glass fiber composition of the present invention has much lower forming temperature and liquidus temperature, which helps to reduce energy consumption and increase the fiber drawing efficiency; furthermore, the present invention offers an improved glass refractive index; in the meantime, the filament strength of the present invention is similar to that of R glass fiber. The improved R glass has a significantly reduced forming temperature, but its crystallization temperature still remains high thereby resulting in a high crystallization risk, and the temperature range fit for fiber forming is very small and thus the efficiency for mass production is very low. Meanwhile, the refractive index of improved R glass is similar to that of traditional R glass. Compared with the improved R glass, the glass fiber composition of the present invention has a much lower liquidus temperature, a much wider temperature range fit for fiber forming and a fairly increased glass refractive index, and also its filament strength is slightly higher. Compared with the traditional E glass, the glass fiber composition of the present invention has much higher filament strength. Specifically, compared with R glass, the glass fiber composition of the present invention has made a breakthrough in terms of the melting performance of glass with significantly reduced amount of bubbles under the same conditions. Furthermore, the overall technical solution of the present invention has a higher cost performance ratio compared with that of traditional R glass or improved R glass, thereby enabling the easy achievement of large-scale industrial production.

[0088] By rationally determining the content ratios among CaO, MgO and SrO, and setting the content of SrO above 3%, the present invention ensures that the resulting glass fiber has higher mechanical properties and lower crystallization temperature and risk, effectively increases the refractive index of glass, and significantly shields against harmful rays for humans; meanwhile, it greatly improves the melting and fiber forming efficiencies of glass by enabling a melting temperature and a fiberizing temperature significantly lower than those of R glass, and further reduces the amount of bubbles, viscosity and crystallization risk of glass. Therefore, the glass fiber composition of the present invention is more suitable for large-scale production with refractory-lined furnaces.

[0089] The glass fiber composition according to the present invention can be used for making glass fibers having the aforementioned excellent properties.

[0090] The glass fiber composition according to the present invention can be used in combination with one or more organic and/or inorganic materials for preparing composite materials having excellent performances, such as glass fiber reinforced base materials.

[0091] 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.

[0092] 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

[0093] The glass fiber composition of the present invention ensures that the resulted glass fiber has higher mechanical properties and lower crystallization temperature and risk, greatly improves the refractive index of glass, and significantly shields against harmful rays for humans; meanwhile, it greatly improves the melting effect and fiber forming efficiencies of glass and enable its melting temperature and fiberizing temperature are significantly lower than those of R glass, and further reduces the amount of bubbles, viscosity and crystallization risk of glass. Therefore, the glass fiber composition of the present invention is more suitable for large-scale production with refractory-lined furnaces. The glass fiber composition according to the present invention can be used for making glass fibers having the aforementioned excellent properties, and the glass fiber composition according to the present invention can be used in combination with one or more organic and/or inorganic materials for preparing composite materials having excellent performances, such as glass fiber reinforced base materials.