Glass fiber, composition for producing the same, and composite material comprising the same

Abstract

A composition for producing a glass fiber, including the following components with corresponding percentage amounts by weight: SiO.sub.2: 57.1-61.4%; Al.sub.2O.sub.3: 17.1-21%; MgO: 10.1-14.5%; Y.sub.2O.sub.3: 1.1-4.3%; CaO: <6.5%; Li.sub.2O+Na.sub.2O+K.sub.2O: 1%; Li.sub.2O: 0.75%; TiO.sub.2: <1.8%; and Fe.sub.2O.sub.3: 0.05-1.2%. The total weight percentage of the above components in the composition is greater than or equal to 98%. The weight percentage ratio of Al.sub.2O.sub.3 to SiO.sub.2 is greater than or equal to 0.285. The invention also provides a glass fiber produced using the composition and a composite material including the glass fiber.

Claims

1. A composition for producing a glass fiber, comprising the following components with corresponding percentage amounts by weight: TABLE-US-00028 SiO.sub.2 57.1-61.4%; Al.sub.2O.sub.3 17.1-21%; MgO 10.1-14.5%; Y.sub.2O.sub.3 1.1-4.3%; CaO <6.5%; Li.sub.2O + Na.sub.2O + K.sub.2O 1%; Li.sub.2O 0.75%; TiO.sub.2 <1.8%; and Fe.sub.2O.sub.3 0.05-1.2%; wherein a total weight percentage of the above components is greater than or equal to 98%; and a weight percentage ratio Al.sub.2O.sub.3/SiO.sub.2 is greater than or equal to 0.305, and a weight percentage ratio (Al.sub.2O.sub.3+MgO+Li.sub.2O)/Y.sub.2O.sub.3 is greater than or equal to 7.45.

2. The composition of claim 1, comprising 10.3-14 wt. % of MgO.

3. The composition of claim 1, wherein a weight percentage of MgO is greater than 11% and less than or equal to 13.5%.

4. The composition of claim 1, comprising 0.05-0.7 wt. % of Li.sub.2O.

5. The composition of claim 1, wherein a total weight percentage of Y.sub.2O.sub.3 2.3-3.9%.

6. The composition of claim 1, wherein a total weight percentage of Li.sub.2O+Na.sub.2O+K.sub.2O is 0.25%-0.98%.

7. The composition of claim 1, wherein a total weight percentage of Al.sub.2O.sub.3+MgO+Li.sub.2O is greater than or equal to 28.1%.

8. The composition of claim 1, further comprising no more than 2 wt. % of CeO.sub.2, SrO, La.sub.2O.sub.3, ZnO, B.sub.2O.sub.3, ZrO.sub.2, or a mixture thereof.

9. The composition of claim 1, wherein a weight percentage ratio Al.sub.2O.sub.3/SiO.sub.2 is 0.305-0.357.

10. The composition of claim 1, wherein a weight percentage ratio MgO/CaO is greater than or equal to 1.6.

11. The composition of claim 1, wherein a weight percentage ratio (Y.sub.2O.sub.3+MgO)/SiO.sub.2 is greater than or equal to 0.2.

12. The composition of claim 1, comprising the following components with corresponding percentage amounts by weight: TABLE-US-00029 SiO.sub.2 57.4-61.4%; Al.sub.2O.sub.3 17.5-20.5%; MgO 10.1-14.5%; Y.sub.2O.sub.3 2-4.2%; CaO 6.3%; Li.sub.2O + Na.sub.2O + K.sub.2O 1%; Li.sub.2O 0.75%; TiO.sub.2 <1.4%; and Fe.sub.2O.sub.3 0.05-1%; wherein a total weight percentage of the above components is greater than or equal to 98%; and a weight percentage ratio Al.sub.2O.sub.3/SiO.sub.2 is greater than or equal to 0.305.

13. The composition of claim 1, comprising the following components with corresponding percentage amounts by weight: TABLE-US-00030 SiO.sub.2 58-60.4% Al.sub.2O.sub.3 17.5-20.5% MgO 10.3-14% Y.sub.2O.sub.3 2-4% CaO 2-6% Li.sub.2O + Na.sub.2O + K.sub.2O 1% Li.sub.2O 0.75% TiO.sub.2 <1.4% Fe.sub.2O.sub.3 0.05-1%; wherein a total weight percentage of the above components is greater than or equal to 98%; and a weight percentage ratio Al.sub.2O.sub.3/SiO.sub.2 is greater than or equal to 0.305.

14. The composition of claim 1, comprising the following components with corresponding percentage amounts by weight: TABLE-US-00031 SiO.sub.2 57.4-61.4%; Al.sub.2O.sub.3 17.5-20.5%; MgO 10.3-14%; Y.sub.2O.sub.3 2-4%; CaO 6.3%; Li.sub.2O + Na.sub.2O + K.sub.2O 1%; Li.sub.2O 0.75%; TiO.sub.2 <1.4%; and Fe.sub.2O.sub.3 0.05-1%; wherein a total weight percentage of the above components is greater than or equal to 98%; a weight percentage ratio Al.sub.2O.sub.3/SiO.sub.2 is greater than or equal to 0.305; and a weight percentage ratio (Al.sub.2O.sub.3+MgO+Li.sub.2O)/Y.sub.2O.sub.3 is greater than or equal to 7.45.

15. The composition of claim 1, comprising the following components with corresponding percentage amounts by weight: TABLE-US-00032 SiO.sub.2 58-60.4%; Al.sub.2O.sub.3 17.5-20.5%; MgO 10.5-14%; Y.sub.2O.sub.3 2-4%; CaO 2-6%; Li.sub.2O + Na.sub.2O + K.sub.2O 1%; Li.sub.2O 0.75%; TiO.sub.2 <1.4%; and Fe.sub.2O.sub.3 0.05-1%; wherein a total weight percentage of the above components is greater than or equal to 98%; a weight percentage ratio Al.sub.2O.sub.3/SiO.sub.2 is greater than or equal to 0.305; a weight percentage ratio (Al.sub.2O.sub.3+MgO+Li.sub.2O)/Y.sub.2O.sub.3 is greater than or equal to 7.45; and a total weight percentage of Al.sub.2O.sub.3+MgO+Li.sub.2O is greater than or equal to 28.1%.

16. The composition of claim 1, comprising the following components with corresponding percentage amounts by weight: TABLE-US-00033 SiO.sub.2 58-60.4%; Al.sub.2O.sub.3 17.7-20.1%; MgO greater than 11% but not greater than 13.5%; Y.sub.2O.sub.3 2-4%; CaO 2.3-5.8%; Li.sub.2O + Na.sub.2O + K.sub.2O 1%; Li.sub.2O 0.05-0.7%; TiO.sub.2 <1.4%; and Fe.sub.2O.sub.3 0.05-1%; wherein a total weight percentage of the above components is greater than or equal to 98%; a weight percentage ratio Al.sub.2O.sub.3/SiO.sub.2 is greater than or equal 0.305; a weight percentage ratio (Al.sub.2O.sub.3+MgO+Li.sub.2O)/Y.sub.2O.sub.3 is greater than or equal to 7.45; and a total weight percentage of Al.sub.2O.sub.3+MgO+Li.sub.2O is greater than or equal to 29.1%.

17. The composition of claim 1, comprising the following components with corresponding percentage amounts by weight: TABLE-US-00034 SiO.sub.2 57.4-61.4%; Al.sub.2O.sub.3 17.5-20.5%; MgO 10.1-14.5%; Y.sub.2O.sub.3 2-4.2%; CaO 6.3%; Li.sub.2O + Na.sub.2O + K.sub.2O 1%; Li.sub.2O 0.75%; TiO.sub.2 <1.4%; Fe.sub.2O.sub.3 0.05-1%; SrO + CeO.sub.2 + F.sub.2 <2%; SrO 0-1.7%; CeO.sub.2 0-0.55%; and F.sub.2 0-0.5%; wherein a weight percentage ratio Al.sub.2O.sub.3/SiO.sub.2 is greater than or equal to 0.305; and a weight percentage ratio (Al.sub.2O.sub.3+MgO+Li.sub.2O)/Y.sub.2O.sub.3 is greater than or equal to 7.45.

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

19. A composite material, comprising the glass fiber of claim 18.

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: 57.1-61.4% SiO.sub.2, 17.1-21% Al.sub.2O.sub.3, 10.1-14.5% MgO, 1.1-4.3% Y.sub.2O.sub.3, lower than 6.5% CaO, not greater than 1% Li.sub.2O+Na.sub.2O+K.sub.2O, not greater than 0.75% Li.sub.2O, lower than 1.8% TiO.sub.2 and 0.05-1.2% Fe.sub.2O.sub.3, wherein the range of the combined weight percentage of these components is greater than or equal to 98% and the range of the weight percentage ratio C1=Al.sub.2O.sub.3/SiO.sub.2 is greater than or equal to 0.285. The composition can significantly increase the glass strength and modulus, effectively reduce the glass crystallization rate, secure a desirable temperature range (T) 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.

(3) The specific content values of SiO.sub.2, Al.sub.2O.sub.3, Y.sub.2O.sub.3, CaO, MgO, Li.sub.2O, 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 R 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 offi.e., the upper limit temperature for glass crystallization.

(6) (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.

(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) Tensile strength, the maximum tensile stress that the glass fiber can withstand, which is to be measured on impregnated glass roving as per ASTM D2343.

(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 1060-1130 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 molds 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 R 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-00024 TABLE 1A A1 A2 A3 A4 A5 A6 A7 Component SiO.sub.2 59.50 59.50 59.50 58.85 58.85 58.85 58.85 Al.sub.2O.sub.3 18.70 18.70 18.70 19.05 19.05 19.05 19.05 CaO 6.40 6.00 5.10 6.30 5.80 5.10 4.10 MgO 11.30 11.30 11.30 10.30 10.80 11.50 12.50 Y.sub.2O.sub.3 1.80 2.30 3.20 3.40 3.40 3.40 3.40 Na.sub.2O 0.08 0.11 0.11 0.13 0.13 0.13 0.13 K.sub.2O 0.17 0.19 0.19 0.30 0.30 0.30 0.30 Li.sub.2O 0.70 0.65 0.65 0.47 0.47 0.47 0.47 Fe.sub.2O.sub.3 0.39 0.45 0.45 0.47 0.47 0.47 0.47 TiO.sub.2 0.64 0.52 0.52 0.53 0.53 0.53 0.53 CeO.sub.2 0.12 0.08 0.08 Ratio C1 0.314 0.314 0.314 0.324 0.324 0.324 0.324 C2 17.06 13.33 9.58 8.77 8.92 9.12 9.42 C3 0.220 0.229 0.244 0.233 0.241 0.253 0.270 Parameter Forming 1304 1307 1309 1314 1311 1309 1306 temperature/ C. Liquidus 1218 1212 1207 1216 1211 1210 1217 temperature/ C. T/ C. 86 95 102 98 100 99 89 Elastic 94.1 94.6 95.8 95.0 95.4 96.3 96.5 modulus/GPa Tensile strength/ 3310 3400 3530 3460 3490 3590 3630 MPa Crystallization 19 15 9 11 10 7 9 area ratio/% Amount of 8 9 10 10 11 9 10 bubbles/pcs

(15) TABLE-US-00025 TABLE 1B A8 A9 A10 A11 A12 A13 A14 Component SiO.sub.2 58.85 58.85 59.00 59.00 59.00 60.00 60.00 Al.sub.2O.sub.3 19.05 19.05 18.80 18.80 18.80 18.30 17.70 CaO 3.10 2.80 6.00 5.30 4.40 2.00 4.90 MgO 13.50 14.00 11.10 11.40 12.00 12.40 11.70 Y.sub.2O.sub.3 3.40 3.40 3.00 3.40 3.70 4.20 3.30 Na.sub.2O 0.13 0.14 0.14 0.14 0.14 0.10 0.15 K.sub.2O 0.30 0.31 0.30 0.30 0.30 0.28 0.20 Li.sub.2O 0.47 0.30 0.50 0.50 0.50 0.60 0.65 Fe.sub.2O.sub.3 0.47 0.42 0.44 0.44 0.44 0.44 0.44 TiO.sub.2 0.53 0.53 0.52 0.52 0.52 0.48 0.46 SrO 1.00 ZrO.sub.2 0.30 Ratio C1 0.324 0.324 0.319 0.319 0.319 0.305 0.295 C2 9.72 9.86 10.13 9.03 8.46 7.45 9.11 C3 0.287 0.296 0.239 0.251 0.266 0.277 0.250 Parameter Forming 1304 1305 1309 1307 1303 1325 1310 temperature/ C. Liquidus 1219 1224 1211 1207 1206 1220 1213 temperature/ C. T/ C. 85 81 98 100 97 105 97 Elastic 95.7 95.2 95.1 96.0 97.3 96.8 95.6 modulus/ GPa Tensile 3540 3500 3460 3540 3630 3670 3510 strength/ MPa Crystallization 14 17 11 8 8 14 9 area ratio/% Amount of 9 8 10 9 9 10 9 bubbles/pcs

(16) TABLE-US-00026 TABLE 1C A15 A16 A17 A18 A19 A20 A21 Component SiO.sub.2 58.00 57.10 59.10 58.40 58.90 60.40 61.40 Al.sub.2O.sub.3 18.60 20.10 17.50 18.80 18.60 17.80 18.00 CaO 6.00 5.80 5.80 6.00 4.80 4.90 3.80 MgO 10.50 10.00 11.00 11.10 11.20 11.30 11.60 Y.sub.2O.sub.3 4.30 4.00 3.70 3.50 3.20 3.30 2.90 Na.sub.2O 0.12 0.10 0.15 0.30 0.21 0.10 0.15 K.sub.2O 0.22 0.20 0.30 0.35 0.31 0.20 0.30 Li.sub.2O 0.60 0.64 0.50 0 0.38 0.65 0.55 Fe.sub.2O.sub.3 0.46 0.46 0.45 0.45 0.44 0.46 0.44 TiO.sub.2 0.60 0.55 0.80 1.20 0.46 0.69 0.51 SrO 0.40 0.85 0.50 0.60 1.30 La.sub.2O.sub.3 0.25 Ratio C1 0.321 0.352 0.296 0.322 0.316 0.295 0.293 C2 6.91 7.69 7.84 8.54 9.43 9.02 10.40 C3 0.255 0.245 0.249 0.250 0.244 0.242 0.236 Parameter Forming 1299 1301 1300 1305 1310 1317 1325 temperature/ C. Liquidus 1210 1200 1209 1212 1210 1227 1235 temperature/ C. T/ C. 90 101 91 93 100 90 90 Elastic 96.3 96.0 95.5 96.1 96.5 95.1 94.9 modulus/ GPa Tensile 3560 3460 3480 3500 3540 3460 3430 strength/ MPa Crystallization 7 13 8 9 11 16 19 area ratio/% Amount of 6 7 8 7 8 10 12 bubbles/pcs

(17) TABLE-US-00027 TABLE 1D S Traditional Improved A22 A23 A24 A25 glass R glass R glass Component SiO.sub.2 57.40 60.00 59.50 58.80 65 60 60.75 Al.sub.2O.sub.3 20.50 19.00 18.40 18.70 25 25 15.80 CaO 4.10 3.90 4.90 5.30 9 13.90 MgO 11.50 11.80 11.20 12.10 10 6 7.90 Y.sub.2O.sub.3 3.90 3.10 3.40 3.20 Na.sub.2O 0.08 0.12 0.12 0.15 trace trace 0.73 amount amount K.sub.2O 0.12 0.21 0.31 0.23 trace trace amount amount Li.sub.2O 0.75 0.60 0.50 0.50 0.48 Fe.sub.2O.sub.3 0.46 0.45 0.45 0.44 trace trace 0.18 amount amount TiO.sub.2 0.34 0.62 0.52 0.48 trace trace 0.12 amount amount SrO 0.55 0.70 CeO.sub.2 0.05 0.10 Ratio C1 0.357 0.317 0.309 0.318 0.385 0.385 0.260 C2 8.40 10.13 8.85 9.78 C3 0.268 0.248 0.245 0.260 0.154 0.100 0.130 Parameter Forming 1306 1321 1306 1303 1571 1430 1278 temperature/ C. Liquidus 1212 1216 1206 1205 1470 1350 1210 temperature/ C. T/ C. 94 105 100 98 101 80 68 Elastic 96.3 95.6 95.2 95.8 90 89 88 modulus/ GPa Tensile 3560 3490 3460 3530 3460 2750 2500 strength/ MPa Crystallization 14 10 8 9 100 70 35 area ratio/% Amount of 8 11 7 8 40 30 25 bubbles/pcs

(18) It can be seen from the values in the above tables that, compared with the 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 increase the fiber drawing efficiency; and (3) smaller amount of bubbles, which indicates a better refining of molten glass.

(19) In addition, compared with the traditional R glass and improved R glass, the composition for producing a glass fiber of the present invention has the following advantages: (1) much higher elastic modulus and strength; (2) much lower crystallization area ratio, which indicate a low crystallization rate and thus helps to reduce the crystallization risk and increase the fiber drawing efficiency; and (3) smaller amount of bubbles, which indicates a better refining of molten glass.

(20) Both S glass and traditional R glass cannot enable the achievement of large-scale production with refractory-lined furnaces and, with respect to improved R glass, part of the glass properties is compromised to reduce the liquidus temperature and forming temperature, so that the production difficulty is decreased and the production with refractory-lined furnaces could be achieved. By contrast, the composition for producing a glass fiber of the present invention not only has a sufficiently low liquidus temperature, forming temperature and crystallization rate which enable the production with refractory-lined furnaces, but also significantly increases the glass modulus and strength, thereby resolving the technical bottleneck that the modulus and strength of S glass fiber cannot be improved with the growth of production scale.

(21) Therefore, it can be seen from the above that, compared with the current main-stream high-performance glasses, the composition for producing a glass fiber of the present invention has made a breakthrough in terms of elastic modulus, strength, crystallization rate and refining performance of the glass, with significantly improved modulus and strength, remarkably reduced crystallization 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.

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

(23) 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.

(24) The composition for producing a glass fiber of the present invention not only results in glass fiber having a sufficiently low liquidus temperature, forming temperature and crystallization rate which enable the production with refractory-lined furnaces, but also significantly increases the glass modulus and strength of the glass fibers, thereby resolving the technical bottleneck that the modulus and strength of S glass fiber cannot be improved with the enhanced production scale. Compared with the current main-stream high-performance glasses, the composition for producing a glass fiber of the present invention has made a breakthrough in terms of elastic modulus, strength, crystallization rate and refining performance of the glass, with significantly improved modulus and strength, remarkably reduced crystallization 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.

(25) Unless otherwise indicated, the numerical ranges involved in the invention include the end values. While particular embodiments of the invention have been shown and described, it will be obvious to those skilled in the art that changes and modifications may be made without departing from the invention in its broader aspects, and therefore, the aim in the appended claims is to cover all such changes and modifications as fall within the true spirit and scope of the invention.