High performance glass fiber composition, and glass fiber and composite material thereof

Abstract

Provided are a high-performance glass fiber composition, and a glass fiber and composite material thereof. The content, given in weight percentage, of each component of the glass fibre composition is as follows: 52-64% of SiO.sub.2, 12-24% of Al.sub.2O.sub.3, 0.05-8% of Y.sub.2O.sub.3+La.sub.2O.sub.3+Gd.sub.2O.sub.3, less than 2.5% of Li.sub.2O+Na.sub.2O+K.sub.2O, more than 1% of K.sub.2O, 10-24% of CaO+MgO+SrO, 2-14% of CaO, less than 13% of MgO, less than 2% of TiO.sub.2, and less than 1.5% of Fe.sub.2O.sub.3. The composition significantly increases the mechanical strength and the elastic modulus of glass, significantly reduces the liquidus temperature and the forming temperature of glass, and under equal conditions, significantly reduces the crystallization rate, the surface tension and the bubble rate of glass. The composition is particularly suitable for the tank furnace production of a high-strength high-modulus glass fiber having a low bubble rate.

Claims

1. A high-performance glass fiber composition, containing the following contents of components in weight percentage: TABLE-US-00035 SiO.sub.2 52-64% Al.sub.2O.sub.3 12-24% RE.sub.2O.sub.3 = Y.sub.2O.sub.3 + La.sub.2O.sub.3 + Gd.sub.2O.sub.3 0.05-8% R.sub.2O = Li.sub.2O + Na.sub.2O + K.sub.2O <2.5% K.sub.2O 1.1% CaO + MgO + SrO 10-24% CaO 2-14% MgO .sup.<13% TiO.sub.2 <2% Fe.sub.2O.sub.3 <1.5%.

2. The high-performance glass fiber composition according to claim 1, wherein the content of Li.sub.2O in weight percentage is 0.1-1%.

3. The high-performance glass fiber composition according to claim 1, wherein the content of Y.sub.2O.sub.3 in weight percentage is 0.05-6%.

4. The high-performance glass fiber composition according to claim 1, wherein the content of Y.sub.2O.sub.3 in weight percentage is 0.5-5%.

5. The high-performance glass fiber composition according to claim 1, wherein the content of La.sub.2O.sub.3 in weight percentage is 0.05-2%.

6. The high-performance glass fiber composition according to claim 1, wherein the content of Gd.sub.2O.sub.3 in weight percentage is 0.05-1%.

7. The high-performance glass fiber composition according to claim 1, further containing CeO.sub.2, the content of which in weight percentage is 0-1%.

8. The high-performance glass fiber composition according to claim 1, wherein the content of SrO in weight percentage is less than 2.5%.

9. The high-performance glass fiber composition according to claim 1, wherein the content of SrO in weight percentage is 0.1-2%.

10. The high-performance glass fiber composition according to claim 1, wherein the content of CaO in weight percentage is 4-11%.

11. The high-performance glass fiber composition according to claim 1, wherein the content of MgO in weight percentage is 6-12%.

12. The high-performance glass fiber composition according to claim 1, wherein the content of SiO.sub.2+Al.sub.2O.sub.3 in weight percentage is less than 80%.

13. The high-performance glass fiber composition according to claim 1, wherein a ratio C1 in weight percentage of K.sub.2O to R.sub.2O, C1=K.sub.2O/R.sub.2O, is greater than 0.44.

14. The high-performance glass fiber composition according to claim 1, wherein a ratio C2 in weight percentage of (MgO+SrO) to CaO, C2=(MgO+SrO)/CaO, is greater than 0.9.

15. The high-performance glass fiber composition according to claim 1, containing the following contents of components in weight percentage: TABLE-US-00036 SiO.sub.2 52-64% Al.sub.2O.sub.3 12-24% RE.sub.2O.sub.3 = Y.sub.2O.sub.3 + La.sub.2O.sub.3 + Gd.sub.2O.sub.3 0.05-8% La.sub.2O.sub.3 0.05-2% R.sub.2O = Li.sub.2O + Na.sub.2O + K.sub.2O <2.5% K.sub.2O 1.1% CaO + MgO + SrO 10-24% CaO 2-14% MgO .sup.<13% TiO.sub.2 <2% Fe.sub.2O.sub.3 <1.5% and, a ratio C1 in weight percentage of K.sub.2O to R.sub.2O, C1=K.sub.2O/R.sub.2O, is greater than 0.44.

16. The high-performance glass fiber composition according to claim 1, containing the following contents of components in weight percentage: TABLE-US-00037 SiO.sub.2 52-64% Al.sub.2O.sub.3 12-24% RE.sub.2O.sub.3 = Y.sub.2O.sub.3 + La.sub.2O.sub.3 + Gd.sub.2O.sub.3 0.05-8%.sup. R.sub.2O = Li.sub.2O + Na.sub.2O + K.sub.2O <2.5% K.sub.2O 1.1% Li.sub.2O 0.1-1% CaO + MgO + SrO 10-24% CaO 2-14% MgO <13% SrO <2.5% TiO.sub.2 .sup.<2% Fe.sub.2O.sub.3 <1.5% and, a ratio C1 in weight percentage of K.sub.2O to R.sub.2O, C1=K.sub.2O/R.sub.2O, is greater than 0.44, and a ratio C2 in weight percentage of (MgO+SrO) to CaO, C2=(MgO+SrO)/CaO, is greater than 0.9.

17. The high-performance glass fiber composition according to claim 1, containing the following contents of components in weight percentage: TABLE-US-00038 SiO.sub.2 52-64% Al.sub.2O.sub.3 12-24% RE.sub.2O.sub.3 = Y.sub.2O.sub.3 + La.sub.2O.sub.3 + Gd.sub.2O.sub.3 0.05-8%.sup. Y.sub.2O.sub.3 0.05-6%.sup. R.sub.2O = Li.sub.2O + Na.sub.2O + K.sub.2O <2.5% K.sub.2O 1.1% Li.sub.2O 0.1-1% CaO + MgO + SrO 10-24% CaO 2-14% MgO <13% SrO <2.5% TiO.sub.2 .sup.<2% Fe.sub.2O.sub.3 <1.5% and, a ratio C1 in weight percentage of K.sub.2O to R.sub.2O, C1=K.sub.2O/R.sub.2O, is greater than 0.44, and a ratio C2 in weight percentage of (MgO+SrO) to CaO, C2=(MgO+SrO)/CaO, is greater than 0.9.

18. The high-performance glass fiber composition according to claim 1, containing the following contents of components in weight percentage: TABLE-US-00039 SiO.sub.2 52-64% Al.sub.2O.sub.3 12-24% RE.sub.2O.sub.3 = Y.sub.2O.sub.3 + La.sub.2O.sub.3 + Gd.sub.2O.sub.3 1-6% R.sub.2O = Li.sub.2O + Na.sub.2O + K.sub.2O <2.5% K.sub.2O 1.1% Li.sub.2O 0.1-1% CaO + MgO + SrO 10-24% CaO 4-11% MgO 6-12% SrO <2.5% TiO.sub.2 .sup.<2% Fe.sub.2O.sub.3 <1.5% and, a ratio C1 in weight percentage of K.sub.2O to R.sub.2O, C1=K.sub.2O/R.sub.2O, is greater than or equal to 0.5, and a ratio C2 in weight percentage of (MgO+SrO) to CaO, C2=(MgO+SrO)/CaO, is greater than or equal to 1.

19. A glass fiber, made of the glass fiber composition according to claim 1.

20. A composite material, comprising the glass fiber according to claim 19.

Description

DETAILED DESCRIPTION OF THE PRESENT INVENTION

(1) In order to make the objectives, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be described clearly and completely. Apparently, the described embodiments are just some of but not all of the embodiments of the present invention. All other embodiments obtained by a person of ordinary skill in the art without paying ant creative effort on the basis of the embodiments in the present invention shall fall into the protection scope of the present invention. It is to be noted that the embodiments in the present application and the features in the embodiments can be combined at will if not conflicted.

(2) The basic idea of the present invention is that the glass fiber composition contains the following contents of components in weight percentage: 52-64% of SiO.sub.2, 12-24% of Al.sub.2O.sub.3, 0.05-8% of Y.sub.2O.sub.3+La.sub.2O.sub.3+Gd.sub.2O.sub.3, less than 2.5% of Li.sub.2O+Na.sub.2O+K.sub.2O, more than 1% of K.sub.2O, 10- 24% of CaO+MgO+SrO, 2-14% of CaO, less than 13% of MgO, less than 2% of TiO.sub.2, and less than 1.5% of Fe.sub.2O.sub.3. The composition can greatly increase the mechanical strength and elastic modulus of glass, and can also significantly reduce the liquidus temperature and the forming temperature of glass, and under equal conditions, can greatly reduce the crystallization rate, the surface tension and the bubble rate of glass. The composition is particularly suitable for the tank furnace production of high-strength high-modulus glass fiber having a low bubble rate.

(3) Specific values of contents of SiO.sub.2, Al.sub.2O.sub.3, Y.sub.2O.sub.3, La.sub.2O.sub.3, Gd.sub.2O.sub.3, CaO, MgO, Li.sub.2O, Na.sub.2O, K.sub.2O, Fe.sub.2O.sub.3, TiO.sub.2 and SrO in the glass fiber composition of the present invention are selected as embodiments for comparing with performance parameters of S glass, conventional R glass and improved R glass. Six performance parameters are used for the performance comparison:

(4) (1) forming temperature, which corresponds to the temperature of molten glass at a viscosity of 10.sup.3 P;

(5) (2) liquidus temperature, which corresponds to the temperature at which crystal nucleuses begin to form when molten glass is cooled, i.e., the ceiling temperature of the crystallization of glass;

(6) (3) T, which is the difference between the forming temperature and the liquidus temperature and represents the range of the temperature for fiber formation;

(7) (4) crystallization peak temperature, which corresponds to the temperature at the highest peak of the crystallization of glass during the DTA testing; in general cases, a higher temperature means more energy is required for the growth of crystal nucleuses and low crystallization tendency of glass;

(8) (5) elastic modulus, which is longitudinal elastic modulus, represents the resistance of the glass against the elastic deformation, and is tested in accordance with ASTM2343;

(9) (6) filament strength, the maximum tensile strength that a single fiber can withstand;

(10) (7) amount of bubbles, wherein the general method for measuring the amount of bubbles is 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 seven parameters and their measurement methods are well known to those skilled in the art, and therefore the performance of the glass fiber composition of the present invention can be represented effectively by the parameters.

(12) The specific process of experiments is as follows: components can be selected from suitable raw materials, various raw materials are mixed in proportion to achieve the final desired weight percentage, and the mixed batches are melted and clarified; then, the molten glass is drawn out through the bushing tips on a bushing to form glass fiber, and the glass fiber is wound onto a rotary collet of a winding machine to form cakes or packages. Of course, such glass fiber can be further processed in a conventional manner to satisfy the expected requirements.

(13) Specific embodiments of the glass fiber composition of the present invention will be given below.

(14) TABLE-US-00025 Embodiment 1 SiO.sub.2 58.6% Al.sub.2O.sub.3 16.9% CaO 7.3% MgO 9.9% Y.sub.2O.sub.3 3.9% La.sub.2O.sub.3 0.3% Na.sub.2O 0.23% K.sub.2O 1.05% Li.sub.2O 0.50% Fe.sub.2O.sub.3 0.44% TiO.sub.2 0.63%
and, a ratio C1 in weight percentage of K.sub.2O to R.sub.2O, C1=K.sub.2O/R.sub.2O, is 0.59, and a ratio C2 in weight percentage of (MgO+SrO) to CaO, C2=(MgO+SrO)/CaO, is 1.36.

(15) Values of six parameters measured in Embodiment 1 are respectively:

(16) TABLE-US-00026 forming temperature 1298 C. liquidus temperature 1206 C. T 92 C. crystallization peak temperature 1033 C. elastic modulus 96.0 GPa filament strength 4290 MPa amount of bubbles 3

(17) TABLE-US-00027 Embodiment 2 SiO.sub.2 58.6% Al.sub.2O.sub.3 16.9% CaO 6.8% MgO 9.6% Y.sub.2O.sub.3 3.9% La.sub.2O.sub.3 0.3% Na.sub.2O 0.23% K.sub.2O 1.05% Li.sub.2O 0.50% Fe.sub.2O.sub.3 0.44% TiO.sub.2 0.63% SrO 0.8%
and, a ratio C1 in weight percentage of K.sub.2O to R.sub.2O, C1=K.sub.2O/R.sub.2O, is 0.59, and a ratio C2 in weight percentage of (MgO+SrO) to CaO, C2=(MgO+SrO)/CaO, is 1.53.

(18) Values of six parameters measured in Embodiment 2 are respectively:

(19) TABLE-US-00028 forming temperature 1300 C. liquidus temperature 1205 C. T 95 C. crystallization peak temperature 1034 C. elastic modulus 96.8 GPa filament strength 4305 MPa amount of bubbles 4

(20) TABLE-US-00029 Embodiment 3 SiO.sub.2 58.6% Al.sub.2O.sub.3 16.9% CaO 7.2% MgO 9.9% Y.sub.2O.sub.3 3.9% La.sub.2O.sub.3 0.3% Na.sub.2O 0.18% K.sub.2O 1.30% Li.sub.2O 0.50% Fe.sub.2O.sub.3 0.44% TiO.sub.2 0.53%
and, a ratio C1 in weight percentage of K.sub.2O to R.sub.2O, C1=K.sub.2O/R.sub.2O, is 0.67, and a ratio C2 in weight percentage of (MgO+SrO) to CaO, C2=(MgO+SrO)/CaO, is 1.38.

(21) Values of six parameters measured in Embodiment 3 are respectively:

(22) TABLE-US-00030 forming temperature 1297 C. liquidus temperature 1205 C. T 92 C. crystallization peak temperature 1033 C. elastic modulus 96.5 GPa filament strength 4330 MPa amount of bubbles 2

(23) TABLE-US-00031 Embodiment 4 SiO.sub.2 59.2% Al.sub.2O.sub.3 16.9% CaO 7.6% MgO 9.8% Y.sub.2O.sub.3 2.9% Na.sub.2O 0.21% K.sub.2O 1.03% Li.sub.2O 0.40% Fe.sub.2O.sub.3 0.44% TiO.sub.2 0.41% SrO 0.8%
and, a ratio C1 in weight percentage of K.sub.2O to R.sub.2O, C1=K.sub.2O/R.sub.2O, is 0.63, and a ratio C2 in weight percentage of (MgO+SrO) to CaO, C2=(MgO+SrO)/CaO, is 1.29.

(24) Values of six parameters measured in Embodiment 4 are respectively:

(25) TABLE-US-00032 forming temperature 1293 C. liquidus temperature 1199 C. T 94 C. crystallization peak temperature 1031 C. elastic modulus 95.3 GPa filament strength 4295 MPa amount of bubbles 3

(26) The comparison of the above embodiments and other embodiments of the glass fiber composition of the present invention with performance parameters of S glass, conventional R glass and improved R glass will be further given below by tables, where the content of the glass fiber composition is represented in weight percentage. It is to be noted that the total content of the components in the embodiments is slightly less than 100%, and it can be understood that the remaining is a trace amount of impurities or a small amount of components which cannot be analyzed.

(27) TABLE-US-00033 TABLE 1A A1 A2 A3 A4 A5 A6 A7 Components SiO.sub.2 59.2 59.3 59.5 58.4 58.0 58.8 58.6 Al.sub.2O.sub.3 16.9 16.8 17.5 17.8 19.1 17.0 16.9 CaO 7.6 6.9 8.9 9.1 6.9 5.7 7.2 MgO 9.8 11.1 9.8 10.1 9.0 10.5 9.9 Y.sub.2O.sub.3 2.9 3.0 3.5 5.0 3.9 La.sub.2O.sub.3 0.3 1.1 0.4 0.3 Gd.sub.2O.sub.3 0.4 Na.sub.2O 0.21 0.21 0.23 0.23 0.13 0.27 0.18 K.sub.2O 1.03 1.05 1.02 1.08 1.10 1.08 1.30 Li.sub.2O 0.40 0.20 0.30 0.60 0.41 0.51 0.45 Fe.sub.2O.sub.3 0.44 0.44 0.44 0.44 0.44 0.43 0.44 TiO.sub.2 0.41 0.41 0.39 0.57 0.76 0.45 0.53 SrO 0.8 0.6 Ratio C1 0.63 0.72 0.66 0.57 0.67 0.58 0.67 C2 1.29 1.61 1.10 1.11 1.30 1.84 1.38 Parameters Forming 1293 1295 1297 1294 1301 1301 1297 temperature/ C. Liquidus 1199 1205 1200 1203 1201 1205 1205 temperature/ C. T/ C. 94 90 97 91 100 96 92 Crystallization 1031 1028 1032 1030 1031 1035 1033 peak temperature/ C. Elastic 95.3 96.1 93.9 93.5 96.8 98.6 96.5 modulus/GPa Filament 4295 4305 4270 4260 4315 4350 4330 strength/MPa Amount of 3 4 4 4 3 3 2 bubbles

(28) TABLE-US-00034 TABLE 1B Conventional R Improved R A8 A9 A10 A11 S glass glass glass Components SiO.sub.2 58.6 58.6 58.6 58.6 65 60 60.75 Al.sub.2O.sub.3 16.9 16.9 16.9 16.9 25 25 15.80 CaO 7.3 8.0 6.8 7.3 9 13.90 MgO 9.9 9.2 9.6 9.9 10 6 7.90 Y.sub.2O.sub.3 3.9 3.9 3.9 3.9 La.sub.2O.sub.3 0.3 0.3 0.3 0.3 Na.sub.2O 0.18 0.23 0.23 0.23 Trace Trace 0.73 amount amount K.sub.2O 1.15 1.05 1.05 1.05 Trace Trace amount amount Li.sub.2O 0.50 0.50 0.50 0.50 0.48 Fe.sub.2O.sub.3 0.44 0.44 0.44 0.44 Trace Trace 0.18 amount amount TiO.sub.2 0.58 0.63 0.63 0.63 Trace Trace 0.12 amount amount SrO 0.8 Ratio C1 0.63 0.59 0.59 0.59 C2 1.36 1.15 1.53 1.36 Parameters Forming 1299 1230 1300 1298 1571 1430 1278 temperature/ C. Liquidus 1204 1205 1205 1206 1470 1350 1210 temperature/ C. T/ C. 95 95 95 92 101 80 68 Crystallization 1034 1034 1034 1033 1010 1016 peak temperature/ C. Elastic 96.5 95.7 96.8 96.0 89 88 87 modulus/ GPa Filament 4320 4280 4305 4290 4220 4109 strength/ MPa Amount 3 3 4 3 40 30 25 of bubbles

(29) It can be known from the above tables that, compared with S glass and conventional R glass, the glass fiber composition of the present invention has the following benefits: (1) the elastic modulus is much higher; (2) the liquidus temperature is much lower, and this is helpful to reduce the risk of crystallization of glass and improve the forming efficiency of fiber; and the crystallization peak temperature is higher, and this means that the formation and growth of crystal nucleuses need more energy during the crystallization of glass, that is, the crystallization rate of the glass of the present invention is lower under equal conditions; (3) the number of bubbles is decreased remarkably, and this means that the clarification effect of glass is significantly improved.

(30) Compared with improved R glass, the glass fiber composition of the present invention has the following benefits: (1) the elastic modulus is much higher; (2) the crystallization peak temperature is higher, and this means that the formation and growth of crystal nucleuses need more energy during the crystallization of glass, that is, the crystallization rate of the glass of the present invention is lower under equal conditions; (3) the filament strength is much higher; (4) the number of bubbles is decreased remarkably, and this means that the clarification effect of glass is significantly improved.

(31) Both S glass and conventional R class cannot realize tank furnace production, and improved R class reduces the liquidus temperature and forming temperature at the cost of certain performance to reduce the production difficulty and realize tank furnace production. In contrast, the composition of the present invention can not only realize tank furnace production with low enough liquidus temperature and lower crystallization rate, but also remarkably improve the modulus of glass. The technical bottleneck that the modulus of S glass and R glass fiber cannot be improved with the increasing production scale is resolved.

(32) Glass fiber having excellent performance can be made from the glass fiber composition of the present invention.

(33) Composite material having excellent performance, for example, glass fiber reinforced base materials, can be manufactured by the combination of the glass fiber composition of the present invention and one or more organic and/or inorganic materials.

(34) Finally, it is to be noted that, as used herein, the term comprise/comprising, contain/containing or any other variants thereof is non-exclusive, so that a process, method, object or device containing a series of elements contains not only these elements, but also other elements not listed clearly, or further contains inherent elements of the process, method, object or device. Without more restrictions, an element defined by the statement comprises a/an . . . does not exclude other identical elements in the process, method, object or device including this element.

(35) The foregoing embodiments are merely used for describing the technical solutions of the present invention and not intended to limit the technical solutions of the present invention. Although the present invention has been described in detail by the foregoing embodiments, it should be understood by a person of ordinary skill in the art that modifications still can be made to the technical solutions recorded in the foregoing embodiments or equivalent replacements can be made to part of technical features, and these modifications or replacements will not make the essence of the corresponding technical solutions depart from the spirit and scope of the technical solutions in the embodiments of the present invention.

INDUSTRIAL APPLICABILITY OF THE PRESENT INVENTION

(36) The composition of the present invention can not only realize tank furnace production with low enough liquidus temperature and lower crystallization rate, but also remarkably improve the modulus of glass. The technical bottleneck that the modulus of S glass and R glass fiber cannot be improved with the increasing production scale is resolved. Compared with the current mainstream high-performance glasses, the glass fiber composition of the present invention has made great progress on the elastic modulus, mechanical strength, crystallization performance and the clarification of glass. Under equal conditions, the elastic modulus and mechanical strength of glass are remarkably improved, the risk of crystallization is significantly decreased, and the amount of bubbles is significantly reduced. Therefore, the whole technical solution is particularly suitable for the tank furnace production of high-strength high-modulus glass fiber having a low bubble rate.