HIGH-MODULUS GLASS FIBER COMPOSITION, GLASS FIBER AND COMPOSITE MATERIAL THEREOF

Abstract

A high-modulus glass fiber composition includes the following components with corresponding amounts by weight percentage: 43-58% of SiO.sub.2, 15.5-23% of Al.sub.2O.sub.3, 8-18% of MgO, ≥25% of Al.sub.2O.sub.3+MgO, 0.1-7.5% of CaO, 7.1-22% of Y.sub.2O.sub.3, ≥16.5% of MgO+Y.sub.2O.sub.3, 0.01-5% of TiO.sub.2, 0.01-1.5% of Fe.sub.2O.sub.3, 0.01-2% of Na.sub.2O, 0-1.5% of K.sub.2O, 0-0.9% of Li.sub.2O, 0-4% of SrO, and 0-5% of La.sub.2O.sub.3+CeO.sub.2.

Claims

1.-28. (canceled)

29. A high-modulus glass fiber composition, comprising the following components with corresponding amounts by weight percentage: TABLE-US-00021 SiO.sub.2  43-58% Al.sub.2O.sub.3 15.5-23%  MgO .sup. 8-18% Al.sub.2O.sub.3 + MgO .sup. ≥25% CaO 0.1-7.5%  Y.sub.2O.sub.3 7.1-22% MgO + Y.sub.2O.sub.3 ≥16.5% TiO.sub.2 0.01-5% Fe.sub.2O.sub.3 0.01-1.5%.sup.  Na.sub.2O 0.01-2% K.sub.2O  0-1.5% Li.sub.2O  0-0.9% SrO   0-4% La.sub.2O.sub.3 + CeO.sub.2    0-5%.

30. The high-modulus glass fiber composition of claim 29, comprising the following components with corresponding amounts by weight percentage: TABLE-US-00022 SiO.sub.2  43-58% Al.sub.2O.sub.3 15.5-23%  MgO .sup. 8-18% Al.sub.2O.sub.3 + MgO .sup. ≥25% CaO 0.1-7.5%  Y.sub.2O.sub.3 7.1-22% MgO + Y.sub.2O.sub.3 ≥16.5% TiO.sub.2 0.01-5% Fe.sub.2O.sub.3 0.01-1.5%.sup.  Na.sub.2O 0.01-2% K.sub.2O  0-1.5% Li.sub.2O  0-0.9% SrO   0-4% La.sub.2O.sub.3 + CeO.sub.2   0-5% ZrO.sub.2    0-2%.

31. The high-modulus glass fiber composition of claim 29, comprising the following components with corresponding amounts by weight percentage: TABLE-US-00023 SiO.sub.2  43-58% Al.sub.2O.sub.3 15.5-23%  MgO .sup. 8-18% Al.sub.2O.sub.3 + MgO .sup. ≥25% CaO 0.1-7.5%  Y.sub.2O.sub.3 7.1-22% MgO + Y.sub.2O.sub.3 ≥16.5% TiO.sub.2 0.01-5% Fe.sub.2O.sub.3 0.01-1.5%.sup.  Na.sub.2O 0.01-2% K.sub.2O  0-1.5% Li.sub.2O  0-0.9% SrO   0-4% La.sub.2O.sub.3 + CeO.sub.2    0-5%, wherein a total weight percentage of the above components is greater than or equal to 98%.

32. The high-modulus glass fiber composition of claim 29, wherein a weight percentage ratio C1═MgO/CaO is greater than or equal to 1.7.

33. The high-modulus glass fiber composition of claim 29, wherein a weight percentage ratio C2═Y.sub.2O.sub.3/MgO is greater than or equal to 0.8.

34. The high-modulus glass fiber composition of claim 29, wherein a weight percentage ratio C3═Y.sub.2O.sub.3/CaO is greater than or equal to 1.9.

35. The high-modulus glass fiber composition of claim 29, wherein a weight percentage ratio C4═Al.sub.2O.sub.3/Y.sub.2O.sub.3 is 1-2.5.

36. The high-modulus glass fiber composition of claim 29, wherein the weight percentage of Y.sub.2O.sub.3 is 10.1-20%.

37. The high-modulus glass fiber composition of claim 29, wherein the weight percentage of SiO.sub.2 is 44-55.9%.

38. The high-modulus glass fiber composition of claim 29, wherein the weight percentage of Al.sub.2O.sub.3 is 15.8-20.4%.

39. The high-modulus glass fiber composition of claim 29, wherein the weight percentage of CaO is 0.5-5.9%.

40. The high-modulus glass fiber composition of claim 29, wherein a weight percentage ratio C1═MgO/CaO is greater than or equal to 1.7, and a weight percentage ratio C2═Y.sub.2O.sub.3/MgO is greater than or equal to 0.8.

41. The high-modulus glass fiber composition of claim 29, wherein a weight percentage ratio C2═Y.sub.2O.sub.3/MgO is greater than or equal to 0.8, and a weight percentage ratio C3═Y.sub.2O.sub.3/CaO is greater than or equal to 2.1.

42. The high-modulus glass fiber composition of claim 29, wherein a weight percentage ratio C1═MgO/CaO is greater than or equal to 1.7, a weight percentage ratio C2═Y.sub.2O.sub.3/MgO is greater than or equal to 0.8, and a weight percentage ratio C3═Y.sub.2O.sub.3/CaO is greater than or equal to 2.1.

43. The high-modulus glass fiber composition of claim 29, comprising the following components with corresponding amounts by weight percentage: TABLE-US-00024 SiO.sub.2 44-55.9% Al.sub.2O.sub.3 15.5-23% MgO   8-18% Al.sub.2O.sub.3 + MgO   ≥25% CaO  0.1-7.5% Y.sub.2O.sub.3 10.1-20% MgO + Y.sub.2O.sub.3 18.1-33% TiO.sub.2  0.01-5% Fe.sub.2O.sub.3 0.01-1.5%  Na.sub.2O  0.01-2% K.sub.2O  0-1.5% Li.sub.2O  0-0.9% SrO    0-4% La.sub.2O.sub.3 + CeO.sub.2   0-5%, wherein a weight percentage ratio C1═MgO/CaO is greater than or equal to 1.7.

44. The high-modulus glass fiber composition of claim 29, comprising the following components with corresponding amounts by weight percentage: TABLE-US-00025 SiO.sub.2 44-55.9%  Al.sub.2O.sub.3 15.8-20.4%   MgO .sup. 8-16% Al.sub.2O.sub.3 + MgO ≥26.5% CaO 0.1-6.5%  Y.sub.2O.sub.3 7.1-22% MgO + Y.sub.2O.sub.3 ≥16.5% TiO.sub.2 0.01-5% Fe.sub.2O.sub.3 0.01-1.5%.sup.  Na.sub.2O 0.01-2% K.sub.2O  0-1.5% Li.sub.2O  0-0.9% SrO   0-4% La.sub.2O.sub.3 + CeO.sub.2    0-5%, wherein a weight percentage ratio C1═MgO/CaO is greater than or equal to 1.7, and a weight percentage ratio C2═Y.sub.2O.sub.3/MgO is greater than or equal to 0.8.

45. The high-modulus glass fiber composition of claim 29, further comprising one or more of ZrO.sub.2, ZnO, B.sub.2O.sub.3, F.sub.2 and SO.sub.3, with a combined weight percentage of the one or more of ZrO.sub.2, ZnO, B.sub.2O.sub.3, F.sub.2 and SO.sub.3 being less than 4%.

46. The high-modulus glass fiber composition of claim 29, comprising the following components with corresponding amounts by weight percentage: TABLE-US-00026 SiO.sub.2 44-55.9%  Al.sub.2O.sub.3 15.5-23%  MgO .sup. 8-18% Al.sub.2O.sub.3 + MgO .sup. ≥25% CaO 0.1-7.5%  Y.sub.2O.sub.3 7.1-22% MgO + Y.sub.2O.sub.3 ≥16.5% TiO.sub.2 0.01-5% Fe.sub.2O.sub.3 0.01-1.5%.sup.  Na.sub.2O 0.01-2% K.sub.2O  0-1.5% Li.sub.2O  0-0.9% SrO   0-4% La.sub.2O.sub.3 + CeO.sub.2    0-5%, wherein the total weight percentage of the above components is greater than or equal to 99.5%.

47. A glass fiber, being produced using the high-modulus glass fiber composition of claim 29.

48. A composite material, comprising the glass fiber of claim 47.

Description

PREFERRED EXAMPLE 1

[0079] The high-modulus glass fiber composition according to the present invention comprises the following components expressed as percentage by weight:

TABLE-US-00008 SiO.sub.2 44-55.9%  Al.sub.2O.sub.3 15.8-20.4%   MgO .sup. 8-18% Al.sub.2O.sub.3 + MgO .sup. ≥25% CaO 0.1-7.5%  Y.sub.2O.sub.3 7.1-22% MgO + Y.sub.2O.sub.3 ≥16.5% TiO.sub.2 0.01-5% Fe.sub.2O.sub.3 0.01-1.5%.sup.  Na.sub.2O 0.01-2% K.sub.2O  0-1.5% Li.sub.2O  0-0.9% SrO   0-4% La.sub.2O.sub.3 + CeO.sub.2   0-5%
wherein, the total weight percentage of the above components is greater than or equal to 98%, the weight percentage ratio C1═MgO/CaO is greater than or equal to 1.7, and the weight percentage ratio C2═Y.sub.2O.sub.3/MgO is greater than or equal to 0.8.

PREFERRED EXAMPLE 2

[0080] The high-modulus glass fiber composition according to the present invention comprises the following components expressed as percentage by weight:

TABLE-US-00009 SiO.sub.2 44-55.9%  Al.sub.2O.sub.3 15.8-20.4%   MgO .sup. 8-16% Al.sub.2O.sub.3 + MgO ≥26.5% CaO 0.1-6.5%  Y.sub.2O.sub.3 7.1-22% MgO + Y.sub.2O.sub.3 ≥16.5% TiO.sub.2 0.01-5% Fe.sub.2O.sub.3 0.01-1.5%.sup.  Na.sub.2O 0.01-2% K.sub.2O  0-1.5% Li.sub.2O  0-0.9% SrO   0-4% La.sub.2O.sub.3 + CeO.sub.2   0-5%
wherein, the weight percentage ratio C1═MgO/CaO is greater than or equal to 2.0, and the weight percentage ratio C2═Y.sub.2O.sub.3/MgO is greater than or equal to 0.9.

PREFERRED EXAMPLE 3

[0081] The high-modulus glass fiber composition according to the present invention comprises the following components expressed as percentage by weight:

TABLE-US-00010 SiO.sub.2 44-55.9% Al.sub.2O.sub.3 15.8-21% MgO 9.4-13.5%  Al.sub.2O.sub.3 + MgO  ≥26.5% CaO  0.1-6.5% Y.sub.2O.sub.3 10.1-20% MgO + Y.sub.2O.sub.3 19.5-33% TiO.sub.2  0.01-5% Fe.sub.2O.sub.3 0.01-1.5%  Na.sub.2O  0.01-2% K.sub.2O  0-1.5% Li.sub.2O  0-0.9% SrO    0-4% La.sub.2O.sub.3 + CeO.sub.2    0-5%

PREFERRED EXAMPLE 4

[0082] The high-modulus glass fiber composition according to the present invention comprises the following components expressed as percentage by weight:

TABLE-US-00011 SiO.sub.2 44-55.9%  Al.sub.2O.sub.3 15.5-23%  MgO .sup. 8-18% Al.sub.2O.sub.3 + MgO .sup. ≥25% CaO 0.1-7.5%  Y.sub.2O.sub.3 7.1-22% MgO + Y.sub.2O.sub.3 ≥16.5% TiO.sub.2 0.01-5% Fe.sub.2O.sub.3 0.01-1.5%.sup.  Na.sub.2O 0.01-2% K.sub.2O  0-1.5% Li.sub.2O  0-0.9% SrO   0-4% La.sub.2O.sub.3 + CeO.sub.2   0-5% ZrO.sub.2  0-0.3%
wherein, the weight percentage ratio C1═MgO/CaO is greater than or equal to 1.7.

PREFERRED EXAMPLE 5

[0083] The high-modulus glass fiber composition according to the present invention comprises the following components expressed as percentage by weight:

TABLE-US-00012 SiO.sub.2 44-55.9%  Al.sub.2O.sub.3 15.5-23%  MgO .sup. 8-18% Al.sub.2O.sub.3 + MgO .sup. ≥25% CaO 0.1-7.5%  Y.sub.2O.sub.3 7.1-22% MgO + Y.sub.2O.sub.3 ≥16.5% TiO.sub.2 0.01-5% Fe.sub.2O.sub.3 0.01-1.5%.sup.  Na.sub.2O 0.01-2% K.sub.2O  0-1.5% Li.sub.2O  0-0.9% SrO   0-4% La.sub.2O.sub.3 + CeO.sub.2   0-5%
wherein, the total weight percentage of the above components is greater than or equal to 98%, the weight percentage ratio C2═Y.sub.2O.sub.3/MgO is greater than or equal to 0.8, and the weight percentage ratio C3═Y.sub.2O.sub.3/CaO is greater than or equal to 2.1.

PREFERRED EXAMPLE 6

[0084] The high-modulus glass fiber composition according to the present invention comprises the following components expressed as percentage by weight:

TABLE-US-00013 SiO.sub.2  43-58% Al.sub.2O.sub.3 15.5-23%  MgO .sup. 8-18% Al.sub.2O.sub.3 + MgO .sup. ≥25% CaO 0.1-7.5%  Y.sub.2O.sub.3 7.1-22% MgO + Y.sub.2O.sub.3 ≥16.5% TiO.sub.2 0.01-5% Fe.sub.2O.sub.3 0.01-1.5%.sup.  Na.sub.2O 0.01-2% K.sub.2O  0-1.5% Li.sub.2O  0-0.9% SrO   0-4% La.sub.2O.sub.3 + CeO.sub.2   0-5%
wherein, the weight percentage ratio C1═MgO/CaO is greater than or equal to 1.7, the weight percentage ratio C2═Y.sub.2O.sub.3/MgO is greater than or equal to 0.8, and the weight percentage ratio C3═Y.sub.2O.sub.3/CaO is greater than or equal to 2.9.

PREFERRED EXAMPLE 7

[0085] The high-modulus glass fiber composition according to the present invention comprises the following components expressed as percentage by weight:

TABLE-US-00014 SiO.sub.2 44-55.9%  Al.sub.2O.sub.3 15.5-23%  MgO .sup. 8-18% Al.sub.2O.sub.3 + MgO .sup. ≥25% CaO 0.1-7.5%  Y.sub.2O.sub.3 7.1-22% MgO + Y.sub.2O.sub.3 ≥16.5% TiO.sub.2 0.01-5% Fe.sub.2O.sub.3 0.01-1.5%.sup.  Na.sub.2O 0.01-2% K.sub.2O  0-1.5% Li.sub.2O  0-0.9% SrO   0-4% La.sub.2O.sub.3 + CeO.sub.2   0-5%
wherein, the weight percentage ratio C3═Y.sub.2O.sub.3/CaO is greater than or equal to 2.9.

PREFERRED EXAMPLE 8

[0086] The high-modulus glass fiber composition according to the present invention comprises the following components expressed as percentage by weight:

TABLE-US-00015 SiO.sub.2  43-58% Al.sub.2O.sub.3 15.5-23%  MgO .sup. 8-18% Al.sub.2O.sub.3 + MgO .sup. ≥25% CaO 0.1-7.5%  Y.sub.2O.sub.3 7.1-22% MgO + Y.sub.2O.sub.3 ≥16.5% TiO.sub.2 0.01-5% Fe.sub.2O.sub.3 0.01-1.5%.sup.  Na.sub.2O 0.01-2% K.sub.2O  0-1.5% Li.sub.2O  0-0.9% SrO   0-4% La.sub.2O.sub.3 + CeO.sub.2   0-5%
wherein, the weight percentage ratio C1═MgO/CaO is greater than or equal to 1.7, the weight percentage ratio C2═Y.sub.2O.sub.3/MgO is greater than or equal to 0.8, and the weight percentage ratio C4═Al.sub.2O.sub.3/Y.sub.2O.sub.3 is 1-2.

DETAILED DESCRIPTION OF THE EMBODIMENTS

[0087] 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.

[0088] The basic concept of the present invention is that the components of the glass fiber composition expressed as percentage by weight are: 43-58% of SiO.sub.2, 15.5-23% of Al.sub.2O.sub.3, 8-18% of MgO, greater than or equal to 25% of (Al.sub.2O.sub.3+MgO), 0.1-7.5% of CaO, 7.1-22% of Y.sub.2O.sub.3, greater than or equal to 16.5% of (MgO+Y.sub.2O.sub.3), 0.01-5% of TiO.sub.2, 0.01-1.5% of Fe.sub.2O.sub.3, 0.01-2% of Na.sub.2O, 0-1.5% of K.sub.2O, 0-0.9% of Li.sub.2O, 0-4% of SrO, and 0-5% of (La.sub.2O.sub.3+CeO.sub.2). The composition can significantly increase the modulus of glass fiber, significantly reduce the refining temperature of molten glass, and improve the refining performance of molten glass; it can also optimize the hardening rate of molten glass, improve the cooling performance of glass fiber and reduce the crystallization rate. The composition is suitable for large-scale production of high-modulus glass fiber.

[0089] The specific content values of SiO.sub.2, Al.sub.2O.sub.3, MgO, CaO, Y.sub.2O.sub.3, TiO.sub.2, Fe.sub.2O.sub.3, Na.sub.2O, K.sub.2O, Li.sub.2O, SrO, La.sub.2O.sub.3, CeO.sub.2 and ZrO.sub.2 in the glass fiber composition of the present invention are selected to be used in the examples, and comparisons with the improved R glass, designated as B1, as disclosed in patent WO2016165506A2, the conventional R glass designated as B2, and the S glass designated as B3, are made in terms of the following eight property parameters,

[0090] (1) Forming temperature, the temperature at which the glass melt has a viscosity of 10.sup.3 poise and which represents the typical temperature for fiber formation.

[0091] (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.

[0092] (3) Refining temperature, the temperature at which the glass melt has a viscosity of 10.sup.2 poise and which represents the relative difficulty in refining molten glass and eliminating bubbles from the glass. Generally, when a refining temperature is lower, it will be more efficient to refine molten glass and eliminate bubbles under the same temperature.

[0093] (4) 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.

[0094] (5) ΔL value, which is the difference between the refining temperature and the forming temperature and indicates the hardening rate of molten glass. It can be used to represent the difficulty of glass melt cooling during fiber formation. Generally speaking, if the ΔL value is relatively small, the glass melt will be easier to cool off under the same fiberizing conditions, which is conducive to efficient drawing of glass fiber.

[0095] (6) Elastic modulus, the modulus defining the ability of glass to resist elastic deformation, which is to be measured on bulk glass according to ASTM E1876. It can be used to represent the modulus property of glass fiber.

[0096] (7) Crystallization area ratio, to be determined in a procedure set out as follows: Cut the bulk glass appropriately to fit in with a porcelain boat trough and then place the cut glass bar sample into the porcelain boat. Put the porcelain boat with the pretreated glass bar sample into a gradient furnace for crystallization and keep the sample for heat preservation for 5 hours. Take the porcelain boat with the sample out of the gradient furnace and air-cool it to room temperature. Finally, examine and measure the amounts and dimensions of crystals on the surfaces of each sample within a temperature range of 1050−1150° C., from a microscopic view by using an optical microscope, and then calculate the relative area ratio of crystallization with reference to S glass. A high area ratio would mean a high crystallization tendency and a high crystallization rate.

[0097] (8) Bubble content, to be determined in a procedure set out as follows: Use special molds to compress the glass batch materials in each example into samples of same shape and dimension, which will then be placed on the sample platform of a high temperature microscope. Heat the samples according to standard procedures up to the pre-set temperature of 1500° C., and then directly cool them off with the cooling of the microscope to the ambient temperature without heat preservation. Finally, each of the glass samples is examined under an optical microscope to determine the amount of bubbles in the samples, and then calculate the relative bubble content with reference to S glass. The higher the bubble content is, the more difficult the refining of the glass will be, and the quality of the molten glass will be hard to be guaranteed. Wherein, the amounts of bubbles are identified according to the magnification of the microscope.

[0098] The aforementioned eight parameters and the methods of measuring thereof are well-known to one skilled in the art. Therefore, these aforementioned parameters can be used to effectively explain the properties of the glass fiber composition according to the present invention.

[0099] The specific procedures for the experiments are as follows: each component can be acquired from the appropriate raw materials, and the raw materials are mixed according to specific proportions so that each component reaches the final expected weight percentage. The mixed batch is melted and refined. 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, normal methods can be used to further process these glass fibers to meet the expected requirements.

[0100] Comparisons of the property parameters used in the examples of the glass fiber composition according to the present invention with those of the S glass, conventional R glass and improved R glass are further made below by way of tables, wherein the component contents of the compositions for producing glass fibers are expressed in weight percentage. What needs to be made clear is that the total amount of the components in an example 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-00016 TABLE 1A A1 A2 A3 A4 A5 A6 A7 Component SiO.sub.2 53.2 52.0 53.0 54.4 54.4 54.4 54.4 Al.sub.2O.sub.3 18.7 19.3 18.7 17.5 18.1 18.7 18.7 CaO 2.9 5.9 4.9 4.0 3.4 3.4 4.8 MgO 11.5 9.2 10.4 13.5 12.6 12.0 10.6 Y.sub.2O.sub.3 12.4 12.4 11.5 9.2 10.1 10.1 10.1 Na.sub.2O 0.15 0.05 0.05 0.25 0.25 0.25 0.25 K.sub.2O 0.25 0.25 0.25 0.25 0.25 0.25 0.25 Li.sub.2O 0 0 0 0 0 0 0 Fe.sub.2O.sub.3 0.35 0.35 0.35 0.35 0.35 0.35 0.35 TiO.sub.2 0.45 0.45 0.45 0.45 0.45 0.45 0.45 SrO 0 0 0 0 0 0 0 La.sub.2O.sub.3 0 0 0 0 0 0 0 CeO.sub.2 0 0 0.30 0 0 0 0 Ratio C1 3.97 1.56 2.12 3.38 3.71 3.53 2.21 C2 1.08 1.35 1.11 0.68 0.80 0.84 0.95 C3 4.28 2.10 2.35 2.30 2.97 2.97 2.10 C4 1.51 1.56 1.63 1.90 1.79 1.85 1.85 Parameter Forming 1283 1274 1280 1279 1284 1286 1290 temperature/° C. Liquidus 1236 1220 1225 1253 1248 1242 1230 temperature/° C. Refining 1443 1432 1440 1439 1445 1447 1452 temperature/° C. ΔT/° C. 47 54 55 26 36 44 60 ΔL/° C. 160 158 160 160 161 161 162 Elastic modulus/GPa 105.0 103.0 104.0 103.2 103.8 103.0 102.2 Crystallization 9 4 5 15 12 10 5 area ratio/% Bubble content/% 6 4 3 5 7 8 9

TABLE-US-00017 TABLE 1B A8 A9 A10 A11 A12 A13 A14 Component SiO.sub.2 54.0 49.8 51.0 52.5 55.9 52.5 56.8 Al.sub.2O.sub.3 19.0 21.0 20.4 19.8 18.6 18.6 16.5 CaO 3.8 4.0 4.0 4.0 4.0 4.0 3.3 MgO 11.0 9.4 10.0 10.0 10.0 10.0 10.4 Y.sub.2O.sub.3 10.5 14.4 13.2 12.3 10.1 13.5 11.6 Na.sub.2O 0.10 0.45 0.45 0.45 0.45 0.45 0.20 K.sub.2O 0.40 0.20 0.20 0.20 0.20 0.20 0.30 Li.sub.2O 0.30 0 0 0 0 0 0 Fe.sub.2O.sub.3 0.20 0.35 0.35 0.35 0.35 0.35 0.40 TiO.sub.2 0.60 0.30 0.30 0.30 0.30 0.30 0.40 SrO 0 0 0 0 0 0 0 La.sub.2O.sub.3 0 0 0 0 0 0 0 CeO.sub.2 0 0 0 0 0 0 0 Ratio C1 2.89 2.35 2.50 2.50 2.50 2.50 3.15 C2 0.95 1.53 1.32 1.23 1.01 1.35 1.12 C3 2.76 3.60 3.30 3.08 2.53 3.38 3.52 C4 1.81 1.46 1.55 1.61 1.84 1.38 1.42 Parameter Forming 1281 1276 1278 1284 1295 1280 1294 temperature/° C. Liquidus 1235 1245 1238 1235 1230 1220 1232 temperature/° C. Refining 1443 1433 1437 1445 1460 1440 1460 temperature/° C. ΔT/° C. 46 31 40 49 65 60 62 ΔL/° C. 162 157 159 161 165 160 166 Elastic modulus/GPa 103.5 106.0 105.3 103.8 102.6 105.0 102.0 Crystallization area 7 16 7 6 6 4 6 ratio/% Bubble content/% 6 5 4 6 11 5 10

TABLE-US-00018 TABLE 1C A15 A16 A17 A18 A19 A20 A21 Component SiO.sub.2 53.5 52.0 54.0 56.5 55.0 53.5 52.2 Al.sub.2O.sub.3 18.9 18.9 18.9 18.5 18.5 18.7 18.7 CaO 2.4 1.0 3.3 3.7 3.7 3.0 3.5 MgO 10.7 10.7 10.2 10.4 10.8 11.0 10.0 Y.sub.2O.sub.3 13.1 16.0 12.0 8.5 8.1 11.4 13.5 Na.sub.2O 0.30 0.30 0.30 0.30 0.30 0.30 0.30 K.sub.2O 0.20 0.20 0.20 0.20 0.20 0.20 0.20 Li.sub.2O 0 0 0.50 0 0 0 0 Fe.sub.2O.sub.3 0.40 0.40 0.30 0.30 0.30 0.40 0.30 TiO.sub.2 0.40 0.40 0.30 1.50 0.90 0.40 0.30 SrO 0 0 0 0 0 1.00 0 La.sub.2O.sub.3 0 0 0 0 2.00 0 0 CeO.sub.2 0 0 0 0 0.10 0 0 ZrO.sub.2 0 0 0 0 0 0 0.90 Ratio C1 4.46 10.70 3.09 2.81 2.92 3.67 2.86 C2 1.22 1.50 1.18 0.82 0.75 1.04 1.35 C3 5.46 16.00 3.64 2.30 2.19 3.80 3.86 C4 1.44 1.18 1.58 2.18 2.28 1.64 1.39 Parameter Forming 1291 1287 1269 1290 1285 1288 1286 temperature/° C. Liquidus 1238 1255 1231 1238 1225 1230 1224 temperature/° C. Refining 1452 1445 1429 1455 1449 1450 1446 temperature/° C. ΔT/° C. 53 32 38 52 60 58 62 ΔL/° C. 161 158 160 165 164 162 160 Elastic modulus/GPa 104.5 106.3 105.2 101.5 100.5 103.5 105.5 Crystallization 10 14 8 12 3 5 5 area ratio/% Bubble content/% 8 7 3 6 7 8 7

TABLE-US-00019 TABLE 1D A22 A23 A24 A25 A26 A27 A28 Component SiO.sub.2 54.9 54.9 53.0 51.9 52.4 52.0 50.0 Al.sub.2O.sub.3 18.0 19.2 19.2 19.2 18.6 19.6 18.6 CaO 3.0 3.0 3.0 3.0 3.0 4.0 3.0 MgO 11.4 10.4 10.4 10.4 10.2 10.6 10.2 Y.sub.2O.sub.3 11.0 11.0 12.9 14.0 14.6 12.6 17.0 Na.sub.2O 0.20 0.20 0.20 0.20 0.25 0.25 0.25 K.sub.2O 0.30 0.30 0.30 0.30 0.20 0.20 0.20 Li.sub.2O 0 0 0.10 0.10 0 0 0 Fe.sub.2O.sub.3 0.40 0.40 0.40 0.40 0.35 0.35 0.35 TiO.sub.2 0.40 0.40 0.40 0.40 0.30 0.30 0.30 SrO 0 0 0 0 0 0 0 La.sub.2O.sub.3 0 0 0 0 0 0 0 CeO.sub.2 0 0.10 0 0 0 0 0 ZrO.sub.2 0.30 0 0 0 0 0 0 Ratio C1 3.80 3.47 3.47 3.47 3.40 2.65 3.40 C2 0.96 1.06 1.24 1.35 1.43 1.19 1.67 C3 3.67 3.67 4.30 4.67 4.87 3.15 5.67 C4 1.64 1.75 1.49 1.37 1.27 1.56 1.09 Parameter Forming 1288 1293 1284 1276 1278 1282 1260 temperature/° C. Liquidus 1236 1233 1230 1225 1220 1235 1217 temperature/° C. Refining 1451 1457 1445 1434 1437 1441 1416 temperature/° C. ΔT/° C. 52 60 54 51 58 47 43 ΔL/° C. 163 164 161 158 159 159 156 Elastic 103.5 103.0 104.5 105.7 106.5 104.5 108.0 modulus/GPa Crystallization 8 7 6 5 4 7 3 area ratio/% Bubble 8 10 6 4 5 6 4 content/%

TABLE-US-00020 TABLE 1E A29 A30 A31 A32 B1 B2 B3 Component SiO.sub.2 57.0 53.4 52.0 52.5 60.1 60 65 Al.sub.2O.sub.3 18.5 18.7 19.3 18.7 17.0 25 25 CaO 4.5 4.5 5.5 2.5 10.2 9 0 MgO 10.0 10.4 9.4 11.5 9.8 6 10 Y.sub.2O.sub.3 8.1 11.4 12.6 13.5 0.5 0 0 Na.sub.2O 0.25 0.45 0.05 0.15 0.21 Trace Trace amount amount K.sub.2O 0.25 0.25 0.25 0.25 0.41 Trace Trace amount amount Li.sub.2O 0.5 0 0 0 0.65 0 0 Fe.sub.2O.sub.3 0.35 0.35 0.35 0.35 0.44 Trace Trace amount amount TiO.sub.2 0.45 0.45 0.45 0.45 0.44 Trace Trace amount amount SrO 0 0 0 0 0 0 0 La.sub.2O.sub.3 0 0 0 0 0 0 0 CeO.sub.2 0 0 0 0 0 0 0 ZrO.sub.2 0 0 0 0 0 0 0 Ratio C1 2.22 2.31 1.71 4.60 0.96 0.67 — C2 0.81 1.10 1.34 1.17 0.05 0 0 C3 1.80 2.53 2.29 5.40 0.05 0 — C4 2.28 1.64 1.53 1.39 34.00 — — Parameter Forming 1293 1286 1275 1284 1300 1430 1571 temperature/° C. Liquidus 1235 1227 1220 1234 1208 1350 1470 temperature/° C. Refining 1459 1448 1433 1444 1498 1620 >1700 temperature/° C. ΔT/° C. 58 59 55 50 92 80 101 ΔL/° C. 166 162 158 160 198 200 — Elastic modulus/GPa 101.9 103.0 103.5 106.0 90.9 89 90 Crystallization 7 5 4 7 20 70 100 area ratio/% Bubble content/% 7 6 4 5 30 75 100

[0101] It can be seen from the values in the above tables that, compared with the composition of S glass, the glass fiber composition according to the present invention has the following advantages: (1) much higher elastic modulus; (2) much lower refining temperature and bubble content, which means the molten glass of the present invention is easier to refine and the bubbles are easier to be discharged; and (3) much lower fiber forming temperature, liquidus temperature and crystallization area ratio.

[0102] Compared with the composition of the conventional R glass, the glass fiber composition according to the present invention has the following advantages: (1) much higher elastic modulus; (2) much lower refining temperature and bubble content, which means the molten glass of the present invention is easier to refine and the bubbles are easier to be discharged; (3) much lower ΔL value, which helps increase the fiber drawing efficiency as the molten glass is easier to cool off; and (4) much lower fiber forming temperature, liquidus temperature and crystallization area ratio.

[0103] Compared with the composition of the improved R glass, the glass fiber composition according to the present invention has the following advantages: (1) much higher elastic modulus; (2) much lower refining temperature and bubble content, which means the molten glass of the present invention is easier to refine and the bubbles are easier to be discharged; (3) much lower ΔL value, which helps increase the fiber drawing efficiency as the molten glass is easier to cool off; and (4) a lower crystallization area ratio, which means the molten glass of the present invention has relatively low crystallization rate and thus help reduce the crystallization risk.

[0104] Therefore, it can be concluded that the glass fiber composition according to the present invention has made a breakthrough in terms of glass modulus, refining and cooling performance, and crystallization rate. According to the present invention, under equal conditions, the modulus of glass is greatly raised, the refining temperature of molten glass is significantly lowered, the amount of bubbles in the molten glass is reduced and the glass shows excellent cooling performance. The overall technical solution of the present invention is excellent.

[0105] The glass fiber composition according to the present invention can be used for making glass fibers having the aforementioned excellent properties.

[0106] 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 performance, such as glass fiber reinforced base materials.

[0107] It is to be noted that, in this text, the terms “comprise/comprising,” “contain/containing” and any other variants thereof are non-exclusive, so that any process, method, object or device containing a series of elements contains not only such factors, but also other factors not listed clearly, or further contains inherent factors of the process, method, object or device. Without further restrictions, a factor limited by the phrase “comprises/comprising an/a . . . ,” does not exclude other identical factors in the process, method, object or device including the factors.

[0108] The foregoing embodiments are provided only for describing instead of limiting the technical solutions of the present invention. While particular embodiments of the invention have been shown and described, it will be obvious to one skilled in the art that modifications can be made to the technical solutions embodied by all the aforementioned embodiments, or that equivalent replacements can be made to some of the technical features embodied by all the aforementioned embodiments, without departing from the spirit and scope of the technical solutions of the present invention.

INDUSTRIAL APPLICABILITY

[0109] The high-modulus glass fiber composition according to the present invention can significantly increase the modulus of glass fiber, significantly reduce the refining temperature of molten glass, and improve the refining performance of molten glass; it can also optimize the hardening rate of molten glass, improve the cooling performance of glass fiber and reduce the crystallization rate. The composition is suitable for large-scale production of high-modulus glass fiber.

[0110] Compared with conventional glass fiber compositions, the glass fiber composition according to the present invention has made a breakthrough in terms of glass modulus, refining and cooling performance, and crystallization rate. According to the present invention, under equal conditions, the modulus of glass is greatly raised, the refining temperature of molten glass is significantly lowered, the amount of bubbles in the molten glass is reduced and the glass shows excellent cooling performance. The overall technical solution of the present invention is excellent.

[0111] Therefore, the present invention has good industrial applicability.