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: 54.2-64% SiO.sub.2, 11-18% Al.sub.2O.sub.3, 20-25.5% CaO, 0.3-3.9% MgO, 0.1-2% of Na.sub.2O+K.sub.2O, 0.1-1.5% TiO.sub.2, and 0.1-1% total iron oxides including ferrous oxide (calculated as FeO). The weight percentage ratio C1=FeO/(iron oxides−FeO) is greater than or equal to 0.53. The total content of the above components in the composition is greater than 97%. 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-00020 SiO.sub.2 54.2-64% Al.sub.2O.sub.3 .sup. 11-18% CaO 20-25.5% MgO  0.3-3.9% Na.sub.2O + K.sub.2O  0.1-2% TiO.sub.2  0.1-1.5% Total iron oxides  0.1-1% wherein the total content of the components listed above is greater than 97%; the iron oxides include ferrous oxide (calculated as FeO); a weight percentage of FeO is greater than or equal to 0.10%; a weight percentage ratio C1=FeO/(iron oxides−FeO) is greater than or equal to 0.53; and a weight percentage ratio C2=(FeO+CaO−MgO)/SiO.sub.2 is greater than 0.33.

2. The composition of claim 1, comprising 13.6-15 wt. % of Al.sub.2O.sub.3.

3. The composition of claim 1, further comprising less than 0.4 wt. % of Li.sub.2O.

4. The composition of claim 1, further comprising 0.15-0.65 wt. % of F.sub.2.

5. The composition of claim 1, comprising 59-64 wt. % of SiO.sub.2.

6. The composition of claim 1, being basically free of B.sub.2O.sub.3.

7. The composition of claim 1, being basically free of P.sub.2O.sub.5.

8. The composition of claim 1, being basically free of Li.sub.2O.

9. The composition of claim 1, comprising the following components with corresponding percentage amounts by weight: TABLE-US-00021 SiO.sub.2  57-62% Al.sub.2O.sub.3  12-17% CaO + MgO 21-26.5%  CaO 20.5-25%  MgO 0.3-2.7% Na.sub.2O + K.sub.2O .sup. 0.2-2% Na.sub.2O 0.1-1.2% K.sub.2O 0.1-1.2% TiO.sub.2 0.1-1.5% Total iron oxides 0.1-0.8% wherein the combined weight percentage of the components listed above is greater than 99%; the iron oxides include ferrous oxide (calculated as FeO); a weight percentage of FeO is greater than or equal to 0.10%; a weight percentage ratio C1=FeO/(iron oxides−FeO) is greater than or equal to 0.53; a weight percentage ratio C2=(FeO+CaO−MgO)/SiO.sub.2 is greater than 0.33; and the composition is basically free of B.sub.2O.sub.3.

10. The composition of claim 1, comprising the following components with corresponding percentage amounts by weight: TABLE-US-00022 SiO.sub.2 57.5-61% Al.sub.2O.sub.3 13-15.5% CaO 21-24.5% MgO >0.4% and <1% Na.sub.2O + K.sub.2O  0.1-2% TiO.sub.2  0.1-1.2% Total iron oxides  0.1-0.8% wherein the combined weight percentage of the components listed above is greater than or equal to 99.2%; the iron oxides include ferrous oxide (calculated as FeO); a weight percentage of FeO is greater than or equal to 0.10%; a weight percentage ratio C1=FeO/(iron oxides−FeO) is greater than or equal to 0.53; and a weight percentage ratio C2=(FeO+CaO−MgO)/SiO.sub.2 is greater than 0.33.

11. The composition of claim 1, comprising the following components with corresponding percentage amounts by weight: TABLE-US-00023 SiO.sub.2 57.5-61% Al.sub.2O.sub.3 13-15.5% CaO 21-24.5% MgO >0.4% and <1% Na.sub.2O + K.sub.2O  0.1-2% TiO.sub.2  0.1-1.2% Total iron oxides  0.1-0.8% wherein the combined weight percentage of the components listed above is greater than 99%; the iron oxides include ferrous oxide (calculated as FeO); a weight percentage of FeO is greater than or equal to 0.10%; a weight percentage ratio C1=FeO/(iron oxides−FeO) is greater than or equal to 0.53; a weight percentage ratio C2=(FeO+CaO−MgO)/SiO.sub.2 is greater than 0.33; and the composition is basically free of B.sub.2O.sub.3.

12. The composition of claim 1, wherein the combined weight percentage of SiO.sub.2, Al.sub.2O.sub.3, CaO, MgO, Na.sub.2O, K.sub.2O, TiO.sub.2 and iron oxides is greater than 99%.

13. The composition of claim 1, wherein a weight percentage ratio C1=FeO/(iron oxides−FeO) is greater than or equal to 0.66.

14. The composition of claim 1, wherein a weight percentage ratio Na.sub.2O/K.sub.2O is greater than 0.65.

15. The composition of claim 1, being produced using glass batch materials with a chemical oxygen demand (COD) value of 500-1200 ppm.

16. The composition of claim 1, being produced using glass batch materials with a SO.sub.3/COD ratio of 2-10; wherein COD refers to chemical oxygen demand.

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

18. A composite material, comprising the glass fiber of claim 17.

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: 54.2-64% SiO.sub.2, 11-18% Al.sub.2O.sub.3, 20-25.5% CaO, 0.3-3.9% MgO, 0.1-2% Na.sub.2O+K.sub.2O, 0.1-1.5% TiO.sub.2, 0.1-1% total iron oxides including ferrous oxide (calculated as FeO), wherein the range of the weight percentage ratio C1=FeO/(iron oxides−FeO) is greater than or equal to 0.53, and the range of the combined weight percentage of these components is greater than 97%. The composition has a low production cost and a high heat absorption. It can not only increase the heat absorption of the glass batch and molten glass and enhance the convection of molten glass, thus improving the melting performance at lowered energy consumption; it can also increase the cooling and hardening rate of molten glass during fiber formation, lower the bubble amount and liquidus temperature of the glass and reduce the glass crystallization rate, thereby broadening the temperature range for fiber formation. Therefore, the composition is particularly suitable for large-scale production of glass fiber with refractory-lined furnaces.

(3) The specific content values of SiO.sub.2, Al.sub.2O.sub.3, CaO, MgO, Na.sub.2O, K.sub.2O, TiO.sub.2, iron oxides and FeO in the composition for producing a glass fiber of the present invention are selected to be used in the examples, and comparisons with traditional E-glass fiber composition (“B1”) and an improved E-glass fiber composition (“B2”) as described in the patent WO96/39362 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) 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.

(8) (5) 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 1000-1150° 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.

(9) (6) 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.

(10) (7) Cool-down time, to be measured as follows: Pour a high temperature molten glass at 1550° C. into a stainless steel mould with a certain thickness, detect the changing temperatures on the surface of the glass bulk using a plurality of infrared temperature instrument sets, and record and calculate the time for the initial molten glass to cool down to a temperature of around 100° C. A short cool-down time means a high rate of the cooling and hardening of molten glass, and vice versa.

(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 traditional E glass and improved E 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-00016 TABLE 1A A1 A2 A3 A4 A5 Component SiO.sub.2 59.2 59.2 59.2 61.0 57.5 Al.sub.2O.sub.3 14.3 14.3 14.3 13.0 15.5 CaO 23.3 22.7 22.1 22.8 23.8 MgO 0.90 1.5 2.1 0.95 1.0 TiO.sub.2 0.50 0.50 0.50 0.35 0.40 B.sub.2O.sub.3 — — — — — Total iron oxides 0.45 0.45 0.45 0.50 0.42 FeO 0.25 0.25 0.25 0.35 0.30 K.sub.2O 0.40 0.40 0.40 0.30 0.30 Na.sub.2O 0.40 0.40 0.40 0.50 0.50 F.sub.2 0.35 0.35 0.35 0.40 0.38 Li.sub.2O — — — — — Ratio C1 1.25 1.25 1.25 2.33 2.50 C2 0.383 0.362 0.342 0.364 0.405 Parameter Forming temperature/° C. 1265 1267 1268 1269 1268 Liquidus temperature/° C. 1163 1166 1169 1167 1265 ΔT/° C. 102 101 99 102 103 Tensile strength/MPa 2380 2330 2290 2340 2360 Crystallization area ratio/% 6 8 10 8 8 Amount of bubbles/pcs 6 7 7 10 8

(15) TABLE-US-00017 TABLE 1B A6 A7 A8 A9 A10 Component SiO.sub.2 59.0 59.0 59.2 59.4 57.5 Al.sub.2O.sub.3 14.1 14.2 14.6 13.6 17.0 CaO 23.3 25.0 21.6 22.4 20.0 MgO 0.90 0.30 2.1 2.7 3.9 TiO.sub.2 1.0 0.15 0.45 0.40 0.20 B.sub.2O.sub.3 — — — — — Total iron oxides 0.45 0.45 0.40 0.35 0.40 FeO 0.25 0.25 0.25 0.27 0.13 K.sub.2O 0.30 0.30 0.35 0.35 0.35 Na.sub.2O 0.45 0.30 0.45 0.45 0.40 F.sub.2 0.30 0.10 0.65 0.15 0.05 Li.sub.2O — — — — — Ratio C1 1.25 1.25 1.67 3.38 0.48 C2 0.384 0.423 0.334 0.336 0.282 Parameter Forming temperature/° C. 1262 1268 1263 1264 1280 Liquidus temperature/° C. 1165 1173 1165 1163 1186 ΔT/° C. 97 95 98 101 94 Tensile strength/MPa 2340 2250 2360 2400 2200 Crystallization area ratio/% 8 12 7 6 18 Amount of bubbles/pcs 6 8 6 5 13

(16) TABLE-US-00018 TABLE 1C A11 A12 A13 A14 A15 Component SiO.sub.2 59.2 60.0 59.3 59.3 58.5 Al.sub.2O.sub.3 14.2 12.0 14.3 14.4 14.6 CaO 23.5 22.6 22.6 23.2 23.2 MgO 0.90 3.0 1.5 1.1 0.75 TiO.sub.2 0.10 0.50 0.30 0.45 1.50 B.sub.2O.sub.3 — — — — — Total iron oxides 0.46 0.45 0.40 0.30 0.45 FeO 0.16 0.30 0.30 0.24 0.35 K.sub.2O 0.50 0.50 0.40 0.60 0.35 Na.sub.2O 0.30 0.30 0.70 0.15 0.45 F.sub.2 0.44 0.45 0.30 0.15 — Li.sub.2O — — — 0.15 — Ratio C1 0.53 2.00 3.00 4.00 3.50 C2 0.381 0.332 0.361 0.377 0.390 Parameter Forming temperature/° C. 1268 1268 1261 1263 1258 Liquidus temperature/° C. 1171 1168 1166 1171 1163 ΔT/° C. 97 100 95 92 95 Tensile strength/MPa 2250 2290 2350 2400 2410 Crystallization area ratio/% 10 9 8 12 6 Amount of bubbles/pcs 8 9 6 7 6

(17) TABLE-US-00019 TABLE 1D A16 A17 A18 B1 B2 Component SiO.sub.2 59.4 59.4 59.4 54.16 59.45 Al.sub.2O.sub.3 14.1 14.1 14.1 14.32 13.48 CaO 23.3 23.3 23.3 22.12 22.69 MgO 0.95 0.95 0.95 0.41 3.23 TiO.sub.2 0.45 0.45 0.45 0.34 0.04 B.sub.2O.sub.3 — — — 7.26 0 Total iron oxides 0.40 0.40 0.40 0.39 0.36 FeO 0.31 0.20 0.11 0.10 0.09 K.sub.2O 0.40 0.40 0.40 0.25 0.63 Na.sub.2O 0.40 0.40 0.40 0.45 0.03 F.sub.2 0.40 0.40 0.40 0.29 0.04 Li.sub.2O — — — — — Ratio C1 3.44 1.00 0.38 0.34 0.33 C2 0.381 0.380 0.378 0.403 0.329 Parameter Forming temperature/° C. 1262 1264 1265 1175 1264 Liquidus temperature/° C. 1162 1167 1177 1075 1193 ΔT/° C. 100 97 88 100 71 Tensile strength/MPa 2410 2290 2190 1982 2191 Crystallization area ratio/% 5 8 15 8 19 Amount of bubbles/pcs 5 7 10 10 13 Cool-down time/s 5.0 6.0 8.5 9.0 10.0

(18) It can be seen from the values in the above tables that, compared with the traditional E glass, the glass fiber composition of the present invention has the following advantages: (1) much higher tensile strength; (2) much lower cost; (3) higher cooling and hardening rate of molten glass; (4) smaller amount of bubbles, which indicates a better refining of molten glass.

(19) Compared with improved E glass, the composition for producing a glass fiber of the present invention has the following advantages: (1) higher tensile strength; (2) higher cooling and hardening rate of molten glass; (3) 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; (4) smaller amount of bubbles, which indicates a better refining of molten glass.

(20) Therefore, it can be seen from the above that, compared with the traditional E glass and improved E glass, the composition for producing a glass fiber of the present invention has made a breakthrough in terms of tensile strength, cooling and hardening rate of molten glass, crystallization temperature and crystallization rate. Thus, the overall technical solution of the present invention enables an easy achievement of large-scale production with refractory-lined furnaces.

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

(22) 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.

(23) The contents described above can be implemented individually or combined with each other in various manners, and all of these variants fall into the scope of protection of the present invention.

(24) 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.

(25) 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 PRESENT INVENTION

(26) The glass fiber composition of the present invention introduces iron oxides, and controls the ratio of ferrous oxide and ferric oxide. The composition can not only increase the heat absorption of the glass batch and molten glass and improve the melting performance at lowered energy consumption; it can also enhance the convection of molten glass, and increase the cooling and hardening rate of molten glass during fiber formation, decrease wire fracture and enhance the glass fiber strength, lower the bubble amount and liquidus temperature of the glass, and improve the glass crystallization rate, thereby broadening the range for fiber formation. Compared with the existing high performance glass, the composition for producing a glass fiber of the present invention has made a breakthrough in terms of tensile strength, cooling and hardening rate of molten glass, crystallization temperature and crystallization rate and clarity. Thus, the tensile strength is greatly increased, the cooling and hardening rate is further improved, crystallization temperature and crystallization rate are decreased, and the bubble amount is also decreased. Therefore, the overall technical solution of the present invention is suitable for large-scale furnace production with low cost.