Glass fiber composition, glass fiber and composite material thereof

Abstract

A composition for producing a glass fiber, including the following components with corresponding percentage amounts by weight: SiO.sub.2: 57.4-60.9%; Al.sub.2O.sub.3: greater than 17% and less than or equal to 19.8%; MgO: greater than 9% and less than or equal to 12.8%; CaO: 6.4-11.8%; SrO: 0-1.6%; Na.sub.2O+K.sub.2O: 0.1-1.1%; Fe.sub.2O.sub.3: 0.05-1%; TiO.sub.2: lower than 0.8%; and SiO.sub.2+Al.sub.2O.sub.3: lower than or equal to 79.4%. The total weight percentage of the above components in the composition is greater than 99%. The weight percentage ratio of Al.sub.2O.sub.3+MgO to SiO.sub.2 is between 0.43 and 0.56, and the weight percentage ratio of CaO+MgO to SiO.sub.2+Al.sub.2O.sub.3 is greater than 0.205. The composition can significantly increase the glass modulus, effectively reduce the glass crystallization rate, secure a desirable temperature range (ΔT) for fiber formation and enhance the refinement of molten glass, thus making it particularly suitable for high performance glass fiber production with refractory-lined furnaces.

Claims

1. A composition for producing a glass fiber, comprising the following components with corresponding percentage amounts by weight: TABLE-US-00022 SiO.sub.2 57.4-60.9%   Al.sub.2O.sub.3 >17% and ≤19.8% MgO  >9% and ≤12.8% CaO 8.1-10.85%.sup.  SrO  0% Na.sub.2O + K.sub.2O 0.1-1.1%  Fe.sub.2O.sub.3 0.05-1% TiO.sub.2 .sup. <0.8% SiO.sub.2 + Al.sub.2O.sub.3 ≤79.4% wherein a total weight percentage e f the above components is greater than 99%; a weight percentage ratio C1=(Al.sub.2O.sub.3+MgO)/SiO.sub.2 is between 0.43 and 0.56; and a weight percentage ratio C2=(CaO+MgO)/(SiO.sub.2+Al.sub.2O.sub.3) greater than 0.205.

2. The composition of 1, comprising the following components with corresponding percentage amounts by weight: TABLE-US-00023 SiO.sub.2 58.1-60.5%   Al.sub.2O.sub.3 17.1-18.8%   MgO 9.1-12.5%.sup.  CaO 8.1-10.85%.sup.  SrO  0% Na.sub.2O + K.sub.2O 0.15-1% Li.sub.2O 0-0.75% Fe.sub.2O.sub.3 0.05-1% TiO.sub.2 .sup. <0.8% SiO.sub.2 + Al.sub.2O.sub.3 .sup. ≤79% wherein a total weight percentage of the above components is greater than 99.5%; a weight percentage ratio C1=(Al.sub.2O.sub.3+MgO)/SiO.sub.2 is between 0.435 and 0.525; and a weight percentage ratio C2=(CaO+MgO)/(SiO.sub.2+Al.sub.2O.sub.3) is between 0.215 and 0.295.

3. The composition of claim 1, comprising the following components with corresponding percentage amounts by weight: TABLE-US-00024 SiO.sub.2 58.1-60.5%   Al.sub.2O.sub.3 17.1-18.8%   MgO 9.1-11.8%.sup.  CaO 8.1-10.85%.sup.  SrO  0% Na.sub.2O + K.sub.2O 0.15-1% Li.sub.2O 0-0.75% Fe.sub.2O.sub.3 0.05-1% TiO.sub.2 .sup. <0.8% F.sub.2 .sup. <0.4% SiO.sub.2 + Al.sub.2O.sub.3 75.4-79%  wherein a weight percentage ratio C1=(Al.sub.2O.sub.3+MgO)/SiO.sub.2 is between 0.435 and 0.525; and a weight percentage ratio C2=(CaO+MgO)/(SiO.sub.2+Al.sub.2O.sub.3) is between 0.215 and 0.295.

4. The composition of claim 1, wherein a combined weight percentage Al.sub.2O.sub.3+MgO is between 26.1% and 31%.

5. The composition of claim 1, wherein a weight percentage ratio C3=(MgO+SrO)/CaO is between 0.8 and 1.6.

6. The composition of claim 1, comprising between 58.1 and 59.9 wt. % of SiO.sub.2.

7. The composition of claim 1, further comprising less than 1 wt. % of Li.sub.2O, ZrO.sub.2, CeO.sub.2, B.sub.2O.sub.3 and F.sub.2, or a mixture thereof.

8. The composition of claim 1, further comprising no more than 0.55 wt. % of Li.sub.2O.

9. The composition of claim 1, wherein, when the weight percentage ratio (CaO+MgO)/Al.sub.2O.sub.3 is greater than 1 and the weight percentage ratio (MgO+SrO)/CaO is greater than 0.9, the composition is free of Li.sub.2O.

10. The composition of claim 1, comprising no more than 0.65 wt. % of Na.sub.2O.

11. The composition of claim 1, comprising MgO with a weight percentage greater than 11% and less than or equal to 12.5%.

12. The composition of claim 2, comprising the following components with corresponding percentage amounts by weight: TABLE-US-00025 SiO.sub.2 58.1-59.9% Al.sub.2O.sub.3 17.1-18.8% MgO  9.1-11.8% CaO 8.1-10.85%.sup.  wherein the composition has a liquidus temperature lower than or equal to 1250° C.

13. A glass fiber, being produced using the composition of claim 1.

14. A composite material, comprising the lass fiber of claim 13.

Description

DETAILED DESCRIPTION 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 composition for producing a glass fiber expressed as percentage amounts by weight are: 57.4-60.9% SiO.sub.2, greater than 17% and less than or equal to 19.8% Al.sub.2O.sub.3, greater than 9% and less than or equal to 12.8% MgO, 6.4-11.8% CaO, 0-1.6% SrO, 0.1-1.1% Na.sub.2O+K.sub.2O, 0.05-1% Fe.sub.2O.sub.3, and lower than 0.8% TiO.sub.2, wherein the range of the combined weight percentage of these components is greater than 99%, the range of the total weight percentage SiO.sub.2+Al.sub.2O.sub.3 is lower than or equal to 79.4%, the range of the weight percentage ratio C1=(Al.sub.2O.sub.3+MgO)/SiO.sub.2 is 0.43-0.56, and the range of the weight percentage ratio C2=(CaO+MgO)/(SiO.sub.2+Al.sub.2O.sub.3) is greater than 0.205. The composition can not only increase the glass modulus, improve the forming properties of the glass and reduce the bubble amount of molten glass, but also significantly lower the liquidus temperature and crystallization rate of the glass, and broaden the temperature range (ΔT) for fiber formation, thereby making it particularly suitable for high performance glass fiber production with refractory-lined furnaces.

(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 and TiO.sub.2 in the composition for producing a glass fiber of the present invention are selected to be used in the examples, and comparisons with S glass, traditional R glass and improved S glass are made in terms of the following seven 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, the difference between the forming temperature and the liquidus temperature, indicating the temperature range at which fiber drawing can be performed.

(7) (4) Elastic modulus, the modulus defining the ability of glass to resist elastic deformation, which is to be measured on bulk glass as per ASTM E1876.

(8) (5) Crystal phase composition, which represents the composition of main crystal phases in the glass melt to be measured and evaluated by using XRD method. The four main crystal phases, i.e. cordierite, anorthite, diopside and enstatite are abbreviated as COR, ANO, DIO and ENS respectively in the tables below. The abbreviations of different crystals are placed in a top-down manner based on their respective contents. For instance, in example A1 of Table 1A, the placing of these abbreviations means the contents of DIO, COR and ANO successively decrease.

(9) (6) 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 glass bar sample into a gradient furnace for crystallization and keep the sample for heat preservation for 6 hours. Take the 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 the temperature range of 1050-1150° C. from a microscopic view by using an optical microscope, and then calculate the area ratio of crystallization. A high area ratio would mean a high crystallization tendency and high crystallization rate.

(10) (7) Amount of bubbles, to be determined in a procedure set out as follows: Use specific moulds to compress the glass batch materials in each example into samples of same 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 spatial temperature 1500° C. and then directly cool them off with the cooling hearth of the microscope to the ambient temperature without heat preservation. Finally, each of the glass samples is examined under a polarizing microscope to determine the amount of bubbles in the samples. A bubble is identified according to a specific amplification of the microscope.

(11) The aforementioned seven parameters and the methods of measuring them are well-known to one skilled in the art. Therefore, these parameters can be effectively used to explain the properties of the composition for producing a glass fiber of the present invention.

(12) 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 requirement.

(13) Comparisons of the property parameters of the examples of the composition for producing a glass fiber according to the present invention with those of the S glass, traditional R glass and improved S glass are further made below by way of tables, where the component contents of the composition for producing a glass fiber 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.

(14) TABLE-US-00018 TABLE 1A A1 A2 A3 A4 A5 A6 A7 Component SiO.sub.2 60.50 59.80 59.15 59.15 58.65 59.45 59.15 Al.sub.2O.sub.3 17.60 17.60 17.60 18.30 18.80 17.60 17.60 CaO 9.55 10.25 10.25 9.55 9.55 9.55 11.30 MgO 10.35 10.35 11.00 11.00 11.00 11.40 9.95 SrO — — — — — — — Na.sub.2O 0.34 0.34 0.34 0.34 0.34 0.34 0.34 K.sub.2O 0.39 0.39 0.39 0.39 0.39 0.39 0.39 Li.sub.2O — — — — — — — Fe.sub.2O.sub.3 0.44 0.44 0.44 0.44 0.44 0.44 0.44 TiO.sub.2 0.58 0.58 0.58 0.58 0.58 0.58 0.58 Ratio C1 0.462 0.467 0.484 0.495 0.508 0.488 0.466 C2 0.255 0.266 0.277 0.265 0.265 0.272 0.277 C3 1.084 1.010 1.073 1.152 1.152 1.194 0.881 Parameter Forming 1322 1312 1307 1310 1308 1308 1305 temperature/° C. Liquidus 1220 1215 1217 1214 1211 1219 1207 temperature/° C. ΔT/° C. 102 97 90 96 97 89 98 Elastic 91.6 91.5 92.4 93.0 93.8 93.1 91.2 modulus/GPa Crystal phase DIO DIO COR COR COR COR DIO composition COR COR DIO DIO ANO DIO ANO ANO ANO ANO ANO DIO ENS COR Crystallization 21 18 20 18 15 20 13 area ratio/% Amount of 13 10 9 8 10 9 7 bubbles/pcs

(15) TABLE-US-00019 TABLE 1B A8 A9 A10 A11 A12 A13 A14 Component SiO.sub.2 57.40 60.10 58.55 58.55 59.55 59.10 59.10 Al.sub.2O.sub.3 19.80 17.10 19.40 18.60 18.80 19.80 18.40 CaO 8.45 10.40 7.30 8.10 6.40 7.50 9.25 MgO 11.20 9.75 11.30 11.00 11.80 10.80 10.80 SrO 0.50 — 0.75 1.00 1.00 — — Na.sub.2O 0.40 0.40 0.40 0.40 0.40 0.35 0.40 K.sub.2O 0.34 0.34 0.34 0.34 0.34 0.24 0.34 Li.sub.2O 0.55 0.55 0.55 0.55 0.40 0.75 0.30 Fe.sub.2O.sub.3 0.46 0.46 0.46 0.46 0.46 0.46 0.46 TiO.sub.2 0.65 0.65 0.70 0.75 0.40 0.75 0.70 F.sub.2 — — — — 0.20 — — Ratio C1 0.540 0.447 0.524 0.506 0.514 0.518 0.494 C2 0.255 0.261 0.239 0.248 0.233 0.232 0.259 C3 1.385 0.938 1.651 1.481 2.000 1.440 1.168 Parameter Forming 1305 1299 1301 1299 1301 1305 1300 temperature/° C. Liquidus 1230 1215 1220 1217 1212 1232 1210 temperature/° C. ΔT/° C. 75 84 81 82 89 73 90 Elastic 93.3 91.3 93.1 92.5 93.3 93.0 92.4 modulus/GPa Crystal phase COR DIO COR COR COR COR COR composition ANO ANO ANO ANO DIO DIO DIO DIO COR DIO DIO ANO ANO ANO Crystallization 31 23 28 24 21 35 21 area ratio/% Amount of 9 8 10 9 5 6 8 bubbles/pcs

(16) TABLE-US-00020 TABLE 1C A15 A16 A17 A18 A19 A20 A21 Component SiO.sub.2 59.70 59.70 59.70 59.70 59.70 59.70 59.70 Al.sub.2O.sub.3 17.80 17.80 17.80 17.80 17.80 17.80 17.80 CaO 9.80 9.50 8.70 10.85 9.55 8.15 7.45 MgO 10.40 10.40 10.40 9.10 10.40 11.80 12.50 SrO 0.20 0.50 1.30 — — — — Na.sub.2O 0.40 0.40 0.40 0.40 0.40 0.40 0.40 K.sub.2O 0.34 0.34 0.34 0.34 0.34 0.34 0.34 Li.sub.2O — — — 0.45 0.45 0.45 0.45 Fe.sub.2O.sub.3 0.46 0.46 0.46 0.46 0.46 0.46 0.46 TiO.sub.2 0.65 0.65 0.65 0.65 0.65 0.65 0.65 Ratio C1 0.472 0.472 0.472 0.451 0.472 0.496 0.508 C2 0.261 0.257 0.246 0.257 0.257 0.257 0.257 C3 1.082 1.147 1.345 0.839 1.089 1.448 1.678 Parameter Forming 1312 1313 1315 1311 1309 1301 1294 temperature/° C. Liquidus 1217 1213 1210 1211 1219 1220 1233 temperature/° C. ΔT/° C. 95 100 105 100 90 81 61 Elastic modulus/GPa 92.3 92.9 94.0 91.4 92.3 93.4 93.8 Crystal phase DIO DIO COR DIO DIO COR COR composition COR COR DIO ANO COR DIO DIO ANO ANO ANO COR ANO ANO ENS Crystallization 19 16 11 17 24 26 31 area ratio/% Amount of 10 11 11 10 9 8 8 bubbles/pcs

(17) TABLE-US-00021 TABLE 1D S Traditional Improved A22 A23 A24 A25 glass R glass S glass Component SiO.sub.2 58.10 58.70 59.90 60.40 65 60 63.05 Al.sub.2O.sub.3 19.40 18.80 17.60 17.10 25 25 23.05 CaO 10.00 10.00 10.00 10.00 — 9 — MgO 10.45 10.45 10.45 10.45 10 6 12.55 SrO — — — — — — — Na.sub.2O 0.40 0.40 0.40 0.40 — — — K.sub.2O 0.34 0.34 0.34 0.34 — — — Li.sub.2O — — — — — — 1.35 Fe.sub.2O.sub.3 0.46 0.46 0.46 0.46 — — — TiO.sub.2 0.60 0.60 0.60 0.60 — — — Ratio C1 0.514 0.498 0.468 0.456 0.538 0.517 0.565 C2 0.264 0.264 0.264 0.264 0.111 0.176 0.146 C3 1.045 1.045 1.045 1.045 — 0.667 — Parameter Forming 1308 1310 1313 1315 1571 1430 1359 temperature/° C. Liquidus 1216 1213 1219 1225 1470 1350 1372 temperature/° C. ΔT/° C. 92 97 94 90 101 80 −13 Elastic 92.7 92.7 91.7 91.2 90 89 90 modulus/GPa Crystal phase COR COR DIO DIO COR ANO COR composition ANO DIO COR ANO DIO ENS DIO ANO ANO COR Crystallization 19 14 20 24 100 70 85 area ratio/% Amount of 8 7 10 13 40 30 25 bubbles/pcs

(18) It can be seen from the values in the above tables that, compared with the S glass, traditional R glass and improved S glass, the composition for producing a glass fiber of the present invention has the following advantages: (1) much higher elastic modulus; (2) much lower liquidus temperature and much lower crystallization area ratio, which indicate a low upper limit temperature for crystallization as well as a low crystallization rate and thus help to reduce the crystallization risk and improve the fiber drawing efficiency; (3) a much lower forming temperature, which means less difficulty in glass melting and thus help to enable large-scale production with refractory lined furnaces at lowered costs; (4) smaller amount of bubbles, which indicates a better refining of molten glass; and (5) a variety of crystal phases after glass crystallization, which helps to inhibit the crystallization rate.

(19) At present, none of the S glass, traditional R glass or improved S glass can enable the achievement of large-scale production with refractory-lined furnaces.

(20) Therefore, it can be seen from the above that, compared with the S glass, traditional R glass and improved S glass, the composition for producing a glass fiber of the present invention has made a breakthrough in terms of elastic modulus, crystallization temperature, crystallization rate and refining performance of the glass, with significantly improved modulus, remarkably reduced crystallization temperature and rate and relatively small amount of bubbles under the same conditions. Thus, the overall technical solution of the present invention enables an easy achievement of large-scale production with refractory-lined furnaces.

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

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

(23) Finally, what 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 such phrase as “contain a . . . ” do not rule out that there are other same factors in the process, method, article or equipment which include said factors.

(24) 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

(25) The composition for producing a glass fiber of the present invention results in glass fiber having higher modulus and improved forming properties; meanwhile, the composition significantly lowers the liquidus temperature, crystallization rate and bubble amount of the glass, and also broadens the temperature range (ΔT) for fiber formation. Compared with the current mainstream high-performance glasses, the composition for producing a glass fiber of the present invention has made a breakthrough in terms of elastic modulus, crystallization temperature, crystallization rate and refining performance of the glass, with significantly improved modulus, remarkably reduced crystallization temperature and rate and relatively small amount of bubbles under the same conditions. Thus, the overall technical solution of the present invention enables an easy achievement of large-scale production with refractory-lined furnaces.